JPS5845111A - Crystalline aluminosilicate, its manufacture and converting method for organic starting material using it - Google Patents

Abstract

PURPOSE:To obtain crystalline aluminosilicate having a specific crystal structure and a high ratio of SiO2/Al2O3 only from inorg. reactive materials by specifying the ratios of SiO2/Al2O3, metallic oxide/SiO2, water/metallic oxide, and the anion of the salt of a mineralizing agent/SiO2 in an aqueous reactive mixture. CONSTITUTION:This crystalline aluminosilicate has a composition expressed by the formula (where M is >=1 kind of metallic cation, (n) is the valence of M, and Z is 0-40) in a molar ratio among oxides, and it has a powder X-ray diffraction diagram showing lattice spacing expressed by the figure. An aqueous reactive mixture having 10-130 ratio of SiO2/Al2O3, 0.03-0.5 ratio of M2/nO/SiO2, 100- 1,000 ratio of H2O/M2/n and 0.01-20 ratio of X<->/SiO2 (where M is >=1 kind of metallic cation, (n) is the valence of M, and X<-> is the anion of the salt of a mineralizing agent) is prepared, and by maintaining the mixture at the crystallization temp. under heating until crystals are formed, the desired crystalline aluminosilicate is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crystalline aluminosilicate, a method for producing the crystalline aluminosilicate, and a method for converting organic raw materials, and particularly relates to a novel crystalline aluminosilicate having molecular shape selectivity and catalytic ability. This invention relates to aluminosilicate and its manufacturing method. To explain in more detail, this material has a unique crystal structure and is suitable for selective catalytic reactions of hydrocarbons.
The present invention provides a crystalline aluminosilicate having a high in,/λ1,0° ratio.

Crystalline aluminosilicate C-salt is generally known as crystalline zeolite, and its crystalline 41
+# structure is an 8i04 tetrahedron in which four ``jt1t7'' formed around silicon-*(81) are arranged at the vertices, and silicon (Si) is replaced with aluminum (AI). It is an aluminosilicate hydrate having a structure based on a three-dimensional framework of AlO4 tetrahedrons.

810, tetrahedrons and AlO4 tetrahedra are 4.5.6.8 or 4-membered rings, 5-shell rings, 8-membered rings, or 12-membered moats formed by connecting 4.5.6.8 or 12 of them, and these 4.6.8 and a 12-membered ring form a double ring or a basic unit, which are linked together to determine the skeletal structure of the crystalline aluminosilicate. A specific cavity exists in the skeleton structure determined by these Q-connection methods, and the entrance of the cavity structure forms a cavity consisting of 6, 8, 10 and 12-membered rings. The formed cavity has a uniform flow, and molecules below a certain size are adsorbed, but larger molecules are prevented from entering the cavity.

Such crystalline aluminosilicate is known as "Molecular 1.1" due to its action, and has the above properties.
H, lateral chemical pro-7 adsorbent and chemical reaction I
It is used as a catalyst and catalyst carrier for I4.

The electron valence of the aluminum-containing aluminum-containing crystalline aluminosilicate described above is kept in equilibrium by containing cations in the crystal.

Natural crystalline alumino I:! = Weir, the cation is Group ■ of the Periodic Table of Elements or the same table! Metals of the It group, especially sodium, potassium, calcium, magnesium and strontium. The above metal cations are also used in synthetic crystalline aluminosilicates, but gold l141
i! In addition to ions, organic nitrogen cations have recently been proposed, such as quaternary alkylammonium ions such as tetraalkylammonium ions. In the synthesis of crystalline aluminosilicate with a high silica/alumina ratio, it has been considered that the use of organic nitrogen-containing compounds as described above as an alkali source is indispensable.

However, when using organic nitrogen-containing compounds,
In addition to the disadvantage of low raw material prices, in order to use the synthesized aluminosilicate produced at wJ'4 as a melting medium, it is necessary to remove the organic nitriding compounds present in the compound by firing at high temperatures. This had the disadvantage of polarizing the manufacturing process.

Furthermore, as mentioned above, in the conventional production method using an amine-based organic compound such as a tetraalkylammonium compound or a primary amine of Ct-Cue, the organic compound is This poses a physiological risk due to the latent toxicity and decomposition of the food, which poses a problem in terms of production safety.

As a result of various studies and experiments, the present inventors have discovered that crystalline alumino-acrylic acid has a novel crystal @4 structure that has favorable Y-shaped selectivity and catalytic ability, and also exhibits excellent performance as an adsorbent. We have now discovered a method by which silicates and silicates can be produced from substantially inorganic materials.

Therefore, the main object of the present invention is to have SIO! / A 110 g molar ratio of crystalline alumino silica salt having a high degree of catalytic activity and this, an aqueous compound consisting essentially only of M-organic reaction materials, a monomer compound, an aluminum compound, an alkali gold-4 compound, and water. It is an object of the present invention to provide a method for producing from a reaction mixture.

Another object of the present invention is to provide a crystalline aluminosilicate fine salt having a unique crystal structure characterized by an X-diffraction pattern, and which exhibits a significant selective decomposition activity of decomposed hydrocarbons. be.

Still another object of the present invention is that the synthetic alumino rII salt is M
, 7nO-A l,o, -8i O,-1 (10 (where M is a metal cation with a valence of four).

) and does not require the heat treatment step of the composite required in the prior art, thus simplifying the manufacturing process 7)
It is an object of the present invention to provide a method for producing crystalline alkyl silicates which is simple and enables reduction of production soot.

The present invention has been completed based on the above-mentioned findings, and can effectively achieve the above object. /n0-AI,O,-10-1008
10,・Zll, 0 (where M is a metal cation, n is the valence of the metal cation, and 2 is 0-
It is 40. ) and has a powder XfM diffraction pattern showing at least the lattice spacing, i.e., d-distance, shown in Table 16 Table 1 11 .2 ± 0.2B.

10.1 ± 0.2 B.

Z5 10.15’ W.

60! l±0.1　　　　　M.

586 ± o, os v, s.

582±o, os s.

376 ± aos.

6.72 ± o, os s.

664 ± o, os s.

The above-mentioned alumino Kash salt having a crystal +4 structure characterized by X-ray and diffraction patterns is hitherto unknown and will be referred to as 1TsZ hereafter.

These values are the results measured by conventional methods.

The radiation was copper K-(X211X'f1M) and a scintillation counter equipped with a strip f'r-tone recorder was used. From the chart the peak height was determined as a function of 20 (θ is the black angle). From these, the relative intensity corresponding to the recorded line and the lattice spacing (d) expressed in angstroms were read.
It is a measurement of people. V in the relative strength of Table 1
, S is the strongest, s is strong, M is medium strong, W is weak, v,
w, shows very m.

The crystalline aluminosilicate according to the invention is characterized by an XkM diffraction pattern obtained by the conventional method of powder (1) diffraction. That is, 12θ=14. The diffraction line of y"Ca=603 people) is a single line (Singl・t), and 2θ=25@ (d=5.86 people) and 2θ=2S
, 5" (d=5.82) are clearly separated from each other, which is the biggest feature that can be distinguished from the crystal structure of the crystalline zeolite proposed in the past.

In addition, in addition to the conventional method, powder XIM diffraction analysis was carried out to measure 2θ (θ is the Bravo angle) with high accuracy, and the results were analyzed. Crystallographically, it was found to belong to monoclinic threads. For example, 102Na, the product of Example 7 described below.
go-102Na・26.28IO,-12.2H,0
TSZ with the composition a=2α159(±(1004
) people, b=19.982 (±(Lo 06) people, C=I
N405 (±0.00.5) people, 1Z=9α51° (±
The lattice constant of the monoclinic system of αO3′) is shown. The measured and calculated values of the lattice spacing of this typical TSZ and the Miller index are listed in Table 2.

Such a specific X@ diffraction pattern is due to changes in the substituted cations of the synthetic aluminosilicate, especially to hydrogen ion weirs, 810
The lattice spacing is not significantly affected by changes in the H/A I 20B ratio or the like.

The preferred composition of TSZ in its as-synthesized form is 0.8 - t 5 M17nO-A 1,0.
25-80SiO, -0-40) (,0, where M is at least one gold cation and n is the valence of the metal cation.) During synthesis At least one of the metal cations present in the metal cations can be removed by ion exchange or the like.Ion exchange is a method of removing hydrogen ions such as metals or metals from group 11 to group ν of the photoelectric periodic table. It can be carried out by using or ammonium ion. By replacing with hydrogen, ammonium, sodium carbonate, or rare earth metal, etc., it imparts catalytic activity, especially activity as a catalyst for hydrocarbon conversion. 810./AI, O, in the molar ratio range of 25-80, even if T, 8Z is converted to the hydrogen ion type, there is no change in the monoclinic thread, and the crystal structure is does not receive any honorable mentions.

The crystalline aluminosilicate according to the invention, namely Ta2, is
It can be manufactured by the following method.

That is, it contains a silica source, an alumina source, an alkali source, and water, and is substantially composed of inorganic reactive materials, and has the following composition expressed by the following molar ratio: s i O, α0
3-α5 Hio/M! ! /n 0 100-tOOO
x-, /sio, (101-20 (where, M is a gold cation selected from Group 1 shi and Y group of the Genkun Circular Table, and n is its is the valence of the metal cation and X'' is the anion of the salt of the mineralizer) and is heated at autogenous pressure in the range of about 20°C to about 250°C. A method of making a crystalline silicate composition comprising maintaining the composition for about 10 hours to about 20 hours is provided.

The preferred composition of the aqueous reaction mixture, expressed in molar ratios, is as follows. - SiO,/Al, 0. 20-12ONap
o/s to, 0.0 s-α3(N
a, o+M2/no)/s iO, (Lo s-α5u
, o/(Na, o+M2/no) 1s o -s o
.

X − /B i O, α05-15 S, 1. The optimal range of composition of the aqueous reaction compound is as follows, expressed in molar ratio of oxides.

sio, /Al, o, 3o-t 1sNa
, o/s io, (105-as(N a
t O+M 2/n O)/S l O* Q, 0
5-α3HtO/(NalO+M2//nO) 20
0-700X -/810! 0・1-
In the above description, M is a metal cation selected from group 1 and Ml of the thoracic table, in particular lithium, barium, calcium and strontium;
n is 1 μ (1) atom of the metal cation.
2/nO and Nil, 0, free 11.7.0 and Na,0, and are generally effective in hydroxide and zeolite synthesis, such as polar neates, such as aluminates, silicates, etc. It is a form. In addition, the above [Yukon N
a, OJ can be further improved by adding aluminum sulfate, sulfuric acid, nitric acid, etc.

In discussing the aqueous reaction mixture, the source of the oxidic reactant of the composition used is one commonly used in the production of synthetic zeolites. For example, silica sources include sodium silicate, silica gel, silicic acid, aqueous cotetraidal silica gel-dissolved silica, powdered silica, amorphous silica, and the like. As the alumina source, various aluminum salts such as activated alumina, r-alumina, alumina trihydrate, fluorium aluminate, and aluminum chloride, nitrate, and sulfate can be used. The metal oxides represented may be in the form of water-soluble salts or in the form of hydroxides.
N11O as a source of sodium cations added to the reaction mixture with S is added in the form of sodium hydroxide, sodium aluminate or sodium silicate, and
LhO as a source of lithium cations is available in hydroxide, hedagenide, sulfate, nitrate and chloride (LiC10
4) Added in the form of hemorrhoids. An aqueous reaction mixture is prepared by mixing the silica source, alumina source, alkaline source, and water. Particularly suitable silica sources include Fium silicate, water glass, cosidical silica, etc., and examples of suitable silica sources include sodium alkene, dermium sulfate, and the like.

In producing the crystalline aluminosilicate TeSz of the present invention,
The water content of the aqueous reaction mixture is important, and as described in 011, the reaction mixture contains Ht O/(N a * 0 +
It is necessary to have a water content in the range of 100 or more, preferably 300 to 500 or more, expressed as MψO) molar ratio. By setting the water content within the above range, mixing and stirring of the reaction reagent gel becomes easy.

After mixing the reaction reagents as described above, the reaction mixture is heated to about α01 at autogenous pressure in the range of about α01 to about 230°C.
- maintained for about 20 hours.

During crystallization, the mineralizing agent is added to the aqueous reaction mixture.
By increasing the crystallinity, the crystallinity of the crystallized product can be further improved, and the generation of non-travel aluminosilicate soil can be suppressed. Mineralizers include NaC1, NJI, C
OB, Na, 804, Na, 8e04, K
Cl, KBr.

Alkali metal or alkaline earth metal neutrals of KF, NACL, or Banr snow can be used. A preferred mineralizer is NaCl. In this case, the amount added is x-
The Cn-valent anion is considered to be a monovalent anion. ), the preferred X-/SiO* molar ratio ranges from about α01 to about 20. Furthermore, the preferable addition amount is about α05-about 15
, and the most recent addition set is in the range from about α05 to about 10.

The produced crystalline aluminosilicon salt 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. More preferably, at least one of the cations in the product is
The part is decentered or exchanged by heat treatment and/or ion exchange. In this case, cation exchange is useful. b′-substituted ion, which can be produced by the desired reaction,
Periodic Table of Elements No. I11, m”s N”% Ib%
Preferably, at least 1 pJ selected from 'Abs 1 and 1 pJ is preferred. Also, i...processing or NH,
What about the 10-day process and heat treatment? Water can be replaced. Preferred substituent ions for conversion reactions such as decomposition, isomerization, and alkylation of Fukiwa Mizushige are hydrogen ions and Group I metals; This can be done by contacting it with a salt. In this case, alkali metal or monoalkaline earth metals of persimmons can be used, in particular,
Chloride 1, nitric acid, sulfate and vinegar t1! Yonghao is preferred.

The hydrogen ion exchange type crystalline aluminosilicate obtained by replacing TBZ with hydrogen ions of the present invention is further brought into contact with an acid to extract alumina, Bto, /mu1
The image molar ratio was increased to 100 or more.

It is possible to further improve sexual performance.

The acids used in the acid extraction process include pure mineral acids,
for example,. In addition to hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, acetic acid,
Organic acids such as formic acid are preferred. Particularly preferred acids are
#Ar1! It is. The concentration of the acid used is in the range of 1 to 12 normal. The temperature of the acid extraction process ranges from room temperature to approximately 9
Up to 5° C.8, but preferably as high a temperature as possible. When the above acid extraction treatment is carried out at 90°C for 4 hours using, for example, 3N concentration hydrochloric acid, the starting material S i O@ /A 1
The molar ratio of electrons can be set to 100 or more.

The T8z according to the invention can be used as a catalyst by ion exchange as described above. It is preferable to improve the catalytic activity by introducing an active metal component or by introducing hydrogen ions through acid treatment. Further, mixing with a carrier such as ordinary silica alumina or alumina is carried out. TIZ
and when containing a quality active ingredient, at a temperature of about 380° C. to about SOO° C., a pressure of about 5 to about 56 ky/s+”, preferably about 10=about 50 ky/c×P, about (L 5−1
1.・5. Ov/H/V, preferably about to-11
+ ”-OV/H/V f) Liquid air + w + 4. degree reaction conditions Te reforming 113j material can be catalytically reformed. Also, transition metals such as Co and Ni or metals such as platinum and palladium can be used for catalytic reforming. TBZ can be used as a catalyst for the dewaxing of gas oil fractions and lubricating oil fractions.The contact temperature is about 250°C to about 450°C.
, preferably about 300°C to about 400°C humidity, -about -
5ky/an' - about 50ky/(ill, preferably Fl 1 'Okg/ax' - about 50 kglts
Snow pressure, approx. (L25V/H/V-Nl 5 V/H/
V, preferably about tOv/H/V - about zOVAvV can be employed. Furthermore, TIZ is capable of hydroisomerization of normal paraffins, hydrodehydrogenation, conversion of desulfurized alcohols to hydrocarbons, alkylation of aromatic TtPti with alcohols, and conversion of disproportionated organic compounds between aromatic compounds. It also exhibits catalytic activity in reactions.

As mentioned above, the TSZ related to Akira Motoyama is based on a specific knowledge, study introduction, and powder? It has interlattice planes as shown by the C-ray diffraction pattern, and has a remarkable effect in the conversion reaction of IiRw and materials, especially in the decomposition reaction of hydrocarbons.

Hereinafter, the crystalline alinosilicate of the present invention,! Regarding 8z, pI according to the example! - to do.

Example 1 An aluminum sulfate solution was prepared by dissolving ycat of aluminum sulfate in 17o, t of pure water and further adding s:yto** acid (?5 vt, l) and 18t of sodium chloride. This aluminum sulfate solution was mixed with 25 f water and 651 water glass (NjLl 0: 91 S v
tJsto Taki: 2 & 4 wtJ! ) (Japanese Industrial Standards No. 5 water glass) and mixed with the Butsukin solution while stirring,
Show it in molar ratio of oxide! L? Nm, 011 Att.
An aqueous reaction mixture was obtained having a composition of 0@ 508101'' 2184 璽鵞0. In this case, the Cj7/IiO,-l ratio of the mineralizing agent sodium chloride was j02. The mixture was placed in an autoclave and heated to 180°C for 20 hours under autoclave.The crystallized solid product was separated by filtration, washed with water, and dried at 110°C.A sample of this solid product was Subjected to chemical analysis, Wage: 2.6vt-(NraO
h: 4.25 vt j g 11%: 848v
t, 1. A chemical composition of O:a4vt, 11 was obtained.

When expressed in terms of the molar ratio of oxides, the following formula was obtained:
” 112 ii!.

This product was subjected to X-ray analysis, and the results shown in Table 3 were obtained.

Table 3 Lattice spacing Relative intensity Lattice spacing (relative intensity 11
18 74 5.73 4
69.76 14 3.49
59.05 1 3.45
107.46 5 5
．． 56 7Zro8 2
561 9 & 72
6 526 5657
11 3.05 1340
1 15 3.00 1
35.72 7 2.98
145.58 10 2.94
85,! S 8 5 5.16 2 5.0 S 6 4.98 7 4.62 5 4.37 6 427 15 409 5 4.01 6 Connection 6 100 3.82 67 576 38 This X-ray analysis This was done using the conventional method of line diffraction. The irradiation glue is 1221lLIIIi+ for steel,
The line tube voltage and tt current are 70 - 40 and 70 -
And so. A scintillator counter equipped with a goniometer and a strip chart pen recorder was used to measure the diffraction angle 2# and the intensity of the diffraction line. At this time, the scanning speed was 2# rotation, 2''1 minute, and the time constant of the rate meter was 1 second.

A portion of the product was calcined at 540° C. for about 3 hours and then degassed under vacuum at 300° C. for about 3 hours.

The zeolite is 7 at i2waHf and 25C.
．． 0 wt- of water, 10 at 20 mHf and 25°C
0 wt. of n-hexane, 45 wt. of cyclohexane were each adsorbed at 2 Qmt and 25°C.

(Evaluation of Activity) In order to clarify the catalytic action of Te8z, an activity comparison was made with a crystalline aluminosilicate having a conventionally known powder x@ diffraction pattern.

! At the 9th point of ion-exchanging the sodium ions of Sz, 5
1) Ion exchange operation was performed at 80° C. for 15 hours using a Di4ct solution. This operation was repeated 4 times, and after completion of the procedure, the product was fired at 600C for 3 hours to obtain M-type τ-z. Next, the R-type TBZ powder was mixed with a separately manufactured alumina binder at a ratio of 7:3 (weight ratio after firing),
After adding water and extrusion molding, a pellet with a diameter of t5 was obtained.

Using the above Wits catalyst, a hexane decomposition reaction was carried out as follows.

A glass reactor was filled with the catalyst &2- crushed to 16,130 mesh, and silica chips 5.2- also crushed to 16,750 mesh were packed on the top of the catalyst bed to improve the agility and heating of the reactants. The catalyst wire was maintained at 500°C.

N-hexane was placed in a saccharide lake maintained at 10°C, and nitrogen was flowed as a carrier gas so that the concentration of n-hexane in the nitrogen gas was 10°.

After a certain period of time after introducing n-hexane I into the reactor system, the remaining amount of hexane is measured by gas chromatography and compared with the amount of n-hexane in the feed to determine the conversion rate (con After that, air was introduced into the reactor system and the catalyst bed temperature was raised to 500℃.
The experiment was carried out by burning the carbonaceous substances adhering to the catalyst, returning the catalyst to a fresh state, and changing the space velocity again.

In this way, the conversion rate of 1-hexy was determined at 300°C and 275°C, and the following results were obtained (Table 4).

Similarly, the hexane decomposition activity of a catalyst obtained by converting a crystalline aluminosilicate having a known powder X-ray diffraction pattern into a hydrogen exchange type was also evaluated, and the results are also listed in the same table. These results revealed that Tgz according to the present invention has remarkable hydrocarbon decomposition activity.

Table 4 1-hexane decomposition activity k (l El -1) -x ts+x Comparative example 1 Reaction temperature (C) 1sOo 300 275
300! to.

($1) (1) 5 (minutes)
-2,71-1160,91 (umbrella 1) 10 - 121 2.35 154
a7920 t81 CL98 12
1 (L?? CL5050 175
(L96 11? (L83 (15145t7
5 α97 114 α7? a5060
t75 0.97 t20 α85 α
49 (Shen 1) Comparative example of decomposition of Muhexane 10011 1 Dissolve 98f of aluminum sulfate in 405t of pure water, add 1t2toe sulfuric acid (95vt, 1g), 5t
st tetrapropylammonium bromide (tpA
lr) and 37.8 t of sodium chloride,
An aluminum sulfate solution was prepared.

This aluminum sulfate solution was mixed with 745f of water and 154.2f of water.
f water glass (Ma2O: 9.15 ft, fj >
1101:2a6vt,-) (Japanese Industrial Standards 3
4.4 (TPA)10' 5. ONml O@d@
An aqueous reaction mixture was obtained having the composition O@"508101'21801E11G.

In this case, 0ct-11 to molar ratio is CL? And nine.

The aqueous reaction mixture was poured into a @UII autocrepe, heated and maintained at 160° C. for 20 hours at autogenous pressure. The crystallized solid product was separated once, washed with water and dried at 110°C. A sample of the solid product was subjected to chemical analysis with a TPM of 10: 10.9vt,
9i, Na1O: IJ8vt Karasu A4G55L83vt
, Yu.

1110@: 71L8vt, %, 110:5, Ov
t, the chemical composition of IG was obtained.

When expressed as the molar ratio of oxides, it was as follows:〇(175(TPA), o-a6sxa, o*zo, @
35.01+10. @74! A portion of this product was calcined at 540 DEG C. for about 5 hours and subjected to XS analysis in the same manner as described in Example 1, giving the results shown in FIG. Furthermore, FIG. 5 shows a secondary electron beam (8M) with a magnification of 5000 times the product.

Example 2-4 2.5t of aluminum sulfate was dissolved in 701g of pure water,
Further, 5.4 f of concentrated sulfuric acid (?5 wt, 1) was added to this to prepare an aluminum sulfate solution (muqueous solution). Next, 25 f pure water and 65 f water glass (Na10
:9.5vtJ, 11101 :28.6wt, steamed rice) was prepared (l solution), and further, an aqueous sodium chloride solution was prepared by dissolving 21f sodium chloride in 10of pure water. The above solution and solution 1 were simultaneously added to a sodium chloride water bath solution with stirring, and expressed as the molar ratio of oxides, 8.8N first 0 "JLttO@"801
An aqueous reaction mixture having a composition of 110 g"54851.0 was obtained.

In this case, the degree of sodium chloride, which is a mineralizing agent, is st
It was 12 mol per o.

The above aqueous reaction mixture was poured into an 8UB autoclave, heated, and maintained at 170° C. for 20 hours at autogenous pressure to crystallize to obtain a solid product.

The obtained solid product was separated by f and after washing with water, 110
Dry at °C. When a sample of this solid product was subjected to chemical analysis and the chemical composition was determined, it was found that "to: 180vt, 1G,
A40@: 3. osyt, -, si amount 0 @: 13
R9vt, 11. [1G 15.5wt, -9 results were obtained. When this was expressed as the molar ratio of oxides, it was as follows.

0.97 Nag O" Pigeon 0@" 5α1! 11
0. -R81110 This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (Example 2).

The above-mentioned liquid and liquid 1 were prepared respectively, and the liquid and liquid 1 were simultaneously added to an aqueous solution of ammonium carbonate in which 142 ammonium carbonate (CO, containing 45% by weight) was dissolved in 1002 pure water, and oxidized. Expressed as a molar ratio of substances, a8 Nag O・Hato 0.・go to ・1s
An aqueous reaction mixture having a composition of 485% was obtained.90 In this case, the concentration of ammonium carbonate as a mineralizing agent was α54 mol with respect to S tO. The aqueous reaction mixture was taken into a 1υ room autoclave, heated to 170°C at autogenous pressure.
℃ for 20 hours to crystallize and obtain a solid product. The obtained 9 solid products were separated by filtration, washed with water, and dried at 110C. When a sample of this solid product was subjected to chemical analysis, it was found that Na2O:t92vt,-,nra0. ;510 vt
,-,810,; 89.0vtj.

A chemical composition of R20: 60 vrt A was obtained. When this was expressed as the molar ratio of oxides, it was as follows.

t02Walo・mu/,O,-48,9810,-1
(L? H,0) This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (
Example 3).

Next, prepare the above-mentioned liquid and liquid 1, and at the same time, 6f
of sodium sulfate was added with stirring to a sodium sulfate aqueous solution dissolved in 100 tons of pure water, and the molar ratio of the oxides was expressed as a8 Nap O 40s, 80s to, 3
An aqueous reaction mixture with a composition of 45811O was obtained. In this case, the concentration of sodium sulfate, which is a mineralizing agent, is 11G,
α was 28 mol. 8Uil of aqueous reaction mixture
The autoclave was filled with heat, the temperature was raised, and the temperature was maintained at 170°C under autogenous pressure for 20 hours. The solid product was separated by filtration, washed with water, and then dried at 110°C. When a sample of this solid product was subjected to chemical analysis, it was found that NagO: 245
vt-IAJ4Ga; 416wt-f4 Hsho
, : 8&8vt, IgtHlo : 5.9vtJ were obtained.

When expressed as the molar ratio of oxides, it was as follows: 0 112Nalo'A40@R47,88101*1
a6110 This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (Example 4).

Table 5 a(i>I/L(I dct
1740g> a(ja tlr,
s) 2.9562. ? 452. F44 Comparative Example 2 The same conditions and operations as in Example 2 were adopted except that no mineralizing agent was used, and as a solid product, Nano: 2.4 S vt j *'ll◎
s: A17 wt, 1.

11%: 8B, 1 vt, 1, H@O: 43
The chemical composition of vt-1 was obtained.

The molar ratio of oxides was as follows.

126N&@O" Pigeon 0@' 472810@@1
t5M@0 This solid product was subjected to X& analysis in the same manner as described in Example 1 and was found to be amorphous alumina-silica.

Example 5-6 A solution prepared by adding α5f sodium aluminate (NUυ, ) and α65f sodium hydroxide to 20f pure water (mu solution) and 5Of colloid Note 2) Dull silica were simultaneously mixed at 55 tons. of sodium chloride 16
5.6) It was added to an aqueous solution of sodium chloride prepared by dissolving it in pure water with stirring.・4
An aqueous reaction mixture was obtained having a composition of 7810.53141.0. In this case, the concentration of sodium chloride is il
The molar ratio was 9.40. A solid product was obtained by heating and maintaining the aqueous reaction mixture at 180° C. at autogenous pressure as in Example 1. After washing this with water and drying it at 110°C, N&! O: A02
wt, excellent μ4' m: 444 wt, excellent, 0 heat; 858vt, 嗟.

■@O: A7 vt, - chemical composition. The molar ratio of oxides was as follows.

t 12Na@O・mu40-・32.1 810!
-1t I M, 0 This product was subjected to X-ray analysis in a manner similar to that described in Example 1, giving the results shown in Table 6 (Example 5).

Next, add the above liquid and 30t of colloidal silica at the same time.
Tit sodium chloride was dissolved in 160 tons of pure water and added to a sodium chloride aqueous solution prepared with stirring, and the molar ratio of oxide was 5.6.
An aqueous reaction mixture was obtained having a composition of '478101'' 5314H@O. In this case, the sodium chloride was at a concentration of α27 in cz/s+to, molar ratio. The aqueous reaction mixture was subjected to the same crystallization conditions as above. A solid product is obtained by maintaining heating at 9.

After washing it with water, drying it at 11 DC, and then )ia
, o: 5.47 vtJ, A40m: 4.1
8 vtJ, ll01: 846 vt, 11°H
@O: It had a chemical composition of 69 vt-m. When this was expressed as the molar ratio of oxides, it was as follows.

125Nk@Osu 40s II SQ, 4 QIO,,
1, 10, 91! , 0 This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 6 were obtained (Example 6).

Note 1), ″V%/Milk sodium disodium 0s: 45.5
vt, *, Na1OS! 0.1vt, -) Note 2), Koroita"yvA) force (sto,:zαOwt, 1.Wag
e; a! 15vrt, -) Table 6 Example 5 Example 6 Gourd 16 2 Kan 152 505 6 a04 5 , LD92 Hair 105 50S12 50615 2.94 6 2.95 5 Comparative Example 5 '' Chloride as mineralizing agent The same crystallization conditions and operations as in Example 5 were adopted except that sodium was used.
What are the results of the chemical analysis of the solid product obtained? Jaw O:
5-55 vt J * pigeon o, : 4.19 v
t-excellent e 41 Sot: 85-3wt -%H,
O: 718wt, *. This is expressed as the molar ratio of oxides as follows.

157 Nat'su40. -54.61110. *9
．． The product with 71 HlO was subjected to X-ray analysis and was found to be amorphous silica-alumina.

From the above results, T8Z obtained by the production method of the present invention
was found to have a unique crystal structure.

Example 7 5.2f of aluminum sulfate was dissolved in 70F pure water,
In addition, 4.5f gk sulfuric acid (951FLJ)
Pigment was carried out, and Kensei aluminum solution (muzu) was added.

Next, 25 tons of pure water and 63F Japanese Industrial Standard No. 5 water glass (Nato; 9.5wt, iG, 8101:28
．． A mixed solution (Liquid II) with 6 wt.
An aqueous sodium chloride solution was prepared by dissolving f sodium chloride in 100 f pure water. The above M solution and B solution were simultaneously added to an aqueous sodium chloride solution while stirring, and the result was 5.8Nh@Os40m·3 expressed as the molar ratio of oxides.
An aqueous reaction mixture was obtained having a composition of 8810,.1685H,0. In this case, the quality of the mineralizing agent, sodium chloride, was 102 moles relative to 8102.

The above aqueous reaction mixture was poured into a LiUg autoclave, heated, and maintained at 170° C. for 20 hours at autogenous pressure to crystallize, and the solid product was obtained.

The solid product obtained was separated and washed with water at 110 ml.
The line turned at ℃. A sample of this solid product was subjected to chemical analysis to determine its chemical composition, and it was found to be Nb2o: 125v1.
-μ401: 5.21 wt, 1g, 1!101:
8[L5ytJ, [10: 1i2Wtl results were obtained. When this was expressed as the molar ratio of oxides, it was as follows.

t02) ralOs4o= e 2628i0@e
12.240 This product was subjected to X-ray analysis in a manner similar to that described in Example 1, and the results shown in Table 7 and FIG. 2 were obtained. Further, FIG. 4 shows the secondary electron Im (II IM) of this product at a magnification of 00 times.

Comparing this with the fa5 diagram, the characteristics of monoclinic crystals are clearly visible.

Example 8 2.5t of aluminum sulfate was dissolved in 130F pure water, and 9t of Il sulfuric acid (95wt, 0) and 21
F sodium chloride was added to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 35F of pure water and 909 Japanese Industrial Standards No. 3 water glass (Nano Den 9.5).
vtJ, 11101: 2B, 6yt, %) with stirring, and expressed as an oxide molar ratio of 1.
0.5Na, O"ago," 1141110.
” 3291 An aqueous reaction mixture with the composition of H,O is obtained.In this case, the mineralizing agent sodium chloride is
s to, the molar ratio was α84. The aqueous reaction mixture was poured into an 8υ autoclave, heated and maintained at 180°C for 20 hours at autogenous pressure. The crystallized solid product was separated by filtration, washed with water and dried at 110°C.

When a sample of this solid product was subjected to chemical analysis, it was found that Na
no; t 11 wt, *, At, o, : 2
j14 wt-,mu0. ;958Wt*.

H! O: 5. The chemical composition of Owt, Is was obtained. When this was expressed as the molar ratio of oxides, it was as follows.

0.89NalO” Pigeon 0. '78.1810!'
&4 M, 0 When this product was subjected to X@ analysis,
The results shown in Table 7 were obtained.

Table 7 Example 87 Example/Example 9 The novel crystalline aluminosilicate obtained in Example 1 (TeSZ
) and commercially available synthetic zeolite (manufactured by Two-Tone! @el・m
In order to compare the activity of 100K), an alcohol conversion reaction was carried out using a glass reactor.

Tlz zeolite was packed into an α55f (approximately tO...) glass reactor, and the catalyst bed was heated at 580°C in a nitrogen stream.
The temperature was then lowered to 300°C in a nitrogen stream for 2 hours. During that time, the temperature of the reactor was maintained at 500°C, and then Kgl was introduced as a carrier gas into the Sachihata reactor, where the partial pressure of methanol was maintained at 165 atm, and methanol was passed through the catalyst bed. did.

The reaction conditions at this time are shown below.

Temperature = 300°C Gasley): 3216 *a/Ir11 cavity M (sv): 2. S 2 v/x/v methanol α81 flHt Methanol partial pressure α163 atm The decomposition product was analyzed by gask electromagnetography to obtain the crystals shown in Table 8.

From the above results, the zeolite obtained by the present invention)t+S
Z has remarkable catalytic ability in alcohol conversion reaction,
It was also found that the selectivity to olefins, which are useful raw materials in the chemical industry, is high.

It has also been proven that it has excellent ability to maintain activity.

[Brief explanation of the drawing]

FIG. 1 is an X-ray diffraction pattern of a crystalline aluminosilicate synthesized by the method described in Comparative Example 1, and FIG. 2 is an X-ray diffraction pattern of a synthesized crystalline aluminosilicate (TliZ) according to the present invention. It is. FIG. 3 is an electron micrograph of a crystalline aluminosilicate synthesized by the method of Comparative Example 1, and FIG. 4 is an electron micrograph of a synthesized crystalline aluminosilicate ('rsz) according to the present invention. Patent Applicant: Toa Fuel Industries Co., Ltd. Figure 3, 1 ↓ Procedural Amendment 11 (Method) Case Indication: Relationship to Patent Application No. 145596 of 1980 Patent Applicant Address: Chiyoda-ku, Tokyo-Tsubashi-chome No. 1 No. 1 Sleeve correction order notification date January 26, 1980 Drawing subject to amendment

Claims (1)

[Claims] 11) 0.8-15M in terms of oxide molar ratio! /1O-AIIOI ・10-100
810.・Has a chemical composition of ZHlo (where M is at least one metal cation, n is the valence of the metal cation, and 2 is 0-40), and at least A crystalline aluminosilicate which is patented as having a powder X@ diffraction diagram showing the lattice spacing shown in Table 1. Table I S, 72 ± α05 S. 5.64 ± α05 S. (2) Expressed as molar ratio of # compound 0.8-'L 5 M4/n O・A 110B ・
25-808101 ・Z JO (where M is at least one metal cation, n is the valence of the metal cation, and 2 is 0-20). The crystalline aluminosilicate according to claim 1, which has a powder X-ray diffraction diagram showing at least the lattice spacing shown in Table 1. (3) In the chemical composition, M is an element in group 1 and 1 of the periodic table.
The crystalline aluminosilicate according to claim 1 or 2, which is at least one selected from the group of Group 1 metal cations. (4) The gold kI4 cation of Groups 1 and 2 of the periodic table is at least one selected from the group of alkali metal ions and alkaline earth ions. Crystalline aluminosilica and salt. (5) The crystalline aluminocarboxylic acid according to claim 4, wherein the alkali metal ion and the alkaline earth metal ion are at least one selected from the group of sodium cations, lithium cations, and calcium cations. Earth. (L) The alkali metal ion is a mixture containing a sodium cation and a lithium V+'A ion. (expressed as molar ratio of 71 minerals: 0.8-15Na, O・AI, O,・25-808 i
02-0-20H10, and the following 9
The crystalline alumino fl! according to claim 1, which has a powder X-diffraction pattern showing the lattice spacings shown in the table! :
Biting tomb. Lattice spacing d(λ) Relative intensity (I/I
. )1t2 ± 0.2 8°,
97 seven 0.2
W. ZS 0.15 W. zl ±0.15 W. 64 ± o, I M. 603 Shi aI
M. 5.58 ± 0.1
M. 503 Shi aI
W. 4.62 ± [LO7W. 4.26±0.07M. 3.86 しαos v,s. 582 ± α05 s. +8)! Expressed by the molar ratio of compounds, [1B-1
5M17no ・All0@ ・10-100Si01
・0-40H10 (where M is a metal cation and n is the valence of the gold j11m ion)-
A synthetic crystalline aluminosilicate having a chemical composition of Quality aluminosilicate. (9) consisting essentially of an inorganic reactive material, having the following composition expressed by the following molar ratios: 810, /A1.0. 10-150M, 7nO
/ S i (h 0.05- [15H,O
/M, /nO1oo-1oo. )(-/Si0.0.0l-20(where,
M is at least one metal cation, n is the valence of the metal cation, and X- is the anion of the mineralizing agent. ) and heating and maintaining the reaction mixture at a crystallization temperature until crystals form; Of crystalline aluminosilicate! 1! Construction method. 0I The aqueous reaction mixture consists essentially of inorganic reactants and has the following composition expressed in molar ratios: Slow/
A1*Om 20-120'M, μO/810.
α03-■Hz O/M*/no
150-800X/810. 0.05-1
5, where M is at least one metal cation, n is its valence, and X″″ is the anion of the salt as mineralizing agent. 9th
A method for producing the crystalline aluminosilicate described in 1. aυ The aqueous reaction mixture consists essentially of inorganic reactants and has the following composition expressed by the following molar ratios: 810, /A
1.03 go-11sM, /nO/S io,
o, os-o, sI (*Q/M*/no
200-700X7810. α
1-10 (where M is at least one metal cation, n is the valence of the metal cation, and X″″ is the anion of the salt as a mineralizing agent) The crystalline aluminosilicon Il! according to claim 10, which has the following: ! Salt manufacturing method. (IJ In the aqueous reaction mixture, M is an element in the periodic table #!I
Claims 9 and 10 are at least one selected from the group of metal cations of the Me and HIT groups in the same table.
V-division method for crystalline aluminophosphate according to item 1 or item 11. (13) The metal cations of Group 1 and Group 1T of the Element Peripheral Law Table are at least one selected from the group consisting of alkali metal cations and alkaline earth metal cations.
A method for producing a crystalline aluminosilicate according to claim 12. Oa The crystalline alumino silica g! ! Method of manufacturing fences. U! 19. The method for producing a crystalline aluminosilicate according to claim 13, wherein the alkali metal cation is a mixture containing sodium ions and lithium cations. 00 of the crystalline aluminosilicate according to claim 9, 10 or 11, wherein the aqueous reaction mixture is at autogenous pressure and a temperature in the range of 120°C to 280°C is adopted as the crystallization temperature. Manufacturing method. a) After heating the aqueous reaction mixture to the crystallization temperature,
The manufacturing method of crystalline alumino ring PII #1 according to claim 16, in which heating is maintained for 20 hours. 12. A method for specializing a crystalline aluminosilicate according to claim 9, 10 or 11, wherein the crystalline aluminosilicate is at least one selected from the following or at least one neutral salt of ammonium. (Crystalline aluminosilicate according to claim 18, wherein the neutral salt of the 19 alkali metal i and the alkaline earth metal is at least one selected from the group of sodium chloride, sodium sulfate, sodium chloride, and barium chloride. Method for producing salt. C,!IJ The molar composition of total oxides in the aqueous reaction mixture is 4NalO-AI, 0.5081012000H
10, contains 10 moles of NaCl as a mineralizing agent based on sio, and the crystallization conditions are about 170° C. for about 20 hours. . eυ Expressed by molar ratio of oxides 0.88-15M17no-A120 ・10-j 0
08 io, -0-40H20 (where M is a metal cation and n is the valence of the metal cation) and has a chemical composition t- of at least Table 1. A method for producing 1M crystalline aluminosilicate by hydrogen ion exchange, which comprises contacting a synthetic crystalline aluminocarate having a powder X-ray diffraction pattern with the lattice spacing shown in FIG. Expressed by molar ratio of Q4 oxides 0.8-15M, /nO, 'AbOs'' 10-1
00S iOt ・0-4 Q HtO (where M is a metal cation and n is the valence of the metal cation) and has the chemical composition at least in Table 1. A method for producing a hydrogen ion exchange type crystalline aluminosilicate by substitution with a synthetic crystalline aluminosilicate TcNH4 having a powder XM diffraction pattern showing the lattice spacing shown. (2) Expressed by the molar ratio of oxides, αB-15Mt
/no HAll0.・1 G-1008101・0
-40H,0 (where M is a metal cation and n
is the valence of the metal cation/ion. ), and has a powder Xl1Ii1 diffraction pattern showing at least the lattice spacing shown in Table 1. Hydrogen ion exchange type crystallinity obtained by contacting an acid with a synthetic crystalline aluminosilicate A method for producing a crystalline aluminosilicate, which comprises increasing the silica/alumina ratio of the hydrogen ion exchange type crystalline aluminosilicate salt by further contacting the aluminosilicate with an acid. @ Under conditions of conversion of organic raw materials, the molar ratio of oxides -
[L8=15M1/,0-AI,O,-10-1008
10,-zH,. (where M is at least one gold mm ion, n is the valence of the metal cation, and 2 is rho4
It is 0. ), and the lattice plane 11 shown in Table 1
A method for the conversion of an organic feedstock comprising contacting it with a catalyst containing a crystalline aluminosilicate having a powder X-ray diffraction pattern exhibiting a 1j spacing. Ql Crystalline aluminosilicate expressed by molar ratio of oxides - 7nO・AhOs ・25-80sto!・o-2o
r+t. (Here, He1 is at least one package of gold-141m ions.) The method for converting an organic feedstock according to claim 24, having a chemical composition of: (, M) The method for converting an organic raw material according to claim 24 or 25, wherein the crystalline aluminosilicate contains hydrogen, ammonia, or rare earth metal.