JPH013007A - Pentasil type crystalline aluminosilicate zeolite - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel pentasil type crystalline aluminosilicate zeolite.

<Prior Art> The basic structure of crystalline aluminosilicate biolite is a three-dimensional network structure in which regular tetrahedrons of 3i0 and AlO4 are bonded together with oxygen atoms. s
The io4 tetrahedron and △QO4 tetrahedron connect 4,5,6,8 or 12 to form a 4,5,6,8 or 12-membered ring, and a double ring in which two of these are overlapped to form a basic structure. The structure and pores of various zeolites are determined by the connection form of these basic units.

The so-called pentasil-type zeolite, which has been discovered in recent years and has 50 rings as a basic unit but has a 10-membered main cavity, has excellent heat resistance and acid resistance due to its unique M4 structure and high silica/alumina ratio, and has a unique molecular structure. Various uses are being investigated as shape-selective neck absorbers and catalysts.

Conventional pentasil type crystalline alumina silicate zeolite is well known as one synthesized by adding a tetraalkyl ammonium salt as an additive to a silica source, an alumina source, an alkali source, and water (Japanese Patent Publication No. 10064/1983). In addition, as a sprinkling agent, for example, alcohol (JP-A-52-43800), aliphatic carboxylic acid (JP-A-57-1999)
-123815>, hydrocarbon (JP-A-57-17901
5> etc. are also known.

The pentasil type crystalline aluminosilicate zeolite synthesized by the conventional method basically has the X-ray diffraction pattern shown in Table 1.

Table 1 11.1 ±0.3 3 10.1 ±0.3 3 9.8 ±0.2 M 3-86+0.08 VS 3.72±0.08 3 3.66±0.05 M However, The lattice spacing is d (unit angstrom A),
The relative intensity (1001/IHAX, THAX is a strong line in the diffraction pattern) is: vS - very strong, S = strong,
It is expressed as M = intermediate strength.

As shown in Table 1, in the X-ray diffraction pattern of the conventionally known pentasil type crystalline aluminosilicate zeolite, there are no two clear peaks with high intensity near the lattice spacing d=10.

<Problems to be Solved by the Invention> Without any modification, these conventionally synthesized pentasil-type crystalline aluminosilicate zeolites have the following aromatic substitutions in which ortho, meta, and para isomers exist: It is known that it does not have so-called para-selectivity, which is the ability to preferentially adsorb, react, or generate para-isomers. To express para-selected ti, e.g. MCI
, P, B, etc. must be impregnated and supported to narrow the pores, but this method has the disadvantage that although the paraselectivity increases, the catalytic activity decreases.

Therefore, the main object of the present invention is to provide a pentasil type crystalline aluminosilicate zeolite with a novel X-ray diffraction pattern.

Another object of the present invention is to provide a pentasil type crystalline aluminosilicate zeolite with a new X-ray diffraction pattern with high paraselectivity and high catalytic activity without any modification.

Means for Solving the Problems> The object of the present invention is to solve the following problems: and Table 2
This is achieved by pentasil-type crystalline aluminosilicate zeolite, which is characterized by an X-ray diffraction pattern of

Table 2 X-ray diffraction pattern 11.2 ±0.2 M 10.1 ±0.2 3-VS 9.9 +0.2 3-VS 9.8 ±0.2 W”M 3.86±o, os vs 3.83±0.08 3~VS 3.75±0.08 M 3.72±0.07 M 3.66±0.05~v~M The zeolite of the present invention has the X-ray diffraction characteristics shown in Table 2. pattern, especially d=10.1±0.2 large, and 9.
It is characterized by having a clear and strong X-ray diffraction pattern of 9±0.2.

Measurement of the X-ray diffraction pattern is carried out according to a conventional method.

In other words, X-ray irradiation is performed on copper by alpha rays, which cause the recording device to
The diffraction pattern was determined using a Kiger counter spectrometer.

From this diffraction pattern, the relative intensity is 100I/INAX
(INAX is the strongest line) and the lattice spacing d (unit angstrom basis) are determined.

Table 3 X-ray diffraction pattern 11.2 ±0.2 M lo, 0 ±0.2 3-VS9.9 ±0
．． 2 8~VS 9.8 ±0.2 W~M 6.37±0.1 W 6,OO+0.1 M 5.71 0.1 M 5.58±0.1 W 4.37±0. 08 W 4.27±0.08 M 3.86±0.08 VS 3.83±0.08 M 3.75±0.07 M 3.72±0.07 3 3.66±0.05 W ~M 3.00±0.05 M2, O○±0.05 M However, relative strength (100I/I, AX> is VS-very strong, S-strong, M-saddle strength, It is expressed as W-weak.

The zeolites 1 to 1 of the present invention include compounds represented by the above general formulas, in which M is ion-exchanged with monovalent, divalent, or polyvalent metal cations, ammonium ions, hydrogen ions, etc. Furthermore, in addition to ion exchange, single or compound components such as iron, cobalt, nickel, chromium, manganese, molybdenum, tungsten, vanadium, rhenium, platinum, rhodium, ruthenium, and palladium may be impregnated or physically mixed.

The pentasil-type crystalline aluminosilicate biAlite of the present invention is synthesized, for example, by reacting a reaction mixture consisting of a silica source, an alumina source, an alkali source, an alcoholic acid, a hydrocarbon, and an alcohol.

Silica sources preferably used to produce the pentasil-type crystals of the present invention [raw aluminosilicate Biolye i-] include silica sol, silica gel, silica aerogel, silica hydrogel, silicic acid, sodium silicate, nisdel silicate, etc. I can list the following. Examples of the alumina source include sodium aluminate, '65 (W aluminum, aluminum nitrate, alumina sol, alumina gel, activated alumina, comma-alumina, and alpha alumina). Examples of the alkali source include caustic soda,
Examples include caustic potash, but caustic soda is preferred. It goes without saying that when sodium silicate is used as a silica source and sodium aluminate is used as an alumina source, they simultaneously serve as an alkali source. The hydrocarbon may be aliphatic, alicyclic, or aromatic, but is preferably liquid at normal temperature and pressure, and aliphatic and alicyclic hydrocarbons have 5 to 15 carbon atoms, and aromatic hydrocarbons have 5 to 15 carbon atoms. 6 to 15 hydrocarbons are preferred, e.g. n
-pentane, n-hebutane, n-decane, isopentane, cyclohexane, decalin, bembin, toluene, xylene, ethylbenzene, diethylbenzene and the like. These hydrocarbons may be used alone or in a mixture of two or more.

Alcohols include methanol, ethanol, isopropanol, etc., preferably ethanol.

The method for producing the zeolite of the present invention involves adding tartaric acid and water to a wrinkle source, alumina source, alkali source, hydrocarbon, and alcohol to prepare a reaction mixture so that the composition falls within the following composition range expressed in molar ratio. is preferable.

(Preferable (more preferable range) New range) S! 02/AI 203 5-500
1O-200H20/5iO21~1005~5゜OH-/S r O20,01-1,000,02~o
,a.

TA/A I2 o30.1~200 0.5~1
00H20/RO11~1000.5~5゜ROH/R
O, 1~50 1.0~10 However, S! 02, Ag
2O3 is 3i derived from silica source and alumina source, respectively.
and Aα, S! 02, represents the number of moles converted to the form of Ad203, Of-1- represents the number of hydroxyl ions derived from the alkali source, TA, H20, R,
ROH represents the number of moles of tartaric acid, water, hydrocarbon, and alcohol, respectively.

Prior to crystallization, the reaction mixture thus prepared may be subjected to a so-called aging operation in which it is left at a temperature lower than the crystallization temperature, for example at room temperature, for several hours to several days, or alternatively, the aging operation may be omitted. You can stay there. The reaction conditions for crystallization are a reaction temperature of 80 to 250'C, preferably 1
00 to 200'C, and the reaction time is from 5 hours to 30 days, preferably from 10 hours to 10 days. Optimal reaction conditions depend on the raw materials used or the composition of the aqueous reaction mixture. Generally, the lower the reaction temperature, the longer the crystallization time is required, and the higher the reaction temperature, the shorter the crystallization time. However, if the temperature is too low or too high, it becomes amorphous or forms undesirable crystals. Similarly, if the reaction time is too short or too long, it may become amorphous or convert into other undesired crystals.

The reaction mixture is crystallized in a closed container, such as an autoclave made of iron, stainless steel, or lined with Teflon. The reaction is therefore usually carried out under naturally occurring pressures that are dependent on temperature.

The reaction mixture may be stirred, if necessary, during crystallization. After cooling, the reaction product crystallized in this manner is taken out from the closed container, washed with water, and filtered. The washed and filtered zeolite is dried if necessary.

The seolide of the present invention is usually in a powder state and is difficult to use in that form, so it is preferably molded. If necessary, a binder can be added to improve the moldability of Zeolite 1 and to impart strength to the molded product.

When using the zeolite of the present invention as an adsorbent,
As a binder, a small amount that can give strength (=l),
It is preferable to add 30% by weight or less, more preferably 20% by weight or less, on an absolute dry small amount basis.

When the zeolite of the present invention is used as a catalyst, it is generally possible to further increase the D content of the binder compared to the case of an adsorbent, and the binder's D content can be increased to 90%.
It is possible that it is more than mω%. The molded body thus prepared is dried and then fired. Drying at 50-250°C, preferably 100-2
It is carried out at 00°C for 0.1 hour or more, preferably 0.5 to 48 hours. Firing at 300-70.0'C for 0.1 hour or more, preferably 400-600'C for 0.5-24 hours
Time is done.

The molded body thus jqed is further subjected to several treatments depending on its purpose of use. For example, when used as an adsorbent, it is ion-exchanged with -valent, divalent, or polyvalent metal cations, ammonium ions, hydrogen ions, etc., if necessary.

The ion exchange method is usually carried out using an aqueous solution, and either a batch method or a flow method may be used. It goes without saying that the ion exchange VA treatment may be performed before molding the zeolite. After ion exchange treatment, it is washed with water and dried. After drying, it is fired before use.

When used as a catalyst, zeolite is generally subjected to ion exchange treatment with an aqueous solution containing ammonium ions, hydrogen ions, or divalent or trivalent metal cations, such as rare earth metal ions, to impart solid acidity to the zeolite.

Biolite with solid acidity can be used in many reactions, e.g.
It exhibits extremely high catalytic activity for reactions such as biogenesis, disproportionation, alkylation, dealgylation, decomposition, reforming, m-combination, and hydrogenolysis. As mentioned above, the ion exchange treatment may be performed before molding the zeolite. After ion exchange, it is washed with water and dried. It is then fired prior to use.

In addition to ion exchange, components such as iron, cobalt, nickel, chromium, manganese, molybdenum, tungsten, vanadium, renicum, platinum, rhodium, ruthenium, and palladium can be combined with zeolite by impregnation or physical mixing to be used as a catalyst. This is also one form of use of the zeolite of the present invention.

Example of implementation Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Solid caustic soda (NaOH95, ○weight ω%, 1-12
0 5.01m%>1.42g, sake EV1t1.25y
was dissolved in 17.98 g of water. 1 ethanol to this solution
Eight mouthfuls of a mixture of 5.07 SF and 15.069 n-hebutane were added and stirred well. Add a sodium aluminate solution (A O20319, 5ml 1%, Na2O0,
2il field'o, 1-12060.3 starvation 1℃1.77'1
9. Water 10.01, Silicic acid powder (SiO291,3 ω?6, H2O
A reaction mixture was prepared by gradually adding 3,7 weight ω%>10.95!7 with stirring. This reaction mixture has the following molar ratio of ethanol and oxides other than n-hebutane: 5,1N a20-AQ203 .50. Is i
02・1.3(TA)20・501.7t120.

The reaction mixture was placed in a 70ml stainless steel autoclave and sealed. Then heat it to 150°C for 710 minutes,
The reaction was allowed to proceed for 96 hours. After the reaction was completed, the product was taken out from the autoclave, washed with distilled water until it became almost 100% solid, filtered, and dried at 120'C overnight.

The IN product was a pentasil-type biolite that showed basically the same X-ray diffraction pattern as listed in Table 3, and its X-ray diffraction pattern is shown in FIG. Also d=1
In order to clarify the shape of the peak near 0 people, the scan speed was reduced to 1/4 and the peak shape near d-10 people (2θ-7~10
Figure 2 shows a diagram in which only the temperature (°) was measured.

As is clear from Figures 1 and 2, this zeolite has 2
θ-8,76° (d-10,09 people) J″3 and 2θ
A strong peak at −8,86° (d=9.98 people)
Was.

Example 2.3.4 Except that the following hydrocarbon was added instead of n-hebutane,
An experiment similar to Example 1 was conducted.

Example Hydrocarbon Addition ♀ (9>2 Decalin 15. O03 Cyclohexane 15.40 4 Toluene 15.05 As a result, the X-ray diffraction pattern of the obtained product is as shown in Table 3 and Figure 1. showed basically the same pattern.

Example 5 The molar ratio of the oxide is 5.1\a20-AQ203 ・50. O3i 02・
1.3 (TA) 0.500H20) Add cyclohexane (R) and ethanol (RO)-1 to the mixture, 1-120/R = 18.8, R○to1/R =1.9
Example 1 from a reaction mixture prepared by adding molar ratios of
It was synthesized in the same manner. The HHied product showed essentially the same X-ray diffraction pattern as in Table 3 and FIG.

Example 6 The molar ratio of the oxide is 5, ON a20-AQ203 ・49.53 i
02・1.2 (TA>20・282.9H20 mixture with cyclohexane (R) ethanol (ROH)
, H20/R=3. 8. It was synthesized in the same manner as in Example 1 from a reaction mixture prepared by adding hO at a molar ratio of ROH/R-1,8. The kltted product showed essentially the same X-ray diffraction pattern as in Table 2 and FIG.

Comparative Example 1 In Example 1, hydrocarbon and ethanol were added and 1'
The reaction mixture was expressed as a molar ratio of oxides, 4.2Na
20-AQ203・50.08i02・1.3(TA)
Synthesis was carried out in the same manner as in Example 1 except that 20.1000H20 was used.

The X-ray diffraction pattern of the obtained product is shown in FIG.

In addition, similar to FIG. 1, d = around 10 people is also shown in FIG. 4. From FIGS. 3 and 4, it can be seen that there are no two clear peaks with high intensity near d=10.

Example 7 Alumina sol was added as a binder to the zeolite powder obtained in Example 4.5 and Comparative Example 1.
03) 15% by weight was added and thoroughly kneaded. The kneaded material was extruded through a screen with a hole diameter of 1.2 #φ and molded.
Dry overnight at 20'C.

Thereafter, it was classified into sizes of 8 to 20 meshes (JIS sieve) and fired at 500'C in the presence of air for 2 hours.

After firing, ammonium ions were exchanged batchwise for 30 minutes at a solid-liquid ratio of 2 (ρ/Kg>) at a temperature of 80 to 90°C using an aqueous solution containing 10 wt% ammonium chloride.

This operation was repeated 5 times. After ion exchange, it was thoroughly washed with distilled water.

After washing with water, the catalyst was dried at 120'C overnight and calcined at 550'C for 4 hours. Using these, toluene disproportionation reaction was carried out under the following reaction conditions.

The results are shown in Table 4.

Reaction temperature 450'C Reaction pressure Normal pressure WH3V 4.0hr-1 H2/F 3.0 mol 1 mol or less As shown in Table 4, the pentasil-type crystalline aluminosilicate zeolite 1 of the present invention has high catalytic activity. It can be used as a catalyst to exhibit high para-selectivity.

<Effects of the Invention> The biolite of the present invention is a pentasil-type crystalline aluminosilicate U olide with a novel X-ray diffraction pattern, and the pore entrance diameter is small. Therefore, it can be stored and used effectively as a catalyst with excellent paraselectivity for aromatic hydrocarbon isomers and high catalytic activity. In addition to the intended purpose, the zeolide according to the present invention has better moldability than the conventional pentasil type zeolites 1 to 1.

[Brief explanation of drawings]

Figures 1 and 2 are X-ray diffraction diagrams of the pentasil type crystal [raw aluminosilicate theolite] of the present invention;
The figure and FIG. 4 are X-ray diffraction diagrams of conventional pentasil type crystalline aluminosilicate zeolites 1 to 1.

Claims (1)

[Claims] General formula (1.0±0.2)M_2_/_nO・Al_2O_3
・10-200SiO_2 ・0-40H_2O (wherein M is an alkali metal and/or alkaline earth metal, n is the valence of M) and exhibits the following X-ray diffraction pattern. Characteristic pentasil type crystalline aluminosilicate zeolite. ¥d(Å) 100I/I_M_A_X¥ 11.2±0.2M 10.1±0.2S~VS 9.9±0.2S~VS 9.8±0.2W~M 3.86±0.08VS 3.83±0.08S~VS 3.75±0.08M 3.72±0.07M 3.66±0.05W~M