JPH0144642B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a new form of zeolite ZSM-11, its preparation and its use in the catalytic conversion of organic compounds. The prior art has produced a wide variety of synthetic aluminosilicates. These aluminosilicates include Zeolite A (U.S. Pat. No. 2,882,243), Zeolite X (U.S. Pat. No. 2,882,244), Zeolite Y (U.S. Pat. No.
3130007), Zeolite ZK-5 (U.S. Patent No.
3247195), Zeolite ZK-4 (U.S. Patent No.
3314752), Zeolite ZSM-5 (U.S. Patent No.
3702886), and silicanoalumina ratio 20−90/
Zeolite ZSM-11 with 1 (U.S. Patent No.
3709979) by letters or other convenient symbols. The SiO ₂ /Al ₂ O ₃ ratio of zeolites can often be varied, for example zeolite
Zeolite Y can be synthesized to have _{a SiO2} / _{Al2O3 ratio} of 3 to _{about 6} . For some zeolites, there is no upper limit on the SiO ₂ /Al ₂ O ₃ ratio, and ZSM-5 is one example.
SiO ₂ /Al ₂ O ₃ is at least 5. US Patent No.
No. 3,941,871 discloses crystalline metal organosilicates that are essentially aluminum-free and yet exhibit the X-ray diffractogram characteristics of ZSM-5 type aluminosilicate. U.S. Patent Nos. 4061724 and 4073865
No. 4,104,294 describes microporous crystalline silicas or organosilicates. This invention relates to a form of ZSM-11 that has a higher silica/alumina ratio than previously disclosed and is effectively alumina-free. Thus, from the aforementioned U.S. Pat. No. 3,709,979, ZSM-
It was unexpected that 11 could be synthesized. Furthermore, the high silica form of ZSM-11, despite its low acid activity, can act as a catalyst for reactions such as the isomerization of xylene, and in fact is similar to the conventional materials disclosed in the aforementioned U.S. Pat. No. 3,709,979. It was unexpected that the improved results, such as reduced xylene losses, would be achieved compared to the conventional materials, and that this high silica ZSM-11 would also be less susceptible to degradation than conventional materials in many reactions. The composition of the new form of ZSM-11, expressed in the form of molar ratio of anhydrous oxide per 100 moles of silica, has the following formula: (0-10)M2 _/o0 :[(a) _Cr2 O ₃ + (b) Fe ₂ O ₃ + (c
)Al ₂ O ₃ ]: (100) SiO ₂ (In the formula, M is at least one cation with a valence n, a=0-4, b=0-5, c=0.001-0.5
(where a and b cannot both be equal to zero at the same time, and if one is zero, the other must be greater than the value of c). Although chromium and iron oxides do not need to exist as Cr ₂ O ₃ or Fe ₂ O ₃ , they are calculated and expressed as such in the formula. In its as-synthesized form, this example of zeolite has the following formula, expressed in the form of molar ratio of oxide per 100 moles of silica after dehydration: (0-3) _R2O :(0-8)M2 _{/ o} O: [(a) Cr ₂ O
₃ + (b) Fe ₂ O ₃ + (c) Al ₂ O ₃ ]: 100SiO ₂ . In the above formula, M is an alkali metal or alkaline earth metal, R ₂ O is an organic compound of an element of group VA of the periodic table, preferably nitrogen or phosphorus, 1
is an organic compound containing at least one alkyl or aryl group containing ~7, preferably 2 to 5 carbon atoms, preferably at least one butyl group, and R ₂ O is More preferably quaternary ammonium compounds containing at least one butyl group, a=0-4, b=0-5 and c=0.001
~0.4, but it is assumed that a and b cannot both be 0 at the same time, and when one is 0, the other is larger than 0 and larger than the value of c. This new form of zeolite contains small amounts of Fe and/or Cr and Al at tetrahedral substitution positions within the silica crystal lattice. The latter has a negative charge to this extent, and when each atom is replaced, one extra electron is generated, which is replaced by a cation. These cations can be at least partially replaced by other ions using conventional ion exchange techniques. In some cases it is necessary to pre-calcinate the zeolite prior to ion exchange due to pore blockage by R ₂ O species. The ions introduced to replace the original alkali metal cations, alkaline earth metal cations and/or organic cations may be any ions as long as they can pass through slots in the crystal lattice. Particularly preferred substituting ions are hydrogen, ammonium, and metals from one or more groups of the periodic table. Particularly preferred among these metals are the rare earth metals, manganese, zinc, and the metals of the groups of the periodic table. ZSM-11 has a characteristic X-ray diffraction pattern that distinguishes it from other crystalline materials, and for the purposes of this specification ZSM-11 is defined by this X-ray diffraction pattern. The X-ray diffraction diagram of this zeolite has the following values in Table 1: First table Lattice spacing D (Å) Relative intensity 11.2 ±0.2 m 10.1 ±0.2 m 6.73±0.2 w 5.75±0.1 w 5.61±0.1 w 5.03±0.1 w 4.62±0.1 w 4.39±0.08 w 3.86±0.07 vs 3.73±0.07 m 3.49±0.07 w (3.07, 3.00)±0.05 w 2.01±0.02 w m in the relative strength symbol in Table 1 is medium , w = weak, vs very strong. Also, in the table above
The box around the 3.07 and 3.00 lines indicates that they are separate, distinguishable lines, but often appear overlapping. These values were determined according to standard techniques. The radiation was a copper K-α twin beam, and a Geiger counting spectrophotometer with a self-recording strip chart was used. The height of the peak as a function of 2θ (θ is the Bragg angle) and its position were read from the spectrophotometer chart. From these the relative intensity 100 I/I ₀ (I ₀ is the intensity of the strongest line or maximum peak) and the lattice spacing D (expressed in angstroms) corresponding to the recorded lines were estimated. ZSM-11 is similar to ZSM-5, but ZSM-5
contains twin lines at approximately 10.1 Å, 3.73 Å, 3.00 Å and 2.01 Å lattice spacings, whereas ZSM−11
are significantly different in that they exhibit a single line at these values. This means that the ZSM-11 class of crystals is different from other zeolite classes. While ZSM−11 is tetragonal,
ZSM-5 is orthorhombic. Even if the cation form of ZSM-11 is different, it shows substantially the same X-ray diffraction pattern with only a slight shift in the lattice spacing and a change in relative intensity. Zeolite ZSM-11 can be used either in alkali metal form such as sodium form, ammonium form, hydrogen form or other monovalent or polyvalent cationic form. When used as a catalyst, it is usually first heat treated to remove some or all of the organic substituents. It is also closely combined with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or noble metals such as platinum or palladium (in which case the hydrogenation-dehydrogenation function is also performed). It can also be used as a catalyst. Such components are ion-exchanged, impregnated, and physically intimately mixed into the composition to the extent that Al is present in the structure. Such components, for example in the case of platinum, can be impregnated into or onto the zeolite by treating the zeolite with a solution containing platinum metal-containing ions. Thus, suitable platinum compounds include a variety of compounds including chloroplatinic acid, platinum chloride, and platinum-ammine complex compounds. At least 371.1°C for ammonium, alkylammonium and arylammonium forms
It can be transformed into other forms by heat treatment at a temperature of (700°) for a period of at least 1 minute but not more than 20 minutes. Although reduced pressure may be used for this heat treatment, atmospheric pressure is preferred for reasons of convenience. Heat treatment can be performed at temperatures up to approximately 926.7°C (1700°C). The heat treated products are particularly useful as catalysts for certain hydrocarbon conversion reactions. When using this catalyst as an adsorbent or as a catalyst, it must be at least partially dehydrated. This is done by heating the zeolite in an atmosphere such as air or nitrogen to a temperature within the range of 200°C to 600°C under normal, reduced or elevated pressure for 1 to 48 hours. Dehydration is also
This can be carried out at room temperature by simply placing ZSM-11 under reduced pressure, but in this case it will take a longer time than above to achieve a sufficient amount of dehydration. ZSM-11 according to this invention is a source material of silica,
Source material for R ₂ O and source material for alkali metal oxides, including e.g. sodium and water, without added alumina, with the following composition in the form of molar ratios of oxides: Reaction examples Wide range of suitable ranges SiO ₂ /R ₂ O 5-30 10-20 M ₂ O/R ₂ O 0.0-6 0.09-3.0 H ₂ O/R ₂ O 100-500 300-400 (In the formula, R ₂ O is an organic group VA element in the periodic table. oxide form of the compound, which can be a compound containing one butyl group, where M is an alkali metal or alkaline earth metal), and the mixture is heated to a crystallization temperature to form crystals. It can be built by keeping it until Since no alumina is added to the reaction mixture, the only aluminum present is as an impurity in the other components of the crystallization catalyst. The chromium and/or iron containing form of this zeolite contains a source of silica, a source of R ₂ O and a source of alkali metal oxides such as sodium, chromium or iron compounds and water; The following composition, expressed in molar ratio of oxides, without added alumina:

[Table] (In the formula, R ₂ O is an oxide form of an organic compound of an element of group VA in the periodic table, and can be a compound containing one butyl group, and M is an alkali metal or an alkaline earth metal. ) and holding said mixture until crystals form.
In this case, alumina is not added again. Preferably the crystallization can be carried out under pressure in an autoclave or in a static bomb reactor, but
However, it can be carried out at 100°C in a polypropylene container. Crystallization temperature is 80℃~250℃, preferably
In the range 100°C to 200°C, lower temperatures, for example about 100°C, require longer crystallization periods.
These periods vary from approximately 6 hours to 90 days. The crystals are then separated from the liquid and collected. The composition can be made using materials that provide the desired oxide. Such compositions include sodium silicate, silica hydrosol, silica gel,
Contains silicic acid, sodium hydroxide, chromium/potassium sulfate, and ammonium ferrous sulfate. The organic compound can be any of the elements of group VA of the periodic table, for example nitrogen, phosphorus, arsenic, antimony. Suitable compounds generally have the formula:

It is a quaternary compound represented by [Formula] or R ₄ L, in the above formula, L is an element of group VA of the periodic table, each R is 1 to 7,
Preferred are alkyl or aryl groups of 2 to 5 carbon atoms. Preferably at least one R is a butyl group. Usually each alkyl or aryl group is the same, but it is not necessary that each group have the same number of carbon atoms in the chain. To make the ammonium species, organically substituted ammonium chlorides are useful, as are organically substituted ammonium hydroxides, which are less preferred. To make this phosphonium species of zeolite, tetrabutylsulfonium chloride is particularly desirable as a means of incorporating quaternary metal compounds into the zeolite. Tetrabutylammonium chloride or the corresponding bromide or, although less preferred, the corresponding hydroxide are useful for making the ammonium species. Since other elements in group VA of the periodic table behave in the same way, the periodic table is used instead of phosphorus.
By the same operation using other metals of the VA group,
Those other elemental inclusions can be made. It is to be understood that the oxide can be provided from more than one source. The reaction mixture can be made batchwise or continuously. Crystal size and crystallization time will vary depending on the nature of the reaction mixture used and the crystallization conditions. It is not necessary to use the quaternary compound as is. They may be prepared in situ by adding appropriate precursors to the reaction mixture. These precursors have the formula R ₁ R ₂ R ₃ L where R ₁ , R ₂ and
R ₃ is alkyl, substituted alkyl, aryl,
selected from substituted aryl, cycloalkyl, substituted chloroalkyl, hydrogen, L is from the periodic table
is an element of group VA) and has the formula R ₄ L, where R ₄ is alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and L is an electron negative group. ). According to a special embodiment of the invention, the process of the invention can be carried out using the compound R ₁ R ₂ R ₃ L alone. In this case, it is estimated that no quaternary compound is produced. Thus, in embodiments of the invention R ₂ O
without adding _R4X as a source of primary and secondary
Primary or tertiary amines or phosphines as well as diamines can be used. The synthesis of the zeolite of this invention is at least 0.001
% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight (based on the total crystalline product), facilitated by the presence of seed crystals. Zeolites can be formed into a variety of particle sizes. Generally speaking, particles are powdered, granular or passed through a 2 mesh (Tyler) sieve, but not a 400 mesh (Tyler) sieve.
It can be in the form of a shaped article, such as an extrudate, with sufficient particle size to remain on the sieve. When the catalyst is a shaped article, such as an extrudate, the zeolite can be extruded before drying, after drying, or after partial drying. When ZSM-11 according to the invention is used as a catalyst, it can be composited with a matrix as described for zeolite ZSM-43 in European Patent No. 0001695. When the zeolites of this invention are used as catalysts (which may contain additional hydrogenation components), heavy petroleum residues, recycled oils and other hydrocrackable feedstocks can be heated from 204.4°C to 435°C. Hydrocracking can be performed using hydrogen/hydrocarbon feedstock molar ratios ranging from 2 to 80 at temperatures between (400 and 815). The pressure used is
Can be varied from 0.7 to 175Kg/ ^cm2 gauge pressure (10 to 2500 psig), liquid hourly space velocity from 0.1 to
It is 10. The hydrocarbon cracking feedstock has a liquid hourly space velocity of about 0.5~50, about 287.8℃~593.3℃ (550〓~
Cracking can be performed at a temperature of 1100㎓) and a pressure of almost reduced pressure to several hundred atmospheres. ZSM-11 according to the present invention can be used to modify modifyable raw materials at temperatures of 700-1000°C. The pressure used here is 7-70
Kg/cm ² gauge pressure (100~1000psig), preferably 14~
49Kg/ ^cm2 gauge pressure (200-700psig). The liquid hourly space velocity is generally between 0.1 and 10, preferably between 0.4 and 4.
The hydrogen/hydrocarbon molar ratio is generally between 1 and 20, preferably between 4 and 12. This zeolite can also be used for the hydroisomerization of normal paraffins if it contains a hydrogen component such as platinum. Hydroisomerization is from 93.3℃ to 371.1℃ (200℃
〓~700〓, preferably 148.9℃~287.8℃ (300〓~
550〓) temperature, a liquid hourly space velocity of 0.01 to 2, preferably 0.25 to 0.50, and a hydrogen/hydrocarbon molar ratio of 1:
It is carried out using a hydrogen amount of 1 to 5:1. Furthermore, this catalyst is -1.1℃~371.1℃ (30〓~700〓
can be used for the isomerization of olefins using temperatures of Other reactions that can be accomplished using catalysts of the invention containing metals such as platinum include hydrogenation-
Included are dehydrogenation and desulfurization reactions, olefin polymerization reactions (oligomerizations) and other organic compound conversion reactions such as, for example, alcohol conversion reactions (conversion of methanol to hydrocarbons). Adsorption data in the examples listed below were determined as follows: A weighed sample of calcined zeolite was
Water vapor at 12 mmHg and cyclohexane vapor at 20 mmHg and n-
Contact with the vapor of the desired pure adsorbate was made by contacting with hexane vapor (the vapor pressure being less than the vapor-liquid equilibrium pressure of the respective adsorbate at room temperature). During the adsorption experiment (which did not exceed about 8 hours) the pressure was kept constant (within a variation of about ±0.5 mm) by adding adsorbate vapor regulated by a pressure regulator. When the adsorbate is adsorbed, the pressure decreases, and this pressure drop causes the valve of the pressure regulator to open, which allows more adsorbate vapor to enter the chamber and maintain the above-mentioned regulated pressure. . Adsorption is complete when the pressure change in the chamber is no longer sufficient to operate the pressure regulator. The weight increase of the sample is calculated as the number of grams per 100 grams of calcined adsorbent and is expressed as the adsorption capacity of the sample. Examples 1 to 4 A starting gel reaction mixture was prepared from sodium silicate (28.8% SiO ₂ , 8.9% Na ₂ O, 62% H ₂ O), tetrabutylammonium bromide, sulfuric acid and water, commercially available as “Q-brand”. I built it. Crystallization is carried out in a polypropylene container at 98.9°C (210°C) or at 210°C.
121.1℃ (250℃) in a stainless steel pressure vessel
〓) I went there. After crystal formation, the solid was separated from unreacted components by filtration, washed with water, and dried at 110°C (230°C). The amounts of starting materials, their names, product compositions and adsorption data are listed in Table 2. Examples 5-15 A starting gel material was made from colloidal silica, tetrabutylammonium bromide, sodium hydroxide, and water. Crystallization in a polypropylene container
Tests were carried out at 98.9°C (210°) or at 148.9°C (300°) in two stainless steel pressure vessels. After crystal formation, the solid is separated from unreacted components by filtration,
Washed with water and dried at 110°C (230°C). The amounts of starting materials, their names, product compositions, adsorption data and catalytic reaction data are listed in Table 3 (Examples 5-8) and Table 3A (Examples 9-15 and Example 18). Example 16 A starting gel mixture was made from fume silica (91.3% SiO ₂ ), tetrabutylammonium bromide, sodium hydroxide and water. Crystallization was carried out at 98.9°C (210°C) in a polypropylene container. After crystal formation, the solid is separated from unreacted components by filtration,
It was washed with water and then dried at 110°C (230°C). The amounts of starting materials, their names, product compositions and catalytic reaction data are listed in Table 4. Example 17 A starting gel mixture was made from colloidal silica, tetrabutylammonium hydroxide (40%) and water. Crystallization in polypropylene container 98.9
It was carried out at ℃ (210〓). After crystal formation, the solid is separated from unreacted components by filtration, washed with water, and heated at 110℃ (230℃).
〓) and dried. The amounts of starting materials, their names, the composition of the products and the catalytic reaction data are listed in Table 5. The data listed in Tables 2 to 5 are based on the Al ₂ O ₃ content (after drying) of the material at the time of synthesis from 0.04% (Example 18).
0.64% (Example 16). However, most of the
Example 12 and Examples 14 to 17). It has been found that performing the synthesis in the presence of seed crystals of ZSM-11 yields a product with high crystallinity (Example 14), such as 130%, in 3 days. Examples 19 to 22 These examples illustrate the use of tetrabutylphosphonium chloride as a source of alkyl Periodic Table Group VA cations, and one example (Example 22) to further promote large crystal growth in the starting mixture. triethanolamine was added to (otherwise Examples 1 to 5)
). Amounts of starting materials, names of those materials,
The product composition, adsorption data and catalytic reaction data are listed in Table 6. The data listed in Table 6 is for Al ₂ O ₃ of the substance at the time of synthesis.
Indicates that the content (after drying) is negligible. Note that for Example 22 not only was triethanolamine introduced to promote the growth of large crystals, but crystallization was carried out for 50 days.
X-ray analysis showed almost 100% ZSM-11 type zeolite. Examples 23 to 34 Sodium silicate (SiO ₂ 28.8%, Na ₂ O 8.9%,
A starting gel reaction mixture was made from H ₂ O (62%), tetrabutylammonium bromide, chromium potassium sulfate, sulfuric acid, and water. Crystallization was carried out at 98.9°C (210°) in a polypropylene vessel, or in a glass-lined stainless steel autoclave [148.9°C (300°)], or in a stirred two-stainless steel pressure vessel from 121.1°C to 148.9°C. ℃
(250〓~300〓). After crystal formation, the solid is separated from unreacted components by filtration, washed with water, and heated at 110°C.
(230〓). The amounts of starting materials, their names, product compositions and adsorption data are listed in Table 7. Examples 35 to 36 Sodium silicate (SiO ₂ 28.0%, Na ₂ O 8.9%,
A starting gel reaction mixture was made from H ₂ O (62%), tetrabutylammonium bromide, ferrous ammonium sulfate, sulfuric acid, and water. Crystallization was carried out at 98.9°C (210°) in a polypropylene vessel or at 148.9°C (300°) in a stainless steel pressure vessel. After crystal formation, the solid is filtered and washed with water.
Dry at 110℃ (230℃). The amounts of starting materials, their names, product compositions and adsorption data are listed in Table 8. Example 37 This example illustrates the production of low alumina ZSM-11 using a specially formulated high purity silica hydrogel. The silica hydrogel used as a source of silica was prepared as follows: A. Tetraethyl orthosilicate Si
(OCH ₂ CH ₃ ) ₄ 2479c.c. Ethanol 782c.c. 4N HNO ₃ 178.7cc This mixture was left to mature at room temperature for 1/2 hour.
It was then cooled to 3.3°C to 6.1°C (38° to 43°). B NH ₄ OH233.3c.c.〔3.3℃〜6.1℃（38〓〜43
Solution B was added to A, mixed for 30 seconds, and the resulting gel was washed with water. Solid content 17.0%. Preparation details are listed in Table 9. The data in Tables 7, 8 and 9 indicate that the Al ₂ O ₃ content (after drying) of the zeolite during synthesis is 370 ppm.
(Example 37) to 0.30% (Example 31). But most of them are 0.2%~0.3% (Example 23~
Example 30, Example 32, Example 33 and Example 34). ZSM−
115% in 5 days if synthesis is performed in the presence of seed crystals
It was also found that a highly crystalline product such as (Example 36) was produced. Examples 38 to 44 A portion of some of the products of the above examples was heated to 537.8°C.
(1000〓) and then ion-exchanged with NH ₄ Cl solution, the resulting NH ₄ ZSM-11 was recalcined to its H form. Their sodium content is as follows: Example base substance Na content (wt%) 38 Example 7 0.02 39 Example 15 0.02 40 Example 9 <0.01 41 Example 6 <0.01 42 Example 3 <0.01 43 Example 14 0.02 44 Example 12 0.034 1.0cc sample of each of these products
The cracking of n-hexane was tested at a liquid hourly space velocity of 537.8°C (1000°). 5
% conversion of n-hexane after passing n-hexane for minutes
and the calculated relative cracking activity of the catalyst is as follows: Example Conversion Relative Cracking Activity 38 2.3 0.4 39 3.1 0.6 40 1.6 0.3 41 3.6 0.7 42 10.3 2.1 43 2.9 0.6 44 0.9 0.3・Journal of Catalysts, Volume 4 (August 1965)
PB Wise (PB) described on pages 527-529
Weisz) and J.N.
In a letter to the author of the report titled ``Superactive Crystalline Aluminosilicate Hydrocarbon Cracking Catalyst'' by J.D. Miale). Most of the samples were tested for oligomerization of propylene. In this test, propylene was passed over a 0.25 g sample of catalyst or over a 0.5 g Sampal at a design flow rate of 1000 c.c./hour and a nominal temperature of 700°C. The weight time space velocity generated here is 0.50g
The catalyst sample loading was approximately 3.5 and the catalyst sample loading of 0.25 g was 7. Catalytic oligomerization data calculated based on actual WHSV and total recoveries are as follows.

[Table] Examples 45 to 50 (Reference Examples) Some of the products of Examples 23, 26, 27, 31 and 36 were subjected to alpha tests for cracking activity. In addition, the products of Examples 23 and 26 were also tested for oligopolymerization of propylene. Both of these tests are the same as those used in Examples 38-44, including all relevant details,
That is, the treatment conditions of the catalyst, the composition after treatment and calcination, the test results, etc. are listed in No. 10. The data listed in Table 10 show that the conversion of n-hexane after 5 minutes ranges from 0.3% by weight (Example 48) to 17.1% by weight.
(Example 46) α value after 5 minutes is 0.06
(Example 48) to 3.6 (Example 46). The best n-hexane conversion and alpha values were obtained from the original Example 26 product.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 The following composition expressed in molar amount of oxide: (0 to 10) M _2/o O: [(a) Cr ₂ O ₃ + (b) Fe ₂ O ₃ +( c
)Al ₂ O ₃ ]: 100SiO ₂ (In the formula, M is at least one cation with a valence n, a is 0 to 4, b is 0 to 5, c is a measurable number of 0.5 or less, and a and b cannot both be equal to zero at the same time, and if one is zero, the other must be greater than the value of c). Zeolite ZSM-11 according to claim 1, wherein 2c is at least 0.001. Zeolite ZSM-11 according to claim 1 or 2, wherein c is 0.4 or less. 4 The following composition: (0-3) R ₂ O (0-8) M _2/o O: [(a) Cr ₂ O ₃
+ (b) Fe ₂ O ₃ + (c) Al ₂ O ₃ ]: 100SiO ₂ (In the formula, R ₂ O is an oxide form of an organic compound containing an element of group VA of the periodic table, and the organic compound is shall contain an alkyl or aryl group of 7 carbon atoms, M is an alkali metal or alkaline earth metal, a is from 0 to 4, b is from 0 to 5, c is a measurable number of 0.5 or less, and a and b cannot both be equal to zero at the same time; if one is zero, the other is c
zeolite ZSM-11 according to any one of claims 1 to 3. 5. Zeolite ZSM-11 according to claim 4, wherein R is tetrabutylammonium and M is sodium. Claims 1 to 3, wherein 6 M is hydrogen, ammonium and/or rare earth metal.
Zeolite ZSM- as described in any one of the items up to
11. 7 Contains an alkali metal oxide source material, a silicon oxide source material, an R ₂ O source material, a chromium oxide and/or iron oxide source material, and water, and has a molar ratio of oxides. The following range expressed in the form: SiO ₂ /R ₂ O = 10 to 20 (Na ₂ O + K ₂ O) / R ₂ O = 0.9 to 3.0 (Cr ₂ O ₃ /Fe ₂ O ₃ ) / R ₂ O = 0.2 ~1.0 _H2O / _R2O =300~400 (wherein _R2O is an oxide form of an organic compound of an element in group VA of the periodic table, and the organic compound is an alkyl group of 1 to 7 carbon atoms) or containing an aryl group, and M is an alkali metal or an alkaline earth metal), and maintaining the reaction mixture until zeolite crystals are formed. 10) M _2/o O: [(a) Cr ₂ O ₃ + (b) Fe ₂ O ₃ + (c
)Al ₂ O ₃ ]: 100SiO ₂ (where M is at least one cation of valence n, a is 0 to 4, b is 0 to 5, c is a measurable number of 0.5 or less, and a and b cannot both be equal to zero at the same time, and if one is zero, the other must be larger than the value of c). 8. The method for producing zeolite ZSM-11 according to claim 7, wherein R ₂ O contains at least one ethyl group or butyl group. 9 (Cr ₂ O ₃ + Fe ₂ O ₃ )/R ₂ O molar ratio is 0.2 to 0.4
A method for producing zeolite ZSM-11 according to claim 7 or 8. 10. The method for producing zeolite ZSM-11 according to any one of claims 7 to 9, wherein R ₂ O is a quaternary compound. 11 Claim 7 in which R is tetrabutylammonium or tetrabutylphosphonium
Zeolite according to any one of Items 1 to 10
Manufacturing method of ZSM-11.