JPH0147406B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a novel crystalline zeolite material. Many crystalline zeolites are known, most often known as aluminosilicates. some stuff,
For example, paulingite and merlinoite exist only naturally, and zeolite A and ZSM-5 only exist synthetically. There are also some, such as mordenite, which exists in both natural and synthetic forms, the synthetic form is known as zeolone, and other examples are faugiasite,
Its synthetic forms are known as Zeolite X and Zeolite Y. These are each identified by X-ray diffraction data. These data are
It shows a three-dimensional lattice consisting of SiO ₄ tetrahedra and AlO ₄ tetrahedra, which are bonded in most cases by sharing oxygen atoms, and constitutes a zeolite.
Supplement with enough cations to balance the negative charge on the _AlO4 tetrahedron. Therefore, aluminosilicate zeolite is represented by the chemical formula below. M _x/o : (AlO ₂ ) _x : (SiO ₂ ) _y In the above formula, M is a cation with a valence of n, x and y are the numbers of aluminum and silicon atoms in the unit cell, respectively, and the unit cell is a geometric unit that repeats in the lattice. This expression can also be expressed in terms of the molar ratio of oxides as shown below. M _2/o O: Al ₂ O ₃ : 2y/xSiO ₂ This can of course be determined experimentally and is the only formula that can represent the zeolite if the contents of the unit cell are unknown. . The only meaningful quantity for such a formula is 2y/x, which is an almost invariant range and is usually filled by many zeolites of various geometric lattice structures, and the chemical formula is used to identify the zeolite. Not limited to. Furthermore, such a formula represents an experimentally derived one, and the cation valence/aluminum atomic ratio deviates from 1, making it impossible to provide a zeolite with a lattice structure from a reaction mixture excluding alumina. Furthermore, both the unit cell formula and the oxide molar ratio formula imply that geometric identification between successive unit cells is achieved by identification of their composition. The inventors have discovered a zeolite (designated ZSM-39) that has a previously unknown lattice structure as evidenced by X-ray diffraction data. According to the invention, crystalline zeolite material,
ZSM-39 is characterized by having a lattice composed of SiO ₄ and optionally AlO ₄ tetrahedra bonded by sharing oxygen atoms, and having the following lattice spacing: Table 1 Lattice spacing D(A) relative strength 11.2±0.2 Weak 6.8±0.15 Medium 5.8±0.1 Strongest 5.6±0.1 Strongest 4.8±0.1 Medium 4.4±0.1 Medium 3.95±0.08 Medium-Strong 3.7±0.08 Strongest 3.4±0.07 Medium- Strong 3.4±0.07 Strongest 3.2±0.07 Weak 3.1±0.06 Weak 3.0±0.06 Weak 2.3±0.05 Weak These values were determined by standard methods.
The radiation was a copper K-alpha twin beam, and a self-recording scintillation counter spectrometer was used. The height of the peak, I, and its position as a function of double θ (θ = Bragg angle) were read from the spectrometer chart. From these values, the relative intensity 100I/Io
(Io is the intensity of the strongest line, ie, the peak) and the lattice spacing d (observed value) in angstroms corresponding to the recorded line were measured. Zeolite ZSM-39 has the following chemical formula expressed in moles of anhydrous oxide per 100 moles of silica: (0-2.5) M2 _/o O: ( _0-2.5 ) _Al2O3 : (100)
SiO ₂ (M is at least one cation selected from alkali metals and alkaline earth metals, and n is the valence of M). Synthetic forms of zeolite are usually made from silica after dehydration.
It is expressed by the following formula expressed as a molar ratio of oxide per 100 moles. (0~2.5) _R2O : (0~2.5) M2 _/o O: (0~
2.5) Al ₂ O ₃ : (100) SiO ₂ In the above formula, M is an alkali metal or alkaline earth metal, R ₂ O is an oxide of an organic compound of nitrogen, and has 1 to 3 carbon atoms. alkyl groups, preferably at least one ethyl group, and most preferably R ₂ O is a quaternary ammonium compound. Zeolite ZSM-39 contains small amounts of Al, Fe and/or Cr at the positions of tetrahedral substitution in the silica lattice.
has. Until this stage, the zeolite has a negative charge, balanced by cations, with one electron in excess for each atomic substitution. These cations may be at least partially replaced by other ions using conventional ion exchange techniques. In some cases it is necessary to calcine the zeolite before ion exchange due to pore blockage by R ₂ O species. The ions introduced to replace the initial alkali, alkaline earth and/or organic cations can be any that can pass through the channels in the zeolite. Particularly preferred substituent ions are hydrogen, ammonium, and metals of Groups 1 to 3 of the periodic table. Among these metals, particularly desirable are rare earth metals,
Manganese, zinc and other groups of the periodic table. Even if the cation form of zeolite is different,
The X-ray diffraction patterns are essentially the same, with only slight changes in lattice spacing and relative intensity. Some changes may also occur depending on the silica/alumina molar ratio and heat treatment. Zeolite ZSM-39 can be used as a catalyst or adsorbent in the form of alkali metals such as sodium, ammonium, hydrogen or other monovalent or polyvalent cations. When used as a catalyst, the zeolite is subjected to a thermal treatment to remove some or all of the organic substituents. This zeolite can also be used as a catalyst in combination with noble metals such as palladium or platinum, which have hydrogenation-dehydrogenation functions, and hydrogenation components such as manganese, chromium, cobalt, nickel, rhenium, molybdenum, vanadium, and tungsten. good.
These components can be incorporated into the composition by impregnation or physical mixing to the extent that Al is present in the structure. These components, for example in the case of platinum, can be impregnated by treating the zeolite with a solution containing platinum metal-containing ions. Examples of suitable platinum compounds include dichloroplatinic acid, platinum chloride, and various compounds containing platinum amine complexes. The zeolites, especially those in the metal, hydrogen, ammonium, alkyl ammonium and arylammonium forms, can be conveniently converted into other forms by heat treatment. This heat treatment generally involves treating these forms at a temperature of at least 371°C (700°C).
This is done by heating for a period of time ranging from 1 minute to 20 hours. Although pressures below atmospheric pressure can be used for the heat treatment, atmospheric pressure is preferred for convenience. Heat treatment is approx.
It is carried out at a temperature below 927℃ (1700〓). The heat treated products are particularly useful in catalyzing certain hydrocarbon conversion reactions. The novel zeolites of the present invention used either as adsorbents or catalysts in the process should be at least partially dehydrated. This dehydration is performed in an atmosphere of air, nitrogen, etc. at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure at 204℃ (400〓) to 593℃.
It is carried out by heating at a temperature of 1100 °C (1100 °C) for 1 to 48 hours. Dehydration may be accomplished by simply placing the ZSM-39 under vacuum at room temperature, but it takes a long time to achieve a sufficient amount of dehydration. The novel zeolites of the present invention are produced from a reaction mixture containing a silica source (an oxide of silicon), R ₂ O, an alkali metal oxide such as sodium, and optionally alumina. The reaction mixture has a composition, expressed in molar ratio of oxides, in the following range: Reactant wide range preferred range R ₂ O/SiO ₂ 0.01-100 0.05-20 M _2/o O/SiO ₂ 0.01-10 0.02-5 Al ₂ O ₃ /SiO ₂ 0-1.0 0-0.5 In the above formula, R ₂ O is an oxide of an organic compound of nitrogen, preferably a compound having one ethyl group, and M is an alkali or alkaline earth metal. The novel zeolite of the present invention is prepared by maintaining the reaction mixture at the crystallization temperature until crystals of the zeolite form. When produced without alumina, the alumina present in the product is introduced as an impurity in the other components of the crystallization medium. Materials manufactured without the addition of alumina and materials manufactured without the presence of aluminum as an impurity do not have ion exchange ability because aluminum is not present. These materials are also considered "zeolites" in the present specification. When producing zeolite ZSM-39, the preferred alkali metal oxide is sodium and the preferred _R2O source is tetraethylammonium (TEA)
ion or n-propylamine, and tetramethylammonium ion may be added to the reaction mixture in varying amounts. Crystallization generally occurs between 93℃ (200〓) and 204℃ (400〓)
Crystallization takes a long time at temperatures lower than 93°C (200°C). Crystallization times are generally about 6 hours to 90 days. Thereafter, the obtained crystals are separated from the mother liquor and collected. Reactive compositions can be prepared using materials that provide suitable oxides. These compositions include sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide, and the like. Organic compounds are organic compounds of nitrogen. Preferred compounds generally have the formula
It is a quaternary compound represented by R ₄ L ⁺ , in which L
is nitrogen, each R is an alkyl group having 1 to 3 carbon atoms, and preferably at least one R group is an ethyl group. Usually each alkyl group is the same, but each group need not have the same number of carbon atoms. In producing ammoniums, organic substituted ammonium chlorides or hydroxides are useful. It should be understood that the oxide can be provided from more than one source. The reaction mixture may be prepared either batchwise or continuously. The crystal size and crystallization time of the novel zeolites of the present invention vary depending on the nature of the reaction mixture and the crystallization conditions. It is not necessary to use the quaternary compound as is.
These can be prepared in situ by adding appropriate precursors. These precursors have the formula R ₁ R ₂ R ₃ L
Compounds and formulas of (R ₁ , R ₂ and R ₃ are selected from C ₁ -C ₃ alkyl, and hydrogen, and L is nitrogen)
_R4X ( _R4 is _C1 - _C3 alkyl and X is a halogen atom). According to a special embodiment of the invention:
The method of the invention can be carried out using only the compound R ₁ R ₂ R ₃ L. In certain embodiments, primary, secondary or tertiary amines as well as diamines may be used as a source of _R2O without the addition of _R4X . Zeolites can be produced in a variety of particle sizes.
Generally, the particles are in the form of powders, granules or extrudates and have a particle size sufficient to pass through a 2 mesh Tyler screen and remain on a 400 mesh Tyler screen. When molding the catalyst by extrusion molding etc.
The zeolite may be extruded before drying.
Alternatively, extrusion molding may be performed after drying or partially drying. For many catalysts, it is desirable to composite the zeolite with materials that are resistant to the temperatures and other conditions used in the organic conversion process. That is,
ZSM-39 may be combined with the parent substances in the amounts and types described in European Patent No. 1695 of the present invention. in a catalytically active form combined with a hydrogenation component.
When using ZSM-39, heavy oil residue, circulating oil and other hydrocracking feedstocks can be
204℃ (400℃) with hydrocarbon raw material molar ratio between 2 and 80
Hydrocracking can be performed at temperatures between 〓) and 441℃ (825〓). The pressure used is 170~17338kPa (10
~2500 psig) and the liquid hourly space velocity is 0.1-10. The catalytically active form of ZSM-39 can be used for catalytic cracking, and the hydrocarbon cracking feedstock is heated at about 288 °C (550
Cracking occurs at temperatures ranging from 〓) to 593℃ (1100℃) and pressures ranging from above atmospheric pressure to several hundred atmospheres. in a catalytically active form combined with a hydrogenation component
When using ZSM-39, the reformed raw material is reformed using temperatures between 371°C (700°) and 538°C (1000°). Pressure is 791 ~
6996kPa (100~1000psig), preferably 1480~
4928kPa (200-700psig). The liquid hourly space velocity is generally between 0.1 and 10, preferably between 0.4 and 4, and the hydrogen/hydrocarbon molar ratio is generally between 1 and 20, preferably between 4 and 12. The catalytically active form of the zeolite of the present invention can also be used for the hydroisomerization of n-paraffins if provided with a hydrogenation component such as platinum. Hydroisomerization uses hydrogen at a hydrogen/hydrocarbon molar ratio of 1/1 to 5/1 to increase the liquid hourly space velocity.
0.01-2, preferably 0.25-0.50 at 93℃ (200
〓)~371℃(700〓), preferably 149℃(300〓)
It is carried out at a temperature of ~288°C (550°C). Additionally, this catalyst can be used for isomerization of olefins using temperatures from -1°C (30°) to 371°C (700°). Examples of other reactions that can be carried out using catalytically active forms of ZSM-39, optionally using metals such as platinum, include hydrogenation-dehydrogenation and desulfurization reactions, olefin polymerization (oligomerization), aromatic alkylation, aromatic isomerization,
There are disproportionation reactions, transalkylation reactions, and other conversion reactions of organic compounds, such as reactions that convert alcohols such as methanol to hydrocarbons. In the examples below, the adsorption data described to compare the adsorption capacities of water, cyclohexane and n-hexane were determined as follows. First, a weighed sample of calcined zeolite was brought into contact with vapor of the desired pure adsorbate in an adsorption chamber at a reduced pressure of 1 mm.
Hg was contacted with cyclohexane and n-hexane vapors. The pressure is below the vapor-liquid equilibrium pressure of the respective adsorbate at room temperature. During the adsorption period (within approximately 8 hours), the pressure is kept constant (within approximately ±0.5 mm) by adjusting the pressure using a pressure regulator and adding adsorbate vapor.
I kept it. As the adsorbate is adsorbed by the zeolite, the pressure decreases causing the pressure regulator to open the valve and adsorbate vapor is introduced into the adsorption chamber to restore the adjusted pressure value. Adsorption is considered complete when the change in pressure is no longer sufficient to activate the pressure regulator. The increase in weight of the zeolite adsorbent was calculated as the adsorption capacity per 100 g of the calcined zeolite adsorbent. Examples 1 and 2 A starting gel mixture was prepared from colloidal silica (30% SiO ₂ ), tetraethylammonium hydroxide (40%), tetramethylammonium hydroxide (25%), sodium aluminate and water. In Example 1, the crystallization was carried out at 160℃ (320〓) with stirring.
I went for 70 hours. In Example 2, crystallization was carried out at 154° C. (310 °C) for 330 hours without stirring.
After crystallization, the solid content is separated from unreacted components by filtration, then washed with water, and then heated to 110°C (230〓).
It was dried. The amounts of starting materials used, their types, and the composition of the products are shown in Table 2 below. Examples 3 and 4 Sodium silicate (28.8% SiO ₂ , 8.9% Na ₂ O, 62% H ₂ O), commercially available as “Q Blend”;
A starting gel reaction mixture was prepared from tetramethylammonium chloride (50%), n-propylamine, sulfuric acid, and water. In Example 3, crystallization was carried out at 160° C. (320° C.) for 53 hours with stirring. In Example 4, the crystallization was carried out at 160 °C (320 °C) without stirring.
〓) I went there for 48 hours. After crystallization, the solid was separated from unreacted components by filtration, then washed with water, and then dried at 110°C (230°C). Starting material usage, product composition and adsorption data are shown in Table 2 below. The X-ray diffraction pattern of the zeolite prepared according to the procedure of Example 4 is shown in Table 3. Example 5 The dried product of Example 4 was heated to 538°C (1000〓) in a nitrogen stream.
It was baked for 3 hours. The calcined product is then drained of excess
0.1N NaCl−0.1N NaOH solution for 2 hours at room temperature.
Ion exchange was performed twice. As a result, the resulting washed product has a sodium content of 0.21% by weight.
It was hot. The X-ray diffraction results for the zeolite product of this example are shown in Table 4.

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[Table] * Increased strength due to crystalline silica phase

Claims (1)

[Claims] 1 Expressed in molar ratio, the following formula (0 to 2.5) M _2/o O: (0 to 2.5) Al ₂ O ₃ : 100 SiO ₂ (M is selected from alkali metals or alkaline earth metals) at least one cation, n is the valence of M), and has a lattice containing SiO ₄ tetrahedra bonded by sharing oxygen atoms, and has the following lattice planes: Spacing Lattice spacing D(A) Relative strength 11.2±0.2 Weak 6.8±0.15 Medium 5.8±0.1 Strongest 5.6±0.1 Strongest 4.8±0.1 Medium 4.4±0.1 Medium 3.95±0.08 Medium-strong 3.7±0.08 Strongest 3.4±0.07 Medium-strong 3.3±0.07 Strongest 3.2±0.07 Weak 3.1±0.06 Weak 3.0±0.06 Weak 2.3±0.05 Weak Crystalline zeolite material. 2. The crystalline zeolite material according to claim 1, wherein the lattice has AlO ₄ tetrahedrons. 3. The crystalline zeolite material according to claim 1, which is substantially free of alumina.