JPH0339973B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a crystalline silicate with a new structure called ISI-2 and a method for producing the same. Specifically, the present invention relates to a crystalline silicate with a new structure (ISI-2) that can be effectively used as a catalyst for various chemical reactions and its efficient method. Regarding the manufacturing method. Many natural and synthetic crystalline silicates have been known, and various methods for producing them have been proposed. These methods are usually carried out by proceeding with a hydrothermal reaction using an aqueous mixture consisting of a silica source, an alumina source, and an alkali metal source as raw materials, but recently organic compounds such as tetrapropylammonium bromide have been added to this aqueous mixture. A method has been developed to produce crystalline aluminosilicate zeolite with a special crystal structure by adding For example, according to JP-A-52-43800 and JP-A-56-134517, ZSM-5 type zeolite, zeta-1, and zeta-3 type zeolites are produced by adding alcohol. Furthermore, JP-A-56-37215 describes that ZSM-5 and ZSM-11 type zeolites can be produced by using alcohol and seed crystals in combination. In addition, Tokukai Akira
No. 54-151600 discloses the production of zeolite using a combination of alcohol and ammonia. It is also known that ZSM-11 type zeolite can be obtained by synthesis using a tetrabutylammonium salt in water as a solvent (US Pat. No. 3,709,979). The present inventors have conducted extensive research to develop a silicate with a completely new composition and crystal structure. As a result, in the conventional method, the amount of alcohol added to the silica source and alumina source was small, but in addition to using a large amount of alcohol to serve as a solvent, tetramethylammonium salt was used as a crystallizing agent. By using large amounts of compounds with bulky molecular structures such as branched alkyl alcohols, branched alkyl amines, cyclic ethers, and cyclic amines for silica sources and alumina sources, crystalline silicates with completely new crystal structures can be created. (ISI-2) was found to be obtained. The present invention was completed based on this knowledge. That is, in the present invention, the composition expressed in molar ratio after firing at 550°C in air has the general formula pM _2/o O・Al ₂ O ₃・qSiO ₂ ...(1) (where M is an alkali It represents one or more elements selected from metals, alkaline earth metals, and hydrogen, and n represents the valence of M. In addition, p and q are selected from the following range: 0.3≦p≦3.0 , q≧10) and an X-ray diffraction pattern shown in Table 1 (hereinafter referred to as the first invention). ). Furthermore, (a) a silica source, (b) an alumina source,
(c) Contains an alkali metal and/or alkaline earth metal source, (d) alcohol, and (e) tetramethylammonium salt, and the molar ratio of each component is silica/alumina ≧10 Alcohol/water = 0.1 to 10 Alcohols/Silica = 1-100 Alkali metal and/or alkaline earth metal source/Silica = 0.1-3 Hydroxide ion/Silica = 0.01-0.5 (excluding hydroxide ions from organic bases) Tetramethyl Ammonium salt/silica = 0.01~
1 is reacted at 100 to 300°C until crystalline silicate (ISI-2) is produced, and the composition expressed in molar ratio after calcination at 550°C in air is The general formula ()
and the X-ray diffraction pattern is shown in Table 1 (hereinafter referred to as the second invention), and (a)
at least one compound selected from a silica source, (b) an alumina source, (c) an alkali metal and/or alkaline earth metal source, (f) a branched alkyl alcohol, a branched alkyl amine, a cyclic ether, and a cyclic amine. and the molar ratio of each component is silica/alumina ≧10 Compound (f) above/water = 0.05-10 Compound (f) above/silica = 2-100 Hydroxide ion/silica = 0.01-0.5 (however, organic (Excluding hydroxide ions from the base.) An aqueous mixture of alkali metal and/or alkaline earth metal/silica = 0.1 to 3 is reacted at 100 to 300°C until crystalline silicate (ISI-2) is formed. The composition expressed in molar ratio after firing at 550°C in air is represented by the general formula (), and the X-ray diffraction pattern is crystalline as shown in Table 1. This invention provides a method for producing silicate (hereinafter referred to as the third invention).

【table】

[Table] According to the method of the second invention, (a) a silica source, (b)
An aqueous mixture is prepared by adding an alumina source, (c) an alkali metal and/or alkaline earth metal source, (d) an alcohol, and (e) a tetramethylammonium salt, and this is reacted under heating. Here, the silica source (a) is not particularly limited, and any silica powder, silicic acid, colloidal silica, dissolved silica, etc. can be used. Examples of the dissolved silica include water glass silicates and alkali metal silicates containing 1 to 5 moles of SiO ₂ per mole of Na ₂ O or K ₂ O. Various sources can be used as the alumina source (b), including aluminum sulfate, sodium aluminate, colloidal alumina, and alumina. In the method of the second invention, the ratio of silica to alumina in the aqueous mixture may be determined as appropriate, but it is preferably the molar ratio of silica (SiO ₂ )/alumina (Al ₂ O ₃ ).
It should be 10 or more, with 40 to 1000 being especially optimal. Next, as (c) the alkali metal and/or alkaline earth metal source, various sources can be used. For example, sodium hydroxide, potassium hydroxide, etc. are used as the alkali metal source, and sodium silicate and sodium aluminate can also serve as a source of silica or alumina. Particularly preferred as the alkali metal is sodium. On the other hand, alkaline earth metal sources include calcium nitrate and calcium chloride. Here, the molar ratio of the alkali metal and/or alkaline earth metal to silica in the aqueous mixture is not particularly limited and may be determined as appropriate depending on various conditions, but is usually 0.1 to 3, particularly preferably 0.2 to 3. It should be 2.8. Next, (d) alcohols are not contained as constituents of the crystalline silicate produced, but play an important role in forming the crystal structure in the manufacturing process. Specific examples include methanol, ethanol, and ethylene glycol, with methanol and ethylene glycol being particularly preferred. It is preferable that the amount of alcohol used is relatively large, and the molar ratio of alcohol/water is 0.1 to
10, particularly preferably from 0.2 to 5, and the alcohol/silica molar ratio should be from 1 to 100, particularly preferably from 3 to 60. Furthermore, (e) tetramethylammonium salt acts as a crystallizing agent. Specific examples include tetramethylammonium bromide, tetramethylammonium chloride, and tetramethylammonium iodide, with tetramethylammonium bromide being particularly preferred. Moreover, instead of the above-mentioned tetramethylammonium salt, a so-called precursor which becomes a tetramethylammonium salt in the process of preparing the crystalline silicate can also be used. The amount of tetramethylammonium salt used is such that the molar ratio to silica is 0.01 to 1.
Particularly preferably it should be between 0.05 and 0.7. In the method of the second invention, these components (a), (b), (c), (d) and (e) are added to water to form an aqueous mixture, and this is reacted. Here, the molar ratio of hydroxide ion to silica in the aqueous mixture that is the reaction system is 0.01 to
It should be 0.5, particularly preferably between 0.05 and 0.4. Note that the number of moles of hydroxide ions in this case is calculated excluding hydroxide ions generated by adding an organic base. Furthermore, when reacting the aqueous mixture, it is sufficient to heat the mixture to a temperature and time necessary to form a crystalline silicate.
The reaction may be carried out at a temperature of 5 hours to 10 days, preferably 10 hours to 5 days. There are no particular restrictions on the pressure, and it is usually carried out under autogenous pressure. Further, the reaction system is usually kept under stirring, and the atmosphere may be replaced with an inert gas if necessary. In addition, the PH of the reaction system
should be adjusted to a neutral to alkaline range, usually PH7.5-14, preferably PH8.0-10.0. The above-mentioned crystallization reactions always involve the use of crystallization agents as crystallization agents.
(e) The process proceeds in the presence of a tetramethylammonium salt and a large amount of alcohol, and if these conditions are not met, the desired crystalline silicate cannot be obtained. In this reaction, there is no particular restriction on the mixing order of the above components, but in a preferred embodiment, (a) a silica source and (c) an alkali metal and/or alkaline earth metal source are added to water, and ( b) Adding a mixture of alumina source and (e) tetramethylammonium salt to water to form an aqueous mixture, and further adding (d) alcohol to this. After the above crystallization reaction, washing with water, drying at about 120°C, and firing in air at 550°C results in a composition represented by the general formula () and an X-ray diffraction pattern shown in Table 1. A crystalline silicate is obtained. According to the method of the third invention, in water (a) a silica source, (b) an alumina source, (c) an alkali metal and/or alkaline earth metal source, and (f) a branched alkyl alcohol,
At least one compound selected from branched alkyl amines, cyclic ethers, and cyclic amines is added to prepare an aqueous mixture, and this is reacted under heating. Here, (a) the silica source, (b) the alumina source, and (c) the alkali metal and/or alkaline earth metal source are the same as in the second invention described above. (f) branched alkyl alcohol in the third invention;
At least one compound selected from branched alkyl amines, cyclic ethers, and cyclic amines acts as a crystallizing agent and a solvent. The branched alkyl alcohol is not particularly limited as long as it is an alcohol having a branched alkyl.
Specifically, isopropyl alcohol, isobutyl alcohol, tert-butyl alcohol, 2-methylbutyl alcohol, 3-methylbutyl alcohol, tert-amyl alcohol, or 2,2-
Examples include dimethylpropyl alcohol, and isopropyl alcohol is particularly preferred. The branched alkylamine is not particularly limited as long as it is an amine having a branched alkyl. Specifically, isopropylamine, isobutylamine, tert-butylamine, 2-methylbutylamine, 3-methylbutylamine, tert-amylamine or 2,
Examples include 2-dimethylpropylamine, with isopropylamine and tert-butylamine being particularly preferred. Examples of the cyclic ether include furan, tetrahydrofuran, α-pyran, γ-pyran, tetrahydropyran, and dioxane, with dioxane being particularly preferred. Specific examples of the cyclic amine include pyrrole, pyridine, piperidine, pyridazine, and morpholine, with piperidine and morpholine being particularly preferred. These compounds are not limited to one type, and may be used in combination. A suitable combination is isopropyl alcohol and morpholine:
1 mixture of dioxane and t-butylamine:
1 mixture or a 1:2 mixture of piperidine and tetrahydrofuran. The amount of the compound (f) above used is 0.05 to 10% of water.
(molar ratio), particularly preferably from 0.2 to 5 (molar ratio), and for silica should be from 2 to 100 (molar ratio), particularly preferably from 3 to 60 (molar ratio). be. In the method of the third invention, these (a), (b), (c) and
Component (f) is added to water to form an aqueous mixture, and this is allowed to react. The molar ratio of hydroxide ions to silica in the aqueous reaction mixture here should be from 0.01 to 0.5, particularly preferably from 0.05 to 0.4. Note that the number of moles of hydroxide ions in this case is calculated excluding hydroxide ions generated by adding an organic base. Furthermore, when reacting the aqueous mixture, it is sufficient to heat the mixture to a temperature and time necessary to form a crystalline silicate. The reaction may be carried out for about 5 hours to 10 days, preferably about 10 hours to 5 days. There are no particular restrictions on the pressure, and it is usually carried out under autogenous pressure. Further, the reaction system is usually kept under stirring, and the atmosphere may be replaced with an inert gas if necessary. The PH of the reaction system is neutral to alkaline, usually PH7.5 to 14, preferably PH8.0 to 10.0.
It should be adjusted within the range of . The above-mentioned crystallization reaction always proceeds in the presence of at least one compound selected from branched alkyl alcohols, branched alkyl amines, cyclic ethers, and cyclic amines, and if these conditions are not satisfied, the desired Crystalline silicates cannot be obtained. In the third invention, there is no particular restriction on the mixing order of the above components, but in a preferred embodiment, (a) a silica source and (c) an alkali metal and/or alkaline earth metal source are added to water, and (b) ) A method of adding an alumina source to water to form an aqueous mixture, and further adding (f) at least one compound selected from branched alkyl alcohols, branched alkyl amines, cyclic ethers, and cyclic amines. I can give it to you. After the above crystallization reaction, wash with water and dry at about 120℃.
Furthermore, if it is fired in air at 550℃, the general formula ()
A crystalline silicate having the composition shown in Table 1 and the X-ray diffraction pattern shown in Table 1 is obtained. This crystalline silicate is a silicate with a completely new crystal structure, and it can be used as a solid acid catalyst, etc.
It can be effectively used as a catalyst carrier, adsorbent, etc. Therefore, the crystalline silicate of the present invention is widely used in the chemical industry in general, and in the petroleum refining industry in particular. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Aluminum sulfate (18 hydrate) 7.52 g, sulfuric acid (97
%) and 25.0 g of tetramethylammonium bromide dissolved in 150 ml of water was used as solution A, and water glass (SiO ₂ 29.0 wt%, Na ₂ O 9.4 wt%,
A solution prepared by dissolving 211.0 g of water (91.6 wt%) in 96 ml of water was used as Solution B, and 376 ml of methanol was used as Solution C. Gradually add and mix liquid A and liquid B at the same time, and then
10.0g of 50% sulfuric acid was added to adjust the pH to 8.5. Further, Solution C was added and mixed, and the mixture was placed in autoclave 1 and reacted for 20 hours at 170° C. under autogenous pressure while stirring. After cooling the reaction mixture, the product was washed 5 times with 1.5 g of water. The filtered solids are then separated,
After drying at 120° C. for 6 hours, 57.0 g of crystalline aluminosilicate (ISI-2) was obtained. X of this product
A line diffraction diagram is shown in FIG. In addition, the composition (mole ratio) after calcining this product in air at 550℃ is
It _{was 0.63Na2O}・_Al2O3・_79.4SiO2 . Also
It contained 5.2wt% carbon. Example 2 Crystalline silicate was produced under exactly the same conditions as in Example 1, except that 376 ml of ethylene glycol was used as liquid C. The composition (molar ratio) of the product after calcining in air at 550°C is 0.68Na ₂ O.
_It was _Al2O3・_76.3SiO2 . It also contained 5.0wt% carbon. Example 3 A solution of 7.52 g of aluminum sulfate (18 hydrate) and 17.6 g of sulfuric acid (97%) dissolved in 100 ml of water was used as solution A, and water glass (SiO ₂ 29.0 wt%, Na ₂ O 9.4 wt%,
A solution of 211.0 g (61.6 wt% of water) dissolved in 46 ml of water was used as Solution B, 100 ml of water was used as Solution C, and 376 ml of tetrahydrofuran was used as Solution D. Gradually drop A and B solutions simultaneously into C solution, mix, and then add 50% sulfuric acid to 10.0%.
g and adjusted the pH to 9.5. Further, Solution D was added and mixed, and this was placed in autoclave 1 and reacted for 20 hours at 170° C. under autogenous pressure while stirring. After cooling the reaction mixture, the product was washed 5 times with 1.5 g of water. Then, the filtered solids are separated,
After drying at 120° C. for 6 hours, 55.0 g of crystalline silicate (ISI-2) was obtained. After this product was calcined in air at 550° C., the composition (molar ratio) was 0.93Na ₂ O.Al _{2 O} 3.75.6SiO ₂ . It also contained 2.9wt% carbon. Example 4 Crystalline silicate (ISI-2) was obtained in the same manner as in Example 3 except that 376 ml of isopropanol was used as liquid D. _The composition (molar _ratio ) of this product _{was 1.02Na2O.Al2O3.80.2SiO2} . It also contained 2.6wt% carbon. Example 5 Crystalline silicate (ISI-2) was obtained in the same manner as in Example 3 except that 376 ml of isopropylamine was used as liquid D. The composition (mole ratio) of this product is 0.62Na ₂ O・Al ₂ O ₃・70.2SiO ₂
It was hot. It also contained 3.1wt% carbon. Example 6 Crystalline silicate (ISI-2) was obtained in the same manner as in Example 3 except that 376 ml of tert-butylamine was used as liquid D. _The composition (molar _ratio ) of this product _{was 1.21Na2O.Al2O3.73.2SiO2} . Example 7 Crystalline silicate (ISI-2) was obtained in the same manner as in Example 3 except that 376 ml of dioxane was used as liquid D. _The composition (mole _ratio ) of this product _{was 0.92Na2O.Al2O3.76.2SiO2} .
It also contained 2.1wt% carbon. Example 8 Crystalline silicate (ISI-2) was obtained in the same manner as in Example 3, except that 376 ml of piperidine was used as liquid D. _The composition (molar _ratio ) of this product _{was 2.25Na2O.Al2O3.65.2SiO2} .
It also contained 2.6wt% carbon. Example 9 Crystalline silicate (ISI-2) was obtained in the same manner as in Example 3 except that 376 ml of morpholine was used as liquid D. _The composition (molar _ratio ) of this product _{was 1.8Na2O.Al2O3.76.2SiO2} .
It also contained 2.9wt% carbon.

[Brief explanation of drawings]

FIG. 1 shows the X-ray diffraction pattern of the crystalline silicate obtained in Example 1. Here, θ indicates the angle of incidence.

Claims (1)

[Claims] 1. The composition expressed in molar ratio after firing at 550°C in air is expressed by the general formula pM _2/o O・Al ₂ O ₃・qSiO ₂ (wherein M is an alkali metal, an alkali It represents one or more elements selected from earth metals and hydrogen, and n represents the valence of M. In addition, p and q are selected from the following ranges: 0.3≦p≦3.0, q≧ 10) and the X-ray diffraction pattern is expressed by lattice spacing d (Å) relative intensity 11.22±0.2 Weak 6.85±0.15 Weak 5.84±0.15 Moderate 5.59±0.15 Moderate 4.84±0.15 Moderate 4.44± 0.15 Weak 3.95±0.10 Moderate 3.72±0.10 Very Strong 3.42±0.07 Moderate 3.27±0.07 Strong 3.22±0.07 Weak 3.06±0.07 Weak 2.95±0.07 Weak 2.71±0.05 Weak 2.52 ±0.05 weak 2.36 A crystalline silicate characterized by the following formula: ±0.05 Weak 2.28±0.05 Weak. 2 Contains (a) a silica source, (b) an alumina source, (c) an alkali metal and/or alkaline earth metal source, (d) an alcohol, and (e) a tetramethylammonium salt, and the molar ratio of each component. Silica/Alumina≧10 Alcohols/Water=0.1~10 Alcohols/Silica=1~100 Alkali metal and/or alkaline earth metal source/Silica=0.1~3 Hydroxide ion/Silica=0.01~0.5 (However, (excluding hydroxyl ions from organic bases) in air, characterized by reacting an aqueous mixture of tetramethylammonium salt/silica = 0.01 to 1 at 100 to 300°C until crystalline silicate is formed. The composition expressed in molar ratio after firing at 550℃ is given by the general formula pM _2/o O・Al ₂ O ₃・qSiO ₂ (where M is selected from alkali metals, alkaline earth metals, and hydrogen). represents one or more elements, n represents the valence of M, and p and q are selected from the following ranges: 0.3≦p≦3.0, q≧10), and The line diffraction pattern has a relative intensity of lattice spacing d (Å) 11.22±0.2 Weak 6.85±0.15 Weak 5.84±0.15 Moderate 5.59±0.15 Moderate 4.84±0.15 Moderate 4.44±0.15 Weak 3.95±0.10 Moderate 3.72 ±0.10 Very strong 3.42±0.07 Moderate 3.27±0.07 Strong 3.22±0.07 Weak 3.06±0.07 Weak 2.95±0.07 Weak 2.71±0.05 Weak 2.52±0.05 Weak 2.36±0.05 Weak 2.2 8±0.05 weak A method for producing a crystalline silicate represented by 3 (a) a silica source, (b) an alumina source, (c) an alkali metal and/or alkaline earth metal source, and (f) at least one selected from branched alkyl alcohols, branched alkyl amines, cyclic ethers, and cyclic amines. Contains a compound, and the molar ratio of each component is silica/alumina ≧10 Compound (f) above/water = 0.05-10 Compound (f) above/silica = 2-100 Hydroxide ion/silica = 0.01-0.5 (however, (excluding hydroxide ions from organic bases). An aqueous mixture of alkali metal and/or alkaline earth metal/silica = 0.1-3 is reacted at 100-300°C until crystalline silicate is formed. The characteristic composition expressed in molar ratio after firing at 550℃ in air is the general formula pM _2/o O・Al ₂ O ₃・qSiO ₂ (where M is an alkali metal, an alkaline earth metal, or Indicates one or more elements selected from hydrogen, and n indicates the valence of M. In addition, p and q are selected from the following range: 0.3≦p≦3.0, q≧10) 11.22±0.2 Weak 6.85± 0.15 Weak 5.84±0.15 Moderate 5.59±0.15 Moderate 4.84±0.15 Moderate 4.44±0.15 Weak 3.95 ±0.10 Moderate 3.72±0.10 Very Strong 3.42±0.07 Moderate 3.27±0.07 Strong 3.22±0.07 Weak 3.06±0.07 Weak 2.95±0.07 Weak 2.71±0.05 Weak 2.52±0.05 Weak 2.36 ±0.05 weak 2.28±0.05 A method for producing crystalline silicate.