JPH0232205B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing crystalline zeolite. More specifically, the present invention relates to a method for producing crystalline zeolite from a raw material mixture containing silica, an alkali metal, a specific metal, water, and a specific organic compound. Crystalline zeolites, whether natural or synthetic, contain cations such as Na, K or H ions. These zeolites are SiO ₄
It is a three-dimensional network structure of AlO ₄ and SiO ₄ .
AlO ₄ is characterized by having a highly ordered tetrahedral structure cross-linked through oxygen atoms. Such crystalline zeolites have a large number of small pores within their crystal structure and are well known as molecular sieves, and are used for various purposes by taking advantage of this property. This crystalline zeolite is not only used in conversion reactions of various hydrocarbons, but also recently it has been used as a catalyst for producing hydrocarbons from synthesis gas via methanol and dimethyl ether.
Methods for producing ZSM-5 or similar zeolites are well known. The method for manufacturing these zeolites uses silica,
The most well-known method is to carry out the reaction by adding tetraalkylammonium ions to a raw material composition consisting of alumina, an alkali metal, and water. However, this method of adding tetraalkylammonium ions has the drawback of being expensive, and is not necessarily suitable as an industrial production method. It has been proposed to use alkylamines, amino alcohols, ammonia, organic sulfur compounds, etc. as additives to overcome this drawback. On the other hand,
A method for producing zeolite that does not require ion exchange treatment from a raw material composition (in the absence of an alkali metal) consisting of silica, metal oxides/hydroxides, water, and hexamethylene diamine has also been proposed. As a result of extensive research into the raw material composition of the method for producing crystalline zeolite, the present inventors have found that when a raw material composition consisting of silica, alkali metal, and water contains a specific metal and a specific organic compound. Furthermore, it was found that the X-ray diffraction pattern of the obtained reaction product was similar to that of the above-mentioned known zeolite ZSM-5. The present invention has been made based on this knowledge. That is, the present invention provides silica; alkali metals; boron, arsenic, antimony, yttrium,
One or more metals selected from zirconium, vanadium, chromium, iron, ruthenium, gallium, tin, phosphorus, lanthanum, titanium and tungsten; water and morpholine, ethanolamine,
A method for producing crystalline zeolite, which comprises maintaining a raw material mixture consisting of an organic compound selected from glutamic acid, alanine, and propionic acid amide under conditions of temperature and time necessary to produce crystalline zeolite. . The X-ray diffraction pattern of the crystalline zeolite powder produced by the method of the present invention was very similar to that of the conventionally known zeolite ZSM-5. Therefore, it can be suitably used in organic compound conversion methods, for example, conversion reactions of hydrocarbon compounds and oxygen-containing compounds such as methanol. A major feature of the synthesis reaction of the present invention is that it can use a raw material mixture consisting of a silica source, an alkali metal source, and water, which are used in the synthesis of ordinary crystalline zeolites, and does not use an alumina source. These raw material mixtures contain one or more metals selected from boron, arsenic, antimony, yttrium, zirconium, vanadium, chromium, iron, ruthenium, gallium, tin, phosphorus, lanthanum, titanium, and tungsten, as well as morpholine, ethanolamine, and glutamic acid. A synthetic reaction is carried out using a raw material mixture to which an organic compound selected from , alanine, and propionic acid amide is further added. The silica source is not particularly limited as long as it is commonly used in the production of crystalline zeolite, and examples thereof include silica powder, silicic acid, colloidal silica, and dissolved silica. Examples of 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. As the alkali metal source, sodium hydroxide, potassium hydroxide, etc. are used, and sodium silicate can also serve as a silica source. Particularly preferred as the alkali metal is sodium, and this alkali metal is used in an amount of 0.01 to 50, preferably 0.1 to 10 mol, per 1 mol of silica ( _SiO2 ) as _M2O . Next, metals include boron, arsenic, antimony, yttrium, zirconium, vanadium,
One or more metals selected from chromium, iron, ruthenium, gallium, tin, phosphorus, lanthanum, titanium, and tungsten are used. These metals are commonly used as oxides, hydroxides, chlorides, nitrates or sulfates. These metals are expressed as M ₂ O ₃ per mole of silica (SiO ₂ ).
It is used in a range of 0.01 to 50 mol, preferably 0.1 to 10 mol. Organic compounds must contain nitrogen and oxygen in their molecules, and these compounds include morpholine, ethanolamine, glutamic acid,
The organic compound is selected from alanine and propionamide. As these compounds, those soluble in water are advantageously used. The amount of these compounds added in the present invention is determined in the range of 0.01 to 50 mol, preferably 0.1 to 10 mol, per 1 mol of silica (SiO ₂ ). In the present invention, silica; one or more metals selected from boron, arsenic, antimony, yttrium, zirconium, vanadium, chromium, iron, ruthenium, gallium, tin, phosphorus, lanthanum, titanium, and tungsten together with an alkali metal; A raw material mixture consisting of an organic compound selected from morpholine, ethanolamine, glutamic acid, alanine and propionic acid amide,
Heating may be carried out at a temperature and time necessary to generate crystalline zeolite. Note that the amount of water is not particularly limited in the present invention. At this time, a mineralizing agent such as lithium chloride may be added to promote crystallization if necessary. The synthesis reaction of the present invention is carried out by heating the raw material mixture at a temperature and time necessary to produce crystalline zeolite. More specifically, the reaction temperature is 80 to 300°C, preferably 120 to 300°C. 200℃
The reaction time ranges from 0.5 hours to 30 days,
Preferably it is 5 hours to 10 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 synthesis reaction is continued by heating the raw material mixture to a desired temperature until sufficient crystalline zeolite is produced. After the reaction mixture in which crystalline zeolite production has been completed is cooled to room temperature, crystals are separated by filtration, decantation, centrifugation, etc., and thoroughly washed with water to obtain crystals. Crystalline zeolite can be obtained by drying these crystals usually at 100°C or higher for several hours. In the present invention, the crystalline zeolite is activated by being calcined in air at a temperature in the range of 300 to 700°C for about 2 to 48 hours before being used as a catalyst, or the alkali metal ions present in the crystalline zeolite are activated. This method includes a method of ion-exchanging part or all of the cation with at least one other cation to obtain H-type crystalline zeolite. This ion exchange method is a well-known technology in the industry.
Suitable cations include metal ions, ammonium ions, hydrogen ions, and mixtures thereof; examples of metal ions include cations of lithium, silver, magnesium, calcium, barium, aluminum, manganese, cobalt, nickel, or rare earth metals. be able to. These selections are arbitrarily determined depending on the type of conversion reaction. In the ion exchange method, the crystalline zeolite may be contacted with an aqueous solution containing a desired cation, and chlorides, nitrates, and nitrates of cations are usually used. After ion exchange, the crystalline zeolite is washed with water, dried, and then calcined in air or inert gas at a temperature of 300 to 700°C for 2 to 48 hours or more to form a catalytically active catalyst. Become. The crystalline zeolite obtained by the method of the invention is of the same type as zeolite ZSM-5 and can be used in conversion reactions of organic compounds such as hydrocarbon compounds and oxygenated compounds such as methanol. Such methods include alkylation of aromatic compounds with olefins; aromatization of olefins and paraffins; isomerization of aromatics, paraffins, and olefins; disproportionation of aromatics; oligomerization of olefins; cracking; I can give you Kratzking. Furthermore, it has the feature of being able to produce hydrocarbons rich in olefins from synthesis gas or its derivatives methanol and dimethyl ether. As detailed above, the method of the present invention relates to an inexpensive and industrially advantageous method for producing crystalline zeolite, and can be used for many purposes including as a catalyst or catalyst support for the various conversion reactions mentioned above. This makes it possible to provide crystalline zeolites suitable for use in other applications, such as adsorbents, extractants, ion exchangers, molecular sieves, etc. Next, the manufacturing method of the present invention will be explained based on Examples. Example 1 Boron oxide 1.6g, monoethanolamine 12.2g
Solution A is a solution of 17.6 g of sulfuric acid (97%) and 250 ml of water. Water glass (SiO ₂ 37.6% by weight,
Na ₂ O 17.5% by weight, water 44.9% by weight) 162g, water 300%
ml as a solution is called Solution B. Solution C is a solution of 79 g of sodium chloride and 122 ml of water.
While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature. This mixture was placed in an autoclave No. 1, and reacted for 20 hours at 170° C. under autogenous pressure while stirring at a rotation speed of 200 rpm. After cooling the reaction mixture, it was washed 5 times with 1 water,
The solid content was then separated by filtration and dried at 120°C for 3 hours to obtain 53g of crystalline zeolite. Table 1 shows the results of the X-ray diffraction pattern of this crystalline zeolite. In addition, this material has the following composition in molar ratio. _{1.7Na2O : 118SiO2} : _1B2O3

【table】

[Table] Example 2 The zeolite obtained in Example 1 was used as Zeolite 1.
It was immersed in 5 ml of 1N ammonium nitrate aqueous solution per gram and stirred occasionally. After 24 hours, the supernatant liquid was removed and the sample was immersed in a fresh 1N ammonium nitrate aqueous solution for 24 hours. Thereafter, the solid content was separated by filtration, thoroughly washed with water, and then dried at 120°C for 3 hours to convert the sodium form into the ammonium (NH ₄ ⁺ ) form. Further, the mixture was calcined at 550° C. for 6 hours in an air stream to obtain H-type zeolite. Example 3 Boron oxide 1.6g, morpholine 8.9g, sulfuric acid (97g)
Solution A is a solution of 17.6 g (%) and 250 ml of water. Water glass (SiO ₂ 37.6% by weight,
Na ₂ O 17.5% by weight, water 44.9% by weight) 162g, water 300%
Solution B is a milliliter solution. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature.
This mixture was placed in a 1 liter autoclave and reacted for 20 hours at 170° C. under autogenous pressure while stirring at 200 rpm. After cooling the reaction mixture, it was washed 5 times with 1 liter of water, then the solid was separated by filtration and dried at 120° C. for 3 hours.
54.0g of crystalline zeolite was obtained. Table 2 shows the results of the X-ray diffraction pattern of this crystalline zeolite. In addition, this material has the following composition in molar ratio. _{1.6Na2O : 110SiO2} : _1B2O3

[Table] Example 4 A solution containing 6.0 g of yttrium nitrate, 12.2 g of monoethanolamine, 17.6 g of sulfuric acid (97%), and 250 ml of water was used as Solution A. Solution B is a solution of 162 g of water glass (37.6% by weight of SiO ₂ , 17.5% by weight of Na ₂ O, 44.9% by weight of water) and 300 ml of water. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature. This mixture was placed in a 1 liter autoclave and reacted for 20 hours at 170° C. under autogenous pressure while stirring at 200 rpm.
After cooling the reaction mixture, it was washed five times with 1 liter of water, then the solid was separated by filtration and
After drying at ℃ for 3 hours, 58.1 g of crystalline zeolite was obtained. Table 3 shows the results of the X-ray diffraction pattern of this crystalline zeolite. In addition, this material has the following composition in molar ratio. _{1.1Na2O : 66.5SiO2} : _1Y2O3

[Table] Example 5 Arsenic oxide 2.0g, monoethanolamine 12.2g,
Solution A is a solution of 17.6 g of sulfuric acid (97%) and 250 ml of water. 162 g of water glass (SiO ₂ 37.6% by weight, Na ₂ O 17.5% by weight, water 44.9% by weight),
Solution B is a solution containing 300 ml of water. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature. This mixture was placed in a 1 liter autoclave and reacted for 20 hours at 170° C. under autogenous pressure while stirring at 200 rpm. After the reaction mixture was cooled, it was washed five times with 1 liter of water, and then the solid content was separated by filtration and dried at 120° C. for 3 hours to obtain 55.1 g of crystalline zeolite. In addition, this material has the following composition in molar ratio. 1.7Na ₂ O: 142.1SiO ₂ : 1As ₂ O _3Example 6 Antimony sulfate 5.4g, L-glutamic acid 14.7
Solution A is a solution of 17.6 g of sulfuric acid (97%) and 250 ml of water. Solution B is a solution of 162 g of water glass (37.6% by weight of SiO ₂ , 17.5% by weight of Na ₂ O, 44.9% by weight of water) and 300 ml of water. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature. This mixture was placed in a 1 liter autoclave and reacted for 20 hours at 170° C. under autogenous pressure while stirring at 200 rpm. After the reaction mixture was cooled, it was washed five times with 1 liter of water, then the solid content was separated by filtration and heated to 120°C.
After drying for 3 hours, 57.5 g of crystalline zeolite was obtained. In addition, this material has the following composition in molar ratio. 1.3Na ₂ O: 72.1SiO ₂ : 1Sb ₂ O _3Example 7 Ferric sulfate 8.1g, monoethanolamine 12.2
Solution A is a solution of 17.6 g of sulfuric acid (97%) and 250 ml of water. Solution B is a solution of 162 g of water glass (37.6% by weight of SiO ₂ , 17.5% by weight of Na ₂ O, 44.9% by weight of water) and 300 ml of water. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature. This mixture was placed in a 1 liter autoclave and reacted for 20 hours at 170° C. under autogenous pressure while stirring at 200 rpm. After the reaction mixture was cooled, it was washed five times with 1 liter of water, then the solid content was separated by filtration and heated to 120°C.
After drying for 3 hours, 59.8 g of crystalline zeolite was obtained. In addition, this material has the following composition in molar ratio. 1.2Na ₂ O: 68.1SiO ₂ : 1Fe ₂ O _3Example 8 Chromium nitrate 8.1g, morpholine 8.7g, sulfuric acid (97
Solution A is a solution of 17.6 g (%) and 250 ml of water. Water glass (SiO ₂ 37.6% by weight,
Na ₂ O 17.5% by weight, water 44.9% by weight) 162g, water 300%
Solution B is a milliliter solution. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature.
This mixture was placed in a 1 liter autoclave and reacted for 20 hours at 170° C. under autogenous pressure while stirring at 200 rpm. After cooling the reaction mixture, it was washed 5 times with 1 liter of water, then the solid was separated by filtration and dried at 120° C. for 3 hours.
58.5g of crystalline zeolite was obtained. In addition, this material has the following composition in molar ratio. 1.1Na ₂ O: 62.1 SiO ₂ : 1Cr ₂ O ₃ Example 9 Example 8 except that 8.0 g of gallium nitrate was used instead of 8.1 g of chromium nitrate in Example 8.
In the same manner as above, 53.1 g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.1Na ₂ O: 65.8 SiO ₂ : 1Ga ₂ O ₃ Example 10 The same procedure as Example 8 was used except that 2.3 g of phosphoric acid was used instead of 8.1 g of chromium nitrate, and 51.3 g of crystallinity was obtained. Obtained zeolite. This material has the following composition in molar ratio. 1.1Na ₂ O: 90.5SiO ₂ : 1P ₂ O _5Example 11 Example 8 except that 6.9 g of stannic chloride was used instead of 8.1 g of chromium nitrate in Example 8.
In the same manner as above, 54.3 g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.1Na ₂ O: 70.2 SiO ₂ : 1SnO ₂ Example 12 Example 8 except that 8.6 g of lanthanum nitrate was used instead of 8.1 g of chromium nitrate in Example 8.
In the same manner as above, 53.1 g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.3Na ₂ O: 65.5SiO ₂ : 1La ₂ O _3Example 13 The same procedure as Example 8 was carried out except that 16.0 g of titanium sulfate solution (30%) was used instead of 8.1 g of chromium nitrate. 58.3g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.1Na ₂ O: 70.2SiO ₂ : 1Ti ₂ O _3Example 14 The same procedure as in Example 8 was used except that 4.5 g of zirconium oxychloride was used instead of 8.1 g of chromium nitrate, yielding 59.3 g of crystals. zeolite was obtained. This material has the following composition in molar ratio. 1.1Na ₂ O: 80.1SiO ₂ : 1Zr ₂ O _4Example 15 Example 8 except that 4.0 g of vanadyl sulfate was used instead of 8.1 g of chromium nitrate in Example 8.
In the same manner as above, 55.1 g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.8Na ₂ O: 72.1SiO ₂ : 1V ₂ O _4Example 16 In Example 8, 9.3 g of ammonium tungstate (50% solution) was used instead of 8.1 g of chromium nitrate.
The procedure was carried out in the same manner as in Example 8 except that 53.8 was used.
g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.1Na ₂ O: 120.5SiO ₂ : 1W ₂ O ₃ Example 17 The same procedure as in Example 8 was used except that 5.0 g of ruthenium trichloride was used instead of 8.1 g of chromium nitrate, and 60.1 g of crystals were obtained. zeolite was obtained. This material has the following composition in molar ratio. 1.8Na ₂ O: 85.1SiO ₂ : 1Ru ₂ O _3Example 18 In Example 1, the amount of boron oxide used was 3.2
Example 1 was repeated, except that 9.0 g of alanine was used instead of 12.2 g of monoethanolamine, and 56.3 g of crystalline zeolite was obtained. This material has the following composition in molar ratio. 1.4Na ₂ O: 85.2SiO ₂ : 1B ₂ O _3Example 19 In Example 1, the amount of boron oxide used was 3.2
Example 1 was repeated, except that 7.4 g of propionic acid amide was used instead of 12.2 g of monoethanolamine, and 57.2 g of crystalline zeolite was obtained. This material has the following composition in molar ratio. _{1.3Na2O : 88.0SiO2} : _1B2O3

Claims (1)

[Claims] 1 Silica; Alkali metal; boron, arsenic, antimony, yttrium, zirconium, vanadium, chromium, iron, ruthenium, gallium, tin,
Crystalline zeolite is produced from a raw material mixture consisting of one or more metals selected from phosphorus, lanthanum, titanium, and tungsten; water and an organic compound selected from among morpholine, ethanolamine, glutamic acid, alanine, and propionic acid amide. A method for producing crystalline zeolite, which comprises maintaining the crystalline zeolite under the conditions of temperature and time necessary for the production of crystalline zeolite.