CN1046487C - Process for preparing beta zeolite - Google Patents
Process for preparing beta zeolite Download PDFInfo
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- CN1046487C CN1046487C CN95117903A CN95117903A CN1046487C CN 1046487 C CN1046487 C CN 1046487C CN 95117903 A CN95117903 A CN 95117903A CN 95117903 A CN95117903 A CN 95117903A CN 1046487 C CN1046487 C CN 1046487C
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Abstract
The present invention relates to a preparation method for beta zeolite, which comprises: a silicon source, an aluminum source, tetraethyl ammonium halide(TEAX), sodium hydroxide and water are crystallized for 40 to 200 hours at 130 to 170 DEG C after being uniformly mixed, wherein according to the molar ratio, a reaction mixture is composed of 10 portions of SiO2, 80 portions of Al2O3, 0.15 portions of TEAX, 0.60 portion of SiO2, 0.12 portion of OH, 0.40 portion of SiO2, 6.0 portions of H2O and 24.0 portions of SiO2. The method has the advantages of no need of a special silicon source and special ammonium hydroxide, and short crystallization time. Thereby, the method is favorable for industrialization production.
Description
The invention relates to β prepare zeolite method, more particularly, is the β prepare zeolite method about being template with the tetraethyl-ammonium halide.
The β zeolite is a kind of macropore crystallized silicon aluminate of high silicon content, synthesizes (US3,308,069) first in 1967 by people such as Wadlinger.Because the high silicon content of β zeolite and stronger acidity, it is with a wide range of applications in the hydrocarbon conversion reactions such as Hydrodewaxing and pour point one class that reduces oil product.
Perez-Pariente, J. wait the people at Appl Catal. 1987,31,35 and Zeolites1988,8, in 46, Camblor, people such as M.A. are at Zeolites 1991,11, all reported in 202 with tetraethyl ammonium hydroxide (TEAOH) to be template, to be the silicon source with the tetraethyl orthosilicate, in the presence of sodium ion, under static or stirring, prepared the method for β zeolite.Other document descriptions similar method, just adopt different silicon sources, as soft silica (EP 55046), (US 3,308 for colloid silica, 064) and silica gel (Bhat, R.N.and Kunan, R.J., Chem.Tech.Biotechnol.1990,48,453).But TEAOH preparation process complexity, cost used in the aforesaid method are very high, so be unfavorable for the suitability for industrialized production of β zeolite.
US 4,847,055 disclose the special silicon of a kind of employing source, be the method that template prepares the β zeolite with tetraethylammonium bromide (TEABr).This special silicon source is to obtain by making mensuration dissolubility silicic salts solution and precipitation agent carry out the successive precipitin reaction under the substantially invariable condition of mol ratio that keeps the two.This is precipitated as the condensed solids that median size is the micro-spherical particle of 50-100 micron.Though it is template that this method adopts lower-cost TEABr, the preparation process complexity in silicon source, operational condition harshness.
People such as M.J.Eapen reported a kind of with the silicon sol be the silicon source, with TEABr combining hydrogen oxidation ammonium be the template method for preparing the β zeolite (Zeolites, 1994, Vol.14,295-302).Though this method has been used ordinary silicon source and lower-cost TEABr, its OH
-/ SiO
2Mol ratio needs up to 0.7-1.05, and the crystallization time of this moment is 2-13 days.According to the viewpoint of this paper, work as OH
-/ SiO
2Mol ratio was reduced to 0.6 o'clock, and crystallization rate will be very slow just.According to this method, not only need to use a large amount of ammonium hydroxide, improve product cost, and reduced output per single reactor.
The object of the present invention is to provide a kind of special silicon source of need not using is template, the short method for preparing the β zeolite of crystallization time with a large amount of ammonium hydroxide, with the tetraethyl-ammonium halide.
β prepare zeolite method provided by the invention is that silicon source, aluminium source, tetraethyl-ammonium halide (TEAX), sodium hydroxide and water were mixed the back at 130-170 ℃ of crystallization 40-200 hour.
In aforesaid method, the composition of reaction mixture (meter in molar ratio) is as follows: SiO
2/ Al
2O
3Be 10-80, TEAX/SiO
2Be 0.15-0.60, OH
-/ SiO
2Be 0.12-0.40, H
2O/SiO
2Be 6.0-24.0; The silicon source is selected from one or more the mixture in silicon sol, silicon gel, the amorphous aluminosilicate; The aluminium source is selected from one or more the mixture in Tai-Ace S 150, sodium metaaluminate, the amorphous aluminosilicate; The tetraethyl-ammonium halide is selected from etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide or their mixture, preferred tetraethylammonium bromide (TEABr).
In aforesaid method, in order to accelerate the crystallization velocity of β zeolite, can in described reaction mixture, add crystal seed, its consumption is 1% of a product weight.
The inventive method is a template with lower-cost tetraethylammonium bromide, neither needs special silicon source, also needn't use ammonium hydroxide, and crystallization time is shorter, greatly reduces cost and helps suitability for industrialized production.
Fig. 1 is the X-ray diffraction spectrogram of the β zeolite that makes with the inventive method.
Further describe the present invention with example below, but the present invention is not subjected to the restriction of these embodiment.
The X-ray diffraction spectrogram of products obtained therefrom all records on Japan D/Max-III of science A diffractometer among each embodiment, and diffraction conditions are CuK α radiation, Ni filtering.
Embodiment 1
In 50 milliliters autoclave, add 10.51 gram silicon sol (Industrial products, pH8-9, SiO
2Content is 27.4 heavy %), (Industrial products, butt contains SiO to 2.82 gram silicon aluminium microspheres
289.5 heavy %, Al
2O
310.5 heavy %), sodium hydroxide solutions 6.10 gram TEABr (Industrial products) and the 19.6 gram water of 2.62 grams, 32 heavy %, the composition of this reaction mixture (counting in molar ratio) is: SiO
2/ Al
2O
3=30, TEABr/SiO
2=0.32, OH
-/ SiO
2=0.23, H
2O/SiO
2=18.0.After mixture stirred, under 150 ℃, left standstill crystallization 5 days.The crystallization product that obtains is filtered, washs and dries down at 110 ℃, promptly get the β zeolite product.The result that its X-ray diffraction (XRD) is analyzed as shown in Figure 1.
Embodiment 2
Except TEABr/SiO
2Be 0.44, crystallization time is 8 beyond the highest heavens, be prepared by the step identical with embodiment 1.The XRD analysis result of the β zeolite product of gained is identical with Fig. 1.
Embodiment 3
Except TEABr/SiO
2Be outside 0.51, be prepared by the step identical with embodiment 1.The XRD analysis result of gained β zeolite product is identical with Fig. 1.
Embodiment 4
In 50 milliliters autoclave, add sodium hydroxide solution, 8.84 gram TEAABr (with embodiment 1) and the 6.0 gram water of 20 gram silicon sol (with embodiment 1), 3.81 grams, 32 heavy %, stir.Under agitation add the solution that contains 1.01 gram Tai-Ace S 150 and 6.6 gram water.At this moment, consisting of of the above-mentioned reaction mixture of counting in molar ratio: SiO
2/ Al
2O
3=60, TEABr/SiO
2=0.47, OH
-/ SiO
2=0.23, H
2O/SiO
2=18.0.After mixture stirred, under 150 ℃, left standstill crystallization 5 days.Crystallization product after filtration, the washing, the oven dry after, promptly get the β zeolite product.Its XRD analysis result is identical with Fig. 1.
Embodiment 5
In 50 milliliters autoclave, add 15.1 sodium hydroxide solutions, 9.37 that restrain silicon sol (with embodiment 1), 1.46 gram silicon aluminium microspheres (with embodiment 1), 3.42 grams, 32 heavy % and restrain TEABr (with embodiment 1) and 16.0 gram water, at this moment consisting of of the above-mentioned reaction mixture of counting in molar ratio: SiO
2/ Al
2O
3=60, TEABr/SiO
2=0.49, OH
-/ SiO
2=0.30, H
2O/SiO
2=18.0.After mixture stirred, under 140 ℃, left standstill crystallization 5 days.Crystallization product after filtration, the washing, the oven dry after, promptly get the β zeolite product.Its XRD analysis result is identical with Fig. 1.
In 50 milliliters autoclave, add 12.72 sodium hydroxide solutions, 7.65 that restrain silicon sol (with embodiment 1), 2.21 gram silicon aluminium microspheres (with embodiment 1), 3.38 grams, 25 heavy % and restrain TEABr (with embodiment 1) and 17.4 gram water, at this moment consisting of of the above-mentioned reaction mixture of counting in molar ratio: SiO
2/ Al
2O
3=40, TEABr/SiO
2=0.40, OH
-/ SiO
2=0.23, H
2O/SiO
2=18.0.After mixture stirred, under 140 ℃, left standstill crystallization 5 days.Crystallization product after filtration, the washing, the oven dry after, promptly get the β zeolite product.Its XRD analysis result is identical with Fig. 1.
Embodiment 7
In 50 milliliters autoclave, add 10.51 sodium hydroxide solutions, 6.05 that restrain silicon sol (with embodiment 1), 3.32 gram silicon aluminium microspheres (with embodiment 1), 2.05 grams, 32 heavy % and restrain TEABr (with embodiment 1) and 5.31 gram water, at this moment consisting of of the above-mentioned reaction mixture of counting in molar ratio: SiO
2/ Al
2O
3=30, TEABr/SiO
2=0.34, OH
-/ SiO
2=0.18, H
2O/SiO
2=9.After mixture stirred, under 150 ℃, left standstill crystallization 5 days.Crystallization product after filtration, the washing, the oven dry, promptly get the β zeolite product.Its XRD analysis result is identical with Fig. 1.
Claims (4)
1. one kind is the method that template prepares the β zeolite with the tetraethyl-ammonium halide, it is characterized in that silicon source, aluminium source, tetraethyl-ammonium halide (TEAX), sodium hydroxide and water were mixed the back at 130-170 ℃ of crystallization 40-200 hour, wherein the reaction mixture of counting in molar ratio is composed as follows: SiO
2/ Al
2O
3Be 10-80, TEAX/SiO
2Be 0.15-0.60, OH
-/ SiO
2Be 0.12-0.40, H
2O/SiO
2Be 6.0-24.0, wherein said silicon source is selected from one or more the mixture in silicon sol, silicon gel, the amorphous aluminosilicate.
2. in accordance with the method for claim 1, it is characterized in that described aluminium source is selected from one or more the mixture in Tai-Ace S 150, sodium metaaluminate, the amorphous aluminosilicate.
3. in accordance with the method for claim 1, it is characterized in that the tetraethyl-ammonium halide is selected from etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide or their mixture.
4. in accordance with the method for claim 3, it is characterized in that the tetraethyl-ammonium halide is a tetraethylammonium bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117903A CN1046487C (en) | 1995-10-30 | 1995-10-30 | Process for preparing beta zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117903A CN1046487C (en) | 1995-10-30 | 1995-10-30 | Process for preparing beta zeolite |
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| Publication Number | Publication Date |
|---|---|
| CN1150119A CN1150119A (en) | 1997-05-21 |
| CN1046487C true CN1046487C (en) | 1999-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117903A Expired - Lifetime CN1046487C (en) | 1995-10-30 | 1995-10-30 | Process for preparing beta zeolite |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556105B (en) * | 2015-01-13 | 2017-01-18 | 大连理工大学 | Aerosol-assisted synthesis method of Beta molecular sieve |
-
1995
- 1995-10-30 CN CN95117903A patent/CN1046487C/en not_active Expired - Lifetime
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