CN1123535C - Preparation process of beta-zeolite - Google Patents
Preparation process of beta-zeolite Download PDFInfo
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- CN1123535C CN1123535C CN98122007A CN98122007A CN1123535C CN 1123535 C CN1123535 C CN 1123535C CN 98122007 A CN98122007 A CN 98122007A CN 98122007 A CN98122007 A CN 98122007A CN 1123535 C CN1123535 C CN 1123535C
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Abstract
The present invention relates to a preparation process of beta-zeolite, an aluminum source, a sodium source, tetraethyl ammonium cation silica gel or/and silica sol and water are taken as raw materials. The powdered aluminum source and the sodium source are dissolved in a tetraethyl ammonium cation water solution first, and then, the mixture is added in silica gel or/and silica sol. The molar ratio of the alkalinity of a reaction system and SiO2 is kept from 0.1 to 0.6, and the beta-zeolite is produced by a crystallization reaction for 10 to 80 hours under the condition of 140 to 160 DEG C. The process has the characteristics of less template agent and water dosage, short crystallization time and no chelator, and the obtained beta-zeolite has high crystalline degree and large crystalline particle diameter. The present invention can be used for industrial production.
Description
The present invention relates to β prepare zeolite technology.
The β zeolite is that the Wadlinger by Mobil company in 1967 is first with unformed SiO
2Be the silicon source, sodium aluminate is aluminium (sodium) source, and tetraethyl ammonium hydroxide (TEA-OH) is (USP3308069) that template and water mixed crystal are combined to.The supersiliceous zeolite of unique a kind of macropore three-dimensional structure that this β zeolite is up to now to be found has the stacking fault structure of three kinds of lattice imperfections.Because the singularity of its structure has catalysis characteristics and structure selectivity.Behind suitable modification or some metal component of load, can be used for refining of petroleum and petrochemical process such as alkane dewaxing, hydrocracking, toluene disproportionation and transalkylation, alkylating aromatic hydrocarbon or etherification of olefine.The reaction system of this patent report, its molar ratio SiO
2/ Al
2O
3Be 10～200, Na
2O/TEAOH is 0～0.1, TEAOH/SiO
2=0.1～1.0, H
2O/TEAOH=20～75.Because the template TEAOH and the H of this method
2The consumption of O is all quite big, therefore to reducing cost in the suitability for industrialized production, it all is very disadvantageous reducing sewage quantity, and this method synthetic β zeolite, its grain size is 0.01～0.05um, and being difficult to satisfy some, to require big crystal grain Beta zeolite be the chemical reaction requirement of catalyzer.
Europe patent EP187522 in 1985 have disclosed a kind of synthetic method of β zeolite.This method is by with Na
2O, SiO
2, Al
2O
3There is or do not have the pressed powder of β zeolite seed crystal, add TEA behind the uniform mixing
+In the aqueous solution, need not add crystal and be combined to the β zeolite.Document method has reduced production cost, has improved β zeolite product yield.But the generated time of this method still reaches 6～10 days, is that industrial production is difficult to accept.The molar feed ratio of document reaction raw materials system is SiO
2/ Al
2O
3=10～200, Na
2O/TEAOH=0.3～1.0, TEAOH/SiO
2=0.01～0.1, H
2O/TEAOH=25～150.From the synthetic example of this method, the relative crystallinity of β zeolite is generally between 50～80%, and is still not very good.
U.S. Mobil companies in 1992 have reported a kind of β zeolite synthesis technology (USP5164169) of big crystal grain.The reaction system feed molar feed ratio of this method is SiO
2/ Al
2O
3=20～＞1000, OH
-/ SiO
2=0.1～0.8, R/SiO
2=0.3～1.0 (R: the organic nitrogen compound ion), H
2O/SiO
2=5～40, M/SiO
2=0.01～0.2 (M: alkalimetal ion), X/SiO
2=0.1～1.0 (X: sequestrant), R
1/ (R
1+ R
2)=0.1～1.0 (R
1: tetraethyl ammonium hydroxide; R
2: the tetraethyl-ammonium halide).In the silicon source of this method, solid content is minimum to be 10% (weight), is preferably 30～90% (weight).SiO in the reaction raw materials mixed system
2/ Al
2O
3More preferably greater than 70, and need add big crystal grain β zeolite seed crystal, synthetic β zeolite crystallinity is 70～130%, and grain size is 0.1～3.0um according to document introduction.The amount ratio of organic nitrogen compound is more in this method, needs to use sequestrant, and from the embodiment of this patent synthetic β zeolite as can be known, its grain size in fact only is 0.3～1.0 μ m.
Introduced a kind of method for synthesis of beta-zeolite among the document Chinese patent CN1106213A, it is with sodium aluminate, tetraethylammonium cation, water, has or do not have sodium hydroxide and silica gel particle is a raw material, forms in 10～60 hours in 140～170 ℃ of following crystallizations.Wherein the reaction raw materials system has following mole composition: SiO
2/ Al
2O
3=20～100, Na
2O/SiO
2=0.01～0.1, TEAOH/SiO
2=0.05～0.15, H
2O/SiO
2=1～3, the used silica gel particle is any aperture and has 20～200 purpose granularities.The scope of disclosed β zeolite grain size is 0.1～10 micron in the document, but confirms that through test its grain size only is 0.1～0.5 micron.
Big crystal grain zeolite is to some catalyzed reaction, and for example reaction such as selective disproportionation can improve the contraposition arenes selectivity.This is because big crystal grain zeolite can make reactant the evolving path on zeolite grain prolong, thereby improves para-selectivity.The synthetic method of the big grain ZSM-5 zeolite of selective disproportionation of toluene has all been described among U.S. Pat P4517402, USP4828679 and the USP465065.These methods are to realize the synthetic of big crystal grain by the control reaction conditions.As the stir speed (S.S.) of organic adding speed, temperature of reaction, pH value, reaction mixture and add sequestrant etc.The grain size of β zeolite generally is the SiO with reaction system
2/ Al
2O
3Mol ratio is correlated with.High silica alumina ratio β zeolite facies answer crystal grain big; The corresponding crystal grain of low silica-alumina ratio beta zeolite is little.
The objective of the invention is in order to overcome the template and the water consumption that exist in the above-mentioned document more, crystallization time length maybe need be used shortcomings such as sequestrant, a kind of new β prepare zeolite technology is provided, this technology is few in template and water consumption, crystallization time is lacked, need do not used under the sequestrant condition, the β zeolite that obtains has high-crystallinity, the characteristics of big crystalline particle.
The objective of the invention is to realize by following technical scheme: a kind of β prepare zeolite technology, or/and silicon sol and water are raw material, the feed molar of reaction system composition is counted with oxide compound: aNa with aluminium source, sodium source, tetraethylammonium cation, silica gel
2ObAl
2O
3C (TEA)
2OdSiO
2: eH
2O, d/b=10～55 wherein, a/d=0.04～0.25, c/d=0.01～0.06, e/d=2～6, TEA is a tetraethyl ammonium; Reactions steps is for being dissolved in pulverous aluminium source and sodium source in the tetraethylammonium cation aqueous solution earlier, joins silica gel then or/and in the silicon sol, wherein the basicity of reaction system and SiO
2Mol ratio OH
-/ SiO
2Be 0.1～0.6, reaction raw materials is 10～80 hours synthetic β zeolites of crystallization under 140～160 ℃ of conditions.
In the technique scheme, the aluminium source can be selected from sodium aluminate, pseudo-boehmite or Tai-Ace S 150; The sodium source can be selected from sodium aluminate or sodium hydroxide; Tetraethylammonium cation is selected from tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide or tetraethyl ammonium iodide and composition thereof; The used silica gel particle has 205～600 purpose granularities; The SiO of used silicon sol
2Content is 20～60 (weight %).
Synthetic β zeolite grain size adopts conventional scanning electron microscope (SEM) or transmission electron microscope (TEM) to measure, and grain size range of the present invention is 0.1～2.0um.
The β zeolite of the present invention's preparation has typical β X zeolite-ray diffraction characteristic peak, its spacing d value () and relative intensity (I/I
0) as follows:
The X-ray diffraction characteristic peak of table 1 β zeolite of the present invention
d() (I/I
0)
11.65 ± the last 0.2 peak
7.58 ± 0.1 weak peak
5.32 ± 0.1 weak peak
4.96 ± 0.1 weak peak
4.11 ± 0.1 weak peak
3.93 ± the last 0.1 peak
3.50 ± 0.1 weak peak
3.32 ± 0.05 weak peak
3.07 ± 0.05 weak peak
3.01 ± 0.05 weak peak
2.91 ± 0.05 weak peak
2.67 ± 0.05 weak peak
2.58 ± 0.05 weak peak
2.07 ± 0.05 weak peak
The β zeolite of this prepared carries out the sodium ion exchange through roasting removed template method and ammonium salt aqueous solution, makes Hydrogen β zeolite.Hydrogen β zeolite activates through steam dealumination, and the VIIA in the periodic table of elements, VA, VIII, VB, VIB element modified after and be selected from binding agents such as aluminum oxide, silicon oxide or clay and mix and extruded mouldings, after high-temperature roasting, can make the petrochemical catalyst that is applicable to disproportionation reaction, transalkylation reaction, alkylation reaction and hydrocracking and isomerization reaction.
The calculating of the relative crystallinity of synthetic β zeolite of the present invention is with the present invention X-ray diffraction peak intensity of measuring and the method synthetic β zeolite that provides according to embodiment 2 in the U.S. Pat 3308069 relatively.For example synthetic β zeolite crystallinity among the US3308069 is set at 100%, then XRD diffraction peak intensity of the present invention is relatively calculated with it.
Among the present invention, be to add, avoided too much water to introduce system, require system basicity to remain on OH simultaneously with the form of solution owing to have only template in the reaction system
-/ SiO
2Mol ratio is 0.1～0.6, thereby has reduced the consumption and the template agent of water in the building-up process, thereby has reduced production cost.Owing to use in the reaction system greater than 200 order solid silicones, the easy mixed solution soaking of solid silicone, behind the crystallization certain hour, the dissolved gradually and crystallization of the solid silicone particle extexine that is soaked goes out the β zeolite granular.The add-on of water is less, make the dissolution rate of solid silicone slow, even at this moment add low template of measuring and aluminium source, sodium source, the content of crystallization element is still higher relatively, helps the raising of crystallization velocity like this and helps the generation of crystal grain, and crystallization time can shorten, the degree of crystallinity and the crystal grain particle diameter of synthetic β zeolite have been improved, synthetic β zeolite crystallinity higher data can reach 152%, and grain size reaches 0.6～2.0 μ m, has obtained effect preferably.
Accompanying drawing 1 is technology synthetic β X zeolite-x ray diffration pattern x of the present invention, and spectrogram is with CuK
αRadiation, Ni filtering obtains; Accompanying drawing 2 is scanning electron microscope (SEM) photos of technology synthetic β zeolite of the present invention.
Give further instruction below by embodiment to technology of the present invention.
[embodiment 1]
After getting 7.3 parts of pseudo-boehmites and 5.7 parts of pressed powders of sodium hydroxide by weight and mixing, add in 45 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, add in 42 part of 205 purpose solid silicone, stir, change over to reactor, 150 ℃ of crystallizations 60 hours are isolated solid product, deionized water wash after the reaction, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=2.75, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=15, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 108%, and grain size range is 0.2～0.8um.
[embodiment 2]
By weight, get 5.5 parts of pseudo-boehmites, 5.8 parts in sodium hydroxide, mix the back and add in 46 parts of tetraethyl-sodium hydroxide (25 weight %) aqueous solution, after stirring and dissolving, add in 42.7 part of 280 purpose solid silicone, stir, change in the crystallizing kettle, 150 ℃ of crystallization 40 hours, isolate solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=2.84, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=20, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 126%, and grain size range is 0.2～1.0um.
[embodiment 3]
By weight, get 4.2 parts of pseudo-boehmites, 4.4 parts in sodium hydroxide, mix the back and add in 34.9 parts of tetraethyl-sodium hydroxide (25 weight %) aqueous solution, after stirring and dissolving, add 40.3 parts of silicon sol (40.3%SiO
2, weight) and 16.2 part of 210 purpose solid silicone in, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours are isolated solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=5.31, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=20, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 70%, and grain size range is 0.1～0.3um.
[embodiment 4]
By weight, get 3.12 parts of pseudo-boehmites, 4.43 parts in sodium hydroxide mixes the back and adds in 35.3 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, adds 40.72 parts of silicon sol (40.3%SiO
2, weight) and 16.43 part of 350 purpose solid silicone in, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours are isolated solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=5.27, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=27.3, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 120%, and grain size range is 0.3～1.3um.
[embodiment 5]
By weight, get 3.28 parts of pseudo-boehmites, 5.91 parts in sodium hydroxide, mixing the back adds in 47.05 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, add in 43.76 part of 250 purpose solid silicone, stir, change in the crystallizing kettle, 150 ℃ of crystallization 20 hours are isolated solid product, deionized water wash after the reaction, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=2.74, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=34.7, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 100%, and grain size range is 0.3～0.9um.
[embodiment 6]
Feed intake by example 5 reaction system proportioning raw materials, 150 ℃ of crystallizations 40 hours are isolated solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.The relative crystallinity of β zeolite is 120%, and grain size range is 0.3～1.0um.
[embodiment 7]
By weight, get 2.82 parts of pseudo-boehmites, 5.08 parts in sodium hydroxide mixes the back and adds in 40.50 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, adds 23.35 parts of silicon sol (40.3%SiO
2Weight) and in 28.25 part of 350 purpose solid silicone, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours are isolated solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=4.01, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=34.7, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 119%, and grain size range is 0.4～1.3um.
[embodiment 8]
By weight, get 4.95 parts of sodium aluminates, 0.25 part in sodium hydroxide, mix the back and add in 45.3 parts of tetraethyl ammonium hydroxides (2.0M concentration) aqueous solution, after stirring and dissolving, add in 49.5 part of 305 purpose solid silicone, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours, isolate solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.04, H
2O/SiO
2=2.3, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=40, OH
-/ SiO
2=0.12.The relative crystallinity of reaction back β zeolite is 78%, and grain size range is 0.3～1.1um.
[embodiment 9]
By weight, get 2.56 parts of pseudo-boehmites, 5.95 parts in sodium hydroxide, mixing the back adds in 47.40 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, add in 44.09 part of 250 purpose solid silicone, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours are isolated solid product, deionized water wash after the reaction, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.102, H
2O/SiO
2=2.71, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=45, OH
-/ SiO
2=0.31.The relative crystallinity of reaction back β zeolite is 115%, and grain size range is 0.2～0.9um.
[embodiment 10]
By weight, get Tai-Ace S 150 (Al
2(SO
4)
318H
2O) 12.01 parts, 10.13 parts in sodium hydroxide mixes the back and adds in 40.34 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, add in 37.52 part of 210 purpose solid silicone, stir, change in the crystallizing kettle, 160 ℃ of crystallization 63 hours, isolate solid product after the reaction, deionized water wash, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.
The reaction system material molar ratio is: Na
2O/SiO
2=0.204, H
2O/SiO
2=3.21, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=34.64, OH
-/ SiO
2=0.52.The relative crystallinity of reaction back β zeolite is 94%, and grain size range is 0.1～0.3um.
[embodiment 11]
By weight, get 3.58 parts of sodium aluminates, 1.89 parts in sodium hydroxide, mixing the back adds in 48.9 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, add in 45.56 part of 600 purpose solid silicone, stir, change in the crystallizing kettle, 150 ℃ of crystallization 80 hours are isolated solid product, deionized water wash after the reaction, 110 ℃ of dryings 2 hours, sodium type β zeolite finished product.The reaction system material molar ratio is: Na
2O/SiO
2=0.075, H
2O/SiO
2=2.69, (TEA)
2O/SiO
2=0.055, SiO
2/ Al
2O
3=50.3, OH
-/ SiO
2=0.172.The relative crystallinity of reaction back β zeolite is 152%, and grain size range is 0.6～2.0 μ m.
[embodiment 12]
By weight, get 4.06 parts of sodium aluminates, 0.50 part in sodium hydroxide, mixing the back adds in 44.73 parts of tetraethyl ammonium hydroxides (25 weight %) aqueous solution, after stirring and dissolving, add in 50.71 part of 500 purpose solid silicone, stir, change in the crystallizing kettle, 160 ℃ of crystallization 60 hours are isolated solid product, deionized water wash after the reaction, 120 ℃ of dryings 2 hours, sodium type β zeolite finished product.The reaction system material molar ratio is: Na
2O/SiO
2=0.052, H
2O/SiO
2=2.2, (TEA)
2O/SiO
2=0.04, SiO
2/ Al
2O
3=49.3, OH
-/ SiO
2=0.105.The relative crystallinity of reaction back β zeolite is 100%, and grain size range is 0.4～1.5 μ m.
" comparative example 1 "
By the β zeolite that the method for the embodiment 1 in the Chinese patent 94102212.9 (CN1106213A) prepares, its relative crystallinity is 102.8% after measured, and β zeolite grain magnitude range is 0.1～0.25 μ m.
" comparative example 2 "
The β zeolite for preparing by the method for the embodiment 7 in the Chinese patent 94102212.9 (CN1106213A) its relative crystallinity after measured is 85.5%, and β zeolite grain magnitude range is 0.1～0.4 μ m.
" comparative example 3 "
By each step of the embodiment of the invention 11, just the grain graininess of the solid silicone that adds is 180 orders, and the relative crystallinity of the β zeolite that makes after the reaction is 95.4%, and grain size range is 0.3～0.9 μ m.
Claims (6)
1. β prepare zeolite technology, or/and silicon sol and water are raw material, the feed molar of reaction system is formed and is counted with oxide compound: aNa with aluminium source, sodium source, tetraethylammonium cation, silica gel
2ObAl
2O
3C (TEA)
2OdSiO
2: eH
2O, d/b=10～55 wherein, a/d=0.04～0.25, c/d=0.01～0.06, e/d=2～6, TEA is a tetraethyl ammonium, reactions steps is for being dissolved in pulverous aluminium source and sodium source in the tetraethylammonium cation aqueous solution earlier, join silica gel then or/and in the silicon sol, wherein the basicity of reaction system and SiO
2Mol ratio OH
-/ SiO
2Be 0.1～0.6, reaction raw materials is 10～80 hours synthetic β zeolites of crystallization under 140～160 ℃ of conditions.
2. according to the described β prepare zeolite of claim 1 technology, it is characterized in that the aluminium source is sodium aluminate, pseudo-boehmite or Tai-Ace S 150.
3. according to the described β prepare zeolite of claim 1 technology, it is characterized in that the sodium source is sodium aluminate or sodium hydroxide.
4. according to the described β prepare zeolite of claim 1 technology, it is characterized in that tetraethylammonium cation is selected from tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide or tetraethyl ammonium iodide and composition thereof.
5. according to the described β prepare zeolite of claim 1 technology, it is characterized in that silica gel particle has 205～600 purpose granularities.
6. according to the described β prepare zeolite of claim 1 technology, it is characterized in that the SiO of silicon sol
2Content is 20～60% by weight percentage.
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|---|---|---|---|
| CN98122007A CN1123535C (en) | 1998-11-18 | 1998-11-18 | Preparation process of beta-zeolite |
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|---|---|---|---|
| CN98122007A CN1123535C (en) | 1998-11-18 | 1998-11-18 | Preparation process of beta-zeolite |
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| CN1123535C true CN1123535C (en) | 2003-10-08 |
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| CN98122007A Expired - Fee Related CN1123535C (en) | 1998-11-18 | 1998-11-18 | Preparation process of beta-zeolite |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116227C (en) * | 2001-03-12 | 2003-07-30 | 复旦大学 | Process for synthesizing beta-zeolite from non-alkali-metal ion system |
| CN100344536C (en) * | 2002-07-05 | 2007-10-24 | 中国石油天然气股份有限公司 | Method for synthesizing beta zeolite by templet agent concentrate nonuniform method |
| CN102923728A (en) * | 2012-11-23 | 2013-02-13 | 山东齐鲁华信高科有限公司 | Large-grain beta molecular sieve and preparation method thereof |
| CN104229821B (en) * | 2014-09-12 | 2016-05-11 | 华微科技（苏州）有限公司 | Beta Zeolite synthesis method |
| CN106185972B (en) * | 2016-07-12 | 2018-06-05 | 太原理工大学 | The preparation method of micro--meso-hole structure Beta molecular sieves |
| CN114433198A (en) * | 2020-10-30 | 2022-05-06 | 中国石油天然气股份有限公司 | Alkylated molecular sieve catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0164208A2 (en) * | 1984-05-10 | 1985-12-11 | Mobil Oil Corporation | Preparation of zeolite beta |
| EP0614853A2 (en) * | 1993-02-02 | 1994-09-14 | Tosoh Corporation | Method of producing zeolite beta |
| CN1108214A (en) * | 1994-03-11 | 1995-09-13 | 中国石油化工总公司 | Method No.2 for synthesizing beta zeolite |
| CN1108213A (en) * | 1994-03-11 | 1995-09-13 | 中国石油化工总公司 | Method No.1 for synthesizing beta zealite |
-
1998
- 1998-11-18 CN CN98122007A patent/CN1123535C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0164208A2 (en) * | 1984-05-10 | 1985-12-11 | Mobil Oil Corporation | Preparation of zeolite beta |
| EP0614853A2 (en) * | 1993-02-02 | 1994-09-14 | Tosoh Corporation | Method of producing zeolite beta |
| CN1108214A (en) * | 1994-03-11 | 1995-09-13 | 中国石油化工总公司 | Method No.2 for synthesizing beta zeolite |
| CN1108213A (en) * | 1994-03-11 | 1995-09-13 | 中国石油化工总公司 | Method No.1 for synthesizing beta zealite |
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|---|---|
| CN1253908A (en) | 2000-05-24 |
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