CN1139537C - Process for preparing beta-zeolite - Google Patents
Process for preparing beta-zeolite Download PDFInfo
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- CN1139537C CN1139537C CNB01105851XA CN01105851A CN1139537C CN 1139537 C CN1139537 C CN 1139537C CN B01105851X A CNB01105851X A CN B01105851XA CN 01105851 A CN01105851 A CN 01105851A CN 1139537 C CN1139537 C CN 1139537C
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- zeolite
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- sio
- tetraethyl
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Abstract
The present invention relates to a preparation process for beta-zeolite, an aluminum source, a sodium source, tetraethyl ammonium cation, silica gel or /and silica sol and water are taken as raw materials, and tetraethyl ammonium halide is taken as a template agent. The crystallization process is divided into two stages, firstly, precrystallization is carried out from 100 to 120 DEG C., and then, a crystallization reaction is carried out under the condition of 140 to 170 DEG C. The method has the characteristics of less template agent dosage, low production cost, short crystallization time and no chelator, the obtained beta-zeolite has high crystalline degree, and the present invention can be used for industrial production.
Description
The present invention relates to β prepare zeolite method.
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, and therefore to reducing cost in the suitability for industrialized production, it all is very disadvantageous reducing sewage quantity.
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%.The amount ratio of organic nitrogen compound is more in this method, need use sequestrant.
The objective of the invention is that more, the synthetic β zeolite cost of the template consumption that exists in the above-mentioned document is higher in order to overcome, the long shortcoming such as sequestrant of maybe need using of crystallization time, a kind of new β prepare zeolite method is provided, this method is few and synthetic cost is low, crystallization time is short, need not use under the sequestrant condition at the template consumption, and the β zeolite of acquisition has the characteristics of high-crystallinity.
The objective of the invention is to realize: a kind of β prepare zeolite method by following technical scheme, with aluminium source, sodium source, tetraethylammonium cation, silica gel or/and silicon sol and water are raw material, the feed molar composition of reaction system is counted with oxide compound: aNa2ObAl2O3c (TEA) 2OdSiO2: eH2O, d/b=10～55 wherein, a/d=0.04～0.25, c/d=0.01～0.06, e/d=2～6, TEA is a tetraethylammonium cation; Reaction raw materials is 40～80 hours synthetic β zeolites of crystallization under 100～170 ℃ of conditions, and wherein the raw material of TEA is the tetraethyl-ammonium halide, and crystallization process divides two sections to carry out, at first 100～120 ℃ of following pre-crystallization, then 140～170 ℃ of following crystallization.
In the technique scheme, aluminium source preferred version is for being selected from sodium aluminate, pseudo-boehmite or Tai-Ace S 150; Sodium source preferred version is for being selected from sodium aluminate or sodium hydroxide; Tetraethyl-ammonium halide preferred version is for being selected from etamon chloride, tetraethylammonium bromide or tetraethyl ammonium iodide and composition thereof, and more preferably scheme is for being selected from tetraethylammonium bromide; Interpolation is pressed the sodium type β zeolite of technique scheme method preparation as crystal seed in reaction system before crystallization, the add-on of crystal seed is 0.5～10% of β zeolite ultimate capacity by weight percentage, and the sodium type β zeolite crystal preferred version that adds in reaction system before the crystallization is not for containing the tetraethyl-ammonium halide; Pre-crystallization time is 25～60 hours under 100～120 ℃, is 15～40 hours at 140～170 ℃ of following crystallization times.
The β zeolite of the present invention's preparation 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, owing to have only the mol ratio of template tetraethyl-ammonium halide and water lower in the reaction system, avoided too much water to introduce system, thereby reduced template agent in the building-up process, lower owing to tetraethyl-ammonium halide price in addition, thus production cost reduced.The technical scheme that does not contain template tetraethyl-ammonium halide is added in employing in reaction system, make the guide effect of β zeolite seed crystal more outstanding, enlarged the contact area of β zeolite seed crystal and crystallization mixed solution, help shortening crystallization time, adopt two sections intensification crystallization in addition, in pre-crystallization process, help generating more crystallization presoma silicon-aluminum polymer, the relative crystallinity that helps shortening crystallization time and improve the β zeolite.The add-on of water is less in addition, 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, help the raising of crystallization velocity like this and help the generation of crystal grain, crystallization time can shorten, and has improved the degree of crystallinity of synthetic β zeolite.By adopting technical scheme of the present invention, synthetic β zeolite crystallinity higher data can reach 170%, and the crystallization time is in 40～80 hours, and production cost is low, need not use sequestrant in the crystallization, has obtained effect preferably.
Below by embodiment method of the present invention is further described.[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 tetraethylammonium bromides (25 weight %) aqueous solution, after stirring and dissolving, add in 42 parts of solid silicones, stir, change over to reactor, earlier 120 ℃ of pre-crystallization 45 hours down, then 170 ℃ of crystallization 10 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=2.75, (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 128%.[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 tetraethylammonium bromides (25 weight %) aqueous solution, after stirring and dissolving, add in 42.7 parts of solid silicones, stir, change in the crystallizing kettle, earlier 100 ℃ of following crystallization 60 hours, 165 ℃ of following crystallization 15 hours, isolate solid product after the reaction, deionized water wash then, 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 142%.[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 etamon chlorides (25 weight %) aqueous solution, after stirring and dissolving, add 40.3 parts of silicon sol (40.3%SiO
2, weight) and 16.2 parts of solid silicones in, stir, change in the crystallizing kettle,, 140 ℃ of following crystallization 40 hours, isolate solid product after the reaction then earlier 105 ℃ of following crystallization 30 hours, 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 105%.[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 tetraethylammonium bromides (25 weight %) aqueous solution, after stirring and dissolving, adds 40.72 parts of silicon sol (40.3%SiO
2Weight), in 1 part of the sodium type β zeolite finished product that makes with 16.43 parts of solid silicones and embodiment 1, stir, change in the crystallizing kettle, earlier 115 ℃ of following crystallization 45 hours, 165 ℃ of following crystallization 25 hours, isolate solid product after the reaction, deionized water wash then, 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 145%.[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 tetraethylammonium bromides (25 weight %) aqueous solution, after stirring and dissolving, add in 3 parts of the sodium type β zeolite finished products of the removed template method tetraethylammonium bromide that 43.76 parts of solid silicones and embodiment 1 make, stir, change in the crystallizing kettle, 110 ℃ of following first crystallization 25 hours, then 160 ℃ of following crystallization 15 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=2.74, (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 135%.[embodiment 6]
By weight, get 3.58 parts of sodium aluminates, 1.89 parts in sodium hydroxide, mixing the back adds in 48.9 parts of tetraethylammonium bromides (25 weight %) aqueous solution, after stirring and dissolving, add in 7 parts of the sodium type β zeolite finished products of the removed template method tetraethylammonium bromide that 45.56 parts of solid silicones and embodiment 1 make, stir, change in the crystallizing kettle, 115 ℃ of following first crystallization 55 hours, then 165 ℃ of following crystallization 15 hours, isolate solid product after the reaction, deionized water wash, 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 170%.[embodiment 7]
By weight, get 4.06 parts of sodium aluminates, 0.50 part in sodium hydroxide, mixing the back adds in 44.73 parts of tetraethylammonium bromides (25 weight %) aqueous solution, after stirring and dissolving, in 9 parts of the sodium type β zeolite finished products of the removed template method tetraethylammonium bromide that adds 50.71 parts of solid silicones and make by embodiment 1, stir, change in the crystallizing kettle, 115 ℃ of following first crystallization 45 hours, then 160 ℃ of following crystallization 15 hours, isolate solid product after the reaction, deionized water wash, dry 2 hours of 120C gets 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 151%.[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.[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%.
Claims (10)
1, a kind of β prepare zeolite method, 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 tetraethylammonium cation, reaction raw materials crystallization under 100～170 ℃ of conditions formed in 40～80 hours, and the raw material that it is characterized in that TEA is the tetraethyl-ammonium halide, and crystallization process divides two sections to carry out, at first 100～120 ℃ of following pre-crystallization, then 140～170 ℃ of following crystallization.
2,, it is characterized in that the aluminium source is sodium aluminate, pseudo-boehmite or Tai-Ace S 150 according to the described β prepare zeolite of claim 1 method.
3,, it is characterized in that the sodium source is sodium aluminate or sodium hydroxide according to the described β prepare zeolite of claim 1 method.
4,, it is characterized in that the tetraethyl-ammonium halide is selected from etamon chloride, tetraethylammonium bromide or tetraethyl ammonium iodide and composition thereof according to the described β prepare zeolite of claim 1 method.
5,, it is characterized in that the tetraethyl-ammonium halide is a tetraethylammonium bromide according to the described β prepare zeolite of claim 4 method.
6,, it is characterized in that before crystallization in reaction system, adding sodium type β zeolite by the preparation of claim 1 method as crystal seed according to the described β prepare zeolite of claim 1 method.
7,, it is characterized in that the add-on of crystal seed is 0.5～10% of β zeolite ultimate capacity by weight percentage according to the described β prepare zeolite of claim 6 method.
8,, it is characterized in that the sodium type β zeolite crystal that adds before the crystallization does not contain the tetraethyl-ammonium halide in reaction system according to the described β prepare zeolite of claim 6 method.
9,, it is characterized in that pre-crystallization time is 25～60 hours under 100～120 ℃ according to the described β prepare zeolite of claim 1 method.
10,, it is characterized in that at 140～170 ℃ of following crystallization times be 15～40 hours according to the described β prepare zeolite of claim 1 method.
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|---|---|---|---|
| CNB01105851XA CN1139537C (en) | 2001-04-04 | 2001-04-04 | Process for preparing beta-zeolite |
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|---|---|---|---|
| CNB01105851XA CN1139537C (en) | 2001-04-04 | 2001-04-04 | Process for preparing beta-zeolite |
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| CN1139537C true CN1139537C (en) | 2004-02-25 |
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331748C (en) * | 2004-09-08 | 2007-08-15 | 中国科学院大连化学物理研究所 | Production of Y-shaped molecular sieve |
| CN100384732C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Method for synthesizing beta zeolite in small crystal grain |
| CN100384731C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Method for preparing beta zeolite in small crystal grain |
| CN101108734B (en) * | 2006-07-19 | 2011-08-24 | 中国石油大学(北京) | Beta type molecular sieve and method of manufacturing the same |
| CN102040233B (en) * | 2009-10-16 | 2012-06-27 | 中国石油化工股份有限公司 | Synthesis method of boron-containing beta zeolite |
| CN102211779B (en) * | 2010-04-07 | 2013-11-06 | 中国石油天然气股份有限公司 | Method for preparing beta zeolite |
| CN102441414B (en) * | 2010-10-13 | 2013-08-28 | 中国石油化工股份有限公司 | Catalyst used in alkylation reaction, preparation method and application of catalyst |
| CN104556096A (en) * | 2014-12-25 | 2015-04-29 | 复旦大学 | Method for synthesizing sub-micron BEA zeolite by virtue of two-step crystallization |
| CN106140249B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of carrier of hydrocracking catalyst |
| CN106140284B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of carrier of hydrocracking catalyst and preparation method thereof |
| CN106140250B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106140286B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | The preparation method of carrier of hydrocracking catalyst |
| CN106140287B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106140280B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN106140251B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and preparation method thereof |
| CN106140281B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of middle oil type hydrocracking catalyst |
| CN110065953B (en) * | 2018-01-22 | 2021-04-30 | 中国石油天然气股份有限公司 | Preparation method of beta molecular sieve |
| CN110143602B (en) * | 2018-02-13 | 2021-01-29 | 中国石油天然气股份有限公司 | Preparation method of beta molecular sieve |
| CN112551538B (en) * | 2020-12-23 | 2023-03-28 | 中触媒新材料股份有限公司 | Synthesis method of nanoscale Sn-Beta |
-
2001
- 2001-04-04 CN CNB01105851XA patent/CN1139537C/en not_active Expired - Lifetime
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