CN101205072B - Method for synthesizing low silica-alumina ratio beta zeolite - Google Patents
Method for synthesizing low silica-alumina ratio beta zeolite Download PDFInfo
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- CN101205072B CN101205072B CN2006101653087A CN200610165308A CN101205072B CN 101205072 B CN101205072 B CN 101205072B CN 2006101653087 A CN2006101653087 A CN 2006101653087A CN 200610165308 A CN200610165308 A CN 200610165308A CN 101205072 B CN101205072 B CN 101205072B
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Abstract
The invention discloses a method for compounding Beta zeolite with a low Si/Al ratio, which comprises the following steps: reaction mixture which is formed by mixing the Beta zeolite with a Si/Al molar ratio of 25 to 30 with aluminum source, positive ion source of tetraethylammonium and water, is crystallized for 0.5 to 2 days in a water temperature of 135 to 170 DEG C; wherein, the molar ratio of the reaction mixture is SiO2/A12O3=4-15, TEAOH/SiO2=0 to 0.10, H2O/SiO2=5.0 to 8.0. The Beta zeolite compounded by the method is characterized in that framework Si/Al ratio is 4 to 15, acid central density of the Beta zeolite is increased, thereby increasing activity and stability of the catalyst in a high space velocity.
Description
Technical field
The present invention is about a kind of synthetic method of zeolite, further says so about a kind of synthetic method of β zeolite of low silica-alumina ratio.
Background technology
The β zeolite be by U.S. Mobile company in 1967 with the hydrothermal crystallization method of classics synthetic (USP3308069) first.This zeolite is unique supersiliceous zeolite with three-dimensional twelve-ring pore passage structure, because its unique topological framework and good heat and hydrothermal stability, the β zeolite shows excellent catalytic performance at aspects such as alkylation, hydrocracking, hydro-isomerization, hydrofining, hydrocarbon crackings, cause people's extensive concern day by day.
The acidity of molecular sieve and pore structure are the important parameters of catalyzer, play conclusive effect in catalyzed reaction, and therefore, the acidity of control molecular sieve and pore structure are the important indicators of preparation novel molecular sieve.
The surface acid property of framework aluminum content and distribution thereof and molecular sieve is closely related in the molecular sieve.The molecular sieve that obtains by hydrothermal synthesis method can not change the silica alumina ratio of molecular sieve unlimitedly, is generally 20～200 as the silica alumina ratio of synthetic β zeolite.Adopt processing means such as molecular sieve dealuminzation, benefit aluminium can obtain the molecular sieve of desirable silica alumina ratio.The benefit aluminium modification of molecular sieve is handled the acidity and the strength of acid thereof that can increase molecular sieve and is distributed to satisfy the requirement of different catalyzed reactions.
Yang Chun (J.Chem.Soc., Faraday Trans., 1997,93 (8), 1675-1680) wait the people to propose to adopt the basic solution treatment process, as with NaOH, KOH, NaAlO
2Homogeneous solution carries out chemical treatment at a certain temperature to Y, ZSM-5, β and mordenite thereof etc., and result of study shows, is 19 β zeolite to Si/Al, NaAlO
2After the solution calorize, Si/Al reduces to 4.3.
People such as T.Sano (13
ThInternational Zeolites Conference, poster, 11-P-10) adopt the acidic solution treatment process, as the β zeolite being carried out chemical treatment at a certain temperature with HCl solution, result of study shows, to the Si/Al behind the dealuminzation is 894 β zeolite, and Si/Al is 21 after the HCl solution-treated.
The β zeolite is a kind of micro porous molecular sieve of the 12-membered ring's of having pore passage structure, and its port size is
In more macromolecular catalyzed reaction, diffusional resistance is big, and catalyst efficiency is low.A kind of method of effective reduction molecular sieve diffusional resistance is that meso-hole structure is incorporated in the micro porous molecular sieve.People such as Xiao Fengshou (Angew.Chem.Int.Ed.2006,45,1-5) mixture with TEAOH and high molecular polymer (PPADMAC) has synthesized the β zeolite with 5～40nm meso-hole structure as template.This zeolite is in benzene and Virahol alkylated reaction, at 200 ℃, benzene/Virahol (mol)=4: 1,2.0MPa, WHSV=10h
-1Under the condition, all more common β zeolite of its transformation efficiency and selectivity has improved 8～12%, but the SiO of its β zeolite
2/ Al
2O
3Be 40.People such as Tang Yi (Fudan Journal (natural science edition) 2002,41 (3) 335-343) be template with polystyrene sphere (PS), with synthetic nanometer β zeolite is the primitive member, adopt restricted clearance and adsorption and sedimentation self-assembly method, assemble nanometer β zeolite in closely packed polystyrene sphere gap, high-temperature roasting is removed polystyrene sphere and is obtained having micropore-the nanometer β zeolite multilevel hole material of macropore geminus then.
It is the silicon source that CN1108213A and CN1108214A have proposed with solid silicone, the synthetic method under the condition of low water silicon ratio.This method can make the template consumption significantly reduce, and has reduced preparation cost; The disclosed a kind of fractional crystallization method of CN1154341A is further optimized segmentation with crystallization condition, thereby is effectively utilized template, reduces its consumption, makes the β zeolite realize suitability for industrialized production.
Up to now, do not see and synthetic have low silica-alumina ratio, have the report of the β zeolite of meso-hole structure simultaneously.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of synthetic method of β zeolite of low silica-alumina ratio.
The synthetic method of beta-molecular sieve provided by the invention, this method feature is conventional β zeolite and aluminium source, tetraethylammonium cation source, water are mixed the reaction mixture that forms, crystallization is 0.5～2 day under 135～170 ℃ of hydrothermal conditions, and wherein, the mole proportioning is SiO in the said reaction mixture
2/ Al
2O
3=4～15, TEAOH/SiO
2=0～0.10, H
2O/SiO
2=5.0～8.0.
In the method provided by the invention, said conventional β zeolite is to adopt the ordinary method preparation, for example with reported method synthetic among CN1108213A, CN1108214A and the CN1154341A, its SiO
2/ Al
2O
3Preferred 25-30.
In the method provided by the invention, said aluminium source is selected from one or more in hydrated aluminum oxide, aluminium hydroxide, Wickenol CPS 325, pseudo-boehmite and the pure aluminium silicate; Used tetraethylammonium cation source is selected from one or more in tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide and the tetraethyl ammonium iodide, wherein preferably tetraethyl ammonium hydroxide or tetraethylammonium bromide.
Method provided by the invention is compared with single stage method, and good reproducibility is difficult for the ZSM-12 stray crystal.
Method synthetic β zeolite provided by the invention, have and conventional hydrothermal method synthetic β zeolite facies XRD crystalline phase figure together, framework si-al ratio is 4～15, near feeding intake silica alumina ratio, the acid site density of β zeolite improves, thereby has improved activity and the activity stability of catalyzer under high-speed.
Synthetic method provided by the invention can obtain having micropore and mesoporous mixed structure, and its pore size distribution range is the β zeolite of the low silica-alumina ratio of 10-50nm.Said mesoporous part derives from the accumulation hole of zeolite, and part derives from the secondary pore that the zeolite crystal surface generates in the secondary crystallization process.Meso-hole structure can effectively reduce the diffusional resistance of molecular sieve, and catalyst efficiency is improved.
Description of drawings
Fig. 1-3 is X-ray diffraction (XRD) the crystalline phase figure of Comparative Examples 1,2 and embodiment 1 gained β zeolite powder.
Fig. 4 is the cryogenic absorption graphic representation of the β zeolite of Comparative Examples 2 gained.
Fig. 5 is the cryogenic absorption graphic representation of embodiment 1 gained β zeolite.
Fig. 6 is the pore distribution integrated curve figure of embodiment 1 gained β zeolite.
Fig. 7 and Fig. 8 are the TEM figure of embodiment 1 gained β zeolite.
Fig. 9 and Figure 10 are respectively embodiment 1 gained β zeolite
29Si MAS NMR and
27Al MASNMR spectrogram.
Embodiment
Below by embodiment the present invention is described further, but content not thereby limiting the invention.
The used instrument of XRD is a Japanese D/MAX-IiIA type of science (CuKa); The used instrument of MAS NMR is Varian
UNITYINOVA 300M NMR spectrometer with superconducting magnet.Low temperature N
2Adsorbing used instrument is Quantachrome Instruments AS-6 type; The used instrument of TEM is TECNAI 20 types.
Wherein all percentage compositions all are benchmark with weight.
Comparative Examples 1
The synthetic β zeolite of CN1154341A is pressed in the explanation of this Comparative Examples.
With sodium aluminate solution (sodium oxide 154.8g/L, aluminum oxide 100.0g/L), tetraethyl ammonium hydroxide (2.03N goes in in a big way emerging good fortune fine chemistry industry institute) adds in the deionized water heating for dissolving, stir, make working solution, with silochrom (80～100 orders, igloss 7.8%, Haiyang Chemical Plant, Qingdao) mixes with above-mentioned working solution, make the silica gel surface wetting by working solution, obtain reaction mixture, wherein the mol ratio of each component is SiO
2/ Al
2O
3=25, Na
2O/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2O/SiO
2=6.5, then with this reaction mixture 120 ℃ of crystallization 24 hours in autoclave,, isolate solid product after being cooled to room temperature again 140 ℃ of crystallization 48 hours, washing, 110 ℃ are drying to obtain the β zeolite.With this β zeolite as the standard substance (both having set its relative crystallinity is 100%) of measuring relative crystallinity, its XRD crystalline phase figure as shown in Figure 1, it is 24.8 that NMR measures its framework si-al ratio.
Comparative Examples 2
Yang Chun (J.Chem.Soc., Faraday Trans., 1997,93 (8), 1675-1680) method synthesizing low silicon aluminum ratio β zeolite are pressed in the explanation of this Comparative Examples.
With the 1 sample roasting of 1g Comparative Examples, and contain 3mmolNaAlO
2The aqueous solution, is handled 8h. and is filtered under the pH=12.6 condition at 70 ℃, washing, and after the drying,
29It is 7.3 that Si MAS NMR measures its framework si-al ratio, and relative crystallinity is 91.4%, and its XRD crystalline phase figure as shown in Figure 2.Fig. 4 is an adsorption isothermal line, and the result shows that the adsorption isothermal line of this product does not have hysteresis loop, does not promptly have meso-hole structure.
Embodiment 1
With sodium aluminate solution (sodium oxide 139.5g/L, aluminum oxide 100.0g/L) 125ml, tetraethyl ammonium hydroxide (2.03N, going in in a big way emerging good fortune fine chemistry industry institute) 340ml adds in the deionized water, stir, make working solution, the β zeolite 500g in the Comparative Examples 1 is mixed with above-mentioned working solution, make solid particles surface wetting by this working solution, obtain reaction mixture, wherein the mol ratio SiO of each component in the synthetic system
2/ Al
2O
3=15, Na
2O/SiO
2=0.06, TEAOH/SiO
2=0.09, H
2O/SiO
2=6.5, then with this reaction mixture 150 ℃ of crystallization 24 hours in autoclave, isolate solid product, washing, drying after being cooled to room temperature.
XRD crystalline phase figure as shown in Figure 3, relative crystallinity is 109.5%.Figure 10 is
27Al MAS NMR spectrogram, this spectrogram is the result show, and this product does not have non-framework aluminum, and Fig. 9 is
29Si MAS NMR spectrogram, measuring its framework si-al ratio is 14.22, approaching with the silica alumina ratio that feeds intake.Fig. 5 is an adsorption isothermal line, and Fig. 6 is the pore distribution integrated curve, and its isothermal adsorption curve table reveals tangible hysteresis loop, is indicated as micropore and mesoporous mixed structure, and the pore distribution integrated curve shows that its pore size distribution range is 10-50nm.
Fig. 7, Fig. 8 are the TEM figure of β zeolite, show that the mesoporous part of zeolite derives from the accumulation hole of molecular sieve, and a part derives from the secondary pore that the molecular sieve crystal surface generates in crystallization.
Embodiment 2
With sodium aluminate solution (sodium oxide 139.5g/L, aluminum oxide 100.0g/L) 262ml, tetraethyl ammonium hydroxide (2.03N, going in in a big way emerging good fortune fine chemistry industry institute) 340ml adds in the deionized water, stir, make working solution, the β zeolite 500g in the Comparative Examples 1 is mixed with above-mentioned working solution, make solid particles surface wetting by this working solution, obtain reaction mixture, wherein the mol ratio SiO of each component in the synthetic system
2/ Al
2O
3=10, Na
2O/SiO
2=0.06, TEAOH/SiO
2=0.09, H
2O/SiO
2=6.5, then with this reaction mixture 150 ℃ of crystallization 24 hours in autoclave, isolate solid product, washing, drying after being cooled to room temperature.
Its XRD as shown in Figure 3, relative crystallinity is 95.4%.
29It is 8.62 that Si MAS NMR measures its framework si-al ratio.
Embodiment 3-8
Sodium aluminate solution, tetraethyl ammonium hydroxide are added in the deionized water, stir, make working solution, β zeolite in the Comparative Examples 1 is mixed with above-mentioned working solution, make solid particles surface wetting, obtain reaction mixture, change the crystallizing kettle crystallization then over to by this working solution.Its raw material composition and crystallization condition and result are as shown in table 1.
Table 1
| Sequence number | Crystallization condition | Degree of crystallinity/% | SiO 2/Al 2O 3 |
| Embodiment 3 | SiO 2∶Al 2O 3∶TEAOH∶H 2O=1: 0.067: 0.07: 6.5 145 ℃ 1 day | 99.6 | 14.42 |
| Embodiment 4 | SiO 2∶Al 2O 3∶TEAOH∶H 2O=1: 083: 0.07: 6.8 150 ℃ 1 day | 100.5 | 11.23 |
| |
SiO 2∶Al 2O 3∶TEAOH∶H 2O=1: 0.10: 0.07: 6.5 160 ℃ 1 day | 98.2 | 9.12 |
| Embodiment 6 | SiO 2∶Al 2O 3∶TEAOH∶H 2O=1: 0.125: 0.09: 6.5 150 ℃ 1 day | 97.6 | 7.12 |
| Embodiment 7 | SiO 2∶Al 2O 3∶H 2O=1: 0.067: 6.5 120 ℃ 1 day, 145 ℃ 1 day | 97.6 | 15.34 |
| Embodiment 8 | SiO 2∶Al 2O 3∶TEAOH∶H 2O=1: 083: 0.07: 6.8 120 ℃ 1 day, 150 ℃ 2 days | 100.5 | 11.20 |
The result shows, the invention provides method synthetic β zeolite, and the silica alumina ratio of sample is near feed ratio.
Comparative Examples 3-4
The catalytic performance of Comparative Examples explanation β zeolite in the liquid phase alkylation reaction of benzene and ethene.
50g Comparative Examples 1,2 sample is carried out ammonium exchange 4 times in 1.5N ammonium chloride solution 350ml, each 2 hours, after the filtration, filter cake is washed with water, 110 ℃ of dryings two hours.Mix by 60% weight ratio with pseudo-boehmite respectively then, add again ammonium chloride mix pinch, moulding, dry after 550 ℃ of roastings 2 hours, the gained sample is used for the liquid phase alkylation reaction of benzene and ethene, and the condition of alkylated reaction is: in CDS-900 continuous flow fixed bed pressurization micro-reactor, and catalyzer loading amount 8ml, catalyst grain size 20～40 orders, 190～250 ℃ of temperature of reaction, reaction pressure 3.5Mpa, benzene liquid volume air speed 3h
-1Gained the results are shown in table 2.
Embodiment 9-10
Embodiment illustrates the catalytic performance of β zeolite in the liquid phase alkylation reaction of benzene and ethene.
50g is carried out ammonium exchange 4 times to embodiment 1,2 sample in 1.5N ammonium chloride solution 350ml, each 2 hours, after the filtration, filter cake is washed with water, 110 ℃ of dryings two hours.Mix by 60% weight ratio with pseudo-boehmite respectively then, add again ammonium chloride mix pinch, moulding, dry after 550 ℃ of roastings 2 hours, the gained sample is used for the liquid phase alkylation reaction of benzene and ethene, gained the results are shown in table 2.
Table 2
| Sample | Ethylbenzene selectivity % | Styroyl selectivity % | |
| Comparative Examples 3 | Comparative Examples 1 | 93.5 | 99.0 |
| Comparative Examples 4 | Comparative Examples 2 | 91.3 | 98.9 |
| Embodiment 9 | Embodiment 1 | 94.5 | 99.5 |
| |
Embodiment 2 | 94.7 | 99.8 |
Table 2 is the result show, when being applied in the liquid phase alkylation reaction of benzene and ethene by the inventive method synthetic low silica-alumina ratio beta zeolite, ethylbenzene selectivity and activity stability all are better than the β zeolite that conventional β zeolite and basic treatment obtain.
Claims (4)
1. the synthetic method of a low silica-alumina ratio beta zeolite, it is characterized in that this synthetic β of method institute zeolite has micropore and mesoporous mixed structure, its pore size distribution range is 10-50nm, be that β zeolite and aluminium source, tetraethylammonium cation source, water that ordinary method obtains are mixed the reaction mixture that forms, crystallization is 0.5～2 day under 135～170 ℃ of hydrothermal conditions, wherein, the mole proportioning is SiO in the said reaction mixture
2/ Al
2O
3=4～15, TEAOH/SiO
2=0～0.10, H
2O/SiO
2=5.0～8.0.
2. according to the method for claim 1, the silica alumina ratio that it is characterized in that the β zeolite that said ordinary method obtains is SiO
2/ Al
2O
3=25～30.
3. according to the method for claim 1, it is characterized in that said aluminium source is selected from one or more in hydrated aluminum oxide, aluminium hydroxide, Wickenol CPS 325 and the pure aluminium silicate.
4. according to the method for claim 1, it is characterized in that said aluminium source is a pseudo-boehmite.
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| PL2571604T3 (en) * | 2010-05-21 | 2014-09-30 | Pq Corp | Metal-containing zeolite beta for nox reduction |
| JP5351216B2 (en) | 2010-07-01 | 2013-11-27 | 日本化学工業株式会社 | Method for producing zeolite |
| JP6034224B2 (en) * | 2012-04-10 | 2016-11-30 | ユニゼオ株式会社 | Beta-type zeolite and method for producing the same |
| CN105621437B (en) * | 2014-10-30 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of method for preparing low silicon Beta zeolites |
| CN105621439B (en) * | 2014-10-30 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of synthetic method of Beta zeolites |
| CN106946274B (en) * | 2016-01-07 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of Beta/ZSM-12 composite molecular screen and its synthetic method |
| CN109665541B (en) * | 2017-10-17 | 2022-04-01 | 中国石油化工股份有限公司 | Synthesis method of ZSM-12 type zeolite molecular sieve with low silica-alumina ratio |
| CN110498725B (en) * | 2018-05-16 | 2022-03-11 | 中国石油化工股份有限公司 | Solid acid catalyzed alkylation method |
| CN111217379B (en) * | 2018-11-26 | 2022-12-06 | 中国石油天然气股份有限公司 | Method for synthesizing MTW type molecular sieve with low silicon-aluminum ratio |
| CN111252782B (en) * | 2018-11-30 | 2022-09-23 | 中国科学院大连化学物理研究所 | Synthetic method of Beta molecular sieve with low silicon-aluminum ratio |
| CN113548676B (en) * | 2020-04-26 | 2022-11-15 | 中国石油化工股份有限公司 | Preparation method of hydrogen type silicon-aluminum ZSM-48 molecular sieve |
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