CN1086792A - Synthetizing BETA zeolite by guide agent method - Google Patents

Synthetizing BETA zeolite by guide agent method Download PDF

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Publication number
CN1086792A
CN1086792A CN 93117593 CN93117593A CN1086792A CN 1086792 A CN1086792 A CN 1086792A CN 93117593 CN93117593 CN 93117593 CN 93117593 A CN93117593 A CN 93117593A CN 1086792 A CN1086792 A CN 1086792A
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China
Prior art keywords
sio
directed agents
beta zeolite
zeolite
preparation
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Granted
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CN 93117593
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CN1032910C (en
Inventor
周群
庞文琴
裘式纶
贾明君
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Jilin University
China Petrochemical Corp
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Jilin University
China Petrochemical Corp
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Priority to CN 93117593 priority Critical patent/CN1032910C/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Abstract

A kind of technology of synthetizing BETA zeolite by guide agent method, it is to be dissolved in tetraethyl ammonium hydroxide and the aqueous sodium hydroxide solution with aluminium salt, adds active silica and prepares directed agents, its formula range is: SiO 2/ Al 2O 3=20～120, TEAOH/SiO 2=0.2～0.5, Na 2O/SiO 2=0.40～0.10, H 2O/SiO 2=7.5～25, the preparation temperature of directed agents is 15～70 ℃, and the ageing temperature is 50～150 ℃, during synthetic zeolite, add directed agents and synthesis material mixture volume ratio be 0.5～10%.

Description

Synthetizing BETA zeolite by guide agent method
The invention relates to zeolite molecular sieve synthetic technology, adopt the method for synthetizing BETA zeolite by guide agent method.
The BETA zeolite is a kind of high silicon large pore zeolite, be by the patented product of U.S. Mobil oil company research and development in 1967, according to USP3,308,069 discloses, this BETA zeolite has unique topological structure and higher silica alumina ratio, so it shows good performance at aspects such as catalysis, absorption, is with a wide range of applications.
In prior art, the synthetic system of BETA zeolite is Na 2O～SiO 2～Al 2O 3～(TEA) 2O～H 2O must add a large amount of quaternary ammonium hydroxide template when synthetic, as tetraethyl ammonium hydroxide (TEAOH), owing to adopt quaternary ammonium salt and corresponding oxyhydroxide, cost an arm and a leg, and is higher to the synthetic cost that makes the BETA zeolite, limited applying of BETA zeolite.
The present invention adopts synthetizing BETA zeolite by guide agent method, only adds the template quaternary ammonium hydroxide when synthesizing directed agents, and no longer add expensive template quaternary ammonium hydroxide when synthesizing the BETA zeolite, only need add a small amount of institute of the present invention synthetic directed agents and get final product.Synthetic BETA guiding agent for zeolite of the present invention is a kind of gel or sol system with special construction, exist zeolite structured similar microcrystals in the directed agents to BETA, these microcrystals are very little, has good dispersiveness, be distributed to equably easily in the reaction system, its activity is considerably beyond general solid crystal.The compound method of directed agents is as follows, aluminium salt is dissolved in tetraethyl ammonium hydroxide and the aqueous sodium hydroxide solution, add active silica then in above-mentioned solution, stir while adding, after ageing, promptly obtain the directed agents that synthetic BETA zeolite is used until obtaining uniform sol.This directed agents requires alkali silicon than higher, and formula range is as follows in molar ratio: SiO 2/ Al 2O 3=20～120, the best is SiO 2/ Al 2O 3=30～90, TEAOH/SiO 2=0.2～0.5, the best is TEAOH/SiO 2=0.25～0.4, Na 2O/SiO 2=0.04～0.10, the best is Na 2O/SiO 2=0.05～0.08, H 2O/SiO 2=7.5～25, the best is H 2O/SiO2=8.0～20.
The preparation temperature of directed agents is 15～70 ℃, and the best is 15～35 ℃; The ageing temperature is 50～150 ℃, and the best is 70～140 ℃.In the synthetic zeolite process, add directed agents and synthesis material mixture volume ratio be 0.5～10%, the best is 1～5%.
The building-up process of BETA zeolite is: aluminium salt is dissolved in the sodium hydroxide solution, under agitation adds active silica then.Proportion of raw materials is by following molar ratio range: SiO 2/ Al 2O 3=5～50, the best is SiO 2/ Al 2O 3=10～40, Na 2O/SiO 2=0.20～0.60, the best is Na 2O/SiO 2=0.25～0.50, H 2O/SiO 2=20～60, the best is H 2O/SiO 2=20～40.The mixture that obtains is transferred in the closed stainless steel reactor, then that the front is prepared directed agents joins in the stainless steel cauldron, crystallization under 120～160 ℃ (the best is 135～160 ℃), obtain the BETA zeolite, analyze with X-ray diffraction, measure the degree of crystallinity of BETA zeolite, measure the component of zeolite with chemical analysis.
To adopt the tangible advantage of synthetizing BETA zeolite by guide agent method be directed agents has the guide effect of intensive crystallization to BETA zeolite synthetic, in unbodied system, owing to introduce directed agents, just can produce the phase region of BETA zeolite.In the prior art, synthetic BETA zeolite need add a large amount of template, and employing synthetizing BETA zeolite by guide agent method of the present invention, just when the preparation directed agents, use template, and when synthetic BETA zeolite, do not need to add again template, therefore with the required template of synthetizing BETA zeolite by guide agent method only be in the past synthesis method 1～10%.Thereby greatly reduce the production cost of BETA zeolite.Secondly, adopt the synthetizing BETA zeolite by guide agent method crystallization rate very fast.In the prior art BETA zeolite crystallization cycle longer, the length in crystallization cycle is relevant with the template dosage that is added, the template dosage of adding is big more, the corresponding shortening of crystallization cycle.And adopt synthetizing BETA zeolite by guide agent method needn't add template more in addition, and crystallization rate is very fast.
In order to be described more specifically the inventive method, enumerate several embodiment below.
Embodiment 1
The preparation of BETA guiding agent for zeolite.
Get and contain Al 2O 3Be that 45% sodium aluminate 0.6g and 0.138g sodium hydroxide are dissolved in the 31.41ml tetraethyl ammonium hydroxide aqueous solution (TEAOH: 1.8542M, d=1.026Kg/L) and in the 12.08ml deionized water, add the 12.71g active silica then while stirring, continue to be stirred to evenly, change in the stainless steel cauldron, placed 5 hours down in 140 ℃, get the BETA guiding agent for zeolite after the cooling, its prescription is: 1Al 2O 380SiO 211(TEA) 2O2.5Na 2O750H 2O.
Embodiment 2
The preparation of BETA guiding agent for zeolite.
Press the method for embodiment 1, the preparation prescription is 1Al 2O 380SiO 212(TEA) 2O2.5Na 2O750H 2The directed agents of O, different is that laying temperature is 80 ℃, be 72 hours storage period.
Embodiment 3
Synthesizing of BETA zeolite.
Get and contain Al 2O 3Be that 45% sodium aluminate 0.64g and 1.80g sodium hydroxide are dissolved in the 41.88ml deionized water, the limit is stirred and is trembled the limit and add the 4.97g active silica then, is transferred to after stirring in the closed stainless steel reactor.Get the directed agents 1.28ml of embodiment 1 preparation, join in the mixture, stir, 140 ℃ of following crystallization 40 hours, obtain BETA zeolite product, use the X-ray diffraction analysis, recording its degree of crystallinity is 100%, and chemical analysis is measured its SiO 2/ Al 2O 3=11.67.
Embodiment 4
Synthesizing of BETA zeolite.
Get and contain Al 2O 3Be that 45% sodium aluminate 0.75g and 2.12g sodium hydroxide are dissolved in the 49ml deionized water, add the 5.96g active silica then while stirring, be transferred to after stirring in the closed stainless steel reactor.Add the directed agents 1.50ml of embodiment 2 preparation again, stir, in 140 ℃ of following crystallization 62 hours, cooling after scouring, suction filtration place 110 ℃ of baking oven dry nights with product, obtain the BETA zeolite and analyze with X-ray diffraction, the degree of crystallinity that records the BETA zeolite is 100%, and chemical analysis is measured SiO 2/ Al 2O 3=12.10.
Embodiment 5(comparative example)
Synthesizing of BETA zeolite.
Press the method for embodiment 3, the preparation prescription is: 1Al 2O 310SiO 22.75Na 2O500H 2The synthetic zeolite mixture of O does not add directed agents, and 140 ℃ of following crystallization 58 hours, it still was amorphous measuring by analysis.
Embodiment 6
Synthesizing of BETA zeolite.
Press the method for embodiment 3, get and contain Al 2O 3Be that 45% sodium aluminate 0.6g and 1.16g sodium hydroxide are dissolved in the 36ml deionized water, add the 3.18g active silica then while stirring, be transferred to after stirring in the closed stainless steel reactor, the directed agents that adds 1.02ml embodiment 1 preparation again, stir, in 140 ℃ of following crystallization 84 hours, cooling after scouring, suction filtration placed 110 ℃ of baking oven dry nights with product.Use the X-ray diffraction analysis, the degree of crystallinity that records the BETA zeolite is 97.17%.
Embodiment 7
Synthesizing of BETA zeolite.
Press the method for embodiment 3, get and contain Al 2O 3Be that 45% sodium aluminate 0.65g and 2.43g sodium hydroxide are dissolved in the 47ml deionized water, add the 4.88g active silica then while stirring, be transferred to after stirring in the closed stainless steel reactor, add the directed agents of 1.3ml embodiment 1 preparation again, continue to stir 30 minutes, in 154 ℃ of following crystallization 35 hours, cooling after scouring, suction filtration place 110 ℃ of baking oven dry nights with product, analyze with X-ray diffraction, the degree of crystallinity that records the BETA zeolite is 99.6%, and chemical analysis is measured its SiO 2/ Al 2O 3=14.16.

Claims (4)

1, a kind of method of synthetic BETA zeolite is characterized in that adopting directed agents, and it is to be dissolved in tetraethyl ammonium hydroxide and the aqueous sodium hydroxide solution by aluminium salt, adds active silica and prepares the formula range of directed agents: SiO 2/ Al 2O 3=20～120, TEAOH/SiO 2=0.2～0.5, Na 2O/SiO 2=0.04～0.10, H 2O/SiO 2=7.5～25; The preparation temperature of directed agents is 15～70 ℃, and the ageing temperature is 50～150 ℃, during synthetic zeolite, add directed agents and synthesis material mixture volume ratio be 0.5～10%.
2, according in the described directed agents preparation of claim 1, it is characterized in that the formula range of directed agents: SiO 2/ Al 2O 3=30～90, TEAOH/SiO 2=0.25～0.4, Na 2O/SiO 2=0.05～0.08, H 2O/SiO 2=8.0～20; The preparation temperature of directed agents is 15～35 ℃, and the ageing temperature is 70～140 ℃; During synthetic zeolite, add directed agents and synthesis material mixture volume ratio be 1～5%.
3, the used aluminium salt of preparation directed agents according to claim 1 is characterized in that adopting sodium aluminate.
4, the used active silica of preparation directed agents according to claim 1 is characterized in that adopting white carbon black.
CN 93117593 1993-09-20 1993-09-20 Synthetizing BETA zeolite by guide agent method Expired - Fee Related CN1032910C (en)

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CN1032910C CN1032910C (en) 1996-10-02

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051055C (en) * 1996-01-11 2000-04-05 中国石油化工总公司 Method for synthesis of beta-zeolite
CN100460325C (en) * 2006-10-19 2009-02-11 华东师范大学 Method for synthesizing ZSM-5 molecular sieve
CN101249968B (en) * 2008-03-10 2010-06-02 吉林大学 Method for synthesizing Beta molecular sieve by organic-free template
CN101096275B (en) * 2006-06-29 2010-08-25 中国石油化工股份有限公司 Method for synthesizing aluminum-enriched beta zeolite
CN101096274B (en) * 2006-06-29 2010-08-25 中国石油化工股份有限公司 Preparation method of aluminum-enriched beta zeolite
CN101723395B (en) * 2008-10-29 2011-04-20 中国石油化工股份有限公司 Method for preparing double-micropore composite molecular sieve
CN102336410A (en) * 2010-07-22 2012-02-01 中国石油天然气股份有限公司 Preparation method for nano aluminum rich beta zeolite
CN109911913A (en) * 2019-04-18 2019-06-21 南开大学 Prepare the method and BEA type molecular sieve of BEA type molecular sieve
CN110860307A (en) * 2019-11-27 2020-03-06 吉林大学 Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method
CN113426405A (en) * 2021-06-21 2021-09-24 碳峰环保科技南通有限公司 Molecular sieve glass fiber VOC adsorption material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051055C (en) * 1996-01-11 2000-04-05 中国石油化工总公司 Method for synthesis of beta-zeolite
CN101096275B (en) * 2006-06-29 2010-08-25 中国石油化工股份有限公司 Method for synthesizing aluminum-enriched beta zeolite
CN101096274B (en) * 2006-06-29 2010-08-25 中国石油化工股份有限公司 Preparation method of aluminum-enriched beta zeolite
CN100460325C (en) * 2006-10-19 2009-02-11 华东师范大学 Method for synthesizing ZSM-5 molecular sieve
CN101249968B (en) * 2008-03-10 2010-06-02 吉林大学 Method for synthesizing Beta molecular sieve by organic-free template
CN101723395B (en) * 2008-10-29 2011-04-20 中国石油化工股份有限公司 Method for preparing double-micropore composite molecular sieve
CN102336410A (en) * 2010-07-22 2012-02-01 中国石油天然气股份有限公司 Preparation method for nano aluminum rich beta zeolite
CN102336410B (en) * 2010-07-22 2013-07-03 中国石油天然气股份有限公司 Preparation method for nano aluminum rich beta zeolite
CN109911913A (en) * 2019-04-18 2019-06-21 南开大学 Prepare the method and BEA type molecular sieve of BEA type molecular sieve
CN110860307A (en) * 2019-11-27 2020-03-06 吉林大学 Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method
CN113426405A (en) * 2021-06-21 2021-09-24 碳峰环保科技南通有限公司 Molecular sieve glass fiber VOC adsorption material

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