CN105621439B - A kind of synthetic method of Beta zeolites - Google Patents
A kind of synthetic method of Beta zeolites Download PDFInfo
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- CN105621439B CN105621439B CN201410591295.4A CN201410591295A CN105621439B CN 105621439 B CN105621439 B CN 105621439B CN 201410591295 A CN201410591295 A CN 201410591295A CN 105621439 B CN105621439 B CN 105621439B
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Abstract
The invention discloses a kind of synthetic method of Beta zeolites, first be placed in aluminum nitrate in high temperature furnace by the Beta zeolites synthetic method, and roasting prepares special aluminum oxide；Then inorganic base, silicon source, silicon source, template and water are mixed, stirs into silica-alumina gel；Then to adding aluminum oxide prepared above in silica-alumina gel；Beta zeolites are obtained after last hydrothermal crystallizing.The Beta zeolites of the inventive method synthesis are low silica-alumina ratio zeolite, and crystallinity is high, not only effectively prevent the generation of stray crystal but also operation is simple.
Description
Technical field
The present invention relates to a kind of synthetic method of Beta zeolites, specifically a kind of synthesis of low silica-alumina ratio Beta zeolites
Method, belongs to molecular sieve catalytic material synthesis field.
Background technology
Beta zeolites were synthesized first in 1967 by Mobil companies, due to failing to solve the problems, such as its structure determination for a long time,
So a very long time fails to arouse enough attention.Until its distinctive Three Dimensions Structure is disclosed within 1988,
Beta zeolites are aroused people's interest again.Beta zeolites have good heat and hydrothermal stability, and appropriate is acid and thermally-stabilised
Property and hydrophobicity, and be unique macropore high-silica zeolite for having and intersecting twelve-ring channel system, table in its catalytic process
The characteristics of revealing hydrocarbon reaction and be difficult coking and long service life, hydrocarbons hydrogenation cracking, hydroisomerization, alkane aromatization,
The aspect such as alkylation and transalkylation reaction shows excellent catalytic performance, is highly important catalysis material.
At present, the oxide silicon aluminum ratio of the Beta zeolites of conventional method synthesis is general 20~200, and is readily synthesized；But
Synthesizing Si-Al is wanted than the rich aluminium Beta zeolites less than 20, it is relatively difficult.Rich aluminium Beta zeolites are relatively low due to its silica alumina ratio,
With sour density higher, catalytic reaction efficiency higher can be shown in some catalytic reactions, be a kind of important urging
Change material.
CN101096275A discloses a kind of synthetic method of rich aluminium Beta zeolites, and synthesis step is（1）With containing silicon source
The aqueous solution or acid solution dipping silicon source, stirring to solidifying, with or without aging dehydration after AMMONIA TREATMENT, by after grinding,
It is calcined at 600~1400 DEG C, obtains silicon and aluminum source；（2）Tetraethylammonium cation compound and hydrofluoric acid are mixed again, in normal pressure
And under not higher than 130 DEG C or vacuum condition, evaporate part moisture；（3）Silicon and aluminum source is added the tetraethyl hydroxide of concentration
In ammonium and hydrofluoric acid mixed solution, then the reactant mixture that will be obtained carries out hydrothermal crystallizing and reclaims crystallization product.Although the patent
The Beta zeolites of low silica-alumina ratio can be synthesized, but its building-up process is comparatively laborious.
CN101096274A discloses a kind of preparation method of rich aluminium Beta zeolites, the synthetic method step of the Beta zeolites
Suddenly it is：（1）Silicon source and silicon source are prepared into silica-alumina cogels in the presence of hydrolytic reagent, is crushed as sial by after aging and roasting
Source；（2）Then silicon and aluminum source is added in the solution being made up of tetraethylammonium cation, ammonium ion, fluorine ion and water, crystallization is simultaneously
Reclaim crystallization product and obtain zeolite.Although the patent can synthesize the Beta zeolites of low silica-alumina ratio, fluorine is additionally used
Ion, not only increases cost, and pollution environment.
CN1086791A discloses directing agent method synthesis Beta zeolites, and the Beta zeolites of synthesis fall within low silica-alumina ratio boiling
Stone.Being mainly characterized by of the patent synthesizes Beta zeolites using directed agents.Its directed agents is to be dissolved in tetraethyl hydrogen-oxygen with aluminium salt
Change in ammonium template and sodium hydrate aqueous solution, add active silica to prepare directed agents, its directed agents formula range is：
SiO2/Al2O3=20~120, TEAOH/SiO2=0.2~0.5, Na2O/SiO2=0.40~0.10, H2O/SiO2=7.5~
25, the preparation temperature of directed agents is 15~70 DEG C, and Aging Temperature is 50~150 DEG C, during synthetic zeolite, added directed agents and synthesis
The volume ratio of raw mixture is 0.5%~10%.
Although prior art discloses the synthetic method of several low silica-alumina ratio Beta zeolites, relative to silicon Beta zeolites high
Synthetic technology is not also overripened, and its synthesis step is also relatively cumbersome.And low silica-alumina ratio Beta zeolites are because have uniqueness
Catalytic property, is a kind of important catalysis material, therefore develops the synthetic method of more advanced rich aluminium Beta zeolites just with weight
The realistic meaning wanted.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of synthetic method of Beta zeolites, the Beta of the method synthesis
Zeolite has the feature of low silica-alumina ratio, and whole preparation process is simple and easy to apply, is adapted to industrialized production.
The Beta zeolite crystal structures that the present invention is provided are typical BEA structures, without other impurity crystal；Silica alumina ratio
Low, oxide silicon aluminum ratio is less than 20, and crystal size scope is 700 ~ 1500nm.
The synthetic method of Beta zeolites of the present invention, comprises the following steps：
（1）Aluminum nitrate is calcined 1~5h at 450~700 DEG C, aluminum oxide is obtained；
（2）By inorganic base, silicon source, silicon source, water and template（TEA）According to 1~8Na of mol ratio2O：30~70SiO2:
A12O3：500~1500H2O：The ratio mixing of 15~40TEA, obtains silica-alumina gel after stirring；
（3）By step（1）The aluminum oxide and step for obtaining（2）The silica-alumina gel mixing for obtaining, in 100~170 DEG C of temperature
Under, then 20~120h of crystallization separating, washing and is dried to obtain Beta zeolites.
In the synthetic method of Beta zeolites of the present invention, step（1）Described in preferably 500~600 DEG C of sintering temperature, roasting
Time preferably 1.5~4h.
In the synthetic method of Beta zeolites of the present invention, step（2）Described in inorganic base can be NaOH, KOH, LiOH
One or more；Silicon source can be one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source can be white
One or more in carbon black, silica gel, Ludox or waterglass；Template is tetraethyl ammonium hydroxide and/or tetraethyl bromination
Ammonium.
In the synthetic method of Beta zeolites of the present invention, step（2）Described in inorganic base, silicon source, silicon source, water and template
Mol ratio is 2~7Na2O：35~60SiO2：A12O3：H2O：20~30TEA.
In the synthetic method of Beta zeolites of the present invention, step（3）Described in aluminum oxide and step（2）Described in silicon source
Mol ratio is 15~1SiO2:A12O3, preferably 10~2SiO2:A12O3。
In the synthetic method of Beta zeolites of the present invention, step（3）Described in crystallization condition be preferably in 110~150 DEG C of temperature
Under degree, 20~72h of crystallization.
In the synthetic method of Beta zeolites of the present invention, step（3）Described in separation and washing be people in the art
Routine operation known to member, such as separates the method that can take filtering, and washing generally refers to be washed with deionized.Generally include
Separating for several times and washing operation, generally 1~6 time.Drying condition is usually that 5~15h is dried under the conditions of 100~140 DEG C.
The Beta zeolites that the present invention is provided can serve as the adsorbent that gas, liquid mixture are separate, it is also possible to used as urging
The carrier or acidic catalyst component of agent, can be widely applied to petrochemical industry.
Compared with prior art, the Beta zeolites and synthetic method that the present invention is provided have advantages below：
In the synthetic method of Beta zeolites of the present invention, aluminum nitrate roasting is allowed to be decomposed into a kind of inert aluminum oxide, this
Planting special inert alumina can show strong inertia in Beta zeolite crystallization courses of reaction, i.e., relative to step（2）
Described in common silicon source can delay participate in zeolite crystallization, can so make Beta zeolite crystallizations react be divided into two ranks
Section, first stage：Step（2）Described in common silicon source first reacted with other raw materials, generate Beta zeolite nucleus；Second-order
Section：Treat step（2）Described in common silicon source consumption reaction completely after, add step（1）Special aluminum oxide is continued to participate in instead
Should, it is possible to achieve slowly discharge aluminium species, can so ensure that the silica alumina ratio of whole reaction system maintains one all the time
Level higher, is conducive to the growth of Beta zeolites, and can suppress the generation of impurity crystal, and then can synthesize high-purity
The low silica-alumina ratio Beta zeolites of degree.Operation is simple for the synthetic method that the present invention is provided, and is adapted to industrialized production.Can be in original
In the material relatively low scope of silica alumina ratio, synthesis obtains low silica-alumina ratio Beta zeolites, and with sour density higher, in some catalytic reactions
In have catalytic reaction efficiency higher.
Brief description of the drawings
Fig. 1 is the XRD spectra of the Beta zeolites that embodiment 1 is obtained.
Specific embodiment
The synthetic method of Beta zeolites of the present invention is described in detail below by specific embodiment, but is not limited to
In embodiment.
Embodiment 1
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 500 DEG C, obtain aluminum oxide；Then 0.27g hydrogen-oxygens are taken
Change sodium, 0.1g sodium aluminates, 30mL25% tetraethyl ammonium hydroxides to be placed in 50mL distilled water, stirring is until all dissolve, then add
8g white carbons, mix after stirring with aluminum oxide, are fitted into closed reactor after stirring, 140 DEG C of crystallization in baking oven
48h.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL1, institute then are dried at 120 DEG C
Sample is obtained as shown in figure 1, being pure Beta zeolites, without other impurity.
Embodiment 2
10g aluminum sulfate is placed in high temperature furnace first, 2h is calcined at 550 DEG C, obtain aluminum oxide；Then 0.27g hydrogen is taken
Sodium oxide molybdena, 0.1g sodium aluminates, 30mL25% tetraethyl ammonium hydroxides are placed in 50mL distilled water, and stirring is until all dissolve, then add
Plus 8g silica gel, mix with aluminum oxide after stirring, it is fitted into closed reactor after stirring, 140 DEG C of crystallization in baking oven
40h.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample is Beta boilings
Stone, numbering is CL2.
Embodiment 3
12g aluminum nitrates are placed in high temperature furnace first, 2.5h is calcined at 700 DEG C, obtain aluminum oxide；Then 0.3g hydrogen is taken
Potassium oxide, 0.2g aluminum nitrates, 30mL25% tetraethyl ammonium hydroxides are placed in 50mL distilled water, and stirring is until all dissolve, then add
Plus 8.5g white carbons, mix with aluminum oxide after stirring, it is fitted into closed reactor after stirring, 150 DEG C in baking oven
Crystallization 50h.By resulting product with water washing is distilled 4 times to neutrality, 120 DEG C dry 12h, and gained sample is Beta zeolites,
Numbering is CL3.
Embodiment 4
17g aluminum nitrates are placed in high temperature furnace first, 2h is calcined at 580 DEG C, obtain aluminum oxide；Then 0.27g hydrogen-oxygens are taken
Change sodium, 0.25g aluminum sulfate, 20g tetraethylammonium bromides to be placed in 60mL distilled water, stirring is until all dissolve, then to add 8g white
Carbon black, mixes after stirring with aluminum oxide, is fitted into closed reactor after stirring, 125 DEG C of crystallization 35h in baking oven.
By resulting product with water washing is distilled 4 times to neutrality, 120 DEG C dry 12h, and gained sample is Beta zeolites, and numbering is
CL4。
Comparative example 1
Take 0.27g NaOH, 0.1g sodium aluminates, 16g aluminum nitrates and 30mL25% tetraethyl ammonium hydroxides and be placed in 50mL steamings
In distilled water, stirring is up to all dissolvings, then adds 8g white carbons, is fitted into closed reactor after stirring, 140 in baking oven
DEG C crystallization 48h.By resulting product with water washing is distilled 4 times to neutrality, 120 DEG C dry 12h, gained sample number into spectrum CL5, institute
It is P type zeolite to obtain sample, it is impossible to synthesize Beta zeolites.
Comparative example 2
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 900 DEG C, obtain aluminum oxide；Then 0.27g hydrogen-oxygens are taken
Change sodium, 0.1g sodium aluminates, 30mL25% tetraethyl ammonium hydroxides to be placed in 50mL distilled water, stirring is until all dissolve, then add
8g white carbons, mix after stirring with aluminum oxide, are fitted into closed reactor after stirring, 140 DEG C of crystallization in baking oven
48h.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL6, institute then are dried at 120 DEG C
It is crystalline alumina to obtain sample, it is impossible to synthesize Beta zeolites.
Comparative example 3
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 300 DEG C, obtain aluminum oxide；Then 0.27g hydrogen-oxygens are taken
Change sodium, 0.1g sodium aluminates, 30mL25% tetraethyl ammonium hydroxides to be placed in 50mL distilled water, stirring is until all dissolve, then add
8g white carbons, mix after stirring with aluminum oxide, are fitted into closed reactor after stirring, 140 DEG C of crystallization in baking oven
48h.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL7, institute then are dried at 120 DEG C
It is P type zeolite to obtain sample, it is impossible to synthesize Beta zeolites.
Comparative example 4
16g aluminum nitrates are dissolved in 200mL distilled water first, 200mL 0.3mol/L are then added dropwise under stirring
Sal volatile, obtain white gels；Gel is placed in again 12h is dried at 120 DEG C, be then calcined 3h at 750 DEG C, obtain oxygen
Change aluminium.Then 0.27g NaOH, 0.1g sodium aluminates, 30mL25% tetraethyl ammonium hydroxides are taken to be placed in 50mL distilled water, is stirred
Mix up to all dissolvings, then add 8g white carbons, mix with the aluminum oxide being previously obtained after stirring, load after stirring
In closed reactor, 140 DEG C of crystallization 48h in baking oven.By resulting product with distillation water washing 4 times to neutral, then 120
12h, gained sample number into spectrum CL8 are dried at DEG C, gained sample is gama-alumina, it is impossible to synthesize Beta zeolites.
Table 1 is the crystalline phase property of embodiment and comparative example products therefrom
Note：The relative crystallinity that table 1 is given is the crystallinity with CL1 as reference.
Claims (8)
1. a kind of synthetic method of Beta zeolites, comprises the following steps：
（1）Aluminum nitrate is calcined 1~5h at 450~700 DEG C, aluminum oxide is obtained；
（2）By inorganic base, silicon source, silicon source, water and template TEA according to 1~8Na of mol ratio2O：30~70SiO2: A12O3：500
~1500H2O：The ratio mixing of 15~40TEA, obtains silica-alumina gel after stirring；
（3）By step（1）The aluminum oxide and step for obtaining（2）The silica-alumina gel mixing for obtaining, it is brilliant at a temperature of 100~170 DEG C
Change 20~120h, then separating, washing and be dried to obtain Beta zeolites.
2. according to the synthetic method described in claim 1, it is characterised in that：Step（1）Described in sintering temperature for 500~
600 DEG C, roasting time is 1.5~4h.
3. according to the synthetic method described in claim 1, it is characterised in that：Step（2）Described in inorganic base be NaOH, KOH,
One or more in LiOH；Silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is white carbon
One or more in black, silica gel, Ludox or waterglass.
4. according to the synthetic method described in claim 1, it is characterised in that：Step（2）Described in template be tetraethyl hydrogen
Amine-oxides and/or tetraethylammonium bromide.
5. according to the synthetic method described in claim 1, it is characterised in that：Step（3）Described in aluminum oxide and step（2）In
The mol ratio of the silicon source is 15~1SiO2:A12O3。
6. according to the synthetic method described in claim 1 or 5, it is characterised in that：Step（3）Described in aluminum oxide and step
（2）Described in silicon source mol ratio be 10~2SiO2:A12O3。
7. according to the synthetic method described in claim 1, it is characterised in that：Step（3）Described in crystallization condition be 110~
At 150 DEG C, 20~72h of crystallization.
8. according to the synthetic method described in claim 1, it is characterised in that：Step（3）Described in drying be at 100~140 DEG C
Under the conditions of dry 5~15h.
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| 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 |
| CN111847473A (en) * | 2020-07-31 | 2020-10-30 | 江苏国瓷新材料科技股份有限公司 | Method for synthesizing large-grain Beta molecular sieve by programmed temperature raising method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096274A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Preparation method of aluminum-enriched beta zeolite |
| CN101096275A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Method for synthesizing aluminum-enriched beta zeolite |
| CN101205072A (en) * | 2006-12-18 | 2008-06-25 | 中国石油化工股份有限公司 | Method for synthesizing low silica-alumina ratio beta zeolite |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096274A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Preparation method of aluminum-enriched beta zeolite |
| CN101096275A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Method for synthesizing aluminum-enriched beta zeolite |
| CN101205072A (en) * | 2006-12-18 | 2008-06-25 | 中国石油化工股份有限公司 | Method for synthesizing low silica-alumina ratio beta zeolite |
Non-Patent Citations (1)
| Title |
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| 低硅Beta分子筛的合成研究;杜君等;《山西大同大学学报（自然科学版）》;20110228;第27卷(第1期);第40-41页 * |
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Effective date of registration: 20230826 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |