CN102923728A - Large-grain beta molecular sieve and preparation method thereof - Google Patents
Large-grain beta molecular sieve and preparation method thereof Download PDFInfo
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- CN102923728A CN102923728A CN2012104807398A CN201210480739A CN102923728A CN 102923728 A CN102923728 A CN 102923728A CN 2012104807398 A CN2012104807398 A CN 2012104807398A CN 201210480739 A CN201210480739 A CN 201210480739A CN 102923728 A CN102923728 A CN 102923728A
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Abstract
The invention relates to a large-grain beta molecular sieve and a preparation method thereof, and belongs to the technical field of chemical industry. The configuration of the molecular sieve is as follows: the crystal size is 0.1-3.0 micron, and the silica alumina ratio is at least 20-1,000. In addition, the large-grain beta molecular sieve basically does not contain amorphous materials. The large-grain beta molecular sieve, which is completely crystalline and has a wide silica alumina ration, is synthesized by a compound containing chelating agent, besides silica sources, alkali, organic directing agent and optional alumina. The preparation method can prepare production with high purity, and is simple and convenient in process and strong in operability.
Description
Technical field
The present invention relates to a kind of large crystal grain beta molecular sieve and preparation method thereof, belong to chemical technology field.
Background technology
No matter be that natural or synthetic zeolitic material all is proved to be the performance that has catalysis in the dissimilar hydrocarbon conversions.Specific zeolitic material is orderly porous silicoaluminate crystal, has crystalline structure specific, that can be measured by X-ray diffraction, and contain in the crystal a large amount of, interconnected and the hole that consists of by many less passages or aperture, these holes and the aperture size in specific zeolitic material is uniform.Because the size of these apertures can be accepted and absorb the molecule of certain size and larger sized molecule is kept outside of the door, so these zeolitic materials molecular sieve that is otherwise known as.No matter this molecular sieve is natural or synthetic, includes various positively charged ion silicate crystals.These silicate can be described to SiO
4With (the AlO for example of oxide elements in the periodic table of elements IIIA group
4) fixedly three-dimensional framework, the Sauerstoffatom cross connection of tetrahedron wherein by sharing, total IIIA family element (for example aluminium) and the ratio of Siliciumatom and Sauerstoffatom are 1:2.Be included in the tetrahedron of IIIA family element (for example aluminium), its electricity price is to come balance by the positively charged ion that comprises, for example: basic metal or alkaline earth metal cation.This can be expressed as wherein IIA group element (for example aluminium) and a series of picture Ca/2, Sr/2, and Na, the ratio between the different positively charged ion such as K or Li is unified.Utilize traditional ion exchange technique a kind of positively charged ion can be exchanged with another kind of positively charged ion whole or in part.Rely on ion-exchange, might change a kind of character of specific silicon hydrochlorate by selecting a kind of suitable positively charged ion.Space between the tetrahedron is taken by water molecules before dehydration.
Previous technology has formed miscellaneous synthetic zeolite, wherein many zeolites all by literal or other easily form explain out, for example: United States Patent (USP) 2,882, Z-type molecular sieve in 243, United States Patent (USP) 2,882, the X-type molecular sieve in 244, United States Patent (USP) 3,130, Y zeolite in 007, United States Patent (USP) 3,247, the ZK-5 type molecular sieve in 195, United States Patent (USP) 3,314, ZK-4 type molecular sieve in 752, United States Patent (USP) 3,702, the type ZSM 5 molecular sieve in 886, United States Patent (USP) 3,709, ZSM-11 type molecular sieve in 979, United States Patent (USP) 3,832, the ZSM-12 type molecular sieve in 449, United States Patent (USP) 3,972, ZSM-20 type molecular sieve in 983, United States Patent (USP) 4,016, the ZSM-35 type molecular sieve in 245, United States Patent (USP) 4, ZSM-23 type molecular sieve in 076,842 etc.
A kind of SiO of given molecular sieve
2/ Al2O
3Normally variable.For example, molecular sieve X can be synthesized into silica alumina ratio from 2-3; Y type 3-6.The silica alumina ratio upper limit of some molecular sieve is very large.ZSM-5 is exactly wherein a kind of, SiO
2/ Al2O
3From at least 5 limit that can reach the present analysis measuring technology.United States Patent (USP) 3,941 has disclosed the porous silicate crystal that reaction mixture is made in 871 (Re.29,948), do not contain the aluminium that specially adds in the prescription of this reaction mixture, and X-ray diffraction demonstrates the characteristic of ZSM-5.United States Patent (USP) 4,061 has been described the silicate crystal of different aluminum oxide and metal content in 724,4,073,865 and 4,104,294.
As everyone knows, the characteristic of zeolite can be subject to changing the impact of its structure silica alumina ratio.Ratio in the synthesis of molecular sieve can change by the relative content of silicon and aluminium in the adjustment precursor material.For example, with respect to aluminium and the amount that increases silicon can be produced the product of high silicon content usually.But after reaching certain silica alumina ratio example, the silicone content that part increases in the reactant not necessarily can affect the silica alumina ratio of the finished product, even also can hinder the desirable the finished product of formation.
The Beta molecular sieve after being invented by Wadlinger in 1967, and large quantities of scientists have done large quantity research, but not yet have so far a kind of clear and definite, method simple, that can produce the large crystal grain beta molecular sieve of extensive silica alumina ratio to come forth out.It is reported, some expert of China uses fluorochemical to produce crystal grain at the Beta of 500nm type molecular sieve, but fluorochemical makes its invention have the difficulty that may overcome hardly in specific implementation process to the high requirement of production unit, also can pollute environment simultaneously.
The molecular sieve of larger crystal grain has longer diffusion path length, can be used for regulating catalyzed reaction.Only change selectivity of catalyst with regard to having described the mesopore ZSM-5 molecular sieve by controlling its crystalline size with way of illustration.The shape characteristics of selecting of ZSM-5 uniqueness are the para-selectivities in toluene disproportionation and alkylating aromatic hydrocarbon.Thereby increase crystalline size and prolong the evolving path, just reach one of method of high para-selectivity.The generation of product selectivity is because the increase of diffusional limitation is imposed on the volume, o-and the diffusion of m-isomer can reduce the generation of these isomer more slowly, increase simultaneously para-isomeride, this content is seen two pieces of " industrial application of shape-selective catalyst " articles of 1989 and 1986.United States Patent (USP) 4,517, passing through of describing in 402 increase the ZSM-5 molecular sieve that crystalline structure obtains highly selective, are included into this paper as a reference.United States Patent (USP) 4,828 has disclosed large grain ZSM-5 molecular sieve in 679 and improved octane income and automobile fuel ultimate production when improving steam stable.United States Patent (USP) 4,650 has been described the reaction conditionss such as stirring that add organic speed, temperature, pH and crystallization medium by the control picture in 656 and has been synthesized large grain ZSM-5.In " gravity is on the impact of silicate crystallization " articles in 1956, external force of gravity is described as be in a kind of means of producing larger crystal molecular sieve in the synthetic silicate process.In 1971 " gel growth of large crystal grain sodium A and sodium X molecular sieve ", described the method for synthetic large grain A-type and X-type molecular sieve, wherein, trolamine is sneaked in the reaction mixture as unique organic reactant.Disclosed the synthetic larger crystal molecular sieve of considerable attention directing for the review of these publications, but be consistent without any the method for the synthetic large crystal grain of publication indication.The crystalline size of Beta molecular sieve is usually relevant with silica alumina ratio, the corresponding macrocrystal size of high-silica zeolite, and the corresponding small crystalline size of low silica-alumina ratio.The technology of synthetic large crystal grain Beta molecular sieve has contained very widely silica alumina ratio, has wherein both comprised low also comprising highly, and this is ideal, and has efficient and high hydrothermal stability energy in vehicle exhaust DeNOx uses.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: a kind of large crystal grain beta molecular sieve is provided, except containing silicon source, alkali, organic directed agents and optional aluminum oxide, also comprise synthesized in the mixture of sequestrant holocrystalline, comprise extensive silica alumina ratio, the product purity that this preparation method makes is high, preparation technology is easy, and is workable.
The technical solution adopted for the present invention to solve the technical problems is: provide a kind of large crystal grain beta molecular sieve, being configured as of described molecular sieve: crystalline size from 0.1 to 3.0micron, silica alumina ratio at least from 20 to 1000.And this large crystal grain beta molecular sieve is substantially gone up and is not contained amorphous substance.
The preparation method of described large crystal grain beta molecular sieve is characterized in that following steps:
(a) preparation contain one or more alkali metal cations, contain the cationic organic cation of Tetrylammonium, the reaction mixture of a kind of tertiary alkanolamine sequestrant, a kind of silicon oxide, water and a kind of aluminum oxide, and this reaction mixture will be according to following molar ratio range:
Wherein R is organic cation, and M is alkali metal cation, and X is sequestrant;
(b) reaction mixture is remained under the condition that forms large crystal grain beta molecular sieve crystal, make large crystal grain beta molecular sieve crystal;
(c) reclaim large crystal grain beta molecular sieve crystal from step (b), the large crystal grain beta molecular sieve of recovery contains at least a organic cation and sequestrant.
The silica source of described reaction mixture is colloidal silica, precipitation silicon or silicon precursor.
The organic cation that represents with R in the large crystal grain beta molecular sieve crystal of the recovery described in the step (b) and the sequestrant that represents with X are by roasting and exchange to the form that small part converts hydrogen to.
The condition of the large crystal grain beta of described formation molecular sieve crystal comprises that temperature range is from 120 ℃ to 175 ℃.
Described organic cation source is one or both in free tetraethyl ammonium hydroxide and the tetraethyl-halogenide.
Described tetraethyl-halide source is selected from tetraethylammonium bromide, etamon chloride or tetraethyl ammonium fluoride.
The present invention uses sequestrant, precipitation silicon as the silicon source in mixture, and adds the starting crystal seed to have produced the large crystal grain beta of holocrystalline high silicon molecular sieve.
It is to synthesize large crystal grain beta molecular sieve from the silicon source with high solids content that the present invention also has a characteristic.
In preparation high-silica zeolite synthetic, silicon is chief component in the reaction mixture.Too high with silicone content in the prescription of traditional process synthesizing high-silicon molecular sieve, synthetic mixture is along with become very thickness and hinder stirring of silicon amount increase.Advantage of the present invention is not run into the problem identical with traditional high silicon formula and the large crystal grain beta molecular sieve that synthesizes high-crystallinity.
Large crystal grain beta molecular sieve with high-crystallinity refer to substantially not contain amorphous silicon oxide and aluminum oxide the Beta molecular sieve and unlike United States Patent (USP) 4,923, the Beta molecular sieve of the partial crystallization of describing in 690.In order to reach high-crystallinity, syntheticly must last till the degree of crystallinity of product more than at least 70%, scope from 80% to 130% preferably can reach by traditional X-ray analysis technology and records degree of crystallinity more than 90%.
The reaction mixture that is used for having synthesized holocrystalline large crystal grain beta molecular sieve can be by making with suitable oxide material.This constituents comprises: the oxyhydroxide of aluminate, aluminum oxide, precipitation silicon, silica hydrosol, silicon precursor, silica gel, silicic acid and silicic acid etc.
For the preparation of every kind of oxide component in the reaction mixture of molecular sieve, can be provided by one or more basic reaction things, they can mix according to certain order.The aqueous solution, sodium hydroxide or a kind of suitable aqueous silicate solution of any oxide compound for example, can be provided; Organic cation can be provided by this cationic directed agents compound, and for instance, as oxyhydroxide or salt, halogenide is for example as muriate, iodide, fluorochemical or bromide.The preparation feedback mixture all can in batches or continuously.
Organic directed agents that should comprise at least a kind of cationic nitrogenous in the organic reactant, and a kind of sequestrant of organic compounds containing nitrogen.
Directed agents in the method should contain a kind of tetraethyl compound or following mixture at least at present, the example of this directed agents is not limited to comprise oxyhydroxide and/or halogenide, for example: tetraethyl ammonium hydroxide (TEAOH), tetraethylammonium bromide (TEABr), etamon chloride (TEACl) and tetraethyl ammonium fluoride (TEAF).
Sequestrant is a kind of for example as the organic compounds containing nitrogen of tertiary alkanolamine, and first-selected tertiary alkanolamine is trolamine.But other feasible tertiary alkanolamine comprises: two (methylol)-2 of tri-isopropanolamine and 2,2-, 2 ', 2 "-nitrilotriethanol.Sequestrant is as being present in the system with the promotor of silicon with the 2-4:1 molar ratio reaction, we are called silicon " setter " visually, in reaction, can not make sial form the Beta structure, but when the reaction termination, be present in the molecular sieve with the weighting material form.Sequestrant is widely used as the screener of silicon in the EDTA titration, it serves to show the response capacity of itself and silicon.
The index in silicon source should be required as a kind of very important condition, can select spray-dried precipitation silicon, high density silicon solution or aerosil, also can be high-purity silicon sol.In order to guarantee to carry out smoothly, its primary particles diameter should be at 3 microns.
The invention has the beneficial effects as follows: except containing silicon source, alkali, organic directed agents and optional aluminum oxide, also comprise synthesized in the mixture of sequestrant holocrystalline, comprise extensive silica alumina ratio, the product purity that this preparation method makes is high, and preparation technology is easy, and is workable.
Description of drawings
Fig. 1 is the electron microscope picture of the product that makes among the embodiment 2;
Fig. 2 is the electron microscope picture of the product that makes among the embodiment 3;
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are described further:
Embodiment 1
Make the high-crystallinity crystal seed
The R=tetraethyl ammonium hydroxide; SiO
2=primary crystallization crystal grain is high-purity precipitation silicon of 3 microns; The aluminium source is sodium aluminate.
Reaction conditions: 140 ℃, 60 rev/mins, 50 hours
Obtain degree of crystallinity 110, silica alumina ratio 28, specific surface 630m
2The beta molecular sieve of/g.
Embodiment 2
The product that obtains in the example 1 adds massfraction 2% as crystal seed as crystal seed.
SiO
2Be the precipitation silicon in the example 1; The aluminium source is sodium aluminate;
R
1=tetraethyl ammonium hydroxide; R
2=tetraethylammonium bromide; The X=trolamine
Reaction conditions: 150 ℃, 80 rev/mins, 85 hours
Obtain degree of crystallinity 108, silica alumina ratio 28, specific surface 598m
2The large crystal grain beta molecular sieve (seeing picture 1) of/g, average crystal grain diameter 300nm.
Embodiment 3
The product that obtains in the example 1 adds massfraction 2% and does crystal seed as crystal seed.
SiO
2Be aerosil; The aluminium source is sodium aluminate;
R
1=tetraethyl ammonium hydroxide; R
2=tetraethylammonium bromide; The X=trolamine
Reaction conditions: 150 ℃, 80 rev/mins, 85 hours
Obtain degree of crystallinity 105, silica alumina ratio 110, specific surface 585m
2The large crystal grain beta molecular sieve (seeing picture 2) of/g, average crystal grain diameter 450nm.
Embodiment 4
The product that obtains in the example 1 is as crystal seed, and the aluminium that adds in the 4%(crystal seed is the aluminium source)
SiO
2Be the precipitation silicon in the example 1;
R
1=tetraethyl ammonium hydroxide; R
2=tetraethylammonium bromide; The X=trolamine
Reaction conditions: 150 ℃, 80 rev/mins, 85 hours
Obtain degree of crystallinity 104, silica alumina ratio 675, specific surface 605m
2The large crystal grain beta molecular sieve of/g, average crystal grain diameter 300nm.
Embodiment 5
The product that obtains in the example 1 adds 2% as crystal seed
SiO
2It is 40% silicon sol;
R
1=tetraethyl ammonium hydroxide; R
2=tetraethylammonium bromide; The X=trolamine
Reaction conditions: 150 ℃, 80 rev/mins, 85 hours
Obtain degree of crystallinity 109, silica alumina ratio 110, specific surface 610m
2The large crystal grain beta molecular sieve of/g, average crystal grain diameter 250nm.
Claims (7)
1. large crystal grain beta molecular sieve is characterized in that being configured as of described molecular sieve: crystalline size from 0.1 to 3.0micron, silica alumina ratio at least from 20 to 1000.
2. the preparation method of large crystal grain beta molecular sieve according to claim 1 is characterized in that following steps:
(a) preparation contain one or more alkali metal cations, contain the cationic organic cation of Tetrylammonium, the reaction mixture of a kind of tertiary alkanolamine sequestrant, a kind of silicon oxide, water and a kind of aluminum oxide, and this reaction mixture will be according to following molar ratio range:
Wherein R is organic cation, and M is alkali metal cation, and X is sequestrant;
(b) reaction mixture is remained under the condition that forms large crystal grain beta molecular sieve crystal, make large crystal grain beta molecular sieve crystal; (c) reclaim large crystal grain beta molecular sieve crystal from step (b), the large crystal grain beta molecular sieve of recovery contains at least a organic cation and sequestrant.
3. the preparation method of large crystal grain beta molecular sieve according to claim 2, the silica source that it is characterized in that described reaction mixture are colloidal silica, precipitation silicon or silicon precursor.
4. the preparation method of large crystal grain beta molecular sieve according to claim 2, it is characterized in that the organic cation that represents with R in the large crystal grain beta molecular sieve crystal of the recovery described in the step (b) and the sequestrant that represents with X by roasting with exchange to the form that small part converts hydrogen to.
5. the preparation method of large crystal grain beta molecular sieve according to claim 2 is characterized in that the condition of the large crystal grain beta of described formation molecular sieve crystal comprises that temperature range is from 120 ℃ to 175 ℃.
6. the preparation method of large crystal grain beta molecular sieve according to claim 2 is characterized in that described organic cation source is one or both in free tetraethyl ammonium hydroxide and the tetraethyl-halogenide.
7. the preparation method of large crystal grain beta molecular sieve according to claim 1 is characterized in that described tetraethyl-halide source is selected from tetraethylammonium bromide, etamon chloride or tetraethyl ammonium fluoride.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314647A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | Silicon-aluminum and silicon-iron Beta molecular sieves, and preparation methods and applications thereof |
| CN105314646A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | AEI-type aluminosilicate molecular sieves, and preparation methods and applications thereof |
| CN105314648A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum molecular sieves, and preparation methods and applications thereof |
| WO2016078016A1 (en) * | 2014-11-19 | 2016-05-26 | 中国石油大学(北京) | Preparation method for beta zeolite |
| CN114620743A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Large-grain RHO-SAPO molecular sieve, and preparation method and application thereof |
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| US5164169A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Zeolite Beta |
| CN1253908A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Preparation process of beta-zeolite |
| CN101108734A (en) * | 2006-07-19 | 2008-01-23 | 中国石油大学(北京) | Beta type molecular sieve and method of manufacturing the same |
| CN101717092A (en) * | 2008-10-10 | 2010-06-02 | 天津海赛纳米材料有限公司 | Method for preparing nanometer high specific surface Beta zeolite |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5164169A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Zeolite Beta |
| CN1253908A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Preparation process of beta-zeolite |
| CN101108734A (en) * | 2006-07-19 | 2008-01-23 | 中国石油大学(北京) | Beta type molecular sieve and method of manufacturing the same |
| CN101717092A (en) * | 2008-10-10 | 2010-06-02 | 天津海赛纳米材料有限公司 | Method for preparing nanometer high specific surface Beta zeolite |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314647A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | Silicon-aluminum and silicon-iron Beta molecular sieves, and preparation methods and applications thereof |
| CN105314646A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | AEI-type aluminosilicate molecular sieves, and preparation methods and applications thereof |
| CN105314648A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum molecular sieves, and preparation methods and applications thereof |
| WO2016078016A1 (en) * | 2014-11-19 | 2016-05-26 | 中国石油大学(北京) | Preparation method for beta zeolite |
| US10287172B2 (en) | 2014-11-19 | 2019-05-14 | China University Of Petroleum-Beijing | Preparation method for beta zeolite |
| CN114620743A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Large-grain RHO-SAPO molecular sieve, and preparation method and application thereof |
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