CN101428818B - Synthesis of nano-ZSM-5 molecular sieve - Google Patents
Synthesis of nano-ZSM-5 molecular sieve Download PDFInfo
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- CN101428818B CN101428818B CN2008102041509A CN200810204150A CN101428818B CN 101428818 B CN101428818 B CN 101428818B CN 2008102041509 A CN2008102041509 A CN 2008102041509A CN 200810204150 A CN200810204150 A CN 200810204150A CN 101428818 B CN101428818 B CN 101428818B
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Abstract
The invention discloses a method for synthesizing nanometer ZSM-5 molecular sieve, which belongs to the technical field of inorganic chemosynthesis. The method comprises steps as follows: sodium metaaluminate or aluminium sulphate, silica sol or water glass, sodium hydroxide and isopropylamine are prepared into reaction mixer; the reaction mixer is subjected to hydrothermal crystallization; and the reaction mixer after the hydrothermal crystallization is filtered, washed, dried and baked conventionally to obtain nanometer ZSM-5 molecular sieve. The synthesized ZSM-5 molecular sieve has the advantages of higher specific surface, short production flow and low cost, and the section of the synthesized ZSM-5 molecular sieve crystal grain has an average diameter not larger than 100 nm, thereby facilitating industrialization production and application.
Description
Technical field
The present invention relates to inorganic chemical synthesis technical field, specifically a kind of synthetic method of nano-ZSM-5 molecular sieve.
Background technology
The ZSM-5 molecular sieve be by U.S. Mobil company in 1972 synthetic (US3,702,886) first.Because of it has the attention that special pore passage structure and catalytic performance, good thermostability and hydrothermal stability are subjected to domestic and international petrochemical complex circle, very important industrial chemical processes such as catalytic cracking, aromizing, alkylation, disproportionation have been widely used in.Yet, high catalytic efficiency requires catalyzer to have many surfactivity centers and short material transfer path as far as possible, thereby the research and development of nano molecular sieve are applied in order to promote an important symbol of catalytic field technical progresses such as oil refinery, petrochemical complex.
In general, the method for synthetic ZSM-5 molecular sieve is divided into use organic bases structure directing agent has amine method non-amine method synthetic and that do not use organic bases to do structure directing agent to synthesize.In non-amine method was synthetic, mineral alkali sodium hydroxide was a kind of good guiding ZSM-5 synthetic structure directing agent.
The formation of molecular sieve mainly comprises two processes, the one, and the presoma that constitutes the framework of molecular sieve atom in the synthetic system forms the molecular sieve nucleus of ad hoc structure under the effect of structure directing agent, and the 2nd, the nucleus further growth in system that forms.In order to obtain the molecular sieve of nanometer, general method is to form many nucleus in molecular sieve synthetic sol-gel system as far as possible, or reduces the speed of nucleus growth, or carries out the formation and the growth of nucleus in the confinement space.In order to reach the purpose of molecular sieve nanometer, all need in the aforesaid method existing collosol and gel synthesis of molecular sieve system is carried out significantly modulation, this has increased the repeatability of operation and the complicacy of last handling process.
Summary of the invention
The technical problem to be solved in the present invention is to release a kind of synthetic method of nano-ZSM-5 molecular sieve, is based on by simple method and disturbs the research of nucleus growth to propose.Promptly in existing ZSM-5 molecular sieve synthetic collosol and gel synthetic system, introduce the structure directing agent-organic bases Isopropylamine of guiding ZSM-23 molecular sieve, by controlling its consumption, make the guide effect of this structure directing agent be in the seemingly metastable state of Cheng Feicheng, thereby disturb the growth of established principal crystalline phase nucleus, reach the purpose of synthesis of nano ZSM-5 molecular sieve.
The present invention has that building-up process is simple, smooth operation, be easy to the advantages such as club shaped structure that mean diameter that suitability for industrialized production and synthetic ZSM-5 molecular sieve have the cross section is not more than 100nm.
Concrete technical scheme of the present invention is:
A kind of synthetic method of nano-ZSM-5 molecular sieve, it comprises following concrete steps:
The first step preparation feedback mixture
Al in the aluminium source in molar ratio
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is (0.01～0.05): 1: (0.1～0.2): (0.1～1.0): get the raw materials ready (8～50), and described aluminium source is sodium metaaluminate or Tai-Ace S 150, and described silicon source is silicon sol or water glass, described alkali source is a sodium hydroxide, described organic bases is an Isopropylamine, and the preparation feedback mixture joins the aluminium source in the aqueous solution of alkali source earlier, stir, add the silicon source, stir, add organic bases, stir, obtain reaction mixture.
The second step hydrothermal crystallizing
The reaction mixture that the first step is made is transferred to and carries out hydrothermal crystallizing in the autoclave, temperature and time is respectively 130～200 ℃ and 12 hours～5 days, the good reaction mixture of hydrothermal crystallizing after the filtration of routine, washing, drying, roasting product, nano-ZSM-5 molecular sieve.
Technical scheme of the present invention is further characterized in that: in the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is (0.01～0.025): 1: (0.12～0.15): (0.2～0.5): (10～25); In second step, the hydrothermal crystallizing temperature is 150～180 ℃, and the time is 18 hours～3 days.
Compared with prior art, the present invention has following remarkable advantage:
1., the mean diameter in synthetic ZSM-5 zeolite crystal cross section is not more than 100nm, has higher specific surface area.
2., Production Flow Chart is short, cost is low, is beneficial to suitability for industrialized production and application.
Description of drawings
The stereoscan photograph figure of the nano-ZSM-5 molecular sieve that Fig. 1 makes for embodiment 1
Embodiment
All embodiment all operate by the operation steps of technique scheme, and each embodiment is only enumerated crucial technical data.
Embodiment 1
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.12: 0.4: 12, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 170 ℃ of hydrothermal crystallizings 3 days.The stereoscan photograph figure of the nano-ZSM-5 molecular sieve that obtains consults Fig. 1, and among the figure: this zeolite crystal is shaped as club shaped structure, the about 90nm of the mean diameter in crystal grain cross section, the about 400nm of length.
Embodiment 2
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.01: 1: 0.2: 1.0: 20, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 170 ℃ of hydrothermal crystallizings 3 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 85nm of the mean diameter in its crystal grain cross section.
Embodiment 3
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.05: 1: 0.2: 1.0: 50, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 170 ℃ of hydrothermal crystallizings 3 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 90nm of the mean diameter in its crystal grain cross section.
Embodiment 4
In the first step, the Al in the described mol ratio aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.1: 0.1: 10, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 170 ℃ of hydrothermal crystallizings 5 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 85nm of the mean diameter in its crystal grain cross section.
Embodiment 5
In the first step, the Al in the described mol ratio aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.12: 0.4: 12, described aluminium source was a Tai-Ace S 150, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 170 ℃ of hydrothermal crystallizings 3 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 95nm of the mean diameter in its crystal grain cross section.
Embodiment 6
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.12: 0.4: 45, described aluminium source was a sodium metaaluminate, and described silicon source is a water glass, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 170 ℃ of hydrothermal crystallizings 3 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 95nm of the mean diameter in its crystal grain cross section.
Embodiment 7
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.12: 0.4: 12, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 130 ℃ of hydrothermal crystallizings 5 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 80nm of the mean diameter in its crystal grain cross section.
Embodiment 8
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.12: 0.4: 12, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 200 ℃ of hydrothermal crystallizings 12 hours.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 75nm of the mean diameter in its crystal grain cross section.
Embodiment 9
In the first step, described mol ratio is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is 0.025: 1: 0.12: 0.4: 12, described aluminium source was a sodium metaaluminate, and described silicon source is a silicon sol, and described alkali source is a sodium hydroxide, and described organic bases is an Isopropylamine.
In second step, in 150 ℃ of hydrothermal crystallizings 4 days.Stereoscan photograph figure and Fig. 1 of the nano-ZSM-5 molecular sieve that obtains are similar, the about 90nm of the mean diameter in its crystal grain cross section.
Claims (3)
1. the synthetic method of a nano-ZSM-5 molecular sieve is characterized in that this method comprises following concrete steps:
(1), preparation feedback mixture
Al in the aluminium source in molar ratio
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is (0.01～0.05): 1: (0.1～0.2): (0.1～1.0): get the raw materials ready (8～50), earlier the aluminium source is joined in the aqueous solution of alkali source, stirs, and adds the silicon source, stirs, and adds organic bases, stirs, and obtains reaction mixture; Wherein said aluminium source is sodium metaaluminate or Tai-Ace S 150; Described silicon source is silicon sol or water glass; Described alkali source is a sodium hydroxide; Described organic bases is an Isopropylamine;
(2), hydrothermal crystallizing
The reaction mixture that (1) step is made is transferred to and carries out hydrothermal crystallizing in the autoclave, temperature is 130～200 ℃, time is 12 hours～5 days, and the reaction mixture behind the hydrothermal crystallizing obtains nano-ZSM-5 molecular sieve after the filtration of routine, washing, drying, roasting.
2. method according to claim 1 is characterized in that the described mol ratio of step (1) is the Al in the aluminium source
2O
3: the SiO in the silicon source
2: the NaOH in the alkali source: organic bases: H
2O is (0.01～0.025): 1: (0.12～0.1 5): (0.2～0.5): (10～25).
3. method according to claim 1 is characterized in that the described hydrothermal crystallizing temperature of step (2) is 150～180 ℃, and the time is 18 hours～3 days.
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| CN101428818B true CN101428818B (en) | 2010-12-15 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8951498B2 (en) | 2010-07-30 | 2015-02-10 | University Of Iowa Research Foundation | Synthesis of hierarchical nanocrystalline zeolites with controlled particle size and mesoporosity |
| CN102000601A (en) * | 2010-09-30 | 2011-04-06 | 上海师范大学 | Multistage pore structure nano molecular sieve catalyst and preparation method thereof |
| CN102049285B (en) * | 2010-11-10 | 2012-07-11 | 上海师范大学 | Multistage pore-structure molecular sieve catalyst and preparation method thereof |
| CN102001680B (en) * | 2010-12-15 | 2012-06-13 | 岳阳怡天化工有限公司 | Method for preparing nano ZSM-5 molecular sieve |
| CN102602959B (en) * | 2011-01-25 | 2013-12-11 | 北京化工大学 | Preparation method of pure nano-silicon ZSM-5 zeolite |
| CN102745714B (en) * | 2011-04-20 | 2014-07-09 | 中国石油化工股份有限公司 | Preparation method of small crystal grain ZSM-5 molecular sieve |
| CN102897792B (en) * | 2011-07-29 | 2014-12-03 | 中国石油化工股份有限公司 | Synthesis method for ZSM-5 molecular sieve |
| CN102826568B (en) * | 2012-09-26 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | The preparation method of nanocrystalline ZSM-5 zeolite cluster and nanocrystalline ZSM-5 zeolite cluster obtained by this method |
| CN103771450B (en) * | 2012-10-24 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of micropore hollow ball molecular sieve |
| CN102874842B (en) * | 2012-10-26 | 2014-12-03 | 江苏水莲蓬新材料有限公司 | Preparation method of ZSM-5 molecular sieve with small crystal grains and large crystal body |
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