CN108128785B - Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step - Google Patents
Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step Download PDFInfo
- Publication number
- CN108128785B CN108128785B CN201810175876.8A CN201810175876A CN108128785B CN 108128785 B CN108128785 B CN 108128785B CN 201810175876 A CN201810175876 A CN 201810175876A CN 108128785 B CN108128785 B CN 108128785B
- Authority
- CN
- China
- Prior art keywords
- nickel
- molecular sieve
- ite
- zeolite molecular
- amine complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the preparation of a molecular sieve, and aims to provide a method for synthesizing an ITE zeolite molecular sieve by using a nickel-amine complex as a template in one step. The method for synthesizing the ITE zeolite molecular sieve by one step by using the nickel-amine complex as the template comprises the following steps: firstly, dissolving nickel salt in deionized water, dropwise adding organic amine into the solution after stirring, then adding sodium hydroxide solid and USY molecular sieve, stirring, and then putting into a reaction kettle for crystallization; and after the reaction is finished, washing the reaction product by using deionized water, and drying at the temperature of 80 ℃ for more than 12 hours to obtain the ITE zeolite molecular sieve. The method for synthesizing the ITE zeolite molecular sieve in one step by using the nickel-amine complex as the template agent takes the nickel-amine complex with low price as the template agent, and has the advantages of low crystallization temperature and short crystallization time, thereby greatly reducing the production cost, improving the synthesis efficiency and reducing the potential safety hazard, and having important significance in the field of actual chemical production.
Description
Technical Field
The invention relates to the field of molecular sieve preparation, in particular to a method for synthesizing an ITE zeolite molecular sieve by one step by using a nickel-amine complex as a template.
Background
Zeolite molecular sieve materials include silico-aluminum molecular sieves, phospho-aluminum molecular sieves, and the like. The silicon-aluminum molecular sieve has the characteristics of large specific surface area, large pore channel volume, uniform distribution of micropore pore channels, excellent thermal stability, excellent hydrothermal stability and the like, and is widely applied to the fields of petrochemical industry, fine chemistry, environmental protection and the like. Early syntheses of molecular sieves such as LTA, FAU, etc. utilized primarily inorganic cations, whereas organic structure directing agents, typically ammonium cations, are now commonly utilized in syntheses to facilitate molecular sieve assembly and ultimately fill the channels. In recent years, organic structure directing agents have been further expanded to quaternary phosphonium salt molecules, sulfides and metal complexes. Metal complexes were originally used to synthesize aluminophosphate molecular sieves such as AFI, CHA, etc., and in recent years metal complexes have also been successfully used in the synthesis of aluminosilicate molecular sieves, UTD-1 and SSZ-13 have been successfully synthesized.
ITE is the first all-silica molecular sieve with two-dimensional eight-membered ring straight channels found by Corma in 1997. Conventional all-silicon ITE requires 1,3,3,6, 6-pentamethyl-6-azabicyclo [3,2,1 ] s]Octane serves as a template agent, and F ions need to be introduced in the synthesis. Aluminum-containing ITE molecular sieve Mu-14 (Si/Al)>18) To make 1-azatricyclo [4,4,4,0 ]1,6]Tetradecane is used as a template agent. The two templates have complex structures and various synthesis steps.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and provide a method for synthesizing an ITE zeolite molecular sieve by using a cheap nickel-amine complex as a template in one step. In order to solve the technical problem, the solution of the invention is as follows:
the method for synthesizing the ITE zeolite molecular sieve in one step by using the nickel-amine complex as the template agent comprises the following steps:
firstly, dissolving nickel salt in deionized water, and dripping organic amine into the solution after stirring; after (fully) stirring, adding sodium hydroxide solid, and stirring; adding the USY molecular sieve into the solution, stirring for 2-3 hours, then putting into a reaction kettle, and crystallizing for 3-8 days at the temperature of 130-200 ℃; after the reaction is finished, washing the reaction product by deionized water, and drying at 80 ℃ for more than 12 hours to obtain the ITE zeolite molecular sieve;
wherein the addition amount of each raw material satisfies the molar ratio range: SiO 22：Al2O3：Na2O：Ni-R：H218.8-21.7: 1: 5.87-6.85: 1.73-5.4: 587; the Ni-R is a nickel amine complex, wherein Ni is a divalent nickel ion and R is an organic amine complexed with nickel;
the nickel salt is nickel nitrate hexahydrate (nickel nitrate; Chinese medicine, AR); the organic amine is pentaethylenehexamine (Aldrich, AR).
In the invention, the crystallization is carried out at 130 ℃ for 5 days when the material is put into a reaction kettle for crystallization reaction.
In the invention, the addition amount of each raw material satisfies the molar ratio range: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：2.6：587。
In the invention, the molar ratio of silicon to aluminum of the USY molecular sieve is as follows: SiO 22：Al2O3The mole ratio of silicon to aluminum of the prepared ITE zeolite molecular sieve is 21.7: SiO 22：Al2O3＝16。
Compared with the prior art, the invention has the beneficial effects that:
1. the method for synthesizing the ITE zeolite molecular sieve in one step by using the nickel-amine complex as the template agent takes the nickel-amine complex with low price as the template agent, and has the advantages of low crystallization temperature and short crystallization time, thereby greatly reducing the production cost, improving the synthesis efficiency and reducing the potential safety hazard, and having important significance in the field of actual chemical production.
2. The product avoids using poisonous F ions, and can obtain aluminum-rich ITE only under the conditions of an alkali source, a template and USY, and the synthesis efficiency is high.
Drawings
FIG. 1 is an XRD spectrum of synthesized product in example (a) ITE molecular sieve (b) as fired ITE molecular sieve.
FIG. 2 is a scanning electron micrograph of the synthesized product in the example.
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
the following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
First, 0.548g of nickel nitrate was dissolved in 8.15g of deionized water to give a green clear solution, and then 0.465g of pentaethylenehexamine (R) was added to give a violet clear solution. Then adding 0.38g of sodium hydroxide, finally adding 1g of USY, stirring for 2 hours, adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 5 days at 130 ℃ to obtain complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：2.6：587。
The structure of the product is ITE zeolite molecular sieve (figure 1) through X-ray diffraction analysis, and the scanning electron micrograph shows that the synthesized product is in a cuboid block shape, and figure 2 is a Scanning Electron Micrograph (SEM) of the product synthesized by the one-step synthesis route of the nickel-amine complex.
In the present embodiment, stirring for 2 hours is replaced by stirring for 3 hours or stirring for 2.5 hours; the crystallization can be realized by changing the crystallization time from 5 days to 8 days; it can also be achieved that the 12 hours taken for drying are replaced by a time exceeding 12 hours.
Example 2
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 0.548g of nickel nitrate, 8.15g of deionized water, 0.465g of pentaethylenehexamine (R), 0.35g of sodium hydroxide, 1g of USY, and crystallization was completed after 5 days at 130 ℃ and, after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：5.87：2.6：587。
Example 3
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 0.548g of nickel nitrate, 8.15g of deionized water, 0.465g of pentaethylenehexamine (R), 0.4g of sodium hydroxide, 1g of USY, and crystallization was completed after 5 days at 130 ℃ and, after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.52：2.6：587。
Example 4
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 0.548g of nickel nitrate, 8.15g of deionized water, 0.465g of pentaethylenehexamine (R), 0.42g of sodium hydroxide, 1g of USY, and crystallization was completed after 5 days at 130 ℃ and, after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.85：2.6：587。
Example 5
The order of addition and the stirring time for the gel preparation were the same as in example 1, the amounts of the individual materialsRespectively nickel nitrate 0.365g, deionized water 8.15g, pentaethylenehexamine (R)0.31g, sodium hydroxide 0.38g and USY 1g, and crystallizing at 130 ℃ for 5 days to obtain complete crystallization, after the reaction is finished, washing the reaction product with deionized water, and drying at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：1.73：587。
Example 6
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 0.82g of nickel nitrate, 8.15g of deionized water, 0.69g of pentaethylenehexamine (R), 0.38g of sodium hydroxide, 1g of USY, and crystallization was completed after 5 days at 130 ℃ and, after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：3.9：587。
Example 7
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 1.14g of nickel nitrate, 8.15g of deionized water, 0.96g of pentaethylenehexamine (R), 0.38g of sodium hydroxide, 1g of USY, and crystallization was completed after 5 days at 130 ℃ and, after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：5.4：587。
Example 8
The gel preparation was carried out in the same order and for the same stirring time as in example 1, with the amounts of nickel nitrate 0.548g, deionized water 8.15g, pentaethylenehexamine (R)0.465g, sodium hydroxide 0.35g, USY (SiO)2/Al2O318.8)1g, crystallization was completed by crystallization at 130 ℃ for 5 days, and after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝18.8：1：6.2：2.6：587。
Example 9
The gel preparation was carried out in the same order and for the same stirring time as in example 1, with the amounts of nickel nitrate 0.548g, deionized water 8.15g, pentaethylenehexamine (R)0.465g, sodium hydroxide 0.35g, USY (SiO)2/Al2O320.4)1g, crystallization was completed by crystallization at 130 ℃ for 5 days, and after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝20.4：1：6.2：2.6：587。
Example 10
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 0.548g of nickel nitrate, 8.15g of deionized water, 0.465g of pentaethylenehexamine (R), 0.38g of sodium hydroxide, 1g of USY, and crystallization was completed after crystallization at 160 ℃ for 4 days, and after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：2.6：587。
Example 11
The order of addition and the stirring time for gel preparation were the same as in example 1, the amounts of each material were 0.548g of nickel nitrate, 8.15g of deionized water, 0.465g of pentaethylenehexamine (R), 0.38g of sodium hydroxide, 1g of USY, and crystallization was completed after 3 days of crystallization at 200 ℃ and, after completion of the reaction, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours. The molar ratio of the reaction raw materials is as follows: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：2.6：587。
Although the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the technical scope of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (3)
1. A method for synthesizing an ITE zeolite molecular sieve in one step by taking a nickel-amine complex as a template is characterized by comprising the following steps:
firstly, dissolving nickel salt in deionized water, and dripping organic amine into the solution after stirring; after stirring, adding sodium hydroxide solid, and stirring; adding the USY molecular sieve into the solution, stirring for 2-3 hours, then putting into a reaction kettle, and crystallizing for 3-8 days at the temperature of 130-200 ℃; after the reaction is finished, washing the reaction product by deionized water, and drying at 80 ℃ for more than 12 hours to obtain the ITE zeolite molecular sieve;
wherein the addition amount of each raw material satisfies the molar ratio range: SiO 22：Al2O3：Na2O：Ni-R：H218.8-21.7: 1: 5.87-6.85: 1.73-5.4: 587; the Ni-R is a nickel amine complex, wherein Ni is a divalent nickel ion and R is an organic amine complexed with nickel;
the nickel salt is nickel nitrate hexahydrate; the organic amine is pentaethylene hexamine.
2. The method for synthesizing the ITE zeolite molecular sieve by using the nickel-amine complex as the template in one step according to claim 1, wherein the crystallization reaction is carried out in a reaction kettle at a temperature of 130 ℃ for 5 days.
3. The method for synthesizing the ITE zeolite molecular sieve by using the nickel-amine complex as the template in one step according to claim 1, wherein the addition amount of each raw material satisfies the molar ratio range: SiO 22：Al2O3：Na2O：Ni-R：H2O＝21.7：1：6.2：2.6：587。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810175876.8A CN108128785B (en) | 2018-03-02 | 2018-03-02 | Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810175876.8A CN108128785B (en) | 2018-03-02 | 2018-03-02 | Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108128785A CN108128785A (en) | 2018-06-08 |
| CN108128785B true CN108128785B (en) | 2020-02-14 |
Family
ID=62431229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810175876.8A Active CN108128785B (en) | 2018-03-02 | 2018-03-02 | Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108128785B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228357A (en) * | 1998-03-05 | 1999-09-15 | 中国石油化工总公司 | Method for preparing catalyst comprising molecular sieve and noble metal |
| CN101242887A (en) * | 2005-06-23 | 2008-08-13 | 切夫里昂美国公司 | Molecular sieve SSZ-56 composition and synthesis thereof |
| CN102070208A (en) * | 2010-12-06 | 2011-05-25 | 北京科技大学 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
| CN103962168A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Rare-earth ultrastable Y-type molecular sieve and preparation method thereof |
| CN106315614A (en) * | 2016-08-29 | 2017-01-11 | 霍普科技（天津）股份有限公司 | Preparation method of modified Y-type molecular sieve |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8822363B2 (en) * | 2007-11-16 | 2014-09-02 | Exxonmobil Chemical Patents Inc. | Catalyst regeneration process |
-
2018
- 2018-03-02 CN CN201810175876.8A patent/CN108128785B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228357A (en) * | 1998-03-05 | 1999-09-15 | 中国石油化工总公司 | Method for preparing catalyst comprising molecular sieve and noble metal |
| CN101242887A (en) * | 2005-06-23 | 2008-08-13 | 切夫里昂美国公司 | Molecular sieve SSZ-56 composition and synthesis thereof |
| CN102070208A (en) * | 2010-12-06 | 2011-05-25 | 北京科技大学 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
| CN103962168A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Rare-earth ultrastable Y-type molecular sieve and preparation method thereof |
| CN106315614A (en) * | 2016-08-29 | 2017-01-11 | 霍普科技（天津）股份有限公司 | Preparation method of modified Y-type molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108128785A (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5027655B2 (en) | Crystalline aluminosilicate zeolitic composition: UZM-15 | |
| US11318451B2 (en) | Molecular sieves and a process for making molecular sieves | |
| US5840264A (en) | Crystalline inorganic oxide compositions prepared by neutral templating route | |
| US11111153B2 (en) | Process for making molecular sieves | |
| JP4964150B2 (en) | Microporous crystalline zeolitic material (zeolite ITQ-32), process for producing the material and use of the material | |
| US5785946A (en) | Crystalline inorganic oxide compositions prepared by neutral templating route | |
| JP5974170B2 (en) | Method for preparing aluminosilicate zeolite SSZ-33 | |
| JP2016528154A (en) | Beta-type molecular sieve having a hierarchical structure and manufacturing method thereof | |
| US9550684B2 (en) | Process for making molecular sieves | |
| EA000242B1 (en) | Ers-10 zeolite and process for its preparation | |
| JP2016527178A (en) | Zeolite SSZ-70 with increased outer surface area | |
| KR20210062085A (en) | Zeolite synthesis and indicator | |
| US11318450B2 (en) | Molecular sieves and a process for making molecular sieves | |
| CN109071247A (en) | The manufacturing method of MSE type zeolite | |
| AU2002302660B2 (en) | Porous crystalline material (zeolite itq-21), the preparation method thereof and use of the same in the catalytic conversion of organic compounds | |
| CN112209397A (en) | CHA type topological structure zinc-silicon molecular sieve with high zinc-silicon ratio and synthesis method thereof | |
| CN108128785B (en) | Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step | |
| JPS6177618A (en) | Iron-containing silicate having zsm-5 crystal structure, manufacture and use for hydrocarbon conversion reaction | |
| JP2018062450A (en) | Kfi zeolite and method for producing the same | |
| CN111348662A (en) | Ultra-large pore silicate molecular sieve NUD-6 and preparation method thereof | |
| JP5613694B2 (en) | Crystalline aluminosilicate zeolitic composition: UZM-15 | |
| JP5118482B2 (en) | UZM-16: crystalline aluminosilicate zeolitic material | |
| JP4663647B2 (en) | Microporous crystalline zeolite (ITQ-28) and process and use of the zeolite | |
| US10183285B2 (en) | Process for preparing a molecular sieve | |
| JP2019085294A (en) | Gme-type zeolite containing phosphorus and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |