CN108128785A - Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves - Google Patents
Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves Download PDFInfo
- Publication number
- CN108128785A CN108128785A CN201810175876.8A CN201810175876A CN108128785A CN 108128785 A CN108128785 A CN 108128785A CN 201810175876 A CN201810175876 A CN 201810175876A CN 108128785 A CN108128785 A CN 108128785A
- Authority
- CN
- China
- Prior art keywords
- nickel
- ite
- template
- molecular sieves
- zeolite molecular
- 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.)
- Granted
Links
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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is standby the present invention relates to system with molecular sieve for preparing, it is desirable to provide using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves.Method of this kind using nickel amine complex as template one-step synthesis ITE zeolite molecular sieves includes step：Nickel salt is dissolved in deionized water first, stirs in backward solution and organic amine is added dropwise, adds sodium hydrate solid and USY molecular sieve, after stirring, is fitted into crystallization in reaction kettle；After the completion of reaction, reaction product is washed with deionized, and 12 hours or more dry at 80 DEG C, obtains ITE zeolite molecular sieves.The present invention is using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves, using cheap nickel amine complex as template, and crystallization temperature is low needed for the present invention, crystallization time is short, greatly reduce production cost, it improves combined coefficient and reduces security risk, be of great significance in practical chemical production field.
Description
Technical field
The present invention relates to molecular sieve preparation fields, are more particularly to boiled by template one-step synthesis ITE of nickel amine complex
The method of stone molecular sieve.
Background technology
Zeolite molecular sieve material, including Si-Al molecular sieve, phosphate aluminium molecular sieve etc..Si-Al molecular sieve, due to its specific surface area
Greatly, the features such as duct volume is big, and micropore canals are distributed uniform and excellent thermal stability and hydrothermal stability, in oil
The fields such as work, fine chemistry and environmental protection have a wide range of applications.The synthesis of the molecular sieve of early stage such as LTA, FAU etc. are mainly sharp
Organic structure directing agent, usually ammonium cation are usually utilized with inorganic cation and now in synthesis, to promote molecular sieve
It assembles and finally fills duct.In recent years, Organic structure directing agent was further extended to quaternary phosphonium molecules of salt, sulfide and gold
Belong to complex compound.Metal complex is initially used to synthesizing P-Al molecular sieve such as AFI, CHA etc., and metal complex was also by success in recent years
It applies in Si-Al molecular sieve synthesis, successfully synthesizes UTD-1 and SSZ-13.
ITE is first silica zeolite with two-dimentional octatomic ring straight hole road that Corma had found in 1997.Traditional
Total silicon ITE is needed with 1,3,3,6,6- pentamethyl -6- azabicyclos [3,2,1] octane as template, and is needed in synthesizing
Introduce F ion.ITE molecular sieve Mu-14 (Si/Al containing aluminium>It 18) will be with 1- aza-tricycles [4,4,4,01,6] tetradecane be template
Agent.The two templates are complicated, and synthesis step is various.
Invention content
It is a primary object of the present invention to overcome deficiency of the prior art, provide it is a kind of using cheap nickel amine complex as
The method of template one-step synthesis ITE zeolite molecular sieves.In order to solve the above technical problems, the solution of the present invention is：
A kind of method using nickel amine complex as template one-step synthesis ITE zeolite molecular sieves is provided, is specifically included following
Step：
Nickel salt is dissolved in deionized water first, stirs in backward solution and organic amine is added dropwise；After (abundant) stirring, then add
Enter sodium hydrate solid, stir；USY molecular sieve is added in into solution again, after stirring 2~3 hours, is fitted into reaction kettle, at 130 DEG C
Crystallization 3~8 days at a temperature of~200 DEG C；After the completion of reaction, reaction product is washed with deionized, and at 80 DEG C dry 12
Hour or more, obtain ITE zeolite molecular sieves；
Wherein, the additive amount of each raw material meets molar ratio range：SiO2：Al2O3：Na2O：Ni-R：H2O=18.8~21.7：
1：5.87~6.85：1.73~5.4：587；The Ni-R is nickel amine complex, and wherein Ni is the nickel ion of divalent, and R is and nickel
The organic amine of complexing；
The nickel salt uses six water nickel nitrate (nickel nitrates；Traditional Chinese medicines, AR)；Organic amine using pentaethylene hexamine (aldrich,
AR)。
In the present invention, when being fitted into progress crystallization in reaction kettle, using crystallization 5 days at a temperature of 130 DEG C.
In the present invention, the additive amount of each raw material meets molar ratio range：SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：
1：6.2：2.6：587.
In the present invention, the molar ratio of the silica alumina ratio of the USY molecular sieve is：SiO2：Al2O3=21.7, ITE obtained
The molar ratio of the silica alumina ratio of zeolite molecular sieve is：SiO2：Al2O3=16.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the present invention is using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves, with cheap nickel amine
Complex compound is template, and crystallization temperature is low needed for the present invention, and crystallization time is short, greatly reduces production cost, is improved
Combined coefficient and security risk is reduced, be of great significance in practical chemical production field.
2nd, this product avoids having used toxic F ion, i.e. available only under conditions of alkali source, template and USY
The ITE of rich aluminium, combined coefficient are high.
Description of the drawings
Fig. 1 is the ITE molecular sieves after XRD spectra (a) the ITE molecular sieves (b) of sintetics in embodiment are burnt.
Fig. 2 is the stereoscan photograph of sintetics in embodiment.
Specific embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
The following examples can make the professional technician of this profession that the present invention be more fully understood, but not with any side
The formula limitation present invention.
Embodiment 1
First, 0.548g nickel nitrates are dissolved in 8.15g deionized waters, 0.465g is added in after obtaining the clear solution of green
Pentaethylene hexamine (R), obtains the clear solution of purple.Then 0.38g sodium hydroxides are added in, are eventually adding 1g USY, stirring 2 is small
When after reaction raw materials are added in polytetrafluoroethylene (PTFE) stainless steel cauldron, 130 DEG C of crystallization 5 days i.e. complete crystallization, after the completion of reaction,
Reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：SiO2：Al2O3：
Na2O：Ni-R：H2O=21.7：1：6.2：2.6：587.
Through X-ray diffraction analysis, its structure is ITE zeolite molecular sieves (Fig. 1), and can be seen by stereoscan photograph
Go out synthesized product and the scanning electron microscope that cuboid bulk attached drawing 2 is nickel amine complex one-step synthesis method route sintetics is presented
Photo (SEM).
In the present embodiment, it stirs and is substituted within 2 hours stirring 3 hours or stirs 2.5 hours, can realize；Crystallization 5 days
It changes crystallization into 8 days, can also realize；It dry 12 hours taken times being substituted for more than 12 hours, can also realize.
Embodiment 2
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.35g, USY 1g, 130 DEG C of crystallization 5 days i.e. complete crystallization, instead
After the completion of answering, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：5.87：2.6：587.
Embodiment 3
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.4g, USY 1g, 130 DEG C of crystallization 5 days i.e. complete crystallization, reaction
After the completion, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.52：2.6：587.
Embodiment 4
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.42g, USY 1g, 130 DEG C of crystallization 5 days i.e. complete crystallization, instead
After the completion of answering, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.85：2.6：587.
Embodiment 5
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.365g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.31g, sodium hydroxide 0.38g, USY 1g, 130 DEG C of crystallization 5 days i.e. complete crystallization, reaction
After the completion, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.2：1.73：587.
Embodiment 6
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.82g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.69g, sodium hydroxide 0.38g, USY 1g, 130 DEG C of crystallization 5 days i.e. complete crystallization, reaction
After the completion, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.2：3.9：587.
Embodiment 7
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 1.14g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.96g, sodium hydroxide 0.38g, USY 1g, 130 DEG C of crystallization 5 days i.e. complete crystallization, reaction
After the completion, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.2：5.4：587.
Embodiment 8
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.35g, USY (SiO2/Al2O3=18.8) 1g, 130 DEG C of crystallization 5
It is complete crystallization, and after the completion of reaction, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.Reaction raw materials
Mol ratio it is as follows：SiO2：Al2O3：Na2O：Ni-R：H2O=18.8：1：6.2：2.6：587.
Embodiment 9
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.35g, USY (SiO2/Al2O3=20.4) 1g, 130 DEG C of crystallization 5
It is complete crystallization, and after the completion of reaction, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.Reaction raw materials
Mol ratio it is as follows：SiO2：Al2O3：Na2O：Ni-R：H2O=20.4：1：6.2：2.6：587.
Embodiment 10
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.38g, USY 1g, 160 DEG C of crystallization 4 days i.e. complete crystallization, instead
After the completion of answering, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.2：2.6：587.
Embodiment 11
For charging sequence and mixing time prepared by gel with example 1, the amount of each material is respectively nickel nitrate 0.548g, go from
Sub- water 8.15g, pentaethylene hexamine (R) 0.465g, sodium hydroxide 0.38g, USY 1g, 200 DEG C of crystallization 3 days i.e. complete crystallization, instead
After the completion of answering, reaction product is washed with deionized, and 12 hours dry at 80 DEG C.The mol ratio of reaction raw materials is as follows：
SiO2：Al2O3：Na2O：Ni-R：H2O=21.7：1：6.2：2.6：587.
The above is only several case study on implementation of the present invention, and limitation in any form is not done to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, it is not limited to the present invention, any skill for being familiar with this profession
Art personnel, without departing from the scope of the present invention, when structure and technology contents using the disclosure above make it is a little
Change or be modified to the equivalence enforcement cases of equivalent variations.But every content without departing from technical solution of the present invention, foundation
Any simple modification, equivalent change and modification that the technical spirit of the present invention makees more than case study on implementation still belongs to the present invention
In the range of technical solution.
Claims (3)
- It is 1. a kind of using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves, which is characterized in that specifically include Following step：Nickel salt is dissolved in deionized water first, stirs in backward solution and organic amine is added dropwise；After agitated, sodium hydroxide is added Solid, stirring；USY molecular sieve is added in into solution again, after stirring 2~3 hours, is fitted into reaction kettle, at 130 DEG C~200 DEG C At a temperature of crystallization 3~8 days；After the completion of reaction, reaction product is washed with deionized, and 12 hours or more dry at 80 DEG C, Obtain ITE zeolite molecular sieves；Wherein, the additive amount of each raw material meets molar ratio range：SiO2：Al2O3：Na2O：Ni-R：H2O=18.8~21.7：1： 5.87~6.85：1.73~5.4：587；The Ni-R is nickel amine complex, and wherein Ni is the nickel ion of divalent, and R is and nickel network The organic amine of conjunction；The nickel salt uses six water nickel nitrates；Organic amine uses pentaethylene hexamine.
- 2. it is according to claim 1 a kind of using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves, It is characterized in that, when being fitted into progress crystallization in reaction kettle, using crystallization 5 days at a temperature of 130 DEG C.
- 3. it is according to claim 1 a kind of using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves, It is characterized in that, the additive amount of each raw material meets molar ratio range：SiO2：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 true CN108128785A (en) | 2018-06-08 |
| CN108128785B 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 (6)
| 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 |
| US20100298117A1 (en) * | 2007-11-16 | 2010-11-25 | Doron Levin | Catalyst Regeneration Process |
| 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 |
-
2018
- 2018-03-02 CN CN201810175876.8A patent/CN108128785B/en active Active
Patent Citations (6)
| 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 |
| US20100298117A1 (en) * | 2007-11-16 | 2010-11-25 | Doron Levin | Catalyst Regeneration Process |
| 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 |
|---|---|
| CN108128785B (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9962688B2 (en) | Method for synthesizing molecular sieve SSZ-13 | |
| CN106517240B (en) | The method for synthesizing flakes ZSM-12 zeolite molecular sieves with single small molecule organic formwork agent | |
| CN107892309B (en) | A kind of preparation method of super big hole silicate molecular sieve | |
| CN102311124B (en) | Method for preparing Silicalite-1/ZSM-5 composite molecular sieve | |
| CN109311687A (en) | The method of continuous synthetic zeolite material | |
| CN107777701A (en) | Molecular sieves of SCM 12 and preparation method thereof | |
| EP0142348B1 (en) | Process for preparing a zeolite of the l type using organic templates | |
| CN109704365A (en) | A kind of fast synthesis method of small crystal grain molecular sieve and application | |
| CN108751221A (en) | The method of the floride-free synthesis Silicon-rich SSZ-13 zeolite molecular sieves of crystal seed auxiliary | |
| CN104229826A (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN106698456A (en) | Method for synthesizing aluminum-containing ITQ-13 molecular sieve with one-step method by linearpoly quaternary ammonium base organic template | |
| CN101519216B (en) | Method for synthesizing boron-containing molecular sieve | |
| CN106564909B (en) | A kind of preparation method of ZSM-12 molecular sieve | |
| CN109279621B (en) | Method for synthesizing silicon-based zeolite molecular sieve by adopting general ionothermal method | |
| CN108217683B (en) | Method for synthesizing silicon-rich ZSM-23 zeolite molecular sieve by adopting seed crystal guiding method | |
| CN107934982B (en) | A kind of macropore silicate molecular sieve and preparation method thereof | |
| CN108545758A (en) | The method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve in strong basicity system | |
| CN106276966B (en) | A kind of alkali metal-free system synthetic method of transgranular phosphorous ZSM-5 molecular sieve | |
| CN100390060C (en) | High-silica octagonal zeolite and synthesizing method thereof | |
| CN112209397A (en) | CHA type topological structure zinc-silicon molecular sieve with high zinc-silicon ratio and synthesis method thereof | |
| CN108128785A (en) | Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves | |
| CN106517229B (en) | The method that hydrothermal synthesis method prepares nano-sheet SAPO-11 molecular sieves | |
| CN107250041A (en) | The pentasil zeolites of high mesoporous surface area, low Si/Al ratio | |
| CN106673001A (en) | Synthesis method of ZSM-11 molecular sieve and ZSM-11 molecular sieve synthesized through same | |
| CN109231236B (en) | Synthesis method of spherical SSZ-13 zeolite molecular sieve |
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 |