CN106542540A - In the method that line style polyquaternary ammonium salt organic formwork synthesizes 7 zeolite molecular sieves of ERS - Google Patents
In the method that line style polyquaternary ammonium salt organic formwork synthesizes 7 zeolite molecular sieves of ERS Download PDFInfo
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- CN106542540A CN106542540A CN201610936682.6A CN201610936682A CN106542540A CN 106542540 A CN106542540 A CN 106542540A CN 201610936682 A CN201610936682 A CN 201610936682A CN 106542540 A CN106542540 A CN 106542540A
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- ammonium salt
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- polyquaternary ammonium
- molecular sieves
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to molecular sieve preparation method, it is desirable to provide a kind of method for synthesizing 7 zeolite molecular sieves of ERS with line style polyquaternary ammonium salt organic formwork.Including step：Water, silicon source, silicon source, alkali source and template are mixed, is stirred until homogeneous, is subsequently placed in reactor, the product Jing sucking filtration of crystallization, drying obtain the former powder of 7 zeolite molecular sieves of ERS.The present invention can not only greatly simplify the synthesis of organic formwork agent, and synthesize phase region to which and can carry out a wide range of broadening.The difficulty for synthesizing this product is it greatly reduces, is that an excellent basis has been established in the application of this product.Product maintains good degree of crystallinity and purity, with good catalytic reaction activity, provides a kind of new thinking for synthetic zeolite.
Description
Technical field
The invention belongs to molecular sieve preparation method, more particularly to a kind of new line style polyquaternary ammonium salt organic formwork synthesis ERS-
The method of 7 zeolite molecular sieves.
Background technology
Molecular sieve has the structure and big surface area of spaciousness because of which, thus is widely used in catalysis, and ion exchange is inhaled
It is attached with the field such as separate.In the synthesis of modern zeolite molecular sieve, the use of organic formwork agent is greatly facilitated zeolite molecular sieve conjunction
Into the development of chemistry.Quaternary ammonium salt has synthesized panoramic zeolite as a big class template of synthesis zeolite
Structure, such as Beta, ZSM-5, ERS-7 etc..Wherein, ERS-7 is a kind of zeolite of one-dimensional octatomic ring structure, by Millini etc.
People's reported first.The generally synthesis of ERS-7 needs to use N, N- dimethyl hydrogen oxyl ammoniums this organic formwork agents, in zeolite
Not only synthesize template process complexity (ion exchange being needed into hydrogen-oxygen type) in preparation process, and synthesize the phase of ERS-7 zeolites
Area is very narrow, and (only feed intake SiO2/Al2O3Pure phase can just be obtained for 25), it is easy to there is the generation of stray crystal.
Therefore, the method that Development of Novel simply synthesizes ERS-7 zeolites, while enabling its synthesis phase region to widen significantly
Have very important significance.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided one kind is with line style polyquaternary ammonium salt
Organic formwork synthesizes the method for ERS-7 zeolite molecular sieves.
To solve technical problem, the solution of the present invention is：
A kind of method for synthesizing ERS-7 zeolite molecular sieves with line style polyquaternary ammonium salt organic formwork is provided, is comprised the steps：
Water, silicon source, silicon source, alkali source and template are mixed, is stirred until homogeneous, is subsequently placed in reactor, 130～
200 DEG C of crystallization 1d～10d, product sucking filtration, drying, that is, obtain the former powder of ERS-7 zeolite molecular sieves；
The template is line style polyquaternary ammonium salt, and its structural formula is shown below：
The addition for controlling each reaction raw materials makes its molar ratio range be：15～50H2O∶SiO2: 0.0025～
0.067Al2O3: 0.1～0.5 (Na2O or K2O): 0.02～0.08 template.
In the present invention, source of aluminium is aluminum sulfate or sodium metaaluminate；Silicon source is the Ludox that dioxide-containing silica is 30%；
Alkali source is potassium hydroxide or sodium hydroxide.
Present invention also offers the method for preparing the line style polyquaternary ammonium salt template for the synthesis of ERS-7 zeolite molecular sieves,
Including step：Isosorbide-5-Nitrae-dibromobutane and N, N, N, N- tetramethyl-Putriscine are weighed for 1: 1 according to mol ratio, be dissolved in second
In alcohol, then 12h is reacted under conditions of under agitation with 80 DEG C of backflows；After reaction terminates, ether is added in product, produced
Raw white solid precipitation Jing is filtered, is dried, and obtains line style polyquaternary ammonium salt template.
Compared with prior art, the beneficial effects of the present invention is：
1st, the present invention can not only greatly simplify the synthesis of organic formwork agent, and synthesize phase region to which and can carry out very big model
The broadening enclosed.The difficulty for synthesizing this product is it greatly reduces, is that an excellent basis has been established in the application of this product.
2nd, compared with prior art, the product that prepared by the present invention maintains good degree of crystallinity and purity, with good
Catalytic reaction activity.
3rd, by the design to organic formwork agent and exploitation come synthesis zeolite, this provides the present invention for synthetic zeolite
A kind of new thinking.
Description of the drawings
Fig. 1：The XRD spectra of the ERS-7 zeolites of line style polyquaternary ammonium salt organic formwork agent synthesis.
Fig. 2：The ERS-7 zeolite stereoscan photograph of line style polyquaternary ammonium salt organic formwork agent synthesis.
Specific embodiment
Embodiment 1：The synthesis of line style polyquaternary ammonium salt organic formwork agent
According to Isosorbide-5-Nitrae-dibromobutane and N, N, N, N- tetramethyl-Putriscine mol ratio be 1: 1, weigh 10g Isosorbide-5-Nitraes-
Dibromobutane and 15g N, N, N, N- tetramethyl-Putriscine are dissolved in 50ml ethanol, and arranging temperature is carried out back for 80 DEG C
Stream, stirs 12h, after reaction terminates, in product adds ether to precipitate with regard to producible white solid, and Jing is filtered, is dried
Required template is obtained.
Embodiment 2：Line style polyquaternary ammonium salt organic formwork agent synthesizes ERS-7 zeolites
By 8.12g H2O, 0.065g NaAlO2, 0.3g NaOH, 0.65g organic formwork agents (T, structure such as Fig. 1) and
The Ludox of 3.32g dioxide-containing silicas 30% is placed in beaker and stirs, and this gel is added to politef then
In stainless steel cauldron, 160 DEG C of crystallization 5d are complete crystallization, and product sucking filtration obtains product after drying.Reaction raw materials with such as
Under：
35H2O:SiO2:0.017Al2O3:0.23Na2O:0.04T
Jing X-ray diffraction analysis its structures is the ERS-7 zeolite molecular sieves (Fig. 2) for belonging to ESV, and passes through scanning electron microscope
Photo can be seen that synthesized product pellet size than more uniform and purity is high, as shown in Figure 3.
Embodiment 3：Line style polyquaternary ammonium salt organic formwork agent high―temperature nuclei ERS-7 zeolites
By 12.67g H2O, 0.028g Al2(SO4)3·18H2O, 0.13g NaOH, 0.65g organic formwork agent (T, structure
Such as Fig. 1) and the Ludox of 3.32g dioxide-containing silicas 30% be placed in beaker and stir, then this gel is added to
In politef stainless steel cauldron, 200 DEG C of crystallization 1d are complete crystallization, and product sucking filtration obtains product after drying.Reaction is former
The proportioning of material is as follows：
50H2O:SiO2:0.0025Al2O3:0.1Na2O:0.04T
Embodiment 4：Line style polyquaternary ammonium salt organic formwork agent low temperature synthesizes ERS-7 zeolites
By 2.17g H2O, 0.26g NaAlO2, 0.54g NaOH, 0.33g organic formwork agents (T, structure such as Fig. 1) and
The Ludox of 3.32g dioxide-containing silicas 30% is placed in beaker and stirs, and this gel is added to politef then
In stainless steel cauldron, 130 DEG C of crystallization 10d are complete crystallization, and product sucking filtration obtains product after drying.The proportioning of reaction raw materials
It is as follows：
15H2O:SiO2:0.067Al2O3:0.5Na2O:0.02T
Embodiment 5：Line style polyquaternary ammonium salt organic formwork agent synthesizes ERS-7 zeolites
By 8.12g H2O, 0.028g Al2(SO4)3·18H2(T, structure is as schemed for O, 0.35g KOH, 1.3g organic formwork agent
1) this gel is added to into poly- four then and the Ludox of 3.32g dioxide-containing silicas 30% is placed in beaker and stirs,
In fluorothene stainless steel cauldron, 160 DEG C of crystallization 5d are complete crystallization, and product sucking filtration obtains product after drying.Reaction raw materials
Proportioning is as follows：
35H2O:SiO2:0.025Al2O3:0.16K2O:0.08T
Embodiment 6：Line style polyquaternary ammonium salt organic formwork agent synthesizes ERS-7 zeolites
By 8.12g H2O, 0.065g NaAlO2, 0.6g NaOH, 0.65g organic formwork agents (T, structure such as Fig. 1) and
The Ludox of 3.32g dioxide-containing silicas 30% is placed in beaker and stirs, and this gel is added to politef then
In stainless steel cauldron, 160 DEG C of crystallization 5d are complete crystallization, and product sucking filtration obtains product after drying.Reaction raw materials with such as
Under：
35H2O:SiO2:0.017Al2O3:0.47Na2O:0.04T
The above, is only several case study on implementation of the present invention, any pro forma restriction is not done to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, but is not limited to the present invention, any to be familiar with this professional skill
Art personnel, in the range of without departing from technical solution of the present invention, when the structure and technology contents using the disclosure above makes a little
Change or be modified to the equivalence enforcement case of equivalent variations.But every content without departing from technical solution of the present invention, foundation
Any simple modification, equivalent variations and modification that the technical spirit of the present invention is made to above case study on implementation, still belong to the present invention
In the range of technical scheme.
Claims (3)
1. it is a kind of with line style polyquaternary ammonium salt organic formwork synthesize ERS-7 zeolite molecular sieves method, it is characterised in that including following
Step：
Water, silicon source, silicon source, alkali source and template are mixed, is stirred until homogeneous, is subsequently placed in reactor, at 130～200 DEG C
Crystallization 1d～10d, product sucking filtration, drying, that is, obtain the former powder of ERS-7 zeolite molecular sieves；
The template is line style polyquaternary ammonium salt, and its structural formula is shown below：
The addition for controlling each reaction raw materials makes its molar ratio range be：15～50H2O∶SiO2: 0.0025～0.067Al2O3∶
0.1～0.5 (Na2O or K2O): 0.02～0.08 template.
2. method according to claim 1, it is characterised in that source of aluminium is aluminum sulfate or sodium metaaluminate；Silicon source is two
Silica content is 30% Ludox；Alkali source is potassium hydroxide or sodium hydroxide.
3. the method for preparing the line style polyquaternary ammonium salt template for the synthesis of ERS-7 zeolite molecular sieves, it is characterised in that including step
Suddenly：Isosorbide-5-Nitrae-dibromobutane and N, N, N, N- tetramethyl-Putriscine are weighed for 1: 1 according to mol ratio, dissolved in ethanol, so
12h is reacted under conditions of under agitation with 80 DEG C of backflows afterwards；After reaction terminates, add ether in product, generation it is white
Color solid precipitation Jing is filtered, is dried, and obtains line style polyquaternary ammonium salt template.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101489648A (en) * | 2006-06-26 | 2009-07-22 | 艾尼股份公司 | Process and zeolitic materials for the separation of gases |
| US20100298117A1 (en) * | 2007-11-16 | 2010-11-25 | Doron Levin | Catalyst Regeneration Process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101489648A (en) * | 2006-06-26 | 2009-07-22 | 艾尼股份公司 | Process and zeolitic materials for the separation of gases |
| CN103626204A (en) * | 2006-06-26 | 2014-03-12 | 艾尼股份公司 | Process and zeolitic materials for the separation of gases |
| US20100298117A1 (en) * | 2007-11-16 | 2010-11-25 | Doron Levin | Catalyst Regeneration Process |
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