CN110078094A - A kind of preparation method of the MWW structure molecular screen of interlayer expansion layer - Google Patents
A kind of preparation method of the MWW structure molecular screen of interlayer expansion layer Download PDFInfo
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- CN110078094A CN110078094A CN201910299243.2A CN201910299243A CN110078094A CN 110078094 A CN110078094 A CN 110078094A CN 201910299243 A CN201910299243 A CN 201910299243A CN 110078094 A CN110078094 A CN 110078094A
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- 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
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Abstract
The invention discloses the preparation methods that a kind of interlayer expands the MWW structure molecular screen of layer, by boracic there is MWW structure stratiform presoma and acid solution to be lauched heat treatment in certain pressure and temperature condition and obtain.The MWW structure molecular screen that interlayer expands layer can be obtained by the method for carrying out mild hydro-thermal process to MWW structure stratiform presoma by the present invention, process is simple, it is easy to operate, process is stablized, it is easy to industrialized production, while also expanding layer for the interlayer of the layer structure molecular sieve of other topological structures and providing new approaches.
Description
Technical field
The invention belongs to inorganic chemical synthesis technical and Application in Chemical Engineering field, it is related to a kind of with MWW structure molecular screen
Preparation method and application are exactly related to a kind of preparation method of MWW structure molecular screen for expanding layer with interlayer.
Background technique
MWW structure molecular screen is a kind of molecular sieve with hole between 10 Yuans circular layers, 12 Yuans annular distance caves and supercage hole series structure
(Science, 1994,264:1910).Catalytic active center aluminium atom is introduced into MWW framework of molecular sieve, forms MCM-22 molecule
It sieves (US 4,954,325).Due to special cellular structure, as acidic catalytic activity component, MCM-22 molecular sieve shows excellent
Different catalytic cracking (US 4,983,276), alkene and benzene alkylation (US 4,992,606, US 4,992,615, US 5,334,
795) catalytic performances such as.The technique for being used for alkene and benzene alkylation reaction as acidic catalytic activity component, MWW structure molecular screen
It has industrialized.Transition metal titanium atom is introduced into MWW framework of molecular sieve, Ti-MWW molecular sieve is formed, passes through hydrothermal crystallization method
Directly synthesis is 2000 at first in Chemistry Letters (Chemistry Letters, 2000:774-775) open report, in hydrocarbon
The selective oxidation field of class shows excellent catalytic performance, such as ammoxidation of cyclohexanone preparing cyclohexanone oxime
(CN20051002447.3), epoxidation of propylene propylene oxide (CN200480015961.4, CN201480052333.7,
) etc. CN201810222684.8 it is had excellent performance in reaction.Therefore, MWW structure molecular screen is aobvious in the fields such as oil refining and petrochemical industry
Wide application prospect is shown.However, being reacted since MWW structure molecular screen interlayer is 10 Yuans ring openings in macromolecule reactant
In limited by steric hindrance and be difficult to play its catalytic action.Therefore, researchers attempt MWW structure molecular screen interlayer
10 Yuans ring openings carry out interlayer and expand layer, to expand its opening, to achieve the purpose that make full use of its reaction compartment.
After Weibin Fan etc. has MWW structure molecular sieve containing titanium stratiform presoma using acid processing, obtained by roasting
Interlayer expands the MWW structure titanium silicon molecular sieve (Ti-YNU-1) of layer, and structure elucidation shows that it is similar to MWW molecular sieve precursor structure
Stratiform Titanium Sieve Molecular Sieve (German applied chemistry, Angew. Chem. Int. Ed. 2004,43,236-240): by piperidines and
Butyl titanate is dissolved in deionized water, then be added boron removal MWW molecular sieve, later in 170 DEG C hydro-thermal process 5 days, then will
Obtained product is in 2M HNO3Reflow treatment in solution finally roasts 10 hours at 550 DEG C and obtains product.Its technology of preparing is special
Sign is that the crystallization product for obtaining hydrothermal crystallizing is in 2M HNO3Reflow treatment in solution.It is found that at reflux in the technology
Reason does not refer to the pressure of reflow process, according to its process description, as opens wide system reflow treatment.In addition the technology
The disadvantage is that titanium source is introduced by way of post-processing boron removal MWW molecular sieve, and the formation of interlayer expansion layer Titanium Sieve Molecular Sieve only exists
It can just be obtained in the case that Ti content is very low, gel mole Si/Ti≤50.
Peng Wu etc. developed between a kind of molecular sieve layer expand layer method (American Chemical Society,
J.Am.Chem.Soc.2008,130,8178-8187), pass through organic-silylation reagent (Me2Si(OEt)2) and lamellar zeolite
Presoma obtains the molecular sieve (IEZ) that interlayer expands layer by dry, roasting later in an acidic solution in 100 DEG C of reflow treatments,
Such as MWW, FER, CDO have layer structure molecular sieve, and interlayer expansion layer can be carried out by the technology and is obtained containing different hetero atoms
The interlayer of (such as aluminium, titanium) expands layer molecular sieve.Its technology of preparing is characterized in that, organic-silylation reagent is used, wherein flowing back
Processing does not refer to the pressure of reflow process yet, according to its process description, as opens wide system reflow treatment.In addition the technology
The shortcomings that be that need to use organic-silylation reagent.
Avelino Corma etc. developed between a kind of molecular sieve layer expand layer method (materials chemistry,
Chem.Mater.2012,24,4371-4375), by pure silicon molecular sieve ITQ-1 with MWW and organic titanium source in template
Under the action of first hydrothermal synthesis obtain stratiform presoma, then by stratiform presoma in an acidic solution in 100 DEG C of reflow treatments,
The molecular sieve (Ti-MWW-exp) that interlayer expands layer is obtained by dry, roasting later.Its technology of preparing is characterized in that, by hydro-thermal crystalline substance
Change obtained crystallization product in 2M HNO3In 100 DEG C of reflow treatments in solution.It is found that the reflow treatment in the technology does not also mention
And the pressure of reflow process as opens wide system reflow treatment according to its process description.In addition the shortcomings that technology is to need
Pure silicon molecular sieve ITQ-1 of the synthesis with MWW first.
Summary of the invention
The object of the present invention is to provide the preparation methods that a kind of interlayer expands the MWW structure molecular screen of layer, by with MWW
Stratiform presoma and the acid solution hydro-thermal process under certain temperature and certain pressure have reached and have simply prepared interlayer expansion layer
Purpose with MWW structure molecular screen, solution prior art preparation process is complicated, content of heteroatoms is low, need to use organosilan
The disadvantages of changing reagent and problem.This method step is simple and convenient to operate, and is easy to industrial applications.
Realizing the specific technical solution of the object of the invention is:
A kind of interlayer expands the preparation method of the MWW structure molecular screen of layer, this method comprising the following specific steps
The preparation of first step reaction mixture
There to be a MWW structure stratiform presoma and concentration be 0.1 ~ 5 mol/L acid solution according to weight ratio is 1: (5~50)
Reaction mixture is prepared, described is boracic with MWW structure stratiform presoma with MWW structure stratiform presoma；It is described
Acid be at least one of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid；
Second step hydro-thermal process
To be transferred in closed reactor through reaction mixture made from upper step, in temperature be 100~120 DEG C, pressure be 0.05 ~
Hydro-thermal process 10~48 hours under the conditions of 1MPa are filtered, washed, dry and roast by conventional, obtain the interlayer and expand layer
MWW structure molecular screen.
Compared with existing technology, the present invention has following remarkable advantage:
1, effectively solve prior art preparation interlayer expand layer MWW structure molecular screen process it is complicated, content of heteroatoms is low, need using
The disadvantages of organic-silylation reagent and problem.
2, synthesis process is simple, easy to operate, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the XRD spectrum of Ti-MWW molecular sieve, the MWW structure molecular sieve containing titanium of interlayer expansion layer and Ti-YNU-1 molecular sieve
Figure；In figure, A is the XRD spectra for the Ti-MWW molecular sieve that embodiment 2 is prepared, and B is that the interlayer that embodiment 4 is prepared expands
The XRD spectra of the MWW structure molecular sieve containing titanium of layer, C is the XRD spectrum for the Ti-YNU-1 molecular sieve that embodiment 3 is prepared in figure
Figure.
It can be seen that Ti-MWW molecular sieve is typically to have MWW structure titanium silicon molecular sieve, Ti-YNU-1 is typical
The MWW structure titanium silicon molecular sieve of interlayer expansion layer (001 and 002 crystallographic plane diffraction peak is obvious)；The MWW structure titaniferous that the present invention obtains point
The XRD spectra of son sieve is similar with the XRD spectra of Ti-YNU-1, illustrates that there is the interlayer similar with Ti-YNU-1 to expand layer structure for it,
The MWW structure molecular sieve containing titanium that interlayer expands layer is obtained.
Specific embodiment
The operating procedure of all embodiments according to the above technical scheme is operated.
Embodiment 1
The preparation of Ti-MWW molecular sieve stratiform presoma.According to document (Chemistry Letters, Chemistry Letters, 2000:
774-775) prepare Ti-MWW molecular sieve stratiform presoma.TiO in titanium source in molar ratio2: the SiO in silicon source2: in boron source
B2O3: organic formwork agent: H2O is that 0.05:1:0.67:1.4:19 prepares reaction mixture, and the titanium source is butyl titanate,
The silicon source is smoke silica gel, and the boron source is boric acid, and the organic formwork agent is piperidines, the reaction mixture
In 170 DEG C hydrothermal crystallizing 7 days, being filtered, washed, dry through conventional, obtaining the Ti-MWW molecular sieve stratiform presoma of boracic
(Si/Ti=20)。
The preparation of MCM-22 molecular sieve stratiform presoma.The preparation of preparation process and Ti-MWW molecular sieve stratiform presoma
Cheng Xiangtong obtains the MCM-22 molecular sieve stratiform of boracic the difference is that changing titanium source (butyl titanate) into silicon source (aluminum sulfate)
Presoma (Si/Al=20).
The preparation of ERB-1 molecular sieve stratiform presoma.The preparation of preparation process and Ti-MWW molecular sieve stratiform presoma
Cheng Xiangtong obtains the ERB-1 molecular sieve stratiform presoma (Si/B=11) of boracic the difference is that not introducing titanium source in synthesis process.
Embodiment 2
The preparation of Ti-MWW molecular sieve.According to according to document (Chemistry Letters, Chemistry Letters, 2000:774-775),
The nitric acid solution of Ti-MWW molecular sieve stratiform presoma and 2mol/L obtained in embodiment 1 are made into instead according to weight ratio 1:50
Answer mixture, handle 20 hours in unlimited system atmospheric pressure reflux in 100 DEG C, later by it is conventional be filtered, washed, dry and
550 DEG C roast 6 hours, obtain Ti-MWW molecular sieve, XRD spectra is as shown in Figure 1A, with document (Chemistry Letters,
Chemistry Letters, 2000:774-775) report it is consistent, it is known that its be typical Ti-MWW molecular sieve.
Embodiment 3
The preparation of Ti-YNU-1 molecular sieve.According to document (German applied chemistry, Angew. Chem. Int. Ed. 2004,43,
236-240) prepare Si/Ti molar ratio be 50 MWW molecular sieve stratiform presoma, later by molecular sieve stratiform presoma with
The nitric acid solution of 2mol/L is made into reaction mixture according to weight ratio 1:50, handles 20 in unlimited system atmospheric pressure reflux in 100 DEG C
Hour, it is filtered, washed, dries and 550 DEG C roast 6 hours by conventional, obtain Ti-YNU-1 molecular sieve, XRD spectra is such as
Shown in Fig. 1 C, with document (German applied chemistry, Angew. Chem. Int. Ed. 2004,43,236-240) report one
It causes, it is known that it is the MWW structure titanium silicon molecular sieve that typical interlayer expands layer.
Embodiment 4
The preparation of first step reaction mixture
The Ti-MWW molecular sieve stratiform presoma of the boracic that embodiment 1 is prepared and concentration be 2 mol/L acid solutions by
Reaction mixture is prepared for 1: 50 according to weight ratio, the acid is nitric acid；
Second step hydro-thermal process
It will be transferred in closed reactor through reaction mixture made from upper step, and by being filled with nitrogen, reach pressure in reaction kettle
To 0.3MPa, in temperature be 100 DEG C hydro-thermal process 20 hours, be filtered, washed, dry and 550 DEG C of roastings 6 are small by conventional
When, obtain zeolite product.
The XRD spectra of products obtained therefrom is as shown in figure 1 shown in B, it is known that it has similar XRD spectra, explanation with Ti-YNU-1
There is the interlayer similar with Ti-YNU-1 to expand layer structure to get the MWW structure molecular sieve containing titanium that interlayer expands layer has been arrived for it.
Embodiment 5
Except for the following differences, remaining is with embodiment 4 for implementation process:
Second step hydro-thermal process
It will be transferred in closed reactor through reaction mixture made from upper step, and by being filled with nitrogen, reach pressure in reaction kettle
To 0.1MPa, in temperature be 110 DEG C hydro-thermal process 12 hours.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MWW structure molecular sieve containing titanium that interlayer expands layer.
Embodiment 6
Except for the following differences, remaining is with embodiment 4 for implementation process:
Second step hydro-thermal process
It will be transferred in closed reactor through reaction mixture made from upper step, and by being filled with nitrogen, reach pressure in reaction kettle
To 0.5MPa, in temperature be 105 DEG C hydro-thermal process 36 hours.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MWW structure molecular sieve containing titanium that interlayer expands layer.
Embodiment 7
Except for the following differences, remaining is with embodiment 4 for implementation process:
Second step hydro-thermal process
It will be transferred in closed reactor through reaction mixture made from upper step, and by being filled with nitrogen, reach pressure in reaction kettle
To 0.05MPa, in temperature be 120 DEG C hydro-thermal process 10 hours.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MWW structure molecular sieve containing titanium that interlayer expands layer.
Embodiment 8
Except for the following differences, remaining is with embodiment 4 for implementation process:
The preparation of first step reaction mixture
The Ti-MWW molecular sieve stratiform presoma and concentration for the boracic that embodiment 1 is prepared are 0.5 mol/L acid solution
Reaction mixture is prepared for 1: 40 according to weight ratio, the acid is sulfuric acid；
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MWW structure molecular sieve containing titanium that interlayer expands layer.
Embodiment 9
Except for the following differences, remaining is with embodiment 4 for implementation process:
The preparation of first step reaction mixture
The Ti-MWW molecular sieve stratiform presoma of the boracic that embodiment 1 is prepared and concentration be 4 mol/L acid solutions by
Reaction mixture is prepared for 1: 30 according to weight ratio, the acid is phosphoric acid；
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MWW structure molecular sieve containing titanium that interlayer expands layer.
Embodiment 10
Except for the following differences, remaining is with embodiment 4 for implementation process:
The preparation of first step reaction mixture
Molecular sieve stratiform presoma is the MCM-22 molecular sieve stratiform presoma for the boracic that embodiment 1 is prepared.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MCM-22 molecular sieve that interlayer expands layer.
Embodiment 11
Except for the following differences, remaining is with embodiment 4 for implementation process:
The preparation of first step reaction mixture
Molecular sieve stratiform presoma is the ERB-1 molecular sieve stratiform presoma for the boracic that embodiment 1 is prepared.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the ERB-1 molecular sieve that interlayer expands layer.
Embodiment 12
Except for the following differences, remaining is with embodiment 7 for implementation process:
The preparation of first step reaction mixture
Molecular sieve stratiform presoma is the MCM-22 molecular sieve stratiform presoma for the boracic that embodiment 1 is prepared.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the MCM-22 molecular sieve that interlayer expands layer.
Embodiment 13
Except for the following differences, remaining is with embodiment 7 for implementation process:
The preparation of first step reaction mixture
Molecular sieve stratiform presoma is the ERB-1 molecular sieve stratiform presoma for the boracic that embodiment 1 is prepared.
The XRD spectra of products obtained therefrom is similar with Figure 1B, illustrates to have obtained the ERB-1 molecular sieve that interlayer expands layer.
Claims (1)
1. the preparation method that a kind of interlayer expands the MWW structure molecular screen of layer, which is characterized in that this method includes walking in detail below
It is rapid:
The preparation of first step reaction mixture
There to be a MWW structure stratiform presoma and concentration be 0.1 ~ 5 mol/L acid solution according to weight ratio is 1: (5~50)
Reaction mixture is prepared, described is boracic with MWW structure stratiform presoma with MWW structure stratiform presoma；It is described
Acid be at least one of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid；
Second step hydro-thermal process
To be transferred in closed reactor through reaction mixture made from the first step, in temperature be 100~120 DEG C, pressure 0.1
Hydro-thermal process 10~48 hours under the conditions of ~ 1MPa being filtered, washed, dry and roasting by conventional, and obtaining described has interlayer
Expand the MWW structure molecular screen of layer.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686795A (en) * | 2005-04-18 | 2005-10-26 | 华东师范大学 | Method of synthesizing Ti-MWW molecular sieve |
| CN101570333A (en) * | 2009-04-18 | 2009-11-04 | 中国科学院山西煤炭化学研究所 | Preparation method for hydrogen type silicon-aluminum layer zeolite |
| CN103183358A (en) * | 2013-01-21 | 2013-07-03 | 华东师范大学 | Preparation method of ZSM-5 molecular sieve |
| CN103864089A (en) * | 2014-03-07 | 2014-06-18 | 北京化工大学 | Method for modifying lamellar molecular sieve titanium intercalation |
| CN105408253A (en) * | 2013-02-05 | 2016-03-16 | 巴斯夫欧洲公司 | Process for preparing a titanium-containing zeolitic material having an MWW framework structure |
-
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- 2019-04-15 CN CN201910299243.2A patent/CN110078094A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686795A (en) * | 2005-04-18 | 2005-10-26 | 华东师范大学 | Method of synthesizing Ti-MWW molecular sieve |
| CN101570333A (en) * | 2009-04-18 | 2009-11-04 | 中国科学院山西煤炭化学研究所 | Preparation method for hydrogen type silicon-aluminum layer zeolite |
| CN103183358A (en) * | 2013-01-21 | 2013-07-03 | 华东师范大学 | Preparation method of ZSM-5 molecular sieve |
| CN105408253A (en) * | 2013-02-05 | 2016-03-16 | 巴斯夫欧洲公司 | Process for preparing a titanium-containing zeolitic material having an MWW framework structure |
| CN103864089A (en) * | 2014-03-07 | 2014-06-18 | 北京化工大学 | Method for modifying lamellar molecular sieve titanium intercalation |
Non-Patent Citations (1)
| Title |
|---|
| PENG WU ET AL.: "Selective liquid-phase oxidation of cyclopentene over MWW type titanosilicate", 《CATALYSIS TODAY》 * |
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