CN105253895A - Beta molecular sieve of high-content Fe in framework and preparing method of beta molecular sieve - Google Patents
Beta molecular sieve of high-content Fe in framework and preparing method of beta molecular sieve Download PDFInfo
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- CN105253895A CN105253895A CN201510709795.8A CN201510709795A CN105253895A CN 105253895 A CN105253895 A CN 105253895A CN 201510709795 A CN201510709795 A CN 201510709795A CN 105253895 A CN105253895 A CN 105253895A
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Abstract
The invention relates to a beta molecular sieve of high-content Fe in a framework and a preparing method of the beta molecular sieve. Tetraethylammonium hydroxide serves as a template agent, a Fe- complex serves as a Fe source, and the Fe-beta zeolite molecular sieve of high-content Fe in the framework is synthesized through a one-step method. The synthesizing method is simple, the silica-alumina ratio can be adjusted, the mass fraction of Fe in the framework can reach 3-8%, and the synthesized Fe-beta zeolite molecular sieve is neat in structure, high in crystallinity and good in application prospect.
Description
Technical field
Beta molecular sieve that the present invention relates to high-content Fe in a kind of skeleton and preparation method thereof.Specifically, be first source of iron, silicon source, aluminium source, alkali source and template are prepared into gel, the Beta molecular sieve (Fe-Beta) utilizing Hydrothermal Synthesis technology one-step synthesis to go out high-content Fe in skeleton.Belong to high-content heteroatoms metallic molecule sieve and synthesis technical field thereof.
Background technology
Beta molecular sieve is a kind of high silica alumina ratio molecular sieve, has open three-dimensional twelve-ring pore passage structure, is 1976 patented products first researched and developed by Mobil company of the U.S..The pore passage structure of its uniqueness and on a large scale adjustable silica alumina ratio, make it have broad application prospects in catalysis and adsorbing domain.The skeleton doping of transition heteroatoms (as Fe) makes sour position and acid (bronsted and Louis) in skeleton increase and strengthen, and the specific catalytic function of transition metal can make doping Beta molecular sieve have dual-function catalyst character.
The synthetic method of sial and pure silicon Beta molecular sieve mostly is water heat transfer, and this method synthesis Beta molecular sieve step is simple, product better crystallinity degree and post-processing step is simple, is the method for the synthesis zeolite be most widely used.
The synthetic method of hetero-atom molecular-sieve then has a lot, such as the isomorphous replacement(method), wet containing pickling process and direct synthesis technique etc.And existing Fe-Beta synthetic system mostly is ion-exchange, wet containing the preparation of impregnating post-treating method.This class methods shortcoming is: iron level low (generally lower than 3%) in skeleton, and in use procedure, active substance easily runs off with coalescent, and synthesis step is loaded down with trivial details.And introduce F in neutral conditions
-ion is the one-step synthesis of mineralizer, owing to introducing the F of hostile environment
-, add the difficulty of post-processing step.If directly introduce inorganic molysite as source of iron, the Fe content can introduced in skeleton is very low again, and the content that will improve Fe in skeleton is further very difficult.
Summary of the invention
In order to solve problems of the prior art, the content of iron in further raising skeleton, the invention provides the Beta molecular sieve of high-content Fe in a kind of skeleton, described molecular sieve refers to that in skeleton, iron-holder is 3% ~ 8%, and there is the zeolite molecular sieve of Beta structure, this molecular sieve can be used for acid catalysis, selective catalytic oxidation and reduction, the fields such as off gas treatment.
In the preferred embodiment of the present invention, Fe atom is combined in the skeleton structure of Beta molecular sieve, but not be carried on the surfaces externally and internally of skeleton.
The present invention also protects the preparation method of above-mentioned molecular sieve, adopts one step hydro thermal method synthesis, comprises the steps:
(1) preparation is with Fe(
,
) complex solution centered by ion is stand-by;
(2) join in template by silicon source, hydrolysis 10-80min obtains homogeneous colloidal solution, then in mixture, drip the Fe complex solution that step (1) obtains, and continues to stir 10-100min and obtain faint yellow collosol intermixture;
(3) under constantly stirring, drip the mixing solutions in alkali source and aluminium source, obtain light yellow gel, this gel, under the water bath condition of 40-95 DEG C, is transferred in hydrothermal reaction kettle after stirring 2-25h, reaction 6-18d;
(4), after the product that step (3) obtains being carried out suction filtration, washing and roasting, the Beta molecular sieve of equally distributed high-content Fe in skeleton can be obtained.
In the preferred embodiment of the present invention, described silicon source is one or more in silicate, TEOS, silicon sol and white carbon black; Described template is tetraethyl ammonium hydroxide solution, and its concentration range is 25-40wt%; Described aluminium source is the mixture of one or more in sodium metaaluminate, aluminum oxide, aluminium hydroxide or Al salt.Described alkali source is one in sodium hydroxide or potassium hydroxide or the two mixture, meets Na
2o (/K
2o): SiO
2=0.03 ~ 0.09(mol ratio); The addition in described silicon source and aluminium source meets SiO
2/ Al
2o
3=20-100(mol ratio).
In the preferred embodiment of the present invention, described Fe(
,
) ion source is one or more in its muriate, nitrate or vitriol etc., its part is one or more in tartrate, oxalic acid, gallic acid, citric acid, methyl ethyl diketone etc.
In the preferred embodiment of the present invention, the addition of Fe title complex can reach Fe/SiO
2=0.0857(mol ratio).
In the preferred embodiment of the present invention, in gained gelling system, the addition in tetraethyl ammonium hydroxide solution and silicon source meets TEAOH/SiO
2=0.56 ~ 0.76(mol ratio).
In the preferred embodiment of the present invention, the suction filtration of step (4), washing process refer to and add deionized water wash filter cake while suction filtrations, and the pH to filtrate is 7-8.
In the preferred embodiment of the present invention, described roasting is that temperature programming, to 400-600 DEG C, is incubated 3-8h under the condition of 0.5-5 DEG C/min.
Compared with prior art, Fe-Beta molecular sieve prepared by the present invention substantially increases the content of Fe in skeleton, and in skeleton, the mass content of Fe atom can reach 3% ~ 8%.Because Fe atom is embedded in the middle of the skeleton of molecular sieve, just make heat and the good hydrothermal stability of its active site, due to the doping of heteroatoms Fe, enhance the acid amount of high silica alumina ratio Beta molecular sieve, and increase acidic site, and the doping of Fe atom imparts this molecular sieve double-function catalyzing performance.This material has broad application prospects, as can be applicable to acid catalysis, selective oxidation, selective reduction, tail gas or sewage disposal etc.
Accompanying drawing explanation
The X-ray powder diffraction figure of Fig. 1: embodiment 1-5 gained sample;
Fig. 2: the SEM figure of embodiment 1 gained sample;
Fig. 3: the HRTEM figure of embodiment 1 gained sample.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these embodiments just further illustrate the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1:
Get 0.93gFeCl
36H
2o and 0.54g tartrate, in beaker, adds 15mL deionized water, is stirred to dissolving stand-by, is designated as solution one.Get 0.054gNaOH and 0.14gNaAlO again
2in another beaker, add 4mL deionized water, be stirred to dissolving, be designated as solution two.Get 21.4mL tetraethyl ammonium hydroxide (35%) in there-necked flask, drip 18mL TEOS wherein, stir 30min and obtain mixed solution three.The solution one of above-mentioned preparation is joined in mixed solution three, continues to stir 30min and obtain faint yellow colloidal sol, more above-mentioned solution two is joined in this yellow sol system.There-necked flask is transferred in water-bath, under 60 DEG C of conditions, after heated and stirred 15h, mixture is proceeded to reactor.Under 130 DEG C of conditions, hydro-thermal reaction 12d.The product obtained is carried out suction filtration, and be 7 with deionized water wash to the pH of filtrate, finally with DEG C insulation 6h roasting of temperature programming to 500 under 5 DEG C/min condition, product is designated as 1#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .a.
Embodiment 2:
Get 1.17gFeCl
36H
2o and 0.67g tartrate, in beaker, adds 15mL deionized water, is stirred to dissolving stand-by, is designated as solution one.Get 0.054gNaOH and 0.28gNaAlO again
2in another beaker, add 4mL deionized water, be stirred to dissolving, be designated as solution two.Get 21.8mL tetraethyl ammonium hydroxide (35%) in there-necked flask, drip 18mL TEOS wherein, stir 30min and obtain mixed solution three.The solution one of above-mentioned preparation is joined in mixed solution three, continues to stir 30min and obtain faint yellow colloidal sol, more above-mentioned solution two is joined in this yellow sol system.There-necked flask is transferred in water-bath, under 60 DEG C of conditions, after heated and stirred 12h, mixture is proceeded to reactor.Under 130 DEG C of conditions, hydro-thermal reaction 12d.The product obtained is carried out suction filtration, and be 7 with deionized water wash to the pH of filtrate, finally with DEG C insulation 4h roasting of temperature programming to 500 under 5 DEG C/min condition, product is designated as 2#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .b.
Embodiment 3:
Get 1.4gFeCl
36H
2o and 0.8g tartrate, in beaker, adds 15mL deionized water, is stirred to dissolving stand-by, is designated as solution one.Get 0.054gNaOH and 0.28gNaAlO again
2in another beaker, add 4mL deionized water, be stirred to dissolving, be designated as solution two.Get 22.2mL tetraethyl ammonium hydroxide (35%) in there-necked flask, drip 18mL TEOS wherein, stir 30min and obtain mixed solution three.The solution one of above-mentioned preparation is joined in mixed solution three, continues to stir 30min and obtain faint yellow colloidal sol, more above-mentioned solution two is joined in this yellow sol system.There-necked flask is transferred in water-bath, under 60 DEG C of conditions, after heated and stirred 24h, mixture is proceeded to reactor.Under 130 DEG C of conditions, hydro-thermal reaction 12d.The product obtained is carried out suction filtration, and be 7 with deionized water wash to the pH of filtrate, finally with DEG C insulation 5h roasting of temperature programming to 500 under 5 DEG C/min condition, product is designated as 3#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .c.
Embodiment 4:
Get 1.62gFeCl
36H
2o and 0.94g gallic acid, in beaker, adds 15mL deionized water, is stirred to dissolving stand-by, is designated as solution one.Get 0.054gNaOH and 0.28gNaAlO again
2in another beaker, add 4mL deionized water, be stirred to dissolving, be designated as solution two.Get 22.6mL tetraethyl ammonium hydroxide (35%) in there-necked flask, drip 18mL TEOS wherein, stir 30min and obtain mixed solution three.The solution one of above-mentioned preparation is joined in mixed solution three, continues to stir 30min and obtain faint yellow colloidal sol, more above-mentioned solution two is joined in this yellow sol system.There-necked flask is transferred in water-bath, under 50 DEG C of conditions, after heated and stirred 10h, mixture is proceeded to reactor.Under 150 DEG C of conditions, hydro-thermal reaction 14d.The product obtained is carried out suction filtration, and be 7 with deionized water wash to the pH of filtrate, finally with DEG C insulation 3h roasting of temperature programming to 400 under 2 DEG C/min condition, product is designated as 4#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .d.
Embodiment 5:
Get 1.86gFeCl
36H
2o and 1.08g tartrate, in beaker, adds 15mL deionized water, is stirred to dissolving stand-by, is designated as solution one.Get 0.054gNaOH and 0.28gNaAlO again
2in another beaker, add 4mL deionized water, be stirred to dissolving, be designated as solution two.Get 23mL tetraethyl ammonium hydroxide (35%) in there-necked flask, drip 18mL TEOS wherein, stir 30min and obtain mixed solution three.The solution one of above-mentioned preparation is joined in mixed solution three, continues to stir 30min and obtain faint yellow colloidal sol, more above-mentioned solution two is joined in this yellow sol system.There-necked flask is transferred in water-bath, under 50 DEG C of conditions, after heated and stirred 10h, mixture is proceeded to reactor.Under 150 DEG C of conditions, hydro-thermal reaction 14d.The product obtained is carried out suction filtration, and be 7 with deionized water wash to the pH of filtrate, finally with DEG C insulation 3h roasting of temperature programming to 400 under 2 DEG C/min condition, product is designated as 5#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .e.
The structural parameter of above-described embodiment gained sample are in table 1:
The structural parameter of table 1. embodiment sample
As can be seen from the above table, by the Fe-Beta molecular sieve of simple hydrothermal synthesis method synthesis of high content, along with Fe content increases, acid amount has remarkable increase, overcome the shortcoming that pure silicon acidic zeolite is weak, hydroxyl in the activation skeleton B that also generation is stronger is sour or L is sour, and its specific surface area, pore volume are all comparatively large, and molecular sieve catalytic performance is greatly improved.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (9)
1. a Beta molecular sieve of high-content Fe in skeleton, it is characterized in that, described molecular sieve refers to that in skeleton, iron-holder is 3% ~ 8%, and has the zeolite molecular sieve of Beta structure.
2. Beta molecular sieve according to claim 1, is characterized in that, Fe atom is combined in the skeleton structure of Beta molecular sieve, but not be carried on the surfaces externally and internally of skeleton.
3. the preparation method of the Beta molecular sieve according to any one of claim 1-2, is characterized in that, adopts one step hydro thermal method synthesis, comprises the steps:
(1) preparation is with Fe(
,
) complex solution centered by ion is stand-by;
(2) join in template by silicon source, hydrolysis 10-80min obtains homogeneous colloidal solution, then in mixture, drip the Fe complex solution that step (1) obtains, and continues to stir 10-100min and obtain faint yellow collosol intermixture;
(3) under constantly stirring, drip the mixing solutions in alkali source and aluminium source, obtain light yellow gel, this gel, under the water bath condition of 40-95 DEG C, is transferred in hydrothermal reaction kettle after stirring 2-25h, reaction 6-18d;
(4), after the product that step (3) obtains being carried out suction filtration, washing and roasting, the Beta molecular sieve of equally distributed high-content Fe in skeleton can be obtained.
4. preparation method according to claim 3, is characterized in that, described silicon source is one or more in silicate, TEOS, silicon sol and white carbon black; Described template is tetraethyl ammonium hydroxide solution, and its concentration range is 25-40wt%; Described aluminium source is the mixture of one or more in sodium metaaluminate, aluminum oxide, aluminium hydroxide or Al salt; Described alkali source is one in sodium hydroxide or potassium hydroxide or the two mixture, meets Na
2o (/K
2o)/SiO
2=0.03 ~ 0.09(mol ratio); The addition in described silicon source and aluminium source meets SiO
2/ Al
2o
3=20-100(mol ratio).
5. preparation method according to claim 3, is characterized in that, described Fe(
,
) ion source is one or more in its muriate, nitrate or vitriol, its part is one or more in tartrate, oxalic acid, gallic acid, citric acid, methyl ethyl diketone.
6. preparation method according to claim 3, is characterized in that, the addition of Fe title complex can reach Fe/SiO
2=0.0857(mol ratio).
7. preparation method according to claim 3, is characterized in that, in gained gelling system, the addition in tetraethyl ammonium hydroxide solution and silicon source meets TEAOH/SiO
2=0.56 ~ 0.76.
8. preparation method according to claim 3, is characterized in that, the suction filtration of step (4), washing process refer to and add deionized water wash filter cake while suction filtration, and the pH to filtrate is 7-8.
9. preparation method according to claim 3, is characterized in that, described roasting is that temperature programming, to 400-600 DEG C, is incubated 3-8h under the condition of 0.5-5 DEG C/min.
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| CN106745030A (en) * | 2016-11-24 | 2017-05-31 | 黑龙江大学 | A kind of method of fabricated in situ Fe/Al Beta zeolite molecular sieves |
| CN106799253A (en) * | 2017-01-22 | 2017-06-06 | 南昌大学 | A kind of preparation method of the step Hydrothermal Synthesiss out of stock catalyst of hierarchical porous structure molecular sieve |
| CN107055564A (en) * | 2017-04-19 | 2017-08-18 | 江苏智道工程技术有限公司 | It is a kind of to be used for mesoporous Si-Al molecular sieve adsorbent that VOCs is handled and preparation method thereof |
| CN109985660A (en) * | 2017-12-29 | 2019-07-09 | 华中科技大学 | A kind of method and its application of the iron-based molecular sieve catalyst of one-step synthesis method |
| CN111943222A (en) * | 2020-08-05 | 2020-11-17 | 正大能源材料(大连)有限公司 | Fe-beta molecular sieve for removing NOx and synthetic method and application thereof |
| CN112694100A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Fe-ZSM-5 molecular sieve, preparation method and application thereof |
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| CN106745030A (en) * | 2016-11-24 | 2017-05-31 | 黑龙江大学 | A kind of method of fabricated in situ Fe/Al Beta zeolite molecular sieves |
| CN106745030B (en) * | 2016-11-24 | 2019-02-05 | 黑龙江大学 | A kind of method of fabricated in situ Fe/Al-Beta zeolite molecular sieve |
| CN106799253A (en) * | 2017-01-22 | 2017-06-06 | 南昌大学 | A kind of preparation method of the step Hydrothermal Synthesiss out of stock catalyst of hierarchical porous structure molecular sieve |
| CN106799253B (en) * | 2017-01-22 | 2019-05-24 | 南昌大学 | A kind of preparation method of step hydrothermal synthesis hierarchical porous structure molecular sieve denitrating catalyst |
| CN107055564A (en) * | 2017-04-19 | 2017-08-18 | 江苏智道工程技术有限公司 | It is a kind of to be used for mesoporous Si-Al molecular sieve adsorbent that VOCs is handled and preparation method thereof |
| CN109985660A (en) * | 2017-12-29 | 2019-07-09 | 华中科技大学 | A kind of method and its application of the iron-based molecular sieve catalyst of one-step synthesis method |
| CN109985660B (en) * | 2017-12-29 | 2020-11-24 | 华中科技大学 | Method for synthesizing iron-based molecular sieve catalyst by one-step method and application thereof |
| CN112694100A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Fe-ZSM-5 molecular sieve, preparation method and application thereof |
| CN112694100B (en) * | 2019-10-22 | 2023-01-24 | 中国石油化工股份有限公司 | Fe-ZSM-5 molecular sieve, preparation method and application thereof |
| CN111943222A (en) * | 2020-08-05 | 2020-11-17 | 正大能源材料(大连)有限公司 | Fe-beta molecular sieve for removing NOx and synthetic method and application thereof |
| CN111943222B (en) * | 2020-08-05 | 2021-12-10 | 正大能源材料(大连)有限公司 | Fe-beta molecular sieve for removing NOx and synthetic method and application thereof |
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