CN105253895B - High content Fe Beta molecular sieves and preparation method thereof in a kind of skeleton - Google Patents
High content Fe Beta molecular sieves and preparation method thereof in a kind of skeleton Download PDFInfo
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- CN105253895B CN105253895B CN201510709795.8A CN201510709795A CN105253895B CN 105253895 B CN105253895 B CN 105253895B CN 201510709795 A CN201510709795 A CN 201510709795A CN 105253895 B CN105253895 B CN 105253895B
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Abstract
The present invention relates to Beta molecular sieves of high content Fe in a kind of skeleton and preparation method thereof, are the Fe Beta zeolite molecular sieves that Fe sources utilize high content Fe in one-step method Hydrothermal Synthesiss skeleton using Fe complexs using tetraethyl ammonium hydroxide as template.Synthetic method of the present invention is simple, and silica alumina ratio is adjustable, and Fe mass fraction is up to 3 8% in skeleton, and the Fe Beta zeolite molecular sieve compound with regular structure of synthesis, crystallinity is high, has good application prospect.
Description
Technical field
The present invention relates to Beta molecular sieves of high content Fe in a kind of skeleton and preparation method thereof.Specifically, it is first will
Source of iron, silicon source, silicon source, alkali source and template are prepared into gel, contain going out height in skeleton using Hydrothermal Synthesiss technology one-step synthesis
Measure Fe Beta molecular sieves（Fe-Beta）.Belong to high content hetero atom metallic molecule sieve and its synthesis technical field.
Background technology
Beta molecular sieves are a kind of high silica alumina ratio molecular sieves, have open three-dimensional twelve-ring pore passage structure, are 1976
The patented product researched and developed first by Mobil companies of the U.S..Its unique pore passage structure and a wide range of adjustable silica alumina ratio, are urging it
Change and adsorbing domain has broad application prospects.Transition hetero atom（Such as Fe）Skeleton doping make sour position and acidity in skeleton（Cloth
Lanace spy and Louis）Increase and strengthen, and the specific catalytic function of transition metal can have doping Beta molecular sieves
Bifunctional catalyst property.
The synthetic method of sial and pure silicon Beta molecular sieves is mostly hydro-thermal method synthesis, and method synthesis Beta molecular sieves step is simple
List, product better crystallinity degree and post-processing step are simple, are the methods for the synthesis zeolite being most widely used.
The synthetic method of hetero-atom molecular-sieve then has a lot, for example the isomorphous replacement method, wet contains infusion process and direct synthesis technique
Deng.And existing Fe-Beta synthetic systems are mostly ion exchange, prepared by wet post-processing approach containing impregnating.Such method shortcoming
For：Iron content is low in skeleton（Generally below 3%）, active material is easy to run off and coalesced during use, and synthesis step is cumbersome.
And F is introduced in neutral conditions-Ion is the one-step synthesis of mineralizer, due to introducing the F of hostile environment-, locate after adding
Manage the difficulty of step.If being introduced directly into inorganic molysite as source of iron, the Fe contents that can be introduced in skeleton are again very low, further
The content for improving Fe in skeleton is extremely difficult.
The content of the invention
In order to solve problems of the prior art, the content of iron in skeleton is further improved, the invention provides one
High content Fe Beta molecular sieves, described molecular sieve refer to that iron-holder is 3% ~ 8% in skeleton in kind skeleton, and with Beta knots
The zeolite molecular sieve of structure, the molecular sieve can be used for the field such as acid catalysis, selective catalytic oxidation and reduction, exhaust-gas treatment.
In the preferred embodiment of the present invention, Fe atoms are incorporated in the skeleton structure of Beta molecular sieves, and non-negative
It is loaded on the surfaces externally and internally of skeleton.
The present invention also protects the preparation method of above-mentioned molecular sieve, is synthesized, comprised the following steps using one step hydro thermal method：
（1）Prepare with Fe（、）Complex solution centered on ion is stand-by；
（2）Silicon source is added in template, hydrolysis 10-80 min obtain homogeneous colloidal solution, then into mixture
Step is added dropwise（1）Obtained Fe complex solutions, and continue stirring 10-100 min and obtain faint yellow collosol intermixture；
（3）The mixed solution of lower dropwise addition alkali source and silicon source is being stirred continuously, is obtaining light yellow gel, the gel is in 40-95
DEG C water bath condition under, be transferred to after stirring 2-25 h in hydrothermal reaction kettle, reaction 6-18 d；
（4）By step（3）After obtained product is filtered, washed and is calcined, you can obtain equally distributed in skeleton
High content Fe Beta molecular sieves.
In the preferred embodiment of the present invention, described silicon source is silicate, TEOS, Ludox and hard charcoal
One or more in black；Described template is tetraethyl ammonium hydroxide solution, and its concentration range is 25-40wt%；The aluminium
Source is one or more of mixtures in sodium metaaluminate, aluminum oxide, aluminium hydroxide or Al salt.Described alkali source is sodium hydroxide
Either one kind in potassium hydroxide or the two mixture, meet Na2O(/K2O): SiO2=0.03~0.09（Mol ratio）；It is described
The addition of silicon source and silicon source meets SiO2/Al2O3=20-100（Mol ratio）.
In the preferred embodiment of the present invention, described Fe（、）Ion source is its chloride, nitrate or sulphur
One or more in hydrochlorate etc., its part be one kind in tartaric acid, oxalic acid, gallic acid, citric acid, acetylacetone,2,4-pentanedione etc. or
It is several.
In the preferred embodiment of the present invention, the addition of Fe complexs can reach Fe/SiO2 =0.0857
（Mol ratio）.
In the preferred embodiment of the present invention, the addition of tetraethyl ammonium hydroxide solution and silicon source in gained gel rubber system
Amount meets TEAOH/SiO2=0.56~0.76（Mol ratio）.
In the preferred embodiment of the present invention, step（4）Suction filtration, washing process refer to filter while add go
Ion water washing filter cake, the pH to filtrate are 7-8.
It is described to be roasted under conditions of 0.5-5 DEG C/min temperature programming extremely in the preferred embodiment of the present invention
400-600 DEG C, insulation 3-8 h.
Compared with prior art, the Fe-Beta molecular sieves that prepared by the present invention substantially increase the content of Fe in skeleton, skeleton
The mass content of middle Fe atoms is up to 3% ~ 8%.Because Fe atoms are embedded among the skeleton of molecular sieve, its catalytic activity is allowed for
The heat and good hydrothermal stability in site, due to hetero atom Fe doping, the acid amount of high silica alumina ratio Beta molecular sieves is enhanced, and increased
More acidic sites, and the doping of Fe atoms imparts the molecular sieve double-function catalyzing performance.Before the material has wide application
Scape, it such as can be applied to acid catalysis, selective oxidation, selective reduction, tail gas or sewage disposal.
Brief description of the drawings
Fig. 1：The X-ray powder diffraction figure of sample obtained by embodiment 1-5；
Fig. 2：The SEM figures of the gained sample of embodiment 1；
Fig. 3：The HRTEM figures of the gained sample of embodiment 1.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It is it should be appreciated that these embodiments simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1：
Take 0.93 g FeCl3·6H2O and 0.54 g tartaric acid add 15 mL deionized waters, stirred to molten in beaker
Solve stand-by, be designated as solution one.0.054 g NaOH and 0.14g NaAlO is taken again2In another beaker, 4 mL deionizations are added
Water, stirring are designated as solution two to dissolving.Take 21.4 mL tetraethyl ammonium hydroxides（35%）In three-necked flask, it is added dropwise thereto
18 mL TEOSs, 30 min of stirring obtain mixed liquor three.The solution one of above-mentioned preparation is added in mixed liquor three,
Continue 30 min of stirring and obtain faint yellow colloidal sol, then above-mentioned solution two is added in the yellow sol system.By three-necked flask
It is transferred in water-bath, mixture is transferred to reactor after the h of heating stirring 15 under the conditions of 60 DEG C.Under the conditions of 130 DEG C,
The d of hydro-thermal reaction 12.Obtained product is filtered, it is 7 to be washed with deionized to the pH of filtrate, finally with 5 DEG C/min
Under the conditions of temperature programming to 500 DEG C of insulation 6 h roastings, product is designated as 1#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .a.
Embodiment 2：
Take 1.17 g FeCl3·6H2O and 0.67 g tartaric acid add 15 mL deionized waters, stirred to molten in beaker
Solve stand-by, be designated as solution one.0.054 g NaOH and 0.28 g NaAlO are taken again2In another beaker, 4 mL deionizations are added
Water, stirring are designated as solution two to dissolving.Take 21.8 mL tetraethyl ammonium hydroxides（35%）In three-necked flask, it is added dropwise thereto
18 mL TEOSs, 30 min of stirring obtain mixed liquor three.The solution one of above-mentioned preparation is added in mixed liquor three,
Continue 30 min of stirring and obtain faint yellow colloidal sol, then above-mentioned solution two is added in the yellow sol system.By three-necked flask
It is transferred in water-bath, mixture is transferred to reactor after the h of heating stirring 12 under the conditions of 60 DEG C.Under the conditions of 130 DEG C,
The d of hydro-thermal reaction 12.Obtained product is filtered, it is 7 to be washed with deionized to the pH of filtrate, finally with 5 DEG C/min
Under the conditions of temperature programming to 500 DEG C of insulation 4 h roastings, product is designated as 2#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .b.
Embodiment 3：
Take 1.4 g FeCl3·6H2O and 0.8 g tartaric acid add 15 mL deionized waters, stirring to dissolving in beaker
It is stand-by, it is designated as solution one.0.054 g NaOH and 0.28 g NaAlO are taken again2In another beaker, 4 mL deionized waters are added,
Stirring is designated as solution two to dissolving.Take 22.2 mL tetraethyl ammonium hydroxides（35%）In three-necked flask, 18 are added dropwise thereto
ML TEOSs, 30 min of stirring obtain mixed liquor three.The solution one of above-mentioned preparation is added in mixed liquor three, continued
Stir 30 min and obtain faint yellow colloidal sol, then above-mentioned solution two is added in the yellow sol system.Three-necked flask is shifted
Into water-bath, mixture is transferred to reactor after the h of heating stirring 24 under the conditions of 60 DEG C.Under the conditions of 130 DEG C, hydro-thermal
React 12 d.Obtained product is filtered, it is 7 to be washed with deionized to the pH of filtrate, finally with 5 DEG C/min conditions
Lower temperature programming to 500 DEG C of insulation 5 h roastings, product is designated as 3#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .c.
Embodiment 4：
Take 1.62 g FeCl3·6H2O and 0.94 g gallic acids add 15 mL deionized waters, stirring is extremely in beaker
Dissolve stand-by, be designated as solution one.0.054 g NaOH and 0.28 g NaAlO are taken again2In another beaker, add 4 mL go from
Sub- water, stirring are designated as solution two to dissolving.Take 22.6 mL tetraethyl ammonium hydroxides（35%）In three-necked flask, drip thereto
Add 18 mL TEOSs, 30 min of stirring obtain mixed liquor three.The solution one of above-mentioned preparation is added to mixed liquor three
In, continue 30 min of stirring and obtain faint yellow colloidal sol, then above-mentioned solution two is added in the yellow sol system.By three mouthfuls of burnings
Bottle is transferred in water-bath, and mixture is transferred into reactor after the h of heating stirring 10 under the conditions of 50 DEG C.In 150 DEG C of conditions
Under, the d of hydro-thermal reaction 14.Obtained product is filtered, be washed with deionized to filtrate pH be 7, finally with 2 DEG C/
Temperature programming to 400 DEG C of insulation 3 h roastings, product is designated as 4# under the conditions of min, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .d.
Embodiment 5：
Take 1.86g FeCl3·6H2O and 1.08g tartaric acid adds 15 mL deionized waters, stirring to dissolving in beaker
It is stand-by, it is designated as solution one.0.054 g NaOH and 0.28 g NaAlO are taken again2In another beaker, 4 mL deionized waters are added,
Stirring is designated as solution two to dissolving.Take 23 mL tetraethyl ammonium hydroxides（35%）In three-necked flask, 18 mL are added dropwise thereto
TEOS, 30 min of stirring obtain mixed liquor three.The solution one of above-mentioned preparation is added in mixed liquor three, continues to stir
Mix 30 min and obtain faint yellow colloidal sol, then above-mentioned solution two is added in the yellow sol system.Three-necked flask is transferred to
In water-bath, mixture is transferred to reactor after the h of heating stirring 10 under the conditions of 50 DEG C.Under the conditions of 150 DEG C, hydro-thermal is anti-
Answer 14 d.Obtained product is filtered, be washed with deionized to filtrate pH be 7, finally with 2 DEG C/min under the conditions of
Temperature programming to 400 DEG C of insulation 3 h roastings, product is designated as 5#, and its x-ray diffractogram of powder spectrum is shown in Fig. 1 .e.
The structural parameters of sample are shown in Table 1 obtained by above-described embodiment：
The structural parameters of the embodiment sample of table 1.
As can be seen from the above table, by the Fe-Beta molecular sieves of simple hydrothermal synthesis method synthesis of high content, as Fe contains
Amount increases, and acid amount dramatically increases, and the shortcomings that overcoming pure silicon acidic zeolite weak, activates the hydroxyl in skeleton and produces stronger
B acid or L acid, its specific surface area, pore volume are larger, molecular sieve catalytic performance is greatly improved.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.
Claims (7)
- A kind of 1. high content Fe Beta molecular sieves in skeleton, it is characterised in that synthesized using one step hydro thermal method, including following step Suddenly：（1）Prepare with Fe（Ⅱ、Ⅲ）Complex solution centered on ion is stand-by；（2）Silicon source is added in template, hydrolysis 10-80 min obtain homogeneous colloidal solution, then are added dropwise into mixture Step（1）Obtained Fe complex solutions, and continue stirring 10-100 min and obtain faint yellow collosol intermixture；（3）The mixed solution of lower dropwise addition alkali source and silicon source is being stirred continuously, is obtaining light yellow gel, the gel is at 40-95 DEG C Under water bath condition, it is transferred to after stirring 2-25 h in hydrothermal reaction kettle, reaction 6-18 d；（4）By step（3）After obtained product is filtered, washed and is calcined, that is, obtain equally distributed high content in skeleton Fe Beta molecular sieves；Described molecular sieve refers to that iron-holder is 4% ~ 8% in skeleton, and the zeolite molecular sieve with Beta structures.
- 2. molecular sieve according to claim 1, it is characterised in that described silicon source be silicate, TEOS and One or more in white carbon；Described template is tetraethyl ammonium hydroxide solution, and its concentration range is 25-40wt%；Institute Silicon source is stated as one or more of mixtures in sodium metaaluminate, aluminum oxide, aluminium hydroxide or Al salt；Described alkali source is hydrogen-oxygen Change the one kind or the two mixture of sodium either in potassium hydroxide, meet with molar ratio computing, Na2O(/K2O)/SiO2=0.03~ 0.09；The addition of the silicon source and silicon source meets with molar ratio computing SiO2/Al2O3=20-100。
- 3. molecular sieve according to claim 1, it is characterised in that described Fe（Ⅱ、Ⅲ）Ion source be its chloride, One or more in nitrate or sulfate, its part are in tartaric acid, oxalic acid, gallic acid, citric acid, acetylacetone,2,4-pentanedione It is one or more of.
- 4. molecular sieve according to claim 1, it is characterised in that with molar ratio computing, the addition highest of Fe complexs can Reach Fe/SiO2 =0.0857。
- 5. molecular sieve according to claim 2, it is characterised in that in gained gel rubber system tetraethyl ammonium hydroxide solution with The addition of silicon source meets TEAOH/SiO2=0.56~0.76。
- 6. molecular sieve according to claim 1, it is characterised in that step（4）Suction filtration, washing process refers in suction filtration Deionized water washing filter cake is added simultaneously, and the pH to filtrate is 7-8.
- 7. molecular sieve according to claim 1, it is characterised in that described is roasted under conditions of 0.5-5 DEG C/min Temperature programming is incubated 3-8 h to 400-600 DEG C.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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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