CN106315609B - A kind of preparation method of rare earth one-step method complexing backbone doped micropore mesoporous composite molecular sieve - Google Patents
A kind of preparation method of rare earth one-step method complexing backbone doped micropore mesoporous composite molecular sieve Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of rare earth one-step method complexing backbone doped micropore mesoporous composite molecular sieve, include the following steps：(1) 15 mesopore molecular sieve presomas of SBA are first synthesized；(2) rare earth nitrate solution is added dropwise into presoma, adds HY type micro porous molecular sieves, one step of self assembly obtains 15 composite molecular screen stostes of rare earth HY/SBA in acid condition；(3) composite molecular screen stoste is put into microwave reaction instrument, filtering is taken out after reaction, is washed with distilled water and ethyl alcohol, dry, calcining obtains 15 micropores of rare earth HY/SBA-mesoporous composite molecular sieve.The present invention not only had adjusted acidity but also while rare earth complex is doped in framework of molecular sieve, save energy consumption, it is environmentally protective, save the time.Rare earth complex skeleton doped and compounded porous molecular sieve, may be reused, content of rare earth is not reduced.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of to utilize citric acid complexing agent by one step bone of Rare-Earth Ce
The method that frame is doped in microporous mesoporous composite molecular screen molecular sieve.
Background technology
Microporous mesoporous composite molecular screen has the highly acid of Y type micro porous molecular sieves and the hole that SBA-15 mesopore molecular sieves are larger concurrently
There is multistage pore canal and stronger acid centre, this structure to be conducive to the degradation of macromolecular and the timely expansion of catabolite in road
The low disadvantage of the surface acidity of the shortcomings that dissipating, avoiding easy carbon deposit, the easy in inactivation of single poromerics and single mesoporous material.
But compound porous molecular sieve is limited since ion-exchange capacity is small, acid content and acid strength are all relatively low
Their development in fields such as chemical industry.Rare earth element is exchanged with skeletal atom, will not be accumulated in duct, not influenced duct
Unobstructed degree, while the addition of rare earth element can also improve the B acid strengths of molecular sieve, i.e., under the premise of not changing pore passage structure,
Effectively increase the surface acidity of molecular sieve.
Patent CN104891524A discloses a kind of method utilizing ion-exchange supported rare earth in mesopore molecular sieve,
Advantage is that content of rare earth is high, duct is not blocked, and catalytic performance significantly improves, the disadvantage is that reusing, effect is poor, and ion is handed over
The rare earth element for changing method load is largely to be reunited on the surface of molecular sieve in the form of rare earth oxide, rather than enter molecule
In the skeleton of sieve, it is very easy to fall off and cause reuse effect poor in pyrosol reaction.
Invention content
The complexing of rare earth one-step method is doped to the method in composite holes framework of molecular sieve the object of the present invention is to provide a kind of,
This method using citric acid as complexing agent, be complexed significant effect, it is rear-earth-doped enter in framework of molecular sieve, be not with oxide
Form reunion shows therefore is not easily disconnected from molecular sieve.
To achieve the above object, the technical solution adopted by the present invention includes the following steps：
(1) SBA-15 mesopore molecular sieve presomas are first synthesized, the mol ratio of the SBA-15 molecular sieve precursors is：
P123: TEOS:H2O:H3Cit =(1-50):(1-85): (10-100):(1-10)；(2) it is added dropwise into the presoma of step 1
Rare earth nitrate solution, adds HY type micro porous molecular sieves, and the mass ratio of HY and P123 are 1:1, rare earth nitrate solution with
The mass ratio of P123 is 0.1-3:1-20, in acid condition one step of self assembly it is former to obtain rare earth-HY/SBA-15 composite molecular screens
Liquid；(3) composite molecular screen stoste is put into microwave reaction instrument, in 100 DEG C of microwave radiation 2h, filtering is taken out after reaction, with steaming
Distilled water and ethyl alcohol wash 4 crystallization products, are dried at 110 DEG C, and 6h is finally calcined at 550 DEG C obtains rare earth-HY/SBA-15
Micropore-mesoporous composite molecular sieve.
A concentration of 0.01mol/L~1mol/L of above-mentioned citric acid.
Above-mentioned rare earth nitrate solution refers to lanthanum (La）, cerium (Ce）, praseodymium (Pr）, neodymium (Nd）, promethium (Pm）, samarium (Sm）, europium
(Eu）, gadolinium (Gd）, terbium (Tb）, dysprosium (Dy）, holmium (Ho）, erbium (Er）, thulium (Tm）, ytterbium (Yb）, lutetium (Lu）, scandium (Sc）With yttrium (Y）'s
Nitrate solution.
In above-mentioned rare earth nitrate solution, the ratio of the amount of rare earth and nitrate solution input substance is 1:1~1:8.
Advantages of the present invention effect is as follows：
The method of the present invention is that rare earth skeleton is doped in microporous mesoporous composite molecular screen using citric acid as complexing agent, should
Method has abandoned the method that traditional SBA-15 mesopore molecular sieves synthesis HCl adjusts acidity, is adjusted by complexing agent and acid of citric acid
Agent is saved, acidity had not only been had adjusted but also while rare earth complex being doped in framework of molecular sieve.Microwave radiation hydro-thermal method generation is used simultaneously
For traditional hydro-thermal method, save energy consumption, it is environmentally protective, save the time.Rare earth complex skeleton doped and compounded porous molecular sieve, Ke Yichong
Multiple to use, content of rare earth is not reduced.It is arranged without three wastes such as a large amount of organic solvents, solid waste and toxic and harmful gas in reaction
It puts, it is environmentally friendly.
Description of the drawings
Fig. 1 is the small angle X ray scattering of the HY/SBA-15 and the Ce-HY/SBA-15 prepared using distinct methods of pure silicon
Figure.
Fig. 2 (a) is to be not added with citric acid complexing agent（CA）Under the conditions of synthesize Ce-HY/SBA-15 TEM figure.
Fig. 2 (b) is adding citric acid complexing agent（CA）Under the conditions of synthesize Ce-HY/SBA-15 TEM figure.
Fig. 3 is HY/SBA-15 (curve 1), Ce-HY/SBA-15 (CA) (curve 2), Ce-HY/SBA-15 (without
CA) (curve 3) and Ce2O3The ultraviolet-visible spectrogram of-HY/SBA-15 (curve 4).
Specific implementation mode
Embodiment 1
4.0g triblock copolymer P123s are dissolved in 30.0g water, until completely dissolved, 9.50g ethyl orthosilicates are added
（TEOS）Abundant magnetic agitation adds 0.10gCe (NO3)3﹒ 6H2O and 120ml mass concentrations are the citric acid of 0.01mol/L
Add 4.0gHY type micro porous molecular sieves（H-type micropore Y type molecular sieve）, after abundant magnetic agitation, it is 1 to adjust pH value, at 100 DEG C
1h is reacted in microwave reaction device, is then washed with distilled water crystallization product, is dried at 110 DEG C, finally calcine 6h at 550 DEG C
Obtain Ce-HY/SBA-15 molecular sieves.
Embodiment 2
1.0g triblock copolymer P123s are dissolved in 20.0g water, until completely dissolved, 6.50g ethyl orthosilicates are added
（TEOS）Abundant magnetic agitation adds 1.0gLa (NO3)3﹒ 6H2O and 240ml mass concentrations be 0.1mol/L citric acid again
1.0gHY type micro porous molecular sieves are added, after abundant magnetic agitation, it is 3 to adjust pH value, is reacted in 100 DEG C of microwave reaction devices
2h, is then washed with distilled water crystallization product, is dried at 110 DEG C, and 6h is finally calcined at 550 DEG C obtains La-HY/SBA-15
Molecular sieve.
Embodiment 3
2.0g triblock copolymer P123s are dissolved in 100.0g water, until completely dissolved, the positive silicic acid second of 18.50g are added
Ester（TEOS）Abundant magnetic agitation adds 1.0g Y (NO3)3﹒ 6H2O and 300ml mass concentrations are the citric acid of 0.5mol/L
Add 2.0gHY type micro porous molecular sieves, after abundant magnetic agitation, it is 5 to adjust pH value, is reacted in 100 DEG C of microwave reaction devices
2h, is then washed with distilled water crystallization product, is dried at 110 DEG C, and 6h is finally calcined at 550 DEG C obtains Y-HY/SBA-15
Molecular sieve.
Embodiment 4
20.0g triblock copolymer P123s are dissolved in 500.0g water, until completely dissolved, the positive silicic acid second of 50.0g are added
Ester（TEOS）Abundant magnetic agitation adds 2.5g Tm (NO3)3﹒ 6H2O and 600ml mass concentrations be 1mol/L citric acid again
20.0gHY type micro porous molecular sieves are added, after abundant magnetic agitation, it is 0.1 to adjust pH value, anti-in 100 DEG C of microwave reaction devices
2h is answered, crystallization product is then washed with distilled water, is dried at 110 DEG C, finally calcining 6h at 550 DEG C obtains Tm-HY/SBA-
15 molecular sieves.
Embodiment 5
1.0g triblock copolymer P123s are dissolved in 30.0g water, until completely dissolved, 9.50g ethyl orthosilicates are added
（TEOS）Abundant magnetic agitation adds 0.5gNd (NO3)3﹒ 6H2O and 300ml mass concentrations be 0.6mol/L citric acid again
1.0gHY type micro porous molecular sieves are added, after abundant magnetic agitation, it is 1 to adjust pH value, is reacted in 100 DEG C of microwave reaction devices
2h, is then washed with distilled water crystallization product, is dried at 110 DEG C, and 6h is finally calcined at 550 DEG C obtains Nd-HY/SBA-15
Molecular sieve.
Embodiment 6
2.5g triblock copolymer P123s are dissolved in 100.0g water, until completely dissolved, 40g ethyl orthosilicates are added
（TEOS）Abundant magnetic agitation adds 3.0gDy (NO3)3﹒ 6H2O and 120ml mass concentrations are that the hydrochloric acid of 0.09mol/L adds again
Enter 2.5gHY type micro porous molecular sieves, after abundant magnetic agitation, it is 2.5 to adjust pH value, is reacted in 100 DEG C of microwave reaction devices
2h, is then washed with distilled water crystallization product, is dried at 110 DEG C, and 6h is finally calcined at 550 DEG C obtains Dy-HY/SBA-15
Molecular sieve.
Synthesized Ce-HY/SBA-15 (CA) by the synthetic method of embodiment 1, and with pure silicon Y/SBA-15 and lemon is not added
The Ce-HY/SBA-15 (without CA) of lemon acid complexing agent synthesis has carried out contrast test, as a result as follows.
Fig. 1 is the HY/SBA-15 of pure silicon and uses distinct methods（Whether citric acid complexing agent is added（CA））The Ce- of preparation
The small angle X ray scattering figure of HY/SBA-15（SAXS）.
As shown in Figure 1,2θTo there is a meso pore characteristics diffraction that intensity is larger and peak shape is more sharp at 1.0 °
The characteristic diffraction peak of peak-hexagonal crystal system (100) crystal face, 2θAbout 2.0 ° or so occur that two intensity are smaller, peak shape is wider
The characteristic diffraction peak of meso pore characteristics diffraction maximum-hexagonal crystal system (110), (200) crystal face, shows and is doped with after Ce elements
Ce-HY/SBA-15 maintains the foam type pore passage structure of HY/SBA-15 substantially.The Ce-HY/ of citric acid complexing agent is not added
SBA-15 (without CA) goes out peak position and the HY/SBA-15 of pure silicon is essentially identical, but has added the Ce- of citric acid complexing agent
The characteristic diffraction peak of HY/SBA-15 (CA) is offset to low-angle direction, this shows that Ce atoms substitution Si atoms enter HY/
In SBA-15 skeletons.Because of Ce3+Radius（rCe=1.17 angstroms）Than Si4+Radius（rSi=1.34 angstroms）It is small, so Ce-O keys
Length ratio Si-O long, when in the cerium ion-doped skeleton to HY/SBA-15, crystal constant will reduce, and go out so as to cause XRD
Peak position is deviated to low angle area.
Fig. 2 (a), (b) are to be not added with and adding citric acid complexing agent（CA）Under the conditions of the TEM of two kinds of Ce-HY/SBA-15 that synthesizes
Figure.
The structure of Ce-HY/SBA-15 further can be reflected intuitively by TEM.TEM in Fig. 2 the result shows that,
The mesoporous area of sample has foam type structure.In Fig. 2 a for the Ce-HY/SBA-15 (without CA) that complexing agent synthesis is not added
In, it can be clearly observed reunion shape substance, color is also deep, it may be possible to Ce2O3.Complexing agent be not added, then greatly
Part Ce is not introduced into SiO2Skeleton in, but with Ce2O3Form is reunited on the surface of HY/SBA-15, this and front
XRD results are consistent.In figure 2b, not finding that aggregate occurs, thus it is speculated that Ce is present in the form of being highly dispersed in skeleton,
The result of XRD also demonstrates this point.This may be and the water of cerium complex because citric acid and cerium ion form complexing
The hydrolysis rate of solution speed and silicon source (TEOS) matches, to form Ce-O-Si skeletons.The all scientific researches of TEM and XRD results prove
The effect of complexing agent is most important, and can be the key that rare earth element be doped into skeleton.
Ultraviolet-visible spectrum is considered as a kind of characterization method for identifying and characterizing metal coordination, sensitive.Fig. 3
It is Ce prepared by the HY/SBA-15 of pure silicon, two Ce-HY/SBA-15 of distinct methods preparation and infusion process2O3-HY/SBA-15
Ultraviolet-visible spectrogram.HY/SBA-15 (curve 1), Ce-HY/SBA-15 (CA) (curve 2), Ce-HY/SBA-15 in Fig. 3
The ultraviolet-visible spectrogram of (without CA) (curve 3) and Ce2O3-HY/SBA-15 (curve 4).
All there is a weaker absorption peak in the position of the non-250nm of wavelength or so in two Ce-HY/SBA-15 samples, and
In Ce2O3All there is an absorption peak for being located at 200nm or so in-HY/SBA-15 and Ce-HY/SBA-15 (without CA),
Peak type is sharp, this peak should belong to Ce2O3The absorption peak of phase.Judged according to the appearance position of absorption peak, wavelength exists
The absorption peak of 250nm belongs to O2-→Ce3+Electronics transfer [3], and all there is this in the sample of two Ce-HY/SBA-15
A peak, but be not Ce2O3The Ce of phase3+, so should be the Ce in skeleton3+Absorption peak.This result also demonstrates again
Not plus complexing agent synthesis Ce-HY/SBA-15 (without CA) there are the Ce of two kinds of forms, on a small quantity to be entrained in skeleton
Form exists, and most of existed in the form of in HY/SBA-15 surface aggregations.Therefore, complexometry is to prepare cerium dopping
The very effective methods of Ce-HY/SBA-15 in skeleton.
Claims (2)
1. a kind of preparation method of rare earth one-step method complexing backbone doped micropore mesoporous composite molecular sieve, it is characterised in that including such as
Lower step：
(1) SBA-15 mesopore molecular sieve presomas are first synthesized, the mol ratio of the SBA-15 molecular sieve precursors is： P123:
TEOS:H2O:H3Cit =(1-50):(1-85): (10-100):(1-10)；(2) rare earth nitre is added dropwise into the presoma of step 1
Acid salt solution, adds HY type micro porous molecular sieves, and the mass ratio of HY and P123 are 1:1, the matter of rare earth nitrate solution and P123
Amount is than being 0.1-3:1-20, in acid condition one step of self assembly obtain rare earth-HY/SBA-15 composite molecular screen stostes；(3)
Composite molecular screen stoste is put into microwave reaction instrument, in 100 DEG C of microwave radiation 2h, filtering is taken out after reaction, with distilled water and
Ethyl alcohol washs 4 crystallization products, is dried at 110 DEG C, and 6h is finally calcined at 550 DEG C obtains rare earth-HY/SBA-15 micropores-
Mesoporous composite molecular sieve；
Above-mentioned rare earth nitrate solution refers to lanthanum (La）, cerium (Ce）, praseodymium (Pr）, neodymium (Nd）, promethium (Pm）, samarium (Sm）, europium (Eu）、
Gadolinium (Gd）, terbium (Tb）, dysprosium (Dy）, holmium (Ho）, erbium (Er）, thulium (Tm）, ytterbium (Yb）, lutetium (Lu）, scandium (Sc）With yttrium (Y）Nitrate
Solution；
In above-mentioned rare earth nitrate solution, the ratio of the amount of rare earth and nitrate solution input substance is 1:1~1:8.
2. a kind of preparation side of rare earth one-step method complexing backbone doped micropore mesoporous composite molecular sieve according to claim 1
Method, it is characterised in that a concentration of 0.01mol/L~1mol/L of above-mentioned citric acid.
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| CN105712366A (en) * | 2016-04-11 | 2016-06-29 | 华南理工大学 | Neodymium-doped SBA-15 mesoporous molecular sieve and preparation method thereof |
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| CN103285907A (en) * | 2013-04-25 | 2013-09-11 | 安徽生力农化有限公司 | Mesoporous molecular sieve supported composite metal oxide alcoholysis catalyst, and preparation method of alcoholysis catalyst |
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