CN110330026A - A method of utilizing the synthesising mesoporous material SBA-15 of natural diatomaceous earth - Google Patents
A method of utilizing the synthesising mesoporous material SBA-15 of natural diatomaceous earth Download PDFInfo
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- CN110330026A CN110330026A CN201910586154.6A CN201910586154A CN110330026A CN 110330026 A CN110330026 A CN 110330026A CN 201910586154 A CN201910586154 A CN 201910586154A CN 110330026 A CN110330026 A CN 110330026A
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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
- 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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Abstract
The invention discloses a kind of methods for preparing mesoporous material SBA-15 using natural diatomaceous earth.Diatomite is template as single silicon source, triblock copolymer P123 (PEG-PPG-PEG), and hydrothermal synthesis method is prepared for mesoporous material SBA-15.Due to synthesis of the invention be using diatomite as raw material, it is cheap, overcome traditional higher limitation of mesoporous material preparation cost.More importantly present invention process is simple, without being purified to diatomite in synthesis process, meets the needs of Green Chemistry, realize the effective use of Diatomite mineral resource and protect the purpose of environment.And the mesoporous material SBA-15 high-sequential of preparation.These features all make SBA-15 have bigger application prospect in fields such as absorption, catalysis and environmental pollution treatments.
Description
Technical field
The invention belongs to mesopore molecular sieve preparation technical fields, and in particular to one kind is for low cost synthesis absorption and catalysis
The method of the SBA-15 of material.
Background technique
Mesoporous molecular sieve SBA-15 belongs to the p6mm space group of two-dimentional six sides, duct be it is parallel to each other, cross section is in
Hexagonal array (Xu Ruren, Pang Wenqin, in the such as Ji Hong molecular sieve and porous material chemistry Beijing [M]: Science Press, 2004,
566.).SBA-15 because its specific surface area with higher and can modulation pore size, be widely applied to absorption, catalysis and
The fields such as environmental pollution treatment.Currently, the synthesis of SBA-15 generallys use TEOS and Na2SiO3It is original Deng expensive chemical reagent
Material, higher synthesis cost limit its large-scale application.It therefore, will be into if preparing low-cost SBA-15
One step expands its business application.
Diatomite is as a kind of natural clay mineral, in China's rich reserves, since it is rich in SiO2, can be used as one kind
Raw material carrys out synthesis zeolite.Researcher has synthesized different kinds of molecules sieve with diatomite, as type A zeolite (Ghosh B.,
Agrawal D.C.,Bhatia S.Synthesis of zeolite A from calcined diatomaceous clay:
optimization studies[J].Industrial&Engineering Chemistry Research,1994,33(9):
2107-2110.), modenite (Sanhueza V., Kelm U., Cid R.Synthesis of mordenite from
diatomite:a case of zeolite synthesis from natural material[J].Journal of
Chemical Technology&Biotechnology, 2003,78 (5): 485-488.), ZSM-5 (Sanhueza V., Kelm
U.,Cid R.,et al.Synthesis of ZSM-5from diatomite:a case of zeolite synthesis
from a natural material[J].Journal of Chemical Technology&Biotechnology,2004,
79 (7): 686-690.), P type zeolite (Du Y., Shi S., Dai H.Water-bathing synthesis of high-
Surface-area zeolite P from diatomite [J] .Particuology, 2011,9 (2): 174-178.), water chestnut
Christianite (Wang Y., Shang Y., Wu J., et al.Recrystallization of magadiite into
offretite in the presence of tetramethylammonium cations[J].Journal of
Chemical Technology&Biotechnology, 2010,85 (2): 279-282.), ferrierite (Wang Y., Yang
Y.,Cui M.,et al.Hydrothermal transformation of magadiite into ferrierite in
Al2O3–Na2O–ethylenediamine–H2O system [J] .Solid State Sciences, 2011,13 (12):
2124-2128.) and MCM-41 (Sanhueza V., L ó pez-Escobar L.Kelm U., et al.Synthesis of a
mesoporous material from two natural sources[J].Journal of Chemical
Technology&Biotechnology, 2006,81 (4): 614-617.) etc., phase has been carried out to obtain in the research work of this respect
To maturation.But patent report is had no by the research of Material synthesis SBA-15 of diatomite, making this kind of synthesis, there is very big
Blindness.
Summary of the invention
The object of the present invention is to provide a kind of methods that low cost prepares SBA-15, and raw material of the present invention is diatom
Soil, different from expensive chemical reagent, it can be effectively reduced the cost of raw material while reducing the pollution for environment.
The present invention, for unique silicon source, purify and do not add to diatomite with diatomite in the process of synthesis
Other auxiliary silicon sources are that template is successfully made by hydrothermal synthesis method with triblock copolymer P123 (PEG-PPG-PEG)
For the mesoporous molecular sieve SBA-15 of high-sequential.
The purpose of the present invention is be achieved by the following technical programs: a kind of to utilize the synthesising mesoporous material of natural diatomaceous earth
The method of SBA-15, includes the following steps:
(1) after mixing by diatomite, NaOH and water, crystallization 2-6h under conditions of being placed in 120-180 DEG C, it is cooling
To room temperature, solution A is obtained；
The mass ratio of diatomite and NaOH in the solution A is 1:(0.3~0.5), preferably 1:0.38；NaOH and
H2Mass ratio 1:(20~30 of O), preferably 1:25；
(2) triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, PEG-
PPG-PEG it) is dissolved in the water, adds concentrated hydrochloric acid and obtain solution B；
The mass ratio of P123 and water in the solution B are as follows: 1:(18~38), preferably 1:25；In the solution B
Concentrated hydrochloric acid and water mass ratio: 1:(3.0~6.5), preferably 1:3.6；(3) by solution A obtained in step (1) by slowly
It is added in solution B obtained in step (2), in 40 DEG C after -45 DEG C of heating stirrings 20-30 hours, then in 80-120 DEG C of condition
Lower progress crystallization 12-48h is cooled to room temperature, and product is filtered, washed, re-dry, after calcining, obtains mesoporous material
SBA-15；
The mass ratio of the solution A and solution B is 1:(1.8-2.2)；
Based on above scheme, preferably, SiO in the diatomite2Content be 85%-95%.
Based on above scheme, preferably, the mode of cooling described in step (1) is to naturally cool to room temperature.
Based on above scheme, preferably, the concentration of concentrated hydrochloric acid described in step (2) is 36%-38%.
Based on above scheme, preferably, the mode of cooling described in step (4) is to naturally cool to room temperature.
Based on above scheme, preferably, washing described in step (4) is to wash to neutrality.
Based on above scheme, preferably, drying condition described in step (4) are as follows: 80 DEG C -120 DEG C dry 4-12h.
Based on above scheme, preferably, calcination condition described in step (4) are as follows: 550 DEG C of calcining 6h are calcined to go
Template agent removing.
It is cheap and simple and easy to get that the present invention considers that diatomite has many advantages, such as, as the original of synthesis SBA-15
Material, the cost that synthesis can be effectively reduced realize the purpose for efficiently utilizing mineral resources again.The present invention uses diatomite conduct
Cost of material can be effectively reduced in silicon source in this way, to preferably widen SBA-15 before the application fields such as absorption and catalysis
Scape.Therefore this synthetic route design is able to achieve the target of inexpensive, easy to operate and environmentally protective production molecular sieve.
The invention has the following advantages:
1, the present invention is cheap using diatomite as raw material, has synthesized SBA-15 mesoporous molecular using natural diatomaceous earth
Sieve, overcomes traditional higher limitation of mesoporous material preparation cost, greatly reduces synthesis cost, is the further of SBA-15
Industrialization provides theoretical basis.
2, using the synthesising mesoporous material of natural diatomaceous earth, diatomite is not purified in synthesis, is effectively reduced
Harm for environment meets the needs of Green Chemistry, realizes effective use and the protection environment of Diatomite mineral resource
Purpose.
3, present invention process is simple, cheap, has synthesized the mesoporous molecular sieve SBA-15 of high-sequential, is SBA-15
Preparation provide it is a kind of low cost, environmentally protective new approaches.These features make SBA-15 in absorption, catalysis and environmental pollution
The fields such as processing have bigger application prospect.
Detailed description of the invention
The present invention shares attached drawing 2 and opens, in which:
Fig. 1 is the XRD spectra of the mesoporous molecular sieve SBA-15 obtained by 1 method of embodiment.
Fig. 2 is the TEM photo of the mesoporous molecular sieve SBA-15 obtained by 1 method of embodiment, wherein (a) diatomite is original
Material, (b) sodium metasilicate is raw material.
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Diatomite in following embodiments is natural diatomaceous earth, and ingredient and content are SiO2, 93.71%；Fe2O3,
2.17%；Al2O3, 2.15%.The concentration of concentrated hydrochloric acid is 36%.
Embodiment 1
(1) 0.34g NaOH, 8.50g H are weighed2Reaction under high pressure made of polytetrafluoroethylene (PTFE) is added in O and 0.90g diatomite
In kettle, after mixing, reaction kettle is placed in 150 DEG C of thermostatic drying chamber and reacts 4h, cooled to room temperature obtains molten
Liquid A；
(2) 0.5g P123 (molecular weight=5800) and 15g H is weighed2O is in stuffed conical flask, and magnetic agitation is until complete
Fully dissolved adds the concentrated hydrochloric acid of 3ml in above-mentioned solution, solution B is made；
(3) solution A is added slowly in solution B, water-bath heating stirring 24 hours at 40 DEG C, then turns mixed liquor
It moves on in the autoclave of polytetrafluoroethylsubstrate substrate, crystallization is for 24 hours at 100 DEG C.
(4) after crystallization, cooled to room temperature, product is through filtration washing to neutrality, 550 after 100 DEG C of dry 6h
DEG C calcining 6h, obtain mesoporous material SBA-15.
Embodiment 2
(1) 0.68g NaOH, 17g H are weighed2Autoclave made of polytetrafluoroethylene (PTFE) is added in O and 1.80g diatomite
In, after mixing, reaction kettle is placed in 150 DEG C of thermostatic drying chamber and reacts 4h, cooled to room temperature obtains solution
A；
(2) 1.2gP123 (molecular weight=5800) and 30gH is weighed2O is in stuffed conical flask, and magnetic agitation is until completely
Dissolution, adds the concentrated hydrochloric acid of 7ml in above-mentioned solution, solution B is made；
(3) solution A is added slowly in solution B, water-bath heating stirring 30 hours at 45 DEG C, then turns mixed liquor
It moves on in the autoclave of polytetrafluoroethylsubstrate substrate, crystallization is for 24 hours at 100 DEG C.
(4) after crystallization, cooled to room temperature, product is through filtration washing to neutrality, at 550 DEG C after 80 DEG C of dry 8h
6h is calcined, mesoporous material SBA-15 is obtained.
Comparative example
It is as follows with the method that chemical reagent sodium metasilicate is Material synthesis SBA-15: by the Na of 1.3g2SiO3·5H2O is dissolved in
3.75g H2Solution A is obtained in O；Then the P123 of 0.5g (molecular weight=5800) is added to 15g H2In O, stir to complete
Dissolution, is then added dropwise 36% concentrated hydrochloric acid of 2.5ml, then above-mentioned mixed liquor is added slowly in solution A, after 40 DEG C of stirrings for 24 hours
Crystallization is for 24 hours at 100 DEG C.Product after reaction be filtered, washed to neutral, 100 DEG C of dry 6h after again through 550 DEG C of calcining 6h
To remove template agent removing.
Fig. 1 is the XRD spectra of the mesoporous molecular sieve SBA-15 obtained by embodiment 1.As shown in Figure 1, the sample of synthesis
Occur tri- apparent characteristic diffraction peaks of SBA-15 between 0.6 ° -2 °, they correspond respectively to (100), (110) and
(200) crystal face illustrates that the SBA-15 sample of synthesis has typical two-dimentional hexagonal hole road structure.It will be appreciated also that ground is seen, lead to
Chemical reagent can be compared completely as raw material (Na by crossing the mesoporous molecular sieve SBA-15 that the present invention synthesizes2SiO3·5H2O it) synthesizes
Sample out.
Fig. 2 is the TEM photo of the mesoporous molecular sieve SBA-15 obtained by embodiment 1.By Fig. 2 it will be clear that being situated between
The typical fringe-like structures of Porous materials, pore size is uniform, illustrates that the SBA-15 sample of synthesis has the two of long-range order
Tie up hexagonal hole road structure.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, anything that does not depart from the technical scheme of the invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (8)
1. a kind of method using the synthesising mesoporous material SBA-15 of natural diatomaceous earth, which comprises the steps of:
(1) after mixing by diatomite, sodium hydroxide and water, crystallization 2-6h under conditions of being placed in 120-180 DEG C, it is cooling
To room temperature, solution A is obtained；
The mass ratio of diatomite and sodium hydroxide is 1:0.3~0.5 in the solution A；The mass ratio 1 of sodium hydroxide and water:
20~30；
(2) triblock copolymer P123 is dissolved in the water, and adds concentrated hydrochloric acid, obtains solution B；
The mass ratio of P123 and water in the solution B are as follows: 1:18~38；The quality of concentrated hydrochloric acid and water in the solution B
Than for 1:3.0~6.5；
(3) solution A obtained in step (1) is added in solution B obtained in step (2), in 40 DEG C of -45 DEG C of stirring 20-
After 30 hours, crystallization 12-48h is carried out under the conditions of 80-120 DEG C, is cooled to room temperature, product is filtered, washed, is done
After dry, calcining, mesoporous material SBA-15 is obtained；
The mass ratio of the solution A and solution B is 1:1.8-2.2.
2. the method according to claim 1, wherein SiO in the diatomite2Content be 85%-95%.
3. the method according to claim 1, wherein drying condition described in step (4) are as follows: 80 DEG C -120 DEG C
Dry 4-12h.
4. the method according to claim 1, wherein calcination condition described in step (4) are as follows: 550 DEG C of calcinings
6h。
5. the method according to claim 1, wherein washing described in step (4) is to wash to neutrality.
6. the method according to claim 1, wherein the mode of cooling described in step (1) is natural cooling
To room temperature.
7. the method according to claim 1, wherein the mode of cooling described in step (4) is natural cooling
To room temperature.
8. the method according to claim 1, wherein the concentration of concentrated hydrochloric acid described in step (2) is 36%-
38%.
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| WO2014125309A2 (en) * | 2013-02-18 | 2014-08-21 | Teesside University | Supported metal catalyst |
| CN104248980A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
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| CN107417820A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107457005A (en) * | 2016-06-06 | 2017-12-12 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
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2019
- 2019-07-01 CN CN201910586154.6A patent/CN110330026A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014125309A2 (en) * | 2013-02-18 | 2014-08-21 | Teesside University | Supported metal catalyst |
| CN104248980A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN105344337A (en) * | 2015-12-08 | 2016-02-24 | 无锡拓能自动化科技有限公司 | Preparation method for heavy metal wastewater adsorbent |
| CN107417820A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107457005A (en) * | 2016-06-06 | 2017-12-12 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
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