CN103845921A - Ultrasonic extraction recovery of organic template agent P123 from SBA-15 - Google Patents
Ultrasonic extraction recovery of organic template agent P123 from SBA-15 Download PDFInfo
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- CN103845921A CN103845921A CN201210505939.4A CN201210505939A CN103845921A CN 103845921 A CN103845921 A CN 103845921A CN 201210505939 A CN201210505939 A CN 201210505939A CN 103845921 A CN103845921 A CN 103845921A
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Abstract
The invention relates to an ultrasonic extraction recovery method of an organic template agent P123 from SBA-15. The method is performed under best extraction technological conditions of ultrasonic extraction recovery of the organic template agent P123 from SBA-15, and has the advantages of being short in extraction time, high in P123 recovery rate, convenient to operate and the like. SBA-15 molecular sieve obtained through ultrasonic extraction has better structural performances compared with SBA-15 molecular sieve obtained through a roasting method, the organic template agent P123 recovered through ultrasonic extraction is basically not different from a standard sample on a micro level and a macro level, and guarantee is provided for cyclic application of P123.
Description
Technical field
The present invention relates to a kind of ultrasonic extraction and reclaim the method for organic formwork agent P123 in SBA-15, belong to technical field of chemical separation.
Background technology
SBA-15 molecular sieve is a research class the most widely in SBA molecular sieve series, especially in recent years along with the development of petroleum refining industry, oil deep processing is more and more higher for the requirement of catalyst, and SBA-15 molecular sieve receives numerous scientists' concern, becomes study hotspot.(SBA represents University of California to SBA-15, Santa Barbara) be a class by scientists such as Stucky G D under strong acidic condition, utilize a kind of non-ionic surface active agent (polyvinylether-polypropylene ether-polyvinylether triblock copolymer, PEO-PPO-PEO, be called for short P123) as the synthetic mesoporous silicon based molecular sieve of template, there is the hexagon straight hole structure of high-sequential, its aperture can change within the scope of 5～50nm, and hole wall thicker (typically at 3-9nm).In the process of SBA-15 Zeolite synthesis, organic formwork agent P123 plays a part very important.Before SBA-15 is applied to petroleum catalyst, need organic formwork agent to remove, could form like this pore passage structure of regular spaciousness.Because a large amount of organic formwork agents is wrapped among the duct of different pore size, and also has the existence of a lot of active forces (Van der Waals force, hydrogen bond, ionic bond and weak interaction etc.), therefore, which type of method to remove the template wrapping up in SBA-15 by, preparing SBA-15 molecular sieve unique, duct homogeneous, is to make it to be applied to oil catalytic field matter of utmost importance to be solved before.Organic formwork agent removes out from the duct of porous compounds following mode: a kind of is that organic formwork agent directly removes from duct with the form of template molecule, and another kind is first organic formwork agent to be decomposed into little molecule to remove from duct with micromolecular form again.At present, the most frequently used method of removed template method is roasting method, but high-temperature roasting method has relatively high expectations for the heat endurance of SBA-15, and easily causes removing and Lattice Contraction phenomenon of framework silicon hydroxyl for general SBA-15, there will be severe skeleton avalanche.Recently, what some were new remove the method for template in porous material is in the news, as solvent extraction, UV ozone method, Microwave Digestion, plasma method and supercritical CO
2extraction.Representative the method with organic formwork agent in organic solvent method extraction MCM-48 is disclosed as CN1843596-A; CN101851002-A discloses a kind of method of using solvent method to remove organic formwork agent in silica duct; SG77145-A1 discloses a kind of method of using supercritical fluid to remove organic formwork agent in porous material.(the Yang J such as Duan Xue, He J, Duan X, et al.Structure and properties of silylated MCM-48[J] .Chinese J.Inorg.Chem., 2002,18 (9): 879-886) propose two one-step baking methods, make first at low temperatures organic formwork agent decompose, and then rise to assigned temperature and carry out roasting, the molecular screen material obtaining so is all better than the material of conventional roasting method gained.(the Zhuang X such as Zhuang, Qian X F, Lv JH, et al.Analternative method to remove PEO-PPO-PEO template in organic-inorganic mesoporous nanocomposites by sulfuric acid extraction [J] .Appl.Surf.Sci., 2010, 256:5343-5348) use sulfuric acid as the template P123 in solvent extraction organic-inorganic meso-porous nano composite, result of study shows, the sulfuric acid solution of service property (quality) mark 48%, under the condition of 90 ℃, reflux extraction 24 hours, almost can remove organic formwork agent P123 completely.(the Grieken R V such as Grieken R V, Calleja G, Stucky G D, et al.Supercritical fluid extraction of a non-ionic surfactant template from SBA-15materials and consequences on the porous structure[J] .Langmuir, 2003,19:3966-3973) use first supercritical CO
2organic formwork agent P123 in extraction SBA-15, result of study shows, uses separately supercritical CO
2extraction is basic identical with the effect of common alcohol solvent extraction; When to supercritical CO
2in while adding ethanol as entrainer, the extraction efficiency of organic formwork agent P123 is significantly improved, under 90 ℃ and 13MPa, extract 24h, the rate of recovery of P123 can reach 81%.
Said method exists very long, the problem such as equipment manufacturing cost is higher and the rate of recovery is lower consuming time.The present invention relates to a kind of ultrasonic extraction and reclaim the method for organic formwork agent P123 in SBA-15.Utilize the ultrasonic cavitation that ultrasonic wave has to reclaim organic formwork agent P123 in SBA-15, ultrasonic cavitation refers to that solvent is because ultrasonication makes to have produced in liquid negative pressure, in the time that negative pressure reaches a certain particular value, liquid is broken, thereby make the local gasification of liquid, the cavitation of its moment has the very release of macro-energy, has certain fuel factor and mechanical effect, thereby reaches good effect of extracting.The advantages such as the method is carried out under the best extractant condition of organic formwork agent P123 in SBA-15 is reclaimed in ultrasonic extraction, has extraction time short, and the P123 rate of recovery is high, easy to operate.The SBA-15 molecular sieve finally obtaining has good structural behaviour with respect to roasting method, and reclaim the organic formwork agent P123 that obtains does not substantially have difference with standard items in microcosmic and macroscopic view, can be it and recycles and provide safeguard.
Summary of the invention
The object of the invention is to overcome the deficiency of existing recovery P123 method, propose the method for organic formwork agent P123 in a kind of ultrasonic extraction recovery SBA-15, this extracting process comprises the following steps:
(1) take the former powder 3-5g of SBA-15 and be placed in extractor, carry out ultrasonic extraction according to the experiment condition designing, the product finally obtaining by suction filtration device with revolve steam kettle device separates concentrate for subsequent use.
(2) by X-ray powder diffraction, thermogravimetric analysis, infrared spectrum and N
2the methods such as adsorption/desorption, characterize the SBA-15 molecular sieve obtaining, as shown in accompanying drawing 1 to 4.
(3) the organic formwork agent P123 by liquid infrared spectrum, gel permeation chromatography, extraction being obtained characterizes, as shown in accompanying drawing 5 and 6.
In a word, enforcement of the present invention has following beneficial effect:
The present invention adopts ultrasonic extraction method to reclaim the organic formwork agent P123 in SBA-15, and its process can significantly shorten extraction time, and step is simple, and P123 organic efficiency is high.
By SBA-15 molecular sieve that relatively the present invention obtains with adopt roasting method to remove the structural behaviour of the SBA-15 molecular sieve that P123 obtains, as shown in accompanying drawing 1-4, the SBA-15 molecular sieve that presentation of results the present invention obtains has framework silicon hydroxyl, lattice does not shrink, do not cause skeleton avalanche phenomenon, has better structural behaviour.Characterize reclaiming the template P123 obtaining by liquid infrared spectrum and gel permeation chromatography, as shown in accompanying drawing 5 and 6, found that P123 that the present invention reclaims and infrared spectrum and the gel infiltration spectrogram of its standard items coincide, show that the P123 reclaiming through the present invention is consistent with structure on macro-level at microcosmic with its standard items, illustrate that the P123 reclaiming through the present invention can be applied in synthesizing of SBA-15 again.
Attached caption
Fig. 1 is the small angle x-ray diffraction (SAXD) spectrogram of SBA-15 molecular sieve.
(the former powder of a-SBA-15; SBA-15 after b-roasting; SBA-15 after c-ultrasonic extraction)
Fig. 2 is the thermogravimetric analysis curve of SBA-15 molecular sieve.
(the former powder of a-SBA-15; SBA-15 after b-ultrasonic extraction)
Fig. 3 is the FFIR figure of SBA-15 molecular sieve.
(the former powder of a-SBA-15; SBA-15 after b-roasting; SBA-15 after c-ultrasonic extraction)
Fig. 4 is the N of SBA-15 molecular sieve
2adsorption/desorption spectrogram.
SBA-15 after (▲-roasting; SBA-15 after ■-ultrasonic extraction)
Fig. 5 is the infrared spectrum of P123.
(a-P123 standard items; The P123 that b-ultrasonic extraction is reclaimed)
Fig. 6 is the gel permeation chromatography figure of P123.
(a-P123 standard items; The P123 that b-ultrasonic extraction is reclaimed)
Specific implementation method
Below in conjunction with embodiment, the present invention is further described:
Embodiment 1
Take the former powder 4g of SBA-15 and be placed in extractor, control ultrasonic extraction optimum process condition: methyl alcohol is solvent, extraction temperature 73-76 ℃, extraction 1h, quantity of solvent 400mL, ultrasonic power 250W.Under this condition, carry out ultrasonic extraction experiment, the product finally obtaining by suction filtration device with revolve steam still separates concentrate for subsequent use, the template P123 rate of recovery can reach 75%.Make solvent with methyl alcohol, from SBA-15, the method for ultrasonic extraction recovery P123 can significantly reduce extraction time, and analysis result shows that the SBA-15 molecular sieve structure performance after extraction is good after tested, reclaims the P123 obtaining and possesses the condition recycling.
Claims (3)
1. (SBA represents University of California to a ultrasonic extraction recovery SBA-15, Santa Barbara) in the method for organic formwork agent P123 (P123 represents polyvinylether-polypropylene ether-polyvinylether triblock copolymer), it is characterized in that comprising the following steps: (1) packs former SBA-15 powder into extraction equipment, with methyl alcohol as extractant, controlling extraction temperature is that 300-500mL, ultrasonic power are that 150-250W and extraction time are 0.5-2h at 60-80 ℃, Solvent quantity, and the organic formwork agent P123 rate of recovery can reach 60-80%; (2) the SBA-15 sample after ultrasonic extraction separates by decompress filter, and solvent steams still concentration and recovery by revolving.
2. method according to claim 1, is characterized in that SBA-15 molecular sieve dry for standby in 100 ℃ of baking ovens of obtaining through decompress filter in step (2), controls to reclaim revolving of solvent and steam still at 70-80 ℃.
3. method according to claim 1, is characterized in that the SBA-15 molecular sieve obtaining in step (2) is by X-ray powder diffraction, thermogravimetric analysis, infrared spectrum and N
2adsorption/desorption carries out analysis and characterization; The organic formwork agent P123 that recovery obtains carries out analysis and characterization by liquid infrared spectrum and gel permeation chromatography.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145142A (en) * | 2015-04-13 | 2016-11-23 | 中国石油化工股份有限公司 | Removing molecular sieve organic formwork agent method |
| WO2020098184A1 (en) * | 2018-11-16 | 2020-05-22 | 浙江大学 | Method for using super/subcritical fluid to remove volatile compounds from foam |
| CN111683901A (en) * | 2018-01-24 | 2020-09-18 | 柏林工业大学 | Method for obtaining mesoporous silica particles with surface functionalization |
| CN114029029A (en) * | 2021-12-06 | 2022-02-11 | 南方海洋科学与工程广东省实验室(广州) | Preparation method of mesoporous silica dehumidifying material and product thereof |
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| WO1996029297A1 (en) * | 1995-03-23 | 1996-09-26 | Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145142A (en) * | 2015-04-13 | 2016-11-23 | 中国石油化工股份有限公司 | Removing molecular sieve organic formwork agent method |
| CN106145142B (en) * | 2015-04-13 | 2019-04-12 | 中国石油化工股份有限公司 | Remove molecular sieve organic formwork agent method |
| CN111683901A (en) * | 2018-01-24 | 2020-09-18 | 柏林工业大学 | Method for obtaining mesoporous silica particles with surface functionalization |
| CN111683901B (en) * | 2018-01-24 | 2024-03-26 | 柏林工业大学 | Method for obtaining mesoporous silica particles with surface functionalization |
| WO2020098184A1 (en) * | 2018-11-16 | 2020-05-22 | 浙江大学 | Method for using super/subcritical fluid to remove volatile compounds from foam |
| CN114029029A (en) * | 2021-12-06 | 2022-02-11 | 南方海洋科学与工程广东省实验室(广州) | Preparation method of mesoporous silica dehumidifying material and product thereof |
| CN114029029B (en) * | 2021-12-06 | 2024-01-02 | 南方海洋科学与工程广东省实验室(广州) | Preparation method of mesoporous silica dehumidification material and product thereof |
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Application publication date: 20140611 |