CN101121525A - Method for synthesizing ordered mesoporous molecular sieve by anion effect - Google Patents
Method for synthesizing ordered mesoporous molecular sieve by anion effect Download PDFInfo
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- CN101121525A CN101121525A CNA2007100557072A CN200710055707A CN101121525A CN 101121525 A CN101121525 A CN 101121525A CN A2007100557072 A CNA2007100557072 A CN A2007100557072A CN 200710055707 A CN200710055707 A CN 200710055707A CN 101121525 A CN101121525 A CN 101121525A
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Abstract
The present invention using an anion effect to synthesize an ordered meso-porous molecular sieve belongs to the technical field of the inorganic chemistry and the catalytic chemistry. The hydrothermal synthesis and the calcinations technology are used to produce the ordered meso-porous molecular sieve. The hydrothermal synthesis is that a silica source is added to a hydrochloric acid and a three-block copolymer template agent liquor and stirred to form a gel. A pH valve is adjusted to between 5 and 7. As a condensation accelerator, the anion is added to the gel which is then crystallized hydrothermally at a temperature between 80DEG C and 140DEG C. The anion comprises a urea, an ammonium sulfate and an ammonium nitrate. The template agent is removed by the calcinations technology process. The meso-porous molecular sieve adulterated with a heteroatom adopts the pH adjustment method. The heteroatom is added to the system at the initial stage of the reaction. After a meso-porous structure is formed basically, the pH valve of the system is adjusted to be neutral or weak alkaline by the urea and then the hydrothermal crystallization proceeds. Because the present invention synthesizes the meso-porous molecular sieve under a moderate hydrothermal condition, the silicon species in a frame condenses highly and the hydroxyl content on the hole wall surface and in the inside is little. The present invention has a good hydrothermal stability.
Description
Technical field
The invention belongs to inorganic chemistry and technical field of catalysis chemistry, specially refer to the preparation method of ordered mesoporous molecular sieve with high hydrothermal stability.
Background technology
Since U.S. Mobil company after synthesizing the mesopore molecular sieve of high-sequential first in 1992, mesopore molecular sieve is subject to people's attention day by day.Because it has the potential purposes at numerous areas such as separating purification, biomaterial, chemosynthesis, semi-conductor, optics, drug delivery, particularly it is having aspect sorbent material, catalyzer and support of the catalyst and important use value.But, be different from traditional micro porous molecular sieve crystal, mesopore molecular sieve is owing to silicon species condensation in the skeleton is incomplete, there are a large amount of hydroxyls in hole wall surface and inside, therefore mesopore molecular sieve has lower hydrothermal stability, plant like this and limited its application, become the focus that people pay close attention to so how to improve the hydrothermal stability of mesopore molecular sieve in catalysis, absorption and fields such as separating.
By the skeleton condensation level that increases mesoporous material is the effective way that improves its hydrothermal stability, is the method for the simplest promotion skeleton condensation level and improve synthesis temperature.Recently there are some researches show, utilize fluorine-containing tensio-active agent to mix as template with hc-surfactant, can be at synthesizing ordered mesopore molecular sieve under the higher temperature (180～220 ℃), product has very high silicon species condensation degree (Q
4/ Q
3=6.5), and hydrothermal stability.But because fluorine-containing tensio-active agent has very high toxicity, environment is polluted, and high temperature is synthetic the drawback of himself (condition harshness, waste energy etc.), and therefore the mesopore molecular sieve of the synthetic high condensation of silicon species has crucial realistic meaning under the condition of gentleness.
In the nineties in last century, people such as kumar discover that a lot of negatively charged ion can quicken the condensation of silicon species, and the crystallization time of minimizing zeolite crystal (Kumar R., Bhaumik A., Ahedi R., Ganapathy S.Nature 1996,381,298-300.).Subsequently, some studies show that negatively charged ion also can quicken the polymerization of silicon in mesopore molecular sieve is synthetic, and improve its hydrothermal stability, but this result only be used in synthesizing alkaline condition under (as, synthesize MCM-41 and MCM-48).Some synthetic mesopore molecular sieves under acidic conditions can't improve hydrothermal stability by anion effect.
Aforesaid Q
4The silicon species Si (OSi) that represents complete condensation
4, Q
3Expression is the silicon species Si (OSi) of complete condensation not
3(OH), by The Fitting Calculation Q
4/ Q
3Ratio just can be represented the completeness of skeleton condensation, traditional mesoporous silicon oxide Q
4/ Q
4＜2.
Summary of the invention
The technical problem to be solved in the present invention is, by in the synthetic system of mesopore molecular sieve, introducing selected negatively charged ion, the synthetic silicon species of preparing in the product skeleton of hydro-thermal is highly condensed under acidic conditions, the meso-porous molecular sieve material of good hydrothermal stability also can be prepared the mesopore molecular sieve of high catalytic activity by introducing various heteroatomss simultaneously.
Method synthetic molecular screen material of the present invention is to make skeleton with silicon-dioxide, comprises the heteroatomic silicon-base oxide of pure silicon oxide compound and containing metal, and metal heteroatom comprises metals such as aluminium, iron, molybdenum, gallium, vanadium, manganese, zirconium, titanium, tungsten, hafnium, niobium.These meso-porous molecular sieve material varying aperture scopes are 20～300 , by SiO
2-M
XO
YForm Si/M=∞～5 wherein, M=Fe
3+, Al
3+, Mo
3+, Ga
3+, Ti
4+, V
4+, Zr
4+, Mn
4+, W
6+, X, Y satisfy the valent numerical value of oxide compound, and M can represent two or more metals; Silicon species is highly condensed on the hole wall, and the silicon hydroxy radical content is few, i.e. Q
4/ Q
3=3～7.And existing orderly meso-hole structure has high hydrothermal stability again.
The method of utilizing the anion effect synthesizing ordered mesoporous molecular sieve of the present invention, do the silicon source with tetraethoxy or water glass or water glass, with triblock copolymer P123 or F127 is template, is solvent with water, and, calcination process synthetic through hydro-thermal prepares orderly meso-porous molecular sieve material.Said hydro-thermal is synthetic to be, the silicon source is added hydrochloric acid, template solution, stir and form gel, regulate pH value to 5～7 with comprising ammoniacal liquor, and the adding negatively charged ion is made condensation accelerator, carried out hydrothermal crystallizing 24～72 hours at 80～140 ℃ then, in molar ratio the silicon source: template: negatively charged ion: hydrochloric acid: water=1.0: 0.005～0.02: 0.25～4: 2～5: 100～200; Said negatively charged ion comprises ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium phosphate.Said calcination process is 400～700 ℃ of calcinings 1～50 hour.
Because some material can slowly decomposite negatively charged ion, for example urea in the aqueous solution.Urea can slowly decomposite ammonium ion and carbanion in temperature is higher than 70 ℃ water, can change the pH value of solution simultaneously lentamente, so the profit that use urea kills two birds with one stone as promotor the having of silicon species condensation.
Therefore, the method for utilizing the anion effect synthesizing ordered mesoporous molecular sieve of the present invention can be to use urea to regulate the pH value; Hydro-thermal building-up process when using urea to regulate the pH value is the silicon source to be added hydrochloric acid, template solution, stirring formation gel, add urea, solution is warming up to 70～95 ℃, treats that the pH value of solution value changes to 5～6, carried out hydrothermal crystallizing 24～72 hours at 80～140 ℃.
Above-mentioned can also comprise some cats products, negatively charged ion just surface-active agent and nonionogenic tenside by the hc-surfactant of anion effect synthesizing ordered mesoporous molecular sieve under the hydrothermal condition of gentleness.
The heteroatomic mesopore molecular sieve that mixes has adopted the method for pH regulator, heteroatoms adds system in initial reaction stage, after meso-hole structure basically forms, with urea regulation system pH value to neutrality or weakly alkaline, carry out hydrothermal crystallizing then, the heteroatoms species transfer polymeric form to from ionic state like this, thereby enter mesoporous framework.Concrete preparation process is as follows:
When the method for utilizing the anion effect synthesizing ordered mesoporous molecular sieve of the present invention, the mesopore molecular sieve of synthesizing blender metal heteroatom, carry out according to aforesaid process, wherein, when adding silicon source tetraethoxy, add source metal, add urea then and carry out hydrothermal crystallizing; Said source metal is one or both in the metal oxide of aluminium, iron, molybdenum, gallium, vanadium, manganese, zirconium, titanium, tungsten, hafnium, niobium; Source metal in molar ratio: the silicon source is greater than 0 to 0.2.
The present invention successfully utilizes the promotor of negatively charged ion as silanol condensation, has synthesized orderly mesopore molecular sieve at gentle hydrothermal condition, and the silicon species in its skeleton is highly condensed, hole wall surface and the inner considerably less (Q of hydroxy radical content
4/ Q
3=3～7), and product has extraordinary hydrothermal stability, handles after 3 hours to have kept meso-hole structure in 780 ℃ of water vapour.
Description of drawings
Fig. 1 is the SBA-15-S that makes of the present invention and the XRD spectra after the SBA-15-S hydrothermal treatment consists.
Fig. 2 is product SBA-15-S
29Si NMR spectrogram.
Fig. 3 is nitrogen adsorption and the desorption isotherm of product SBA-15-S through 3 hours front and back of 780 ℃ of steam treatment.The starting point of thermoisopleth A is 300cm
3/ g.
Fig. 4 is the SBA-15-U that makes of the present invention and the XRD spectra after the SBA-15-U hydrothermal treatment consists.
Fig. 5 is product SBA-15-U
29Si NMR spectrogram.
Fig. 6 is the XRD spectra of product SBA-16-S.
Fig. 7 is the XRD spectra after product A l-SBA-15-U and the Al-SBA-15-U hydrothermal treatment consists.
Fig. 8 is product A l-SBA-15-U
29Al NMR spectrogram.
Fig. 9 is the XRD spectra that contains various heteroatomic SBA-15-U that the present invention makes.
Figure 10 is the XRD spectra that contains bimetal AlFe-SBA-15-U that the present invention makes.
Embodiment
Following illustrative example illustrates mesopore molecular sieve that these have high catalytic activity center and hydrothermally stable and preparation method thereof.
Embodiment 1: the hydro-thermal of the ordered mesoporous molecular sieve SBA-15-S of hydrothermally stable is synthetic.
(P123) is dissolved in the 25mL deionized water with the 0.8g triblock copolymer, and the back that stirs adds 3mL hydrochloric acid, after stirring to clarify, adds silicon source tetraethoxy (TEOS) 2.08g.Above-mentioned solution was stirred 20 hours at 40 ℃, regulate pH value to 7 and add 2.64g ammonium sulfate with ammoniacal liquor then, mixture is transferred in the reactor, under 100 ℃ of conditions, placed 48 hours.With the product pumping rate, the room temperature oven dry obtains former powder.Former powder is warming up to 550 ℃ and kept 5 hours in air, can removes tensio-active agent, thereby obtain open duct, this molecular sieve called after SBA-15-S.
By the result of little angle X-ray diffraction (see figure 1) as can be known, SBA-15-S has the two-dimentional hexagonal hole road of rule.Among Fig. 1, the SBA-15-S of A for obtaining after calcining, B is for calcining after 780 ℃ of steam treatment SBA-15-S after three hours.Among Fig. 2,
29Si NMR result shows in the former powder of SBA-15-S, the silicon species Si (OSi) of complete condensation
4Occupy significant proportion, obtain Q by match
4/ Q
3Value be 6.3, condensation level of silicon species is very high in this explanation skeleton.In addition, after 780 ℃ of steam treatment, the x-ray diffraction spectra of SBA-15-S shows demonstration, and it has kept regular meso-hole structure.The nitrogen adsorption experimental result shows (Fig. 3), the SBA-15-S after the hydrothermal treatment consists with handle before the same IV type adsorption isothermal line that provided, indicated that it has kept meso-hole structure in the hydrothermal treatment consists process, and pore distribution does not have considerable change.The above results shows, by the method for anion effect and pH regulator, just can synthesize the mesopore molecular sieve of the highly condensed hydrothermally stable of silicon species under the condition of gentleness.
Embodiment 2: the hydro-thermal of the ordered mesoporous molecular sieve SBA-15-U of hydrothermally stable is synthetic.
(P123) is dissolved in the 25mL deionized water with the 0.8g triblock copolymer, and the back that stirs adds 3mL hydrochloric acid, after stirring to clarify, adds silicon source tetraethoxy (TEOS) 2.08g.Above-mentioned solution was stirred 3～4 hours at 40 ℃, add urea 3～6g then, solution is warming up to about 90 ℃, treat that the pH value of solution value changes to 5～6 gradually, mixture is moved to reactor, under 100 ℃ of conditions, placed 48 hours.With the product pumping rate, the room temperature oven dry obtains former powder.Former powder is warming up to 550 ℃ and kept 5 hours in air, can removes tensio-active agent, thereby obtain open duct, this molecular sieve called after SBA-15-U.
Among Fig. 4, the SBA-15-U of A for obtaining after calcining, B is for calcining after 780 ℃ of steam treatment SBA-15-U after three hours.The result shows that similar to SBA-15-S, SBA-15-U also is a kind of mesopore molecular sieve of high-sequential, and very high hydrothermal stability is also arranged.
29Si NMR result shows that silicon species also has very high condensation level, obtains Q by match in the former powder of SBA-15-U (Fig. 5)
4/ Q
3Value be 4.3.These presentation of results, urea both can be used as the conditioning agent of pH value of solution value, also can be used as the promotor of silicon species condensation.
Embodiment 3: the high temperature of the ordered mesoporous molecular sieve SBA-16-S of hydrothermally stable is synthetic.
0.8g triblock copolymer (F127) is as template, other step that feeds intake, treatment process are identical with embodiment 1, and the product that obtains is designated as SBA-16-S.By low angle x-ray diffraction spectra (Fig. 6) and the high-resolution-ration transmission electric-lens cubic mesoporous duct of product SBA-16-S with rule as can be seen.
29Si NMR result shows in the former powder of SBA-16-S, the silicon species Si (OSi) of complete condensation
4Occupy significant proportion, silicon species also is highly condensed in the former powder of this explanation SBA-16-S.Therefore, SBA-16-S also demonstrates good hydrothermal stability, has still kept the cubic mesoporous duct of rule after three hours through 780 ℃ of steam treatment.
Embodiment 4: the hydro-thermal of the mesopore molecular sieve Al-SBA-15-U of high-sequential is synthetic.
(P123) is dissolved in the 25mL deionized water with the 0.8g triblock copolymer, and the back that stirs adds 3mL hydrochloric acid, after stirring to clarify, adds silicon source tetraethoxy (TEOS) 2.08g.Above-mentioned solution was stirred 3～4 hours at 40 ℃, add the Tai-Ace S 150 of 0.3～1.5g, add urea 3～6g then, other step that feeds intake, treatment process are identical with embodiment 2.
From the X-ray spectrogram of Al-SBA-15-U (Fig. 7, A) in as can be seen, mix up the molecular sieve of aluminium and the same two-dimentional hexagonal structure of sample of pure silicon with high-sequential.Simultaneously because heteroatomic introducing Al-SBA-15-U demonstrates higher hydrothermal stability than the sample SBA-15-U of pure silicon, through 780 ℃ of steam treatment 5 hours, meso-hole structure still well keep (Fig. 7, B).In addition,
27AlNMR spectrogram (Fig. 8) shows that most aluminium are to exist with the four-coordination form in the sample, and this interpret sample has stronger acidity, can be as the solid acid catalyst of bulky molecular catalysis conversion.
Embodiment 5: the hydro-thermal that contains various heteroatomic mesoporous molecular sieve SBA-15-U is synthetic.
Utilize the method that adopts among the present invention, heteroatomss such as iron, molybdenum, gallium, vanadium, manganese, zirconium, titanium, tungsten, hafnium, niobium be directed in the skeleton of mesopore molecular sieve.The step, treatment process of specifically feeding intake is identical with embodiment 4, and just the corresponding metal source replaces aluminium source, source metal in molar ratio: silicon source=0.1.Fig. 9, low angle X-ray spectrogram show that after the different sorts heteroatoms was introduced among mesoporous molecular sieve SBA-15-U, sample equally had the two-dimentional hexagonal structure of high-sequential.And, similarly be that they have also all demonstrated than the better hydrothermal stability of pure silicon sample with Al-SBA-15-U.In addition, owing to contain dissimilar metal heteroatoms, so these samples can be applied in the dissimilar bulky molecular catalysis reactions.
Embodiment 6: the hydro-thermal that contains bimetallic mesoporous molecular sieve SBA-15-U is synthetic.
In some organic chemical reactions, need two or more metal actings in conjunction, thereby play katalysis.In the present invention, at urea during as the promotor of silicon species condensation, because himself decomposes the pH value that slowly changes solution, so also can be used as some heteroatomic precipitation from homogeneous solution agent, can introduce two or more metal heteroatoms simultaneously in mesoporous molecular sieve framework.
(P123) is dissolved in the 25mL deionized water with the 0.8g triblock copolymer, and the back that stirs adds 3mL hydrochloric acid, after stirring to clarify, adds silicon source tetraethoxy (TEOS) 2.08g.Above-mentioned solution was stirred 3～4 hours at 40 ℃, add aluminium source and source of iron, aluminium source in molar ratio: source of iron: silicon source=0.1: 0.1: 1, add urea 3～6g then, other step that feeds intake, treatment process are identical with embodiment 2.From low angle X-ray spectrogram (Figure 10) as can be seen, after having introduced bimetal Al, Fe, mesoporous molecular sieve SBA-15-U still has the two-dimentional hexagonal structure of high-sequential.
Claims (3)
1. method of utilizing the anion effect synthesizing ordered mesoporous molecular sieve, do the silicon source with tetraethoxy or water glass or water glass, with triblock copolymer P123 or F127 is template, is solvent with water, and, calcination process synthetic through hydro-thermal prepares orderly meso-porous molecular sieve material; Said calcination process is 400～700 ℃ of calcinings 1～50 hour; It is characterized in that, said hydro-thermal is synthetic to be, the silicon source is added hydrochloric acid, template solution, stir and form gel, regulate pH value to 5～7 with comprising ammoniacal liquor, and add negatively charged ion and make condensation accelerator, carried out hydrothermal crystallizing 24～72 hours at 80～140 ℃ then, in molar ratio the silicon source: template: negatively charged ion: hydrochloric acid: water=1.0: 0.005～0.02: 0.25～4: 2～5: 100～200; Said negatively charged ion comprises ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium phosphate.
2. according to the described method of utilizing the anion effect synthesizing ordered mesoporous molecular sieve of claim 1, it is characterized in that, be to use urea to regulate the pH value; Hydro-thermal building-up process when using urea to regulate the pH value is the silicon source to be added hydrochloric acid, template solution, stirring formation gel, add urea, solution is warming up to 70～95 ℃, treats that the pH value of solution value changes to 5～6, carried out hydrothermal crystallizing 24～72 hours at 80～140 ℃.
3. method of utilizing the anion effect synthesizing ordered mesoporous molecular sieve, the mesopore molecular sieve of synthesizing blender metal heteroatom carries out according to the described process of claim 1, wherein, when adding silicon source tetraethoxy, add source metal, add urea then and carry out hydrothermal crystallizing; Said source metal is one or both in the metal oxide of aluminium, iron, molybdenum, gallium, vanadium, manganese, zirconium, titanium, tungsten, hafnium, niobium; Source metal in molar ratio: the silicon source is greater than 0 to 0.2.
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