CN1160249C - Mesoporous molecular sieve material with strong acidity and high hydrothermal stability and its prepn - Google Patents
Mesoporous molecular sieve material with strong acidity and high hydrothermal stability and its prepn Download PDFInfo
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- CN1160249C CN1160249C CNB011356243A CN01135624A CN1160249C CN 1160249 C CN1160249 C CN 1160249C CN B011356243 A CNB011356243 A CN B011356243A CN 01135624 A CN01135624 A CN 01135624A CN 1160249 C CN1160249 C CN 1160249C
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Abstract
The present invention relates to a mesoporous molecular sieve material with strong acidity and super high hydrothermal stability and a preparation method thereof. The mesoporous pore diameter range of the molecular sieve material is from 20 to 500 A, and pore walls comprise primary or secondary basic structure units of zeolites. The stable mesoporous molecular sieve material is formed by that firstly, precursors containing the primary or secondary basic structure units of zeolites are prepared; then the precursors and surface active agents are self-assembled. The acid strength of the mesoporous molecular sieve material of the present invention is similar to that of zeolite molecular sieves, and the mesoporous molecular sieve material has high hydrothermal stability and thermal stability and high catalytic activity so that the mesoporous molecular sieve material is suitable for the chemical industry production and application.
Description
The invention belongs to inorganic chemistry and physical chemistry field, specially refer to mesopore molecular sieve and technology of preparing thereof with strongly-acid and high hydrothermal stability.
The background technology close with the present invention is that name is called the Chinese patent application of " micro porous molecular sieve and synthetic method thereof in compound ", open day on February 24th, 1999, publication number CN1208718A.The disclosed molecular sieve of this application for a patent for invention is the double-hole structure that mesopore, micropore communicate, but its specification sheets has provided two kinds of dissimilar spectrum peaks of X-ray diffraction, a kind ofly appears at 1.5-6 °, corresponding mesopore phase character peak, another kind appears at 8-30 °, corresponding micropore phase character peak.This explanation products therefrom can only be the mechanical mixture of mesopore, micro porous molecular sieve.Disclosed method is a single stage method, just will wear out aging temperature 20-35 ℃ before crystallization by common way.
The objective of the invention is to overcome the weakness of background technology, prepare novel meso-porous molecular sieve material, introduced the elementary of zeolite and secondary basic structural unit on the hole wall of these novel mesopore molecular sieves, therefore have strongly-acid and superelevation hydrothermal stability.
Meso-porous molecular sieve material of the present invention is made up of silicon, aluminium, oxygen element.Its structure is hexagonal mesoporous structure, and mesoporous pore diameter range is at 20-500 .Contain the elementary of zeolite on the hole wall or/and secondary building unit.Infrared spectra shows, at 400-600cm
-1There is the characteristic absorbance of zeolite basic structural unit in the zone.NH
3The temperature programmed desorption(TPD) temperature is 350-450 ℃.NH
3Temperature programmed desorption(TPD) (TPD) experiment condition: sample is N under 500 ℃ of conditions
2NH is at room temperature introduced in middle heating 3 hours
3, again in N
2In 150 ℃ of NH that eliminate down physical absorption
3TPD-NH
3Heat-up rate is 15 ℃ of per minutes in the research.The MCM-41 mesopore molecular sieve of prior art and a kind of mesopore molecular sieve of the present invention---the infrared spectra of called after MAS-5 is provided by Fig. 1 relatively.A is the infrared spectra of MCM-41, and b is the infrared spectra of MAS-5 of the present invention.The TPD-NH of two kinds of molecular sieves
3Curve is provided by Fig. 2.A is the NH of MCM-41
3Adsorption curve, b is the NH of MAS-5 of the present invention
3Adsorption curve.
The preparation method of meso-porous molecular sieve material of the present invention comprises two steps: at first with the silicon source, the aluminium source stirs in the presence of little template (1), and ageing obtains presoma then; (2) big template such as tensio-active agent are joined carry out hydrothermal crystallizing in the precursor solution again.Specifically be stated as:
With silicon source and aluminium source is raw material, with tetrapropylammonium cation (TPA
+) or tetraethylammonium cation (TEA
+), or K
+Or Na
+Or they be combined as template, be tensio-active agent with cetyl trimethylammonium bromide or triblock copolymer, its proportioning is Al
2O
3/ SiO
2/ template/tensio-active agent/H
2O=1.0/5～700/1.5～75/2.0～3.6/200～10000; Synthetic by hydrothermal method, make finished product through filtration, washing, drying at room temperature, it is characterized in that, earlier silicon source and aluminium source are stirred with template and water, be 100～140 ℃ of heating 1～3 hour or be 25～90 ℃ in temperature and placed 10～100 hours in temperature, make and contain the elementary of zeolite or/and the precursor solution of secondary basic structural unit; Said hydrothermal method be with presoma with the tensio-active agent hydrothermal crystallizing, self-assembly forms meso-porous molecular sieve material.
With silicon source, aluminium source is raw material, and the silicon source can be white carbon black, silicon sol, and tetraethyl silicate etc., the aluminium source can be a Tai-Ace S 150, meta-aluminic acid is received etc.Template can be that organic ion also can be a mineral ion; TPA
+TPAOH can be used or/and TPABr, TEA
+TEAOH can be used or/and TEABr, Na
+Or K
+Can be with NaOH or KOH.By changing different proportionings, can make the mesopore molecular sieve of different zeolites basic structural unit, concrete ratio can be referring to embodiment.
Said hydrothermal crystallizing is tensio-active agent to be mixed stirring back adding presoma stir with water, and the autoclave of packing into carries out crystallization.The potential of hydrogen PH=10 of reaction mixture～11 or＜1.0, can regulate by strong acid or highly basic.Crystallization temperature is at 80～140 ℃, and crystallization time is 1～10 day.
Enumerate embodiment below, mesopore molecular sieve that these have strongly-acid and superelevation hydrothermal stability and preparation method thereof is described.
Embodiment 1: have the basic structural unit of Beta molecular sieve the sial presoma preparation and have strongly-acid and the preparation of the mesopore molecular sieve MAS-5 of superelevation hydrothermal stability
(1) synthetic sial presoma with the basic structural unit of Beta molecular sieve
Meta-aluminic acid is received and the TEAOH mixing, added white carbon black.After this system stirs to clarify solution, again 100-140 ℃ of heating 1-3 hour.At this moment, the presoma of preparation mesopore molecular sieve just forms.This presoma can find that through infrared spectrum characterization tangible spectrum peak appears at 520-600cm
-1, this exists T-O-T (the T=Si or AL) structure of 5 yuan of rings owing to this presoma.
(2) has the mesopore molecular sieve MAS-5 and preparation method thereof of strongly-acid and superelevation hydrothermal stability
Add tensio-active agent cetyl trimethylammonium bromide (CTAB) in preparing presoma, the regulation system pH value is 10～11, put into again reactor inherent 100-140 ℃ crystallization 1-5 days.The crystallization solid product by filtration, flushing and drying after, obtain required product, its product S iO
2/ Al
2O
3Ratio can change between 6.0-350, our called after MAS-5 of these materials.
Al
2O
3/ SiO
2/ TEAOH/CTAB/H
2O ratio is: 1.0/28.0-350/10.0-63.0/12.0-32.0/500-20000.
MAS-5 has very high hydrothermal stability, the product of embodiment 1 (was positioned in the boiling water 300 hours through experiment, with 800 ℃ of water vapors 2 hours) prove that not only the stability in ebullient water surpasses 300 hours, but also to the stability of 800 ℃ water vapour above 2 hours.
High resolution TEM and the bright MAS-5 of electron-diffraction diagram stave have very regular hexagonal mesoporous structure, and its pore size is greatly about about 27 .Fig. 2 has provided the TPD-NH of MAS-5
3The desorption curve, the result shows that MAS-5 has and the very similar strength of acid of Beta zeolite.In Fig. 2, curve a, b, c is corresponding MCM-41, MAS-5 and Beta zeolite respectively.
Table 1 has provided MAS-5 to 1,3, and the catalytic cracking activity of 5-triisopropylbenzene is compared with other sample, and MAS-5 has not only provided the highest catalytic conversion, and gives best catalytic stability.
Table 1. different catalysts is to 1,3, the catalytic cracking activity of 5-triisopropylbenzene
Sample SiO
2/ Al
2O
3The treatment condition rate, the % temperature of reaction, ℃
HZSM-5 84 --- 1.7 250
HMCM-41 80 --- 65.8 250
HMCM-41 80 boiling water 6h＜0.1 250
80 600 ℃ of water vapour＜0.1 250 of HMCM-41
2h
MAS-5 81 --- 78.8 250
MAS-5 81 boiling water 300h 79.1 250
81 600 ℃ of water vapour of MAS-5 78.9 250
4h
80 800 ℃ of water vapour of MAS-5 77.5 250
2h
MAS-5 123 --- 87.0 320
MAS-5 81 --- 90.1 320
MAS-5 59 --- 95.2 320
(catalyzed reaction is a pulse reaction, and the catalysis data are the result after the pulse 10 times.In each reaction, catalyst levels 50mg, reactant pulse are 0.4 μ ml, and carrier gas flux is 53.7ml/min.)
Further, we also characterize MAS-5 by technology such as IR, NMR and UVRaman.The IR result of MAS-5 demonstrates fairly obvious 520-590cm
-1The spectrum peak shows that MAS-5 exists zeolite basic structural units (Fig. 1) such as 5-or 6-unit ring; MAS-5's
27A1 NMR spectrogram provides 61ppm, and this extremely is similar to the spectrum peak of Beta zeolite, and different significantly with the 54ppm of MCM-41, and this shows that the A1 species are basic identical in the chemical environment of the chemical environment of MAS-5 and Beta zeolite.
Embodiment 2: have mesopore molecular sieve MAS-7 of strongly-acid and superelevation hydrothermal stability and preparation method thereof
The presoma of preparation mesopore molecular sieve is as described in the example 1.After preparing mesopore molecular sieve synthetic presoma, add triblock copolymer (Pluronic P-123) again,,, put into again behind the reactor 40 ℃ of stirrings after 20 hours less than 1 with hydrochloric acid regulation system pH value at 100 ℃ of crystallization 1-3 days.The crystallization solid product by filtration, flushing and drying after, obtain required product, its product S iO
2/ Al
2O
3Ratio can change between 30-350, our called after MAS-7 of these materials.The batching Al of synthesising mesoporous molecular sieve MAS-7
2O
3/ SiO
2/ TEAOH/P123/H
2The ratio of O is 1.0-6.5/28.0-350/10.0-63.0/20.0-30.0/800-1000.
The XRD of MAS-7 and TEM have provided a symmetric regular meso-hole structure of typical six sides.Handled 2 hours under the condition of ebullient water placement 300 hours or 800 ℃ of water vapour, its XRD spectra is constant substantially, and this has shown that equally MAS-7 has high hydrothermal stability.
Employing comprises the precursor solution of other zeolite basic structural units, the similar preparation method of application and MAS-5 and MAS-7 can prepare a series of mesopore molecular sieves with strongly-acid and superelevation hydrothermal stability, below is the preparation method's of part presoma embodiment.
Embodiment 3: the preparation method of presoma with silico-aluminate of X zeolite and Y basic structural unit
Synthetic batching Na with sial presoma of X and Y molecular sieve basic structural unit
2O/Al
2O
3/ SiO
2/ H
2O ratio is 20-35/1.0/15-20/300-600.
At first, a certain amount of NaOH is dissolved in the quantitative water, until clarification.Then, add water glass again, stirred 15-30 minute, until clarification.At last, placed 10-30 hour at 25-30 ℃.
Embodiment 4: the preparation method of presoma with silico-aluminate of zeolite L basic structural unit
Synthetic batching K with sial presoma of the basic structural unit of L molecular sieve
2O/Na
2O/Al
2O
3/ SiO
2/ H
2O ratio is 8-12/6-8/1.0/15-40/200-400.
At first, a certain amount of KOH and NaOH are dissolved in the quantitative water, until clarification.Then, add white carbon black again, stirred 10-40 minute, until clarification.At last, placed 20-60 hour at 25-30 ℃.
Embodiment 5: the preparation method of presoma with silico-aluminate of zeolite MFI basic structural unit
Synthetic batching Al with sial presoma of the basic structural unit of MFI molecular sieve
2O
3/ SiO
2/ TPABr orTPAOH/H
2O ratio is 0-1.0/10-70/3-7.5/500-2000.
At first, a certain amount of aluminium salt (Tai-Ace S 150 or sodium metaaluminate) is dissolved in the quantitative TPA of containing
+In the aqueous solution, until clarification.Then, add silicon source (white carbon black, silicon sol or tetraethyl silicate) again, stir until translucent colloidal sol.At last, placed 10-100 hour at 45-90 ℃.The infrared spectra spectrogram of sample is at 550cm
-1Provide a spectrum peak, this is owing to the T-O-T vibration of 5 yuan of rings.
Meso-porous molecular sieve material of the present invention has strongly-acid, high hydrothermal stability.Since the existence of zeolite basic structural unit, product catalytic activity height, stability is strong, in catalysis, and absorption, fields such as separation have applied value and application prospect widely.The method for preparing meso-porous molecular sieve material of the present invention can be applied to prepare the meso-porous molecular sieve material with various zeolite basic structural units.
Description of drawings:
Fig. 1 is the infrared spectrogram (a:MCM-41 of a kind of mesopore molecular sieve of the present invention; B:MAS-5)
Fig. 2 is the NH of a kind of mesopore molecular sieve of the present invention
3Temperature programming adsorption curve figure.(a:MCM-41; B:MAS-5; The c:Beta zeolite)
Claims (3)
1, the meso-porous molecular sieve material of a kind of strongly-acid and high hydrothermal stability is a basal component with silicon, aluminium, oxygen, has hexagonal mesoporous structure, it is characterized in that, contains the elementary of zeolite or/and the secondary basic structural unit on hole wall; Its infrared spectra is presented at 400～600cm
-1Absorption peak is arranged in the scope; NH
3Program is given birth to warm desorption experiment and is shown that its desorption temperature is 350～450 ℃.
2, the preparation method of the meso-porous molecular sieve material of the strongly-acid that provides of a kind of claim 1 and high hydrothermal stability is a raw material with silicon source and aluminium source, with tetrapropylammonium cation or tetraethylammonium cation, or K
+Or Na
+Or they be combined as template, be tensio-active agent with cetyl trimethylammonium bromide or triblock copolymer, its proportioning is Al
2O
3/ SiO
2/ template/tensio-active agent/H
2O=1.0/5～700/1.5～75/2.0～3.6/200～10000; Synthetic by hydrothermal method, make finished product through filtration, washing, drying at room temperature, it is characterized in that, earlier silicon source and aluminium source are stirred with template and water, be 100～140 ℃ of heating 1-3 hour or be 25～90 ℃ in temperature and placed 10～100 hours in temperature, make and contain the elementary of zeolite or/and the precursor solution of secondary basic structural unit; Said hydrothermal method be with presoma with the tensio-active agent hydrothermal crystallizing, self-assembly forms meso-porous molecular sieve material.
3, according to the preparation method of the meso-porous molecular sieve material of described strongly-acid of claim 2 and high hydrothermal stability, it is characterized in that the acidity-basicity ph value of reaction mixture is 10～11 or less than 1.0 in the said hydrothermal method.
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| CN100343167C (en) * | 2004-07-07 | 2007-10-17 | 南开大学 | Synthesis method of mesoporous molecular sieve |
| HUE061093T2 (en) | 2004-12-28 | 2023-05-28 | Neste Oyj | Method for the preparation of catalytic materials |
| CN101683620B (en) * | 2008-09-27 | 2013-04-10 | 北京石油化工学院 | Cubic mesoporous molecular sieve catalyst with micropore canals, preparation method and use thereof |
| CN101746773B (en) * | 2008-12-09 | 2012-05-09 | 复旦大学 | Preparation method of water-surface active agent-alcohol system small crystal grain Beta zeolite |
| CN101941711B (en) * | 2009-07-09 | 2012-09-12 | 中国石油化工股份有限公司 | Preparation method of highly stable MSUY-41 molecular sieve |
| CN103193244B (en) * | 2013-04-02 | 2015-03-04 | 复旦大学 | Method for increasing hydrothermal stability of mesoporous material |
| CN104891526B (en) * | 2014-03-07 | 2019-01-04 | 中国石油天然气股份有限公司 | Preparation method of high-stability mesoporous molecular sieve |
| CN104891524B (en) * | 2014-03-07 | 2019-01-04 | 中国石油天然气股份有限公司 | Preparation method of high-stability mesoporous molecular sieve containing rare earth heteroatoms |
| CN104891525B (en) * | 2014-03-07 | 2018-09-25 | 中国石油天然气股份有限公司 | Preparation method of strong-acid high-stability mesoporous molecular sieve |
| CN107129157A (en) * | 2017-05-08 | 2017-09-05 | 浙江理工大学 | A kind of preparation method of three-dimensional porous bioactivity glass |
| CN111460947B (en) * | 2020-03-15 | 2022-05-31 | 吉林大学 | BP neural network-based method and system for identifying metal minerals under microscope |
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