CN1281315C - Molecular sieve containing secondary structure unit of beta zeolite and its preparing process - Google Patents
Molecular sieve containing secondary structure unit of beta zeolite and its preparing process Download PDFInfo
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- CN1281315C CN1281315C CN 01126503 CN01126503A CN1281315C CN 1281315 C CN1281315 C CN 1281315C CN 01126503 CN01126503 CN 01126503 CN 01126503 A CN01126503 A CN 01126503A CN 1281315 C CN1281315 C CN 1281315C
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Abstract
The present invention relates to a mesoporous molecular sieve or a mesoporous and microporous composite molecular sieve novel catalytic material with a beta zeolite secondary structure unit and a preparation method of the novel catalytic material. In the method of the present invention, a synthetic mixture is preprocessed and used as an inorganic precursor, and the beta zeolite secondary structure unit is introduced into the frameworks of mesoporous molecular sieves with a surface active agent supramolecular self-assembly method so that SBU-MCM-41, SBU-MCM-48 and mesoporous and microporous composite molecular sieves are successfully designed and systhesized. The novel molecular sieve with the beta zeolite secondary structure unit has favorable catalytic reaction performance and superior thermal stability and hydrothermal stability.
Description
Technical field
The present invention relates to a class and contain the mesoporous molecular sieve of secondary structure unit of beta zeolite or design of middle mesoporous-microporous composite molecular sieve new catalytic material and preparation method thereof.
Background technology
Since the researcher of Mobil company in 1992 utilizes the synthetic M41S series of the supermolecule self assembly effect mesoporous molecular sieve of surfactant, this mesopore material (MCM-41 and MCM-48) is with its adjustable regular duct, big specific area and good characteristics such as heat endurance, become the heat subject of catalysis material research, people wish that mesoporous molecular sieve can be used in the bulky molecular catalysis reaction.But mesoporous molecular sieve is compared with traditional micro-pore zeolite molecular sieve, has evident difference on skeleton structure.Mesoporous molecular sieve does not have the repetition single cell structure unit in the micro-pore zeolite, the inside unit structure is similar to unformed oxide, do not contain the crystalline structure zone, only there is the local order structure, therefore, it is similar to unformed alumino-silicate to contain the aluminium mesoporous molecular sieve, has more weak and acidity moderate strength, add that hydrothermal stability is relatively poor, thereby limited mesoporous molecular sieve to a great extent in industrial application.People adopt the methods such as the synthetic calorize of Al-MCM-41 and back of synthetic high alumina amount to improve the acidity of mesoporous molecular sieve mostly at present, but these methods have just changed the distribution of aluminium in the mesoporous molecular sieve skeleton, fundamentally do not change the unformed skeleton structure feature of mesoporous molecular sieve, thereby be difficult to reach the purpose that improves acidity effectively.
Micro porous molecular sieve that some are important such as β zeolite etc., because its unique topological structure, good heat and hydrothermal stability and excellent catalytic activity, in the industrial important use that obtained, (＜0.8nm=can not satisfy the requirement of macromolecular reaction but its aperture belongs to range of micropores.We know in the building-up process of micro-pore zeolite molecular sieve, the organic formwork agent molecule can be arranged in the secondary structure unit with zeolite structured feature to the inorganic oxide species, secondary structure unit (Secondary Building Unit) abbreviates SBU as, these secondary structure units can with the IR spectral detection to and on XRD figure spectrum, do not occur.The secondary structure unit of β zeolite is made up of two single four-membered rings and two 5-3 rings, its maximum one dimension physical dimension is much smaller than the pore wall thickness of mesoporous molecular sieve, if the secondary structure unit of β zeolite is incorporated on the mesoporous molecular sieve skeleton structure, can improve the unformed skeleton structure performance of mesoporous molecular sieve, and improve the acidity of mesoporous molecular sieve effectively, up to the present, this type of work does not still have report.
Summary of the invention
The objective of the invention is to develop a class contains the novel mesoporous molecular sieve or the middle mesoporous-microporous composite molecular sieve catalysis material of secondary structure unit of beta zeolite, applied range, function admirable and its preparation method is provided.
Novel molecular sieve catalysis material of the present invention is mesoporous molecular sieve or the middle mesoporous-microporous composite molecular sieve that a class contains secondary structure unit of beta zeolite, and they have following characteristics:
(1) the mesopore hole wall contains the secondary structure unit of β zeolite, and pore wall thickness exceeds 32%～58% than traditional mesoporous molecular sieve; (2) mesoporous molecular sieve that the contains secondary structure unit of beta zeolite SBU-MCM-41 that comprises the hexagonal phase and two kinds of cube mutually SBU-MCM-48; (3) mesoporous-microporous composite molecular sieve is by mesoporous molecular sieve that contains secondary structure unit of beta zeolite and two phase compositions of β micro-pore zeolite in; (4) heat and hydrothermal stability are good, handle 24～48 hours (h) back skeleton structures and do not destroy mesoporous molecular sieve or the middle mesoporous-microporous composite molecular sieve that (5) contain secondary structure unit of beta zeolite and all have good catalytic perfomance in 800～1000 ℃ of roastings or boiling water.
In the present invention, the preparation that contains the mesoporous molecular sieve of secondary structure unit of beta zeolite is achieved like this: the reactant mixture that can form the β zeolite carries out preliminary treatment under uniform temperature and stirring condition, strict control pretreatment time; Occur can detected secondary structure unit of beta zeolite and when not generating the β zeolite crystal again with FT-IR when reactant mixture, stops preprocessing process at once; Utilize liquid crystal micelle that the self assembly of surfactant supermolecule forms then and by interface interaction the inorganic species that contain secondary structure unit of beta zeolite are directed to the mesoporous molecular sieve of regular pore passage structure, the hole wall of this SBU mesopore material thereby have the architectural feature of β zeolite through pretreated inorganic species.At first a certain amount of aluminium source such as boehmite etc. are dissolved in tetraethyl ammonium hydroxide (TEAOH) aqueous solution during preparation, add aerosil then, packing into after stirring has in the stainless steel cauldron of polytetrafluoroethylene bushing, at 130～150 ℃ of stirring reaction 20～140h.The pretreated colloidal sol of above-mentioned process is splashed in certain density softex kw (CTAB) solution and regulates pH is 9.6～12.5, then continues crystallization 24～72h at 100～150 ℃.It is extremely neutral through suction filtration, washing that crystallization finishes the back solid product, in 100 ℃ of oven dry.Dried sample flows down 550 ℃ of roastings one hour at nitrogen earlier, and roasting 6 hours again under the same temperature in air atmosphere then promptly gets roasting type sample.
When preparation contained the mesoporous molecular sieve of secondary structure unit of beta zeolite, used material should reach following molar ratio range: SiO
2/ Al
2O
3=20～150, (TEA)
2O/SiO
2=0.15～0.30, CTAB/SiO
2=0.20～0.49, H
2O/SiO
2=30～100.
Among the above-mentioned preparation method, reactant mixture pretreatment temperature preferably is 135～145 ℃, and pretreatment time is 21～135h.Pretreated requirement is that reactant mixture occurs can detected secondary structure unit of beta zeolite and do not form the β zeolite crystal with FT-IR.
Among the above-mentioned preparation method, used material molar ratio range preferably is: SiO
2/ Al
2O
3=25～100, (TEA)
2O/SiO
2=0.22～0.28, CTAB/SiO
2=0.25～0.41, H
2O/SiO
2=39～96.
In the preparation method of the mesoporous molecular sieve that contains secondary structure unit of beta zeolite, preparation process is finished in two steps: make the synthesized gel rubber that contains secondary structure unit of beta zeolite earlier, then synthesized gel rubber is self-assembled into mesoporous molecular sieve as inorganic precursor with the Surfactant CTAB supermolecule.
In the present invention, the preparation method who contains the middle mesoporous-microporous composite molecular sieve of secondary structure unit of beta zeolite is earlier with a certain amount of aluminium source such as NaAlO
2, silicon source such as aerosil etc. be dissolved in the tetraethyl ammonium hydroxide aqueous solution, in the reactor of packing into after stirring, at 120～160 ℃ of crystallization 36～240h; Take out reactor, the gel in the still is splashed in the CTAB solution, regulating pH is 9.6～10.5, continues crystallization 24～72h at 90～110 ℃ then, and the synthetic mixture molar ratio range is: SiO
2/ Al
2O
3=20～60, (TEA)
2O/SiO
2=0.10～0.20, CTAB/SiO
2=0.12～0.25, H
2O/SiO
2=20～50.Crystallization finishes through suction filtration, washing, and 100 ℃ of oven dry down obtain solid sample.Dried sample flows down at nitrogen and slowly is warming up to 550 ℃ of roastings one hour, is transferred to then in the muffle furnace, at 550 ℃ of roasting 6h again, obtains roasting type sample.
Among the above-mentioned preparation method, after aluminium source, silicon source, tetraethyl ammonium hydroxide and water mixed, crystallization temperature was 130～150 ℃ preferably, and crystallization time is 48～192h.
Among the above-mentioned preparation method, synthetic mixture molar ratio range preferably is: SiO
2/ Al
2O
3=25～40, (TEA)
2O/SiO
2=0.12～0.16, CTAB/SiO
2=0.14～0.20, H
2O/SiO
2=25～35.
Among the above-mentioned preparation method, the preparation process that contains the middle mesoporous-microporous composite molecular sieve of secondary structure unit of beta zeolite realizes in two steps: at first make the synthesized gel rubber that contains secondary structure unit of beta zeolite, then synthesized gel rubber is self-assembled into middle mesoporous-microporous composite molecular sieve as inorganic precursor with the Surfactant CTAB supermolecule.
Mesoporous molecular sieve or the middle mesoporous-microporous composite molecular sieve that contains secondary structure unit of beta zeolite of the present invention is a kind of catalysis material.The introducing of secondary structure unit of beta zeolite has improved the unformed skeleton structure performance of mesoporous molecular sieve, and the acid amount of SBU-MCM-41, SBU-MCM-48 and middle mesoporous-microporous composite molecular sieve is improved largely, thereby shows good catalytic perfomance.Compare with corresponding mesoporous molecular sieve, the acidity of SBU-MCM-41 strengthens, and the isopropylbenzene pyrolysis reactivity has improved more than 68%; And the isopropylbenzene pyrolysis reactivity of SBU-MCM-48 has been not only than corresponding mesoporous molecular sieve much higher (having improved more than 148%), and exceeds more than 13% than the SBU-MCM-41 of identical gel silica alumina ratio.Middle mesoporous-microporous composite molecular sieve has more strong acid amount than mechanical impurity, particularly strong B acid amount, thereby show better catalytic cracking reaction activity (the normal heptane pyrolysis reactivity has improved 30%).
Description of drawings
Novel molecular sieve catalysis material of the present invention has the characterization result of typical Fig. 1-5.
Fig. 1 is XRD figure spectrum (a) 25 of SBU-MCM-41 mesoporous molecular sieve of the roasting of different synthesized gel rubber silica alumina ratios; (b) 50; (c) 100.As seen from the figure, the XRD figure spectrum of the SBU-MCM-41 of different synthesized gel rubber silica alumina ratios is similar, all locate to demonstrate stronger hexagonal mesopore phase character diffraction maximum in (100), (110) with the more weak representative hexagonal mesopore of (200) equal strength mutually the characteristic diffraction peak of fine structure then differentiate not open, between 4 °～5 ° diffraction zones of XRD figure spectrum, show as hill born of the same parents peak.
Fig. 2 is the XRD figure spectrum through the SBU-MCM-48 mesoporous molecular sieve of roasting.Demonstrate the several characteristic diffraction maximum of typical cube of mesopore phase among the figure, that is: 211,220,400,420 and 332.
Fig. 3 is XRD figure spectrum (S1) 16% of middle mesoporous-microporous composite molecular sieve of the roasting of different crystallinity; (S2) 19%; (S3) 28%; (S4) 39%.In the mesopore diffraction region, the diffraction maximum of 2 θ between 1.9 °～2.3 ° is that the distinctive hexagonal of MCM-41 is arranged diffraction maximum, and in the micropore diffraction region, near the diffraction maximum of 2 θ 7.8 °, 22.4 ° is β zeolite characteristic diffraction peak.
Fig. 4 is (a) SBU-MCM-41 and (b) the IR skeletal vibration spectrum of mesopore tester.On the IR of SBU-MCM-41 spectrogram, can see 569cm
-1And 520cm
-1The distinctive dicyclo absorption of vibrations of β zeolite bands of a spectrum have appearred in two places, and the secondary structure unit that existence has the Beta zeolite structures feature on the middle hole on framework of SBU-MCM-41 is described.And 650～500cm on the IR of mesopore tester spectrogram
-1Do not observe between vibrating area and the relevant characteristic absorption band of zeolitic frameworks vibration, demonstrate unformed skeleton structure feature.
Fig. 5 is a mesoporous-microporous composite molecular sieve in (a); (b) β zeolite and MCM-41 mechanical impurity
129The XeNMR spectrum.As can be seen from the figure, under close equilibrium adsorption pressure, the not Xe gas peak of absorption all appears in composite molecular screen and mechanical impurity near chemical shift 0ppm.Chemical shift is that chemical shift is that the adsorption peak of 120.8ppm is corresponding in adsorption peak and the mechanical impurity of 119.2ppm in the composite molecular screen, belongs to the Xe absorption for β micropore phase.Chemical shift is the adsorption peak of the peak of 96.3ppm corresponding to MCM-41 mesopore phase in the mechanical impurity, and the chemical shift of the corresponding adsorption peak of composite molecular screen is at the 109.1ppm place, exceed 12.8ppm, show there is stronger absorption in Xe, mesoporous-microporous composite molecular sieve contains the mesopore pore passage structure that is different from mechanical impurity in this shows, this is because have the secondary structure unit of β zeolite on the middle hole on framework of composite molecular screen, thereby shows stronger Xe adsorption capacity.
The specific embodiment
Embodiment 1
With 0.067g boehmite (51wt%Al
2O
3) be dissolved in the 10.0g tetraethyl ammonium hydroxide solution (25wt%), add the 2.0g aerosil then, packing into after stirring has in the stainless steel cauldron of polytetrafluoroethylene bushing, at 140 ℃ of following stirring reaction 22h.The pretreated colloidal sol of above-mentioned process is splashed in the CTAB solution that concentration is 15.8wt%, and at this moment the synthetic mixture mole consists of: SiO
2: 0.01Al
2O
3: 0.25 (TEA) 2
O: 0.28CTAB: 39H
2O.Then regulating pH with dilute sulfuric acid is 10.5, at 100 ℃ of following crystallization 48h, obtains SBU-MCM-41 mesoporous molecular sieve (SiO
2/ Al
2O
3=91.1).
Take by weighing 0.1g boehmite (51wt% Al
2O
3), be dissolved in the 7.0g tetraethyl ammonium hydroxide solution (25wt%), add the 1.5g aerosil then, packing into after stirring has in the stainless steel cauldron of polytetrafluoroethylene bushing, at 135 ℃ of following stirring reaction 56h.The pretreated colloidal sol of above-mentioned process is splashed in the CTAB solution that concentration is 14.1wt%, and at this moment the synthetic mixture mole consists of: SiO
2: 0.02Al
2O
3: 0.23 (TEA)
2O: 0.25CTAB: 53H
2O.Then regulating pH with dilute sulfuric acid is 10.0, at 95 ℃ of following crystallization 60h, obtains SBU-MCM-41 mesoporous molecular sieve (SiO
2/ Al
2O
3=47.7).
Embodiment 3
With 0.133g boehmite (51wt%Al
2O
3) be dissolved in the 5.0g tetraethyl ammonium hydroxide solution (25wt%), add the 1.0g aerosil then, packing into after stirring has in the stainless steel cauldron of polytetrafluoroethylene bushing, at 145 ℃ of following stirring reaction 124h.The pretreated colloidal sol of above-mentioned process is splashed in the CTAB solution that concentration is 16.2wt%, and at this moment the synthetic mixture mole consists of: SiO
2: 0.04Al
2O
3: 0.25 (TEA)
2O: 0.29CTAB: 61H
2O.Then regulating pH with dilute sulfuric acid is 10.5, at 105 ℃ of following crystallization 72h, obtains SBU-MCM-41 mesoporous molecular sieve (SiO
2/ Al
2O
3=22.4).
Take by weighing 0.033g boehmite (51wt%Al
2O
3), be dissolved in the 5.0g tetraethyl ammonium hydroxide solution (25wt%), add the 1.0g aerosil then, packing into after stirring has in the stainless steel cauldron of polytetrafluoroethylene bushing, at 140 ℃ of following stirring reaction 23h.The pretreated colloidal sol of above-mentioned process is splashed in the CTAB solution that concentration is 9.1wt%, and at this moment the synthetic mixture mole consists of: SiO
2: 0.01Al
2O
3: 0.25 (TEA)
2O: 0.41CTAB: 94H
2O.Regulating pH with dilute sulfuric acid again is 11.8, at 135 ℃ of following crystallization 36h, obtains SBU-MCM-48 mesoporous molecular sieve (SiO
2/ Al
2O
3=82.1).
Claims (3)
1, a kind of preparation method who contains the mesoporous molecular sieve of secondary structure unit of beta zeolite, it is characterized in that the reactant mixture of when mesoporous molecular sieve prepares aerosil, aluminium source, tetraethyl ammonium hydroxide and water being formed stirs, 130～150 ℃ of stirring reaction preliminary treatment 20～140 hours, then it is joined in the softex kw solution, reaction system has following mole and forms: SiO
2/ Al
2O
3=20～150, (TEA)
2O/SiO
2=0.15～0.30, CTAB/SiO
2=0.20～0.49, H
2O/SiO
2=30～100; Then at 100--150 ℃, pH is a crystallization 24～72 hours under 9.6～12.5 the condition, makes the molecular sieve that contains secondary structure unit of beta zeolite, and its pore wall thickness exceeds the molecular sieve 32～58% that does not contain secondary structure unit of beta zeolite.
2, the preparation method who contains the mesoporous molecular sieve of secondary structure unit of beta zeolite according to claim 1 is characterized in that reactant mixture was 135～145 ℃ of stirring reaction preliminary treatment 21～135 hours.
3, the preparation method who contains the mesoporous molecular sieve of secondary structure unit of beta zeolite according to claim 1 is characterized in that the reaction system molar ratio range is: SiO
2/ Al
2O
3=25～100, (TEA)
2O/SiO
2=0.22～0.28, CTAB/SiO
2=0.25～0.41, H
2O/SiO
2=39～96.
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| CN101491773B (en) * | 2008-01-25 | 2013-06-12 | 北京石油化工学院 | MCM-41 molecular sieve catalyst containing phosphor aluminum structure unit, 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 |
| CN104261422A (en) * | 2014-09-18 | 2015-01-07 | 陕西宝姜新能源技术研发有限公司 | Synthesis method of composite molecular sieve |
| CN104944437B (en) * | 2015-06-24 | 2017-03-22 | 辽宁工业大学 | Preparation method of mesoporous molecular sieve with mesoporous walls of Beta zeolite structures |
| CN109234217A (en) * | 2018-06-29 | 2019-01-18 | 安徽瑞赛生化科技有限公司 | Produce the immobilization and its application of 2,5- furandicarboxylic acid recombination engineering bacteria |
| CN112934254B (en) * | 2019-12-11 | 2023-06-20 | 中国科学院大连化学物理研究所 | Dual-function catalyst for catalyzing n-heptane conversion and preparation method thereof |
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