CN1313207C - Method for preparing uniform nanometer molecular sieve material with high catalytic activity - Google Patents
Method for preparing uniform nanometer molecular sieve material with high catalytic activity Download PDFInfo
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- CN1313207C CN1313207C CNB2004100394527A CN200410039452A CN1313207C CN 1313207 C CN1313207 C CN 1313207C CN B2004100394527 A CNB2004100394527 A CN B2004100394527A CN 200410039452 A CN200410039452 A CN 200410039452A CN 1313207 C CN1313207 C CN 1313207C
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Abstract
The present invention relates to a method for preparing uniform nanometer molecular sieve materials with high catalytic activity, which belongs to the field of inorganic chemistry and physical chemistry, and the present invention is relevant to a method of preparing molecular sieve catalysts. Compared with the prior art, the present invention which is suitable for production has the advantage of simple technology; nano molecular sieves prepared by the method have the advantages of high uniformity, large specific surface area, favorable catalytic activity; the nano molecular sieves can be used as adsorbing agents, catalysts and catalyst carriers widely applied to the field of chemical industry.
Description
Technical field
The present invention relates to a kind of preparation method with homogeneous nano molecular sieve material of high catalytic activity, it is the preparation method who belongs to inorganic chemistry and the relevant molecular sieve catalyst in physical chemistry field.
Background technology
And extensive use on catalysis synthetic since the success of zeolite molecular sieve, people are devoted to strengthen the catalysis of molecular sieve always, one of them importance is exactly to synthesize the nano molecular sieve with specific function, the size and the uniformity how to control nano molecular sieve always are the focus that people study, ZSM-5 in these molecular sieves, TS-1's is synthetic more noticeable, because they are widely used as catalyst (in TS-1 respectively in catalytic cracking and environmental friendliness catalysis many petrochemical industries such as (utilizing solution for oxidation of phenol with hydrogen peroxide to be benzenediol) and fine chemistry industry process, titanium species has three kinds of co-ordination states usually, in these co-ordination states, it is most important that the four-coordination titanium is used for catalytic oxidation).
See Iver Schmidt, Clars Madsen and ClausJ.H.Jacobsen, Inorg.Chem.2000,39,2279-2283 with the most close background technology of the present invention.The preparation method of the disclosed nano molecular sieve of this article prepares very the molecular sieve presoma of low concentration to grow in the pore structure of mesoporous material, utilizes limited space, duct to come the synthesis of nano molecular sieve.But the specific area of the ZSM-5 that makes is lower than 440m
2/ g, and the adjusting of reactant and the accurate adjusting of concentration of molecular sieve presoma all are the difficulties of synthesizing in synthetic.Because the specific area of prepared molecular sieve is lower, causes it also to exist many weak points in commercial Application.
Summary of the invention
Purpose of the present invention provides a kind of preparation method with homogeneous nano molecular sieve material of high catalytic activity with regard to being to avoid above-mentioned the deficiencies in the prior art part.This preparation with homogeneous nano molecular sieve material of high catalytic activity, be with butyl silicate, ten hydrazine aluminum sulfates, NaOH, the uniform high molecular polymer bead of butyl titanate and water is a raw material, prepare presoma with the organic amine for the template agent, and by mixing, hydro-thermal is synthetic to be got with roast, its major technology characteristics be its preparation presoma be with butyl silicate, ten hydrazine aluminum sulfates, NaOH, butyl titanate and organic formwork agent be colloidal sol mutually, and 100～140 ℃ of placements 0.5～5.5 hour, stir at the uniform macromolecule bead of the water of 100-300 nanometer with granularity then and be beneficial to even mixing in 5～8 hours, then in that to carry out hydro-thermal synthetic, the mixture that is about to obtain is transferred in the anticorrosion reactor and was left standstill 4～5 days under 100～140 ℃ of temperature, and at last that hydro-thermal is synthetic semi-finished product can obtain the purpose product in roast 8-10 hour under 550 ℃ of temperature.Wherein, the agent of organic amine template is TPAOH, TEAOH, TPABr, TEABr.In order better to carry out roast, can be in the process of roast be raised to 500 ℃ from 25 ℃, again 500～600 ℃ of temperature lower calcinations 4～8 hours with 1 ℃/min speed.
The specific embodiment
Come enumeration technical characterstic of the present invention below in conjunction with specific embodiment.
In actual fabrication, best building-up process can be carried out in two steps, i.e. presoma preparation evenly mixes back hydro-thermal under 100～140 ℃ of temperature with the macromolecule bead again and synthesized 4～5 days.Best calcination process need be raised to 500 ℃ from 25 ℃ with 1 ℃/min speed, again 500～600 ℃ of temperature lower calcinations 4～8 hours.Nano molecular sieve material specific area of the present invention can be at 500m under optimum condition
2More than/the g, the uniformity can be more than 90%.
Embodiment 1: the preparation of even molecular sieve ZSM-5
Do the silicon source with butyl silicate etc., do the template agent, the batching Al of synthetic traditional Z SM-5 with TPAOH
2O
3/ SiO
2/ template agent/H
2The O molar ratio is 1.0/30/8/375.At first, the template agent is soluble in water, then to wherein adding aluminium source and silicon source.After treating that this solution stirs clarification, make its abundant hydrolysis to wherein adding NaOH then, make pH value 7～9.The colloidal sol that obtains was clear sol in synthetic 3 hours 140 ℃ of hydro-thermals, colloidal sol that will synthesize and macromolecule bead mix 8 hours dress stills of stirring, synthetic 4 days of hydro-thermal, sample are warming up to 550 ℃ of calcinings 8～10 hours since 25 ℃ of speed with 1 ℃/min at last through the washing oven dry.
This sample granularity is 200nm evenly approximately, and the ZSM-5 spectrum peak of the position at XRD spectrum peak and standard is consistent, but the peak shape broad, this better interpret sample be nano particle (as Fig. 1).Characterize by the nitrogen adsorption desorption, sample also has a more precipitous absorption to further illustrate the absorption second time of nano particle at specific pressure 0.8 place, and the BET area surpasses 520m
2/ g (as Fig. 2).In addition, we also characterize the granularity and the uniformity (as Fig. 3) of observing nano particle by TEM, and Fig. 3 shows that the sample granularity that is synthesized is distributed in the 190-210nm interval, and further specifying sample is even-grained nano particle.And the even ZSM-5 that synthesizes is 1,3,5, and activity is higher than traditional ZSM-5 far away in triisopropylbenzene (TIPB) bulky molecular catalysis, as table-1 (catalyst amount reduces 60% than positive usual amounts in the table-1).
Table-1 nano-ZSM-5 and traditional Z SM-5 are in the comparison of little molecule and bulky molecular catalysis.
| Sample E | Specific area m 2/g | Si/Al A | The cumene conversion ratio B ％ | 1,3,5, the triisopropylbenzene conversion ratio B％ |
| Nano-ZSM-5 | 495 | 62 | 61 | 53.9 |
| Conventional ZSM-5 | 350 | 35 | 40 | 4.4 |
Embodiment 2: the preparation of the nanometer TS-1 molecular sieve of high-specific surface area uniformly
Do the titanium source with butyl titanate etc., do the silicon source, do the template agent with TPAOH with butyl silicate etc.Batching is example (TiO in molar ratio
2/ SiO
2/ TPAOH/C
2H
5OH/H
2O=1.0/30/8/120/375).Technical process is also substantially the same manner as Example 1.The titanium-silicon molecular sieve TS-1 that contains Ti that makes is in specific area, and granularity is also roughly the same, and the four-coordination species by UV, visible light spectrogram (figure-4) the sample Ti that as seen we synthesized are main coordination mode in addition.Simultaneously, its reactivity of even TS-1 that we synthesize also is better than traditional TS-1, as figure-5 and figure-6.Figure-5 has illustrated that when normal catalytic agent consumption nanometer TS-1 reacts at the beginning speed faster than traditional TS-1, and arrive reaction end prior to traditional TS-1: figure the-6th, reduce by 60% o'clock measured result at catalyst amount than positive usual amounts, illustrate in the nanometer TS-1 entire reaction course all obviously active high-speed fast than traditional TS-1.
Embodiment 3: the evenly preparation of the nanometer Beta molecular sieve of high-specific surface area
Do the silicon source with butyl silicate etc., do the template agent, synthetic traditional batching Al with TEAOH
2O
3/ SiO
2/ template agent/H
2The O molar ratio is 1.0/30/8/375.At first, the template agent is soluble in water, then to wherein adding aluminium source and silicon source.After treating that this solution stirs clarification, make its abundant hydrolysis to wherein adding NaOH then, make pH value 7～9.The colloidal sol that obtains was clear sol in synthetic 4.5 hours 140 ℃ of hydro-thermals, colloidal sol that will synthesize and macromolecule bead mix 8 hours dress still hydro-thermals of stirring and synthesized 1 day, the sample that synthesizes is warming up to 550 ℃ of calcinings 8～10 hours since 25 ℃ of speed with 1 ℃/min at last through the washing oven dry.Obtained sample granularity is distributed in about 200nm.
The invention effect
Method of the present invention is compared with background technology, and technique is very simple, is suitable for producing; And the nano molecular sieve uniformity that makes is high, has high-specific surface area, and catalytic activity is high; And can be used as adsorbent, catalyst and catalyst carrier is widely used at chemical field.
Claims (3)
1. the preparation method who has the homogeneous nano molecular sieve material of high catalytic activity, it is with butyl silicate, ten hydrazine aluminum sulfates, NaOH, the uniform high molecular polymer bead of butyl titanate and water is a raw material, with the organic amine is that organic formwork agent prepares presoma, and by mixing, hydro-thermal is synthetic to be got with roasting, it is characterized in that preparing presoma is with butyl silicate, ten hydrazine aluminum sulfates, NaOH, butyl titanate mixes mutually with organic formwork agent, and 100～140 ℃ of placements 0.5～5.5 hour, stir at the uniform high molecular polymer bead of the water of 100-300 nanometer with granularity then and be beneficial to even mixing in 5～8 hours, and then carry out hydro-thermal and synthesize, the mixture that is about to obtain is transferred in the anticorrosion reactor and was left standstill 4～5 days under 100～140 ℃ of temperature, and at last that hydro-thermal is synthetic semi-finished product promptly obtained the purpose product in 8～10 hours at 550 ℃ of roasting temperatures.
2. the preparation method with homogeneous nano molecular sieve material of high catalytic activity according to claim 1 is characterized in that described roasting process need be raised to 550 ℃ from 25 ℃ with 1 ℃/min speed, calcines 8～10 hours again.
3. the preparation method with homogeneous nano molecular sieve material of high catalytic activity according to claim 1 is characterized in that described organic formwork agent is tetrapropyl oxyammonia, tetraethyl oxyammonia, tetrapropyl amine bromide, tetraethyl amine bromide.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493902A (en) * | 1983-02-25 | 1985-01-15 | Engelhard Corporation | Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making |
| CN1342608A (en) * | 2001-08-24 | 2002-04-03 | 复旦大学 | Process for preparing multi-class sequential macroreticular-micropore material |
| CN1348920A (en) * | 2001-09-26 | 2002-05-15 | 复旦大学 | Prepn of silica with great specific surface area |
| CN1393402A (en) * | 2001-07-04 | 2003-01-29 | 中国科学院大连化学物理研究所 | Process for preparing nano Y zeolite molecular sieve carried by kaolin microspheres |
| CN1394806A (en) * | 2002-06-27 | 2003-02-05 | 复旦大学 | Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493902A (en) * | 1983-02-25 | 1985-01-15 | Engelhard Corporation | Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making |
| CN1393402A (en) * | 2001-07-04 | 2003-01-29 | 中国科学院大连化学物理研究所 | Process for preparing nano Y zeolite molecular sieve carried by kaolin microspheres |
| CN1342608A (en) * | 2001-08-24 | 2002-04-03 | 复旦大学 | Process for preparing multi-class sequential macroreticular-micropore material |
| CN1348920A (en) * | 2001-09-26 | 2002-05-15 | 复旦大学 | Prepn of silica with great specific surface area |
| CN1394806A (en) * | 2002-06-27 | 2003-02-05 | 复旦大学 | Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead |
Non-Patent Citations (1)
| Title |
|---|
| 微孔－大孔双孔结构β沸石材料的构筑规律 王星东等，复旦学报（自然科学版），第41卷第3期 2002 * |
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