CN101024503A - Method for preparing ordered mesoporous aluminium oxide - Google Patents
Method for preparing ordered mesoporous aluminium oxide Download PDFInfo
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- CN101024503A CN101024503A CN 200710063718 CN200710063718A CN101024503A CN 101024503 A CN101024503 A CN 101024503A CN 200710063718 CN200710063718 CN 200710063718 CN 200710063718 A CN200710063718 A CN 200710063718A CN 101024503 A CN101024503 A CN 101024503A
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Abstract
The invention relates to a manufacturing method for ordered medium aperture alumina that includes the following steps: adding surface activator into inorganic aluminum salt as template agent, making precipitant solution, adding inorganic aluminum salt solution into hypergravity reactor, adding precipitant, when the reacting solution reaching a certain pH value, the precursor sol would be gained; taking aging, filtering, washing, and drying to the precursor sol to gain precursor powder. The powder could be made into ordered medium aperture alumina after taking sintering. The invention has the advantages of simple technology, safe to operate, low cost, etc. The specific surface of the product reaches 250-300m2/g, and the shape has certain orderliness. It has crucial application value in adsorption and catalyzing process.
Description
Technical field
The invention belongs to the batch preparations of nano structural material preparation field, particularly ordered mesoporous aluminium oxide.
Background technology
Aluminum oxide is the solid materials of a kind of porousness, high degree of dispersion, has good adsorption performance, surface acidity and thermostability.Can be used as sorbent material, catalyzer and carrier is applied in many chemical processes.Ordered mesoporous aluminium oxide is that a kind of specific surface is big, the aperture between 2-50nm, pore size distribution is narrow and the duct is big or small, the novel nano structured material of shape certain ordered.Along with the develop rapidly of petrochemical complex and Materials science, especially under the promotion of mesopore molecular sieve MCM-41 achievement in research, the technology of preparing of ordered mesoporous aluminium oxide has begun to be paid attention to by people,
Aluminum oxide with order mesoporous structure has multiple outstanding physicochemical property than traditional aluminum oxide, its specific surface is big, compound with regular structure, the aperture is big, the surface has acid sites outstanding feature fractionation by adsorption and the aspect such as enzyme immobilization conversion in the macromolecular catalytic cracking of heavy oil, heterogeneous catalyst, petrochemical process has important use and be worth, and the preparation method who grasps this ordered mesoporous aluminium oxide has great importance.
The method that synthesizing ordered mesoporous material is commonly used is to be template with the tensio-active agent, utilizes physical and chemical processes such as sol-gel, precipitation, emulsification or microemulsified, generates ordered mesoporous material by the interface interaction self-assembly between organism and the inorganics.
In above-mentioned several synthesizing ordered mesoporous method of alumina, the organoaluminum source and the template that mostly are costliness that adopt, its cost is higher, processing condition are wayward, all only rest on laboratory study at present, be difficult for realizing the industrialization amplification, realize that suitability for industrialized production is the difficult point of current mesoporous material technology of preparing.
High-gravity technology can realize that quick microcosmic mixes and very big reinforcing mass transfer, can control chemical reaction, nucleation crystallisation process effectively on molecular scale, obtains the nanoparticle that particle is little, be evenly distributed, and is characterized in that technology is simple, is easy to industrialization and amplifies.
It is raw material that patent CN03122259.5 has described with zinc nitrate and hydrogen sulfide, utilizes high-gravity reactive precipitation to prepare nano-zinc sulfide.Preparing nano-zinc sulfide according to the method for its invention, to prepare the zinc sulphide cost than original technology lower, and particle diameter is even, narrow particle size distribution, and crystal formation is more complete.But high-gravity technology is applied to prepare ordered mesoporous material yet there are no report.
Summary of the invention
At the deficiency that exists on the prior art, the method for preparing ordered mesoporous aluminium oxide that the object of the present invention is to provide that a kind of technology is simple, operational safety, cost are low, is easy to industrial amplification production.The present invention is based on nanostructure self-assembly mechanism, adopt the precipitator method to prepare ordered mesoporous aluminium oxide, the aluminum nitrate of choosing (aluminium source), volatile salt (precipitation agent) and the equal price of non-ionic type template polyoxyethylene glycol are cheap, adopt supergravity reactor to realize the small serial production of ordered mesoporous aluminium oxide simultaneously.Big (the 250-300m of the specific surface area of synthesising mesoporous aluminum oxide
2/ g), and pore size distribution narrow (4-10nm), the duct is vermiform and has certain order.
Concrete preparation process of the present invention is as follows:
A. prepare the inorganic aluminum salting liquid of 0.1～0.6mol/l, again to the surfactant polyethylene 1540 that wherein adds 0.9g as template; The precipitation agent sal volatile of cofabrication 0.6mol/l; Described inorganic aluminate is: a kind of in aluminum nitrate, the Tai-Ace S 150.
B. the inorganic aluminum salting liquid of being prepared is added in the hypergravity reaction unit, setting the hypergravity level is 120～170g, and temperature of reaction is 60～70 ℃, adds precipitation agent with 5～50ml/min speed, after the reaction soln pH value reaches 7～8, obtain hydrated alumina colloidal sol; Preferable hypergravity level is that 140～150g, preferable precipitation agent adding speed are 8～40ml/min.
C. with gained hydrated alumina colloidal sol among the step B at 20～70 ℃ of down aging 6～12h, through filtration, washing, 80 ℃ dry down alumina hydrate powder;
D. with gained alumina hydrate powder among the step C under nitrogen protection, be warmed up to 330 ℃ with 2～3 ℃/min speed and kept 3 hours, under the condition of logical oxygen, be warmed up to 550 ℃ with 2～3 ℃/min speed and kept 3 hours then, make ordered mesoporous aluminium oxide.
The structure of reactor of hypergravity is described (as shown in Figure 1) in patent publication CN03122259.5 to some extent, the technical process of step B is: inorganic aluminum salting liquid is added in the stirring tank (4), through recycle pump (5) feed liquid is circulated between stirring tank (4) and high-gravity rotating bed (1), utilize circulating hot water to keep the temperature of reaction.By charge pump (3) volatile salt is added high-gravity rotating bed (1), emit gained alumina in Nano level hydrate colloidal sol after reaction is finished.
In the present invention, the synthesis mechanism of ordered mesoporous aluminium oxide is a nanostructure self-assembly mechanism, the reaction of inorganic aluminate and precipitation agent generates alumina in Nano level hydrate colloidal sol, afterwards alumina in Nano level hydrate colloidal sol under the template effect directed be piled into orderly mesoporous.Therefore generating rate and the accumulation rate of controlling the nano aluminium oxide hydrate particles are its important links.Particle diameter, shape, the homogenizing degree of nano aluminium oxide hydrate also have material impact to the order of meso-hole structure simultaneously.
In the present invention, utilize supergravity reactor can realize the characteristics that quick microcosmic mixes, reinforcing mass transfer also greatly improves the nanoparticle dispersiveness, on molecular scale, control chemical reaction, nucleation crystallisation process effectively, obtain nano aluminium oxide hydrate big or small, that shape evenly reaches good dispersity, when generating the nano aluminium oxide hydrate, make itself and template thorough mixing, build meso-hole structure for nano particle ordered accumulation and create advantageous conditions.
Supergravity reactor hypergravity level used in the present invention is high more, and strong more to the reinforcement of transmittance process and dispersion process, the size of nano aluminium oxide hydrate, shape are even more, and dispersiveness is good more.
The precipitation agent feed rate can be controlled the generating rate and the accumulation rate of nano inoganic particle effectively among the present invention.
The crystal formation of reaction end pH value decision nano aluminium oxide hydrate of the present invention, and then influence institute's meso-hole structure aheap.
Aging temperature and digestion time are the important factors that influences nano aluminium oxide hydrate particles accumulation rate among the present invention.Have only strict control aging temperature and digestion time, just can prepare orderly meso-porous alumina.
Among the present invention because the special physical properties of aluminum oxide; therefore in calcination process, must control the speed that removes of water and template; avoid influencing the order of meso-hole structure owing to cave in; adopting nitrogen protection is in order to delay the speed that removes of water in the initial oxidation aluminium hydrate; the later stage aerating oxygen is for organic formwork agent is removed fully; strict simultaneously control heat-up rate is avoided mesoporous the caving in of piling up.
Its constitutional features of ordered mesoporous aluminium oxide of preparation can be observed by TEM, and as shown in Figure 2, the mesopore orbit of formation is vermiform, and the duct size, and shape has certain order.Nitrogen isothermal adsorption desorption curve shows that the orderly interface meso-porous alumina of preparation has the mesoporous curve of typical VI type among Fig. 3, Fig. 4 then shows the narrow 4nm of pore size distribution of the meso-porous alumina of preparation, the duct order is strong, and these constitutional featuress have essential distinction with common aluminum oxide.The ordered mesoporous aluminium oxide specific surface area of preparation is 299m
2/ g, pore volume are 0.26cm
3/ g, the aperture is 4.7nm.Near the strong diffraction peak that occurs 1 ° of the ordered mesoporous aluminium oxide Small angle XRD diffractogram of Fig. 5 preparation shows that the mesopore orbit of formation is orderly.The wide-angle XRD diffractogram of Fig. 6 illustrates that then the meso-porous alumina of formation is unformed.
The specific surface area of the synthesising mesoporous aluminum oxide of the present invention is big, and scope is at 250-300m
2/ g, the narrow 4nm of pore size distribution, the duct is vermiform and has certain order, and its special structure is different from conventional aluminium oxide, and is big in chemical process absorption and catalytic field using value.The method applied in the present invention technology is simple, operational safety, and cost is low, is easy to industrial amplification production.
Description of drawings
Fig. 1 is a hypergravity reaction unit synoptic diagram of the present invention.
1-rotating bed 2-thermometer 3-charge pump 4-stirring tank
5-recycle pump 6-under meter 7-variable valve 8-adds the hot water inlet
Fig. 2 is the transmission electron microscope photo of the ordered mesoporous aluminium oxide of the embodiment of the invention 1 preparation.
Fig. 3 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 1 preparation.
Fig. 4 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 1 preparation.
Fig. 5 is the Small angle XRD figure of the ordered mesoporous aluminium oxide of the embodiment of the invention 1 preparation.
Fig. 6 is the wide-angle XRD figure of the ordered mesoporous aluminium oxide of the embodiment of the invention 1 preparation.
Fig. 7 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 2 preparations.
Fig. 8 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 2 preparations.
Fig. 9 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 3 preparations.
Figure 10 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 3 preparations.
Figure 11 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 4 preparations.
Figure 12 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 4 preparations.
Figure 13 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 5 preparations.
Figure 14 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 5 preparations.
Figure 15 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 6 preparations.
Figure 16 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 6 preparations.
Figure 17 is the ordered mesoporous aluminium oxide nitrogen isothermal adsorption desorption graphic representation of the embodiment of the invention 7 preparations.
Figure 18 is the ordered mesoporous aluminium oxide graph of pore diameter distribution of the embodiment of the invention 7 preparations.
Embodiment
A. with the aluminum nitrate solution of the 0.6mol/l of 2200ml preparation, the polyoxyethylene glycol that adds 0.9g is as template;
B. the dissolving back adds in the supergravity reactor (as shown in Figure 1), keeping the hypergravity level is 140g, and 70 ℃ of temperature of reaction add the sal volatile of the 0.6mol/l that 1650ml/l configures with the speed of 8ml/min, when the reaction end pH value reaches 7, obtain hydrated alumina colloidal sol.
C. gained hydrated alumina colloidal sol was worn out 6 hours under 70 ℃ of temperature, the hydrated alumina colloidal sol process vacuum pump suction filtration after wearing out, and wash filter cake 2-3 time with water, 80 ℃ of following obtaining of drying aluminium hydrate powder.
D. the gained alumina hydrate powder is calcined; concrete calcination process is: 3 ℃/min speed is warmed up to 330 ℃ under nitrogen protection, keeps 3 hours, and the following 3 ℃/min of the condition speed of logical oxygen is warmed up to 550 ℃ then; kept 3 hours, and obtained ordered mesoporous aluminium oxide.
By TEM observation, as shown in Figure 2, the mesopore orbit of formation is vermiform, and the duct size, and shape has certain order.Nitrogen isothermal adsorption desorption curve (as shown in Figure 3) shows that the aluminum oxide of preparation has the mesoporous curve of typical VI type, and graph of pore diameter distribution shown in Figure 4 shows that pore size distribution is narrow.Specific surface area is 298.6m
2/ g, pore volume are 0.26cm
3/ g, the aperture is 5.3nm.Near the strong diffraction peak that occurs 1 ° in the Small angle XRD diffractogram of Fig. 5 shows that the mesopore orbit of formation is orderly.The wide-angle XRD diffractogram of Fig. 6 illustrates that then the mesoporous material of formation is unformed.
A. with the aluminum nitrate solution of the 0.1mol/l of 2200ml preparation, the polyoxyethylene glycol that adds 0.9g is as template;
Other steps are with embodiment 1.
The aluminum oxide specific surface area of preparation is 254m
2/ g, pore volume are 0.28cm
3/ g, the aperture is 4.7nm.By nitrogen isothermal adsorption desorption tracing analysis (shown in Figure 7), its adsorption curve is a VI type curve, and Fig. 8 shows that its pore size distribution narrows down, and shows that its order strengthens.
Operate identically with embodiment 1, that different is digestion time 12h, and aging temperature is 30 ℃.
The aluminum oxide specific surface area of preparation is 301m
2/ g, pore volume are 0.28cm
3/ g, the aperture is 5.4nm.By nitrogen isothermal adsorption desorption tracing analysis (shown in Figure 9), its adsorption curve is a VI type curve, and significantly the H ring becomes big, and Figure 10 shows that pore size distribution is narrow, and its mesoporous feature is obvious.
Operate identically with embodiment 1, different is that feed rate is 40ml/min.
The aluminum oxide specific surface area of preparation is 271m
2/ g, pore volume are 0.24cm
3/ g, the aperture is 3.5nm.By nitrogen isothermal adsorption desorption tracing analysis (shown in Figure 11), its adsorption curve is a VI type curve, but significantly the H ring diminishes, and Figure 12 shows that pore size distribution moves to range of micropores, and its mesoporous feature weakens to some extent.
Operate identically with embodiment 1, different is that the hypergravity level is 150g.60 ℃ of temperature
The aluminum oxide specific surface area of preparation is 262m
2/ g, pore volume are 0.28cm
3/ g, the aperture is 4.3nm.By nitrogen isothermal adsorption desorption tracing analysis (shown in Figure 13), its adsorption curve is a VI type curve, and the H chain rate is bigger.Figure 14 pore size distribution shows that then mesoporous feature is obvious.
Operate identically with embodiment 1, different is that used aluminium source is a Tai-Ace S 150, and reaction end PH is 8.
The aluminum oxide specific surface area of preparation is 309.3m
2/ g, pore volume are 0.48cm
3/ g, the aperture is 6.3nm.By nitrogen isothermal adsorption desorption tracing analysis (shown in Figure 15), its adsorption curve is a VI type curve, and the H chain rate is bigger, and mesoporous feature is very obvious.Figure 16 shows that pore size distribution shows that then pore distribution is narrow, and the duct order is strong.
Comparative Examples (with embodiment 1 contrast)
Other steps are with embodiment 1.
Just the step changes the supergravity reactor that rapid B adopts into stirred-tank reactor, and stirring velocity is 1400rpm/min.
The aluminum oxide specific surface area of preparation is 300m
2/ g, pore volume are 0.21cm
3/ g, the aperture is 2.8nm.By nitrogen isothermal adsorption desorption tracing analysis (shown in Figure 17), its adsorption curve is an I type curve, performance be the feature of poromerics, pore distribution curve has also proved this feature (shown in Figure 180), pore distribution mainly concentrates on range of micropores.Illustrate and adopt this kind reactor can not prepare ordered mesoporous aluminium oxide.
Thereby confirmed supergravity reactor owing to can realize that quick microcosmic mixes, reinforcing mass transfer also greatly improves the nanoparticle dispersiveness, therefore be fit to prepare ordered mesoporous aluminium oxide.
Claims (3)
1. method for preparing ordered mesoporous aluminium oxide, concrete preparation process is as follows:
A. prepare the inorganic aluminum salting liquid of 0.1～0.6mol/l, again to the surfactant polyethylene 1540 that wherein adds 0.9g as template; Prepare the precipitation agent sal volatile of 0.6mol/l again; Described inorganic aluminate is a kind of in aluminum nitrate or the Tai-Ace S 150;
B. the inorganic aluminum salting liquid with the steps A preparation adds in the hypergravity reaction unit, setting the hypergravity level is 120～170g, and temperature of reaction is 60～70 ℃, adds precipitation agent with 5～50ml/min speed, after the reaction soln pH value reaches 7～8, obtain hydrated alumina colloidal sol;
C. with gained hydrated alumina colloidal sol among the step B at 20～70 ℃ of down aging 6～12h, through filtration, washing, 80 ℃ dry down alumina hydrate powder;
D. with gained alumina hydrate powder among the step C under nitrogen protection, be warmed up to 330 ℃ with 2～3 ℃/min speed and kept 3 hours, under the condition of logical oxygen, be warmed up to 550 ℃ with 2～3 ℃/min speed and kept 3 hours then, make ordered mesoporous aluminium oxide.
2. the method for preparing ordered mesoporous aluminium oxide according to claim 1 is characterized in that the adding speed that the described hypergravity level of step B is 140～150g, precipitation agent is 8～40ml/min.
3. the method for preparing ordered mesoporous aluminium oxide according to claim 1, it is characterized in that the technical process of the described material of step B in supergravity reactor is, inorganic aluminum salting liquid is added in the stirring tank (4), through recycle pump (5) feed liquid is circulated between stirring tank (4) and high-gravity rotating bed (1), utilize circulating hot water to keep the temperature of reaction, by charge pump (3) volatile salt is added high-gravity rotating bed (1), emit gained alumina in Nano level hydrate colloidal sol after reaction is finished.
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