CN101096015A - Sphericity spinel material with cage construction and method for preparing the same - Google Patents
Sphericity spinel material with cage construction and method for preparing the same Download PDFInfo
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- CN101096015A CN101096015A CNA2006100895093A CN200610089509A CN101096015A CN 101096015 A CN101096015 A CN 101096015A CN A2006100895093 A CNA2006100895093 A CN A2006100895093A CN 200610089509 A CN200610089509 A CN 200610089509A CN 101096015 A CN101096015 A CN 101096015A
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Abstract
The invention relates to a spherical spinel framework material and the preparation method. In the invention sphericalgamma-Al2O3 is used as hard template. By in-situ growth technology, reaction temperature, reaction time and reaction concentration are controlled so that hydrotalcite-like material is grown in the nanometer channel ofgamma-Al2O3. Then the hydrotalcite-like material, as precursor, is baked under high temperature so that hydrotalcite-like material is changed into spinel. And then matrixgamma-Al2O3 is dissolved by sodium hydroxide solution and is baked to obtain spherical spinel framework material finally. Grain diameter of the material is in 0.1-2mm and group density is in 0.25-0.4g/cm3. Specific surface area is in 40-100m2/g and pore volume is in 0.5-0.6cm3/g. Most probable pore size distribution is in 17-30nm. Because the body is spherical and pore size distribution is in meso-porous range, when the invention is used in catalyzing or separating field directly there is no need of forming moment; mass transferring resistance can be reduced and carbon deposition generation can be decreased.
Description
Technical field
The present invention relates to a kind of spherical spinel skeleton structure material and preparation method thereof, be specifically related to a kind of with spherical gamma-Al
2O
3Be hard template, at first growth in situ houghite material in its nanoscale duct is a presoma with it then, through roasting, corrosion and again roasting etc. handle back acquisition spherical spinel skeleton structure preparation methods.
Background technology
Since Bragg and Nishikawa had determined the crystal structure of spinelle, people had had darker understanding to spinel compound.It is found that most spinel compounds belong to the Fd3m space group, normally the O that arranges by face-centered cubic
2-Form, a unit cell is made up of 56 ions, and wherein, 32 is O
2-, 24 is metal cation, and 96 cell gap are arranged between the anion of cubic units structure cell, and wherein, 64 is the tetrahedral interstice, and 32 is octahedral interstice.According to cation M
II, M
IIIDistribution situation in two kinds of gaps can be divided into spinelle two kinds in " positive " and " anti-phase " spinelle." positive " spinelle has 8 M
II8 tetrahedrons have been occupied, remaining 16 M
IIIThen occupied 1/2 of 32 octahedral interstices, its general formula can be expressed as (M
II) [M
III]
2O
4" anti-phase " spinelle then has 8 B to occupy 8 four sides positions, remaining 8 M
IIIWith 8 M
IIOccupied 16 octahedral interstices, its general formula can be expressed as (M
III) [M
IIM
III] O
4Under these two kinds of limiting cases, also exist the intermediate state cation to distribute, its total chemical general formula can be expressed as: (M
II 1-xM
III x) [M
III 2-xM
II x] O
4
Wherein, M
IICan be cations such as Mg, Ni, Co, Zn, Cu, Ca; M
IIICan be cations such as Al, Fe, Mn; () represents the position, tetrahedral interstice; [] represents the octahedral interstice position; X represents reverse link parameter, 0≤x≤1.
Therefore, the physics of spinelle and chemical characteristic not only depend on M
IIAnd M
IIIThe characteristic of cation itself, but also with the be distributed with much relations of these cations in different crystallography position.
Spinelle preparation method commonly used has solid phase method and wet chemistry method etc., and wherein, solid phase method is normally containing M
IIOxide with contain M
IIIOxide or contain M
IISalt with contain M
IIISalt put together and utilize Mechanical Method or additive method mixed, handle obtaining target product through moulding, pre-burning and high-temperature roasting etc.; Wet chemistry method normally utilizes chemical reaction to make to contain M
IIAnd M
IIIPrecursor compound, and then, finally obtain target product through the processing such as roasting of uniform temperature.
Stratiform houghite (LDHs) material is a kind of inorganic material with unique structural characteristics: form as element and have the adjustable sex change in relative broad range, the adjustable sex change of pore structure and the designability of interlayer intercalant anion kind etc. and established this class material and might become the industrial catalyst with potential application foreground or the basis of catalyst precursor.Especially, this class material is through high-temperature roasting, the laminate metal cation can change homodisperse composite metal oxide with spinel structure on molecular scale into, therefore, we can be by obtaining to have the spinelle composite metal oxide of strict stoichiometric proportion or non-stoichiometric to designs such as the kind of laminate metal cation and proportionings.
γ-Al
2O
3Can be used as the catalyst except having abundant surface-OH, also be often used as some transition metal of catalyst carrier load, rare earth metal and noble metal etc. as catalyst because having physical property such as higher specific surface area, excellent mechanical intensity and heat endurance.In addition, as transition state of alumina, γ-Al
2O
3Be a kind of compound with strong both sexes, utilize this characteristic, we can carry out corrosion with chemical method to it to aluminium oxide and handle
At document Chem.Mater.2004,16, among the 1597-1602, people such as Feng Li are synthesizing stratiform MgFe
2+Fe
3+On the basis of-LDHs, through 1100 ℃ of following 2h roastings, the stratiform presoma just changes the MgFe with strict stoichiometric proportion into
2O
4At document Chem.Mater.1998,10, among the 4055-4061, people such as Toshiyuki Hibino have introduced MgAlCO
3LDH has obtained the magnesium aluminate spinel of non-stoichiometric again through after repeatedly the structure memory is handled through 1000 ℃ high-temperature roasting.
At the document Fudan Journal, 2003,42 (3): 333-338, J.Am.Chem.Soc.1995,117,11471-11481 and Chem.Mater.2001,13,, introduced respectively among the 297-303 with distinct methods at γ-Al
2O
3The example of surface in situ growth houghite material.After calcination process, can directly be used as catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of spherical spinel skeleton structure material and preparation method thereof, promptly with spherical gamma-Al
2O
3Be hard template, outer surface growth in situ houghite material at first within it is a presoma with it again obtains to have the composite metal oxide of spinel structure through high-temperature roasting, at last by chemolysis γ-Al wherein
2O
3Obtain spherical spinel skeleton structure material.Because this material be spherical, and the corrosion back aperture distributes and is within the bigger mesoporous scope, and it is directly used in catalysis or separation field, do not need through formative stage, and can reduce the generation of resistance to mass tranfer and reduction carbon distribution.
Spherical spinel skeleton structure material provided by the invention has following characteristics:
1) chemical general formula of spinelle is: M
IIOxAl
2O
3
Wherein, M
IIRepresent bivalent metal ion Mg
2+, Ni
2+, Co
2+, Zn
2+In any
The span of x is 0.67≤x≤3.3.
2) particle diameter of this spinelle skeleton ball is between 0.1～2mm;
3) bulk density is 0.25～0.4g/cm
3
4) specific area drops on 40～100m
2Between/the g;
5) pore volume is in 0.5～0.6cm
3Between/the g;
6) the most probable pore-size distribution is between 17～30nm.
Concrete preparation process of the present invention is as follows:
A: with diameter is spherical gamma-Al of 0.1～2mm
2O
3Behind activation 2h under 500～600 ℃, under 80～100 ℃ of hydrothermal conditions, handle 6～24h with urea liquid, after cooling, and in the adding maceration extract that weighs up in advance, M
IIThe addition of Y is by making [M in the dipping
II] concentration is 0.5～2M, and [urea]/[M
II] mol ratio is 1～5, handles 2～8h 90～130 ℃ of crystallization again, obtain at spherical gamma-Al
2O
3Mesopore orbit in the houghite stratified material of growth in situ (be abbreviated as: M
IIAl-LDHs/ γ-Al
2O
3); Above-mentioned M
IIAmong the Y, M
IIBe Mg
2+Or Zn
2+Y is Cl
-, NO
3 -, F
-, Br
-, SO
4 2-In any, be preferably NO
3 -, Cl
-Or SO
4 2-Be more preferably NO
3 -
Another kind method is: with M
II(NO
3)
2Be dissolved in pH and be in 1M ammonium nitrate-ammoniacal liquor cushioning liquid of 6.5～8.2, make M in the solution
II(NO
3)
2Concentration is 0.05～0.3M, and regulation system pH is between 6.5～8.2, with spherical gamma-Al again
2O
3Be immersed in above-mentioned M behind the activation 2h down at 500～600 ℃
II(NO
3)
2In the solution, under room temperature, flood 4～36h, handle 8～40h 25～70 ℃ of following crystallization again; Acquisition is at spherical gamma-Al
2O
3Mesopore orbit in the houghite stratified material M of growth in situ
IIAl-LDHs/ γ-Al
2O
3Wherein, M
IIBe Ni
2+, Co
2+, Zn
2+In any.
B: the M of steps A preparation
IIAl-LDHs/ γ-Al
2O
3At 800～1000 ℃ of following roasting 4～10h, obtain to have the composite metal oxide M of spinel structure
IIOxAl
2O
3/ γ-Al
2O
3
C: the M of step B preparation
IIOxAl
2O
3/ γ-Al
2O
3NaOH solution corrosion under 120～180 ℃ hydrothermal condition with 0.2～1M was handled 2～5 days, with the molten γ-Al that goes wherein
2O
3
D: the spherical products of step C again at 800～1000 ℃ of following roasting 4～10h, is obtained spherical spinel skeleton structure material M
IIOxAl
2O
3
Urea is a kind of very weak Br nsted alkali (pK
b=13.8), and very high solubility arranged in water.Urea in the decomposition mechanism in the water shown in following reaction equation:
CO (NH
2)
2→ NH
4CNO: slow
NH
4CNO+2H
2O → (NH
4)
2CO
3: fast
When temperature when 60 ℃ rise to 100 ℃, this reaction rate constants can increase about 200 times.Can provide OH for solution after the ammonium carbonate hydrolysis that produces
-And CO
3 2-, the pH value of solution is near 7～9, thereby can provides suitable pH condition for LDHs synthetic.The present invention activates γ-Al by the synthesis temperature of control steps A
2O
3The Al of duct inner surface makes it to change into AlO
2 -, introduce the Mg that adds again
2+, make the AlO in itself and the duct
2 -Under hydrothermal condition, carry out the crystallization growth, thereby obtain at γ-Al
2O
3The M of the growth in situ in the mesopore orbit
IIAl-LDHs/ γ-Al
2O
3
With NH
4NO
3-NH
3H
2O is in the system of cushioning liquid, and reaction exists two balances, i.e. NH in solution
3H
2O ionization generates NH
4+And OH
-Ionization equilibrium and NH
3H
2O and M
IIInteract and generate [M
II(NH
3)
6]
2+The complexation equilibrium of complex ion, each component concentrations is subjected to the common restriction of ionization equilibrium and complexation equilibrium in the reaction system.In the course of reaction, γ-Al
2O
3The Al source on surface is activated and constantly consumes OH
-, NH
3H
2The ionization equilibrium of O moves to positive direction, and the result that this balance moves makes NH
3H
2The concentration of O descends, and has promoted [M in the solution
II(NH
3)
6]
2+Dissociate M
IIIon is released, and makes NH in the solution simultaneously
3H
2The Al source that O concentration has certain rising again and continues activated surface.M
II, Al
3+, OH
-, CO
3 2-And NO
3 -Constitute the condition that the houghite material forms jointly, and suppressed the carrying out of body phase reaction, thereby at spherical gamma-Al
2O
3The duct in growth in situ the houghite persursor material.
The round for preparing the processing stage of adopting Shimadu XRD-6000 type powder x-ray diffraction to each carries out qualitative analysis, and the result is as follows:
Fig. 1 is the XRD spectra of the material that steps A obtained, wherein 1a, 1b and 1c are respectively the spectrogram of embodiment 1,4 and 6 samples, (003) of houghite material, (006), (012), (015), (110) and (113) characteristic peak have all occurred as seen from the figure, have illustrated that houghite generates.
The XRD spectra of the material that Fig. 2 is obtained for step B, wherein 2a, 2b and 2c are respectively the spectrogram of embodiment 1,4 and 6 samples, as seen from the figure, occurred (111), (220), (311), (400), (511) and (440) characteristic peak respectively, the composite metal oxide that has generated spinel structure has been described.
Fig. 3 is embodiment 1 a step C gained sample XRD spectra, and the result shows: after the hydro-thermal corrosion through NaOH solution, except the characteristic peak of spinel structure, occurred the characteristic peak of houghite material again on the XRD spectra.
Fig. 4 is embodiment 1 a step D gained sample XRD spectra, and the result shows: through the hydro-thermal corrosion of NaOH solution and 900 ℃ high temperature roasting again, each peak position of XRD spectra belongs to a cube phase spinel structure fully, and can't see γ-Al substantially
2O
3Characteristic peak.
Fig. 5 is microscope (SEM) photograph and the constituency EDX spectrogram of sample behind the growth in situ hydrotalcite of embodiment 1 preparation, and as seen from the figure, sample is a spherical structure, and has occurred element M g on the EDX spectrogram.
Fig. 6 is the face scanning analysis spectrogram of spherical sample section, and the result shows: the distribution of Mg element is more uniform, and has confirmed that the houghite material realized growth in situ really in the duct.
Fig. 7 has then provided the SEM photo of the sample that is obtained after step D handles, as we can see from the figure, after repeatedly handling, sample is still keeping intact spherical structure.
Fig. 8 a and 8b have provided the TEM photo of being made up of the microstructure of the prepared ball-type skeleton structure of embodiment 1.As can be seen from the figure: spherical skeleton structure is made up of the nano bar-shape magnesium aluminate spinel that spinel nano particle and part particle are formed by connecting, and nearly all rod is not discrete the existence.
Fig. 9 is the HRTEM photo of selected nanometer rods, and as can be seen, the spacing of lattice of the high-resolution phase of nano bar-shape material is 0.2466nm from the figure, with the d of the magnesium aluminate spinel of standard
(311)=0.2437nm is consistent.Can prove further that thus the nano bar-shape thing is magnesium aluminate spinel (JCPDS Card:21-1152).
Adopt the U.S. AS-1C-VP of Kang Ta company type specific surface-pore-size distribution analyzer, the working sample pore-size distribution finds, specific area and the pore structure analysis such as the table 1 of each the stage sample that is obtained by embodiment 1.
Table 1
| Sample | Specific area (m 2/g) | Pore volume (cc/g) | Aperture (nm) |
| γ-Al 2O 3MgAl-LDHs/γ-Al 2O 3MgO·xAl 2O 3/γ-Al 2O 3MgO·0.68Al 2O 3 | 160.83 132.4 111.3 92.48 | 0.89 0.51 0.70 0.65 | 17.7 12.6 17.9 17.4 |
Can find out significantly from table 1:
After processing of step A, with blank γ-Al
2O
3Bead is compared, product MgAl-LDHs/ γ-Al
2O
3Specific area drop to 132.4m
2/ g, pore volume drops to 0.51cc/g, and average pore size also drops to 12.6nm from 17.7nm, and this result has confirmed at γ-Al
2O
3The duct in filled certain material really, again in conjunction with Fig. 1 a, this explanation has utilized γ-Al really
2O
3The aluminium source growth in situ of duct inner surface magnesia-alumina water stone material.
After step B handles, product MgOxAl
2O
3/ γ-Al
2O
3Specific area further descend, pore volume then increases to some extent, average pore size then increases to and γ-Al
2O
3Average pore size suitable, can judge that in view of the above presoma changes the process of spinelle into through roasting, owing to counterdiffusion mutually between the element al in laminate metallic element Mg and the form cage structure, move and cause.
Resulting spherical MgO0.68Al after step C and D processing
2O
3Magnesium aluminate spinel composite metal oxide before spinelle composite metal oxide and the corrosion compares: specific area drops to 92.48m
2/ g, average pore size then remains unchanged substantially, still, pore volume further reduces, this may be since after the corrosion again the MgO that produces of roasting stopped up some tiny holes, perhaps some tiny holes subside because of roasting and cause.
Data by table 1 can draw: the spherical spinel skeleton structure is a mesoporous material.
Adopt inductively coupled plasma atomic emission that the spinelle skeleton ball that is obtained is carried out elementary analysis, can obtain M
IIOxAl
2O
3Middle M
II/ Al ratio is 0.15～0.74, i.e. 0.67≤x≤3.3.
Outstanding contributions of the present invention are to have prepared the spherical spinel skeleton structure first, by chemical force at spherical gamma-Al
2O
3The duct in growth in situ houghite material, and then, finally prepared spherical spinel skeleton structure material through roasting, corrosion and processing such as roasting again.Adopt method provided by the invention to prepare spherical spinel skeleton structure, simple synthetic method.
Description of drawings
Fig. 1 is embodiment 1,2 and 3 XRD spectras that obtained after processing of step A;
Fig. 2 is embodiment 1,2 and 3 XRD spectras that obtained after step B handles;
Fig. 3 is the XRD spectra that embodiment 1 is obtained after step C handles;
The XRD spectra of Fig. 4 spherical spinel skeleton structure that to be embodiment 1 obtained after step D handles;
Fig. 5 is the SEM photograph and the constituency EDX spectrogram of embodiment 1 gained sample after processing of step A;
Fig. 6 is the section face scanning spectrogram of embodiment 1 gained sample after processing of step A;
The SEM photo of Fig. 7 spherical spinel skeleton structure that to be embodiment 1 obtained after step D handles;
The TEM photo of Fig. 8 spherical spinel skeleton structure that to be embodiment 1 obtained after step D handles;
The HRTEM photo of Fig. 9 spherical spinel skeleton structure that to be embodiment 1 obtained after step D handles;
The specific embodiment
The invention will be further described below in conjunction with embodiment:
A. take by weighing γ-Al that the 2g particle diameter is 0.4～0.6mm
2O
3Bead is put into the 100ml autoclave of inner liner polytetrafluoroethylene behind activation 2h under 600 ℃, add 5.4566g urea, adds the ultrasonic processing of 45ml deionized water 5min then, puts into 90 ℃ baking oven hydrothermal treatment consists 10h after the sealing; After the cooling, add 7.6937gMg (NO
3)
26H
2O, after stirring was dissolved it fully, sealing also was warming up to 130 ℃ rapidly, hydrothermal treatment consists 6h.The product that obtains after abundant ultrasonic cleaning, obtain MgAl-LDHs/ γ-Al after placing 70 ℃ of baking oven inner dryings to handle 12h
2O
3Product;
B. MgAl-LDHs/ γ-Al that steps A obtained
2O
3Product obtains spherical MgOxAl at 900 ℃ of following roasting 4h
2O
3/ γ-Al
2O
3Product;
C. the spherical MgOxAl that step B is obtained
2O
3/ γ-Al
2O
3Product is put into the 50ml autoclave, adds the NaOH solution 20ml of 0.5M then, puts into 150 ℃ baking oven hydrothermal treatment consists 4 days after the sealing.
D. the product after step C handles at 900 ℃ of following roasting 4h, obtain spherical MgO0.68Al
2O
3The spinelle composite metal oxide.
Embodiment 2
Take by weighing γ-Al that the 2g particle diameter is 0.1～0.2mm
2O
3Bead, activation 2h is stand-by down at 600 ℃.
A. take by weighing γ-Al that the 2g particle diameter is 0.1～0.2mm
2O
3Bead is put into the 100ml autoclave of inner liner polytetrafluoroethylene behind activation 2h under 600 ℃, add 9.1256g urea, adds the ultrasonic processing of 40ml deionized water 5min then, puts into 90 ℃ baking oven hydrothermal treatment consists 10h after the sealing; After the cooling, add 14.905gZn (NO
3)
26H
2O, after stirring was dissolved it fully, sealing also was warming up to 130 ℃ rapidly, hydrothermal treatment consists 6h.The product that obtains after abundant ultrasonic cleaning, obtain ZnAlLDHs/ γ-Al after placing 70 ℃ of baking oven inner dryings to handle 12h
2O
3Product;
B. ZnAlLDHs/ γ-Al that steps A obtained
2O
3Product obtains spherical ZnOxAl at 900 ℃ of following roasting 4h
2O
3/ γ-Al
2O
3Product;
C. the spherical ZnOxAl that step B is obtained
2O
3/ γ-Al
2O
3Product is put into the 50ml autoclave, adds the NaOH solution 20ml of 0.5M then, puts into 150 ℃ baking oven hydrothermal treatment consists 4 days after the sealing.
D. the product after step C handles at 900 ℃ of following roasting 4h, obtain spherical ZnO0.68Al
2O
3The spinelle composite metal oxide.
Embodiment 3
A. take by weighing γ-Al that the 2g particle diameter is 0.4～0.6mm
2O
3Bead is down being put into the 250mL three-necked bottle behind the activation 2h at 600 ℃, and with 100ml Ni (NO
3)
2With NH
4NO
3Mixed solution (wherein, NH
4 +Concentration be 1.0mol/L, Ni
2+Concentration be 0.1mol/L, the pH of mixed solution is 7.2) dipping, ultrasonic processing 5min also floods 5h under room temperature, then static crystallization 36h in 50 ℃ water-bath.Subsequently, with 1M, pH value be 7.2 NH successively
4NO
3-NH
3H
2O cushioning liquid and deionized water fully wash sample, obtain NiAlLDHs/ γ-Al after placing 70 ℃ baking oven oven dry to handle 12h then
2O
3Product;
B. NiAlLDH/ γ-Al that steps A obtained
2O
3Product obtains spherical Ni OxAl at 900 ℃ of following roasting 4h
2O
3/ γ-Al
2O
3Product;
C. the spherical Ni OxAl that step B is obtained
2O
3/ γ-Al
2O
3Product is put into the 50ml autoclave, adds the NaOH solution 20ml of 0.5M then, puts into 150 ℃ baking oven hydrothermal treatment consists 4 days after the sealing.
D. the product after step C handles at 900 ℃ of following roasting 4h, obtain the spherical spinel composite metal oxide.
Embodiment 4
Take by weighing γ-Al that the 2g particle diameter is 0.4～0.6mm
2O
3Bead, activation 2h is stand-by down at 600 ℃.
A. take by weighing γ-Al that the 2g particle diameter is 0.4～0.6mm
2O
3Bead is down being put into the 250mL three-necked bottle behind the activation 2h at 600 ℃, and with 100ml Ni (NO
3)
2With NH
4NO
3Mixed solution (wherein, NH
4 +Concentration be 1.0mol/L, Ni
2+Concentration be 0.2mol/L, the pH of mixed solution is 7.8) dipping, ultrasonic processing 5min also floods 5h under room temperature, then static crystallization 36h in 50 ℃ water-bath.Subsequently, with 1M, pH value be 7.8 NH successively
4NO
3-NH
3H
2O cushioning liquid and deionized water fully wash sample, obtain NiAlLDHs/ γ-Al after placing 70 ℃ baking oven oven dry to handle 12 h then
2O
3Product;
B. NiAlLDHs/ γ-Al that steps A obtained
2O
3Product obtains spherical Ni OxAl at 900 ℃ of following roasting 4h
2O
3/ γ-Al
2O
3Product;
C. the spherical Ni OxAl that step B is obtained
2O
3/ γ-Al
2O
3Product is put into the 50ml autoclave, adds the NaOH solution 20ml of 0.5M then, puts into 150 ℃ baking oven hydrothermal treatment consists 4 days after the sealing.
D. the product after step C handles at 900 ℃ of following roasting 4h, obtain the spherical spinel composite metal oxide.
A. take by weighing γ-Al that the 2g particle diameter is 0.4～0.6mm
2O
3Bead is down being put into the 250mL three-necked bottle behind the activation 2h at 600 ℃, and with 100ml Co (NO
3)
2With NH
4NO
3Mixed solution (wherein, NH
4 +Concentration be 1.0mol/L, Co
2+Concentration be 0.2mol/L, the pH of mixed solution is 6.8) dipping, ultrasonic processing 5min and at N
2Under room temperature, flood 5h under the atmosphere protection, then static crystallization 36h in 50 ℃ water-bath.Subsequently, with 1M, pH value be 6.8 NH successively
4NO
3-NH
3H
2O cushioning liquid and deionized water fully wash sample, obtain CoAlLDHs/ γ-Al after placing 50 ℃ vacuum drying chamber oven dry to handle 12h then
2O
3Product;
B. CoAlLDHs/ γ-Al that steps A obtained
2O
3Product obtains spherical CoOxAl at 900 ℃ of following roasting 4h
2O
3/ γ-Al
2O
3Product;
C. the spherical CoOxAl that step B is obtained
2O
3/ γ-Al
2O
3Product is put into the 50ml autoclave, adds the NaOH solution 20ml of 0.5M then, puts into 150 ℃ baking oven hydrothermal treatment consists 4 days after the sealing.
D. the product after step C handles at 900 ℃ of following roasting 4h, obtain the spherical spinel composite metal oxide.
Embodiment 6
Get γ-Al that the 2g particle diameter is 0.4～0.6mm
2O
3Bead, activation 2h is stand-by down at 600 ℃.Concrete steps are the [Co of maceration extract with embodiment 5
2+] become 0.3M.
Claims (5)
1. spherical spinel skeleton structure preparation methods, concrete preparation process is as follows:
A: with diameter is spherical gamma-Al of 0.1～2mm
2O
3Behind activation 2h under 500～600 ℃, under 80～100 ℃ of hydrothermal conditions, handle 6～24h with urea liquid, after cooling, and in the adding maceration extract that weighs up in advance, M
IIThe addition of Y is by making [M in the dipping
II] concentration is 0.5～2M, and [urea]/[M
II] mol ratio is 1～5, handles 2～8h 90～130 ℃ of crystallization again, obtain at spherical gamma-Al
2O
3Mesopore orbit in the houghite stratified material of growth in situ (be abbreviated as: M
IIAl-LDHs/ γ-Al
2O
3); Above-mentioned M
IIAmong the Y, M
IIBe Mg
2+Or Zn
2+Y is Cl
-, NO
3 -, F
-, Br
-, SO
4 2-In any,
B: the M of steps A preparation
IIAl-LDHs/ γ-Al
2O
3At 800～1000 ℃ of following roasting 4～10h, obtain to have the composite metal oxide of spinel structure;
C: the product of step B preparation was handled 2～5 days with NaOH solution corrosion under 120～180 ℃ hydrothermal condition of 0.2～1M, with the molten γ-Al that goes wherein
2O
3
D: the spherical products of step C again at 800～1000 ℃ of following roasting 4～10h, is obtained spherical spinel skeleton structure material.
2. spherical spinel skeleton structure preparation methods according to claim 1 is characterized in that the described M of steps A
IIAmong the Y, Y is NO
3 -, Cl
-Or SO
4 2-
3. according to the described spherical spinel skeleton structure of claim l preparation methods, it is characterized in that the described M of steps A
IIAmong the Y, Y is NO
3 -
4. spherical spinel skeleton structure preparation methods, concrete preparation process is as follows:
With M
II(NO
3)
2Be dissolved in pH and be in 1M ammonium nitrate-ammoniacal liquor cushioning liquid of 6.5～8.2, make MII (NO in the solution
3)
2Concentration is 0.05～0.3M, and regulation system pH is between 6.5～8.2, with spherical gamma-Al again
2O
3Be immersed in above-mentioned M behind the activation 2h down at 500～600 ℃
II(NO
3)
2In the solution, under room temperature, flood 4～36h, handle 8～40h 25～70 ℃ of following crystallization again; Acquisition is at spherical gamma-Al
2O
3Mesopore orbit in the houghite stratified material M of growth in situ
IIAl-LDHs/ γ-Al
2O
3Wherein, M
IIBe Ni
2+, Co
2+, Zn
2+In any;
B: the M of steps A preparation
IIAl-LDHs/ γ-Al
2O
3At 800～1000 ℃ of following roasting 4～10h, obtain to have the composite metal oxide of spinel structure;
C: the product of step B preparation was handled 2～5 days with NaOH solution corrosion under 120～180 ℃ hydrothermal condition of 0.2～1M, with the molten γ-Al that goes wherein
2O
3
D: the spherical products of step C again at 800～1000 ℃ of following roasting 4～10h, is obtained spherical spinel skeleton structure material.
5. spherical spinel skeleton structure material by claim 1, the preparation of 2 or 3 and 4 described spherical spinel skeleton structure material preparation methods, its chemical general formula is:
M
IIO·xAl
2O
3
Wherein, M
IIRepresent bivalent metal ion Mg
2+, Ni
2+, Co
2+, Zn
2+In the span of any x be 0.67≤x≤3.3; Particle diameter is between 0.1～2mm; Bulk density is 0.25～0.4g/cm
3Specific area is at 40～100m
2Between/the g; Pore volume is at 0.5～0.6cm
3Between/the g; The most probable pore-size distribution is between 17～30nm.
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