CN101659417B - Porous silicate nanometer hollow granule and preparation method thereof - Google Patents
Porous silicate nanometer hollow granule and preparation method thereof Download PDFInfo
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- CN101659417B CN101659417B CN2008101957397A CN200810195739A CN101659417B CN 101659417 B CN101659417 B CN 101659417B CN 2008101957397 A CN2008101957397 A CN 2008101957397A CN 200810195739 A CN200810195739 A CN 200810195739A CN 101659417 B CN101659417 B CN 101659417B
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Abstract
The invention discloses a porous silicate nanometer hollow granule and a preparation method thereof. The hollow granule is nanometer hollow granular magnesium metasilicate or nickelous silicate or cupric silicate or cadmium silicate or cobaltous silicate, wherein the grain size of the granule is 0.1-1mum, the surface of the shell is poroid, the specific surface area is 450-550m<2>/g, the thickness of the shell is 40-200nm, and the pore diameter of a pore is 3-5nm. The preparation method comprises the following steps: firstly, ultrasonically dispersing silicon dioxide granules the grain size of which is 0.1-1mum into water, obtaining a dispersion the concentration of which is 1-3g/L; then adding magnesium salt and ammonium chloride to the dispersion to obtain mixed liquor, or adding nickel salt or nantokite or cadmium salt or cobalt salt to the dispersion to obtain mixed liquor; then adding ammonia to the mixed liquor to obtain a precursor solution; subsequently, firstly putting the precursor solution under the conditions that the temperature is 120-160 DEG C, and the pressure is self-generated pressure to react for at least 8h, obtaining deposit products; then using water to wash the deposit products until neutrality, thereby preparing the porous silicate nanometer hollow granule. The porous silicate nanometer hollow granule can be widely used for absorbing inorganic and organic pollutants.
Description
Technical field
The present invention relates to a kind of nanometer hollow granule and preparation method, especially a kind of porous silicate nanometer hollow granule and preparation method thereof.
Background technology
As everyone knows, along with the high speed development of world economy, environmental pollution is also day by day seriously got up, and contains multiple inorganic and organic pollutant in the sewage of industrial discharge at large.For this reason, people attempt to select for use silicate material nontoxic, tasteless, environmental sound to be used as sorbent material or catalyzer, the problem that exceeds standard with the contaminated solution thing, as a kind of " preparation method of micropore and the crystalline metal silicate of mesopore, the product and the application thereof that obtain by this method " that discloses among the disclosed Chinese invention patent ublic specification of application CN1168860A on December 31st, 1997.It is intended to provide a kind of method to prepare the common metal silicate of high purity phase and high catalytic activity; Wherein, the preparation method makes product for carry out hydro-thermal reaction by siliceous and material metal when template is arranged, and resulting product consists of (Si
2)
1-x(A
mO
n)
x, wherein A is Ti, Al, B, V or Zr, x is between 0.005～0.1.But, no matter be product, or the preparation method, all exist weak point, at first, product is a solid, this just makes its difficulty that bigger specific surface area is arranged, the performance of effect when having restricted it and using as sorbent material or catalyzer; Secondly, product is used as oxide catalyst to be used, so be difficult to the multiple inorganic and organic pollutant in the sewage is carried out effective adsorption treatment; Once more, the preparation method can not make the silicate material that presents hollow structure.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of porous silicate nanometer hollow granule hollow structure, that can be used for inorganic and organic pollutant are carried out adsorption treatment that is for overcoming weak point of the prior art.
Another technical problem that the present invention will solve is for providing a kind of preparation method of porous silicate nanometer hollow granule.
What the present invention will solve also has a technical problem for a kind of application of porous silicate nanometer hollow granule is provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: porous silicate nanometer hollow granule comprises silicate, particularly described silicate is Magnesium Silicate q-agent or silicic acid nickel or cupric silicate or cadmium metasilicate or cobaltous silicate, described Magnesium Silicate q-agent or silicic acid nickel or cupric silicate or cadmium metasilicate or cobaltous silicate are the nanometer hollow granule shape, and the particle diameter of described nanometer hollow granule is that 0.1～1 μ m, shell surface are 450～550m for vesicular, specific surface area
2/ g, the thickness of described shell are 40～200nm, and the aperture in described hole is 3～5nm.
As the further improvement of porous silicate nanometer hollow granule, described nanometer hollow granule is spherical or linear; The spherical diameter of described ball shaped nano hollow bead is 0.1～1 μ m; The line of described linear nanometer hollow granule directly is that 50～500nm, line length are 0.1～1 μ m.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of porous silicate nanometer hollow granule comprises hydrothermal method, particularly completing steps is as follows: step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.1～1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 1～3g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, in mixed solution, add ammoniacal liquor then and stir and obtain precursor solution, wherein, magnesium salts in the precursor solution, ammonium chloride, mol ratio between ammoniacal liquor and the water is 1～2:10～30:10～30:5000, perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.1～1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 1～3g/L, in dispersion liquid, add nickel salt or mantoquita or cadmium salt or cobalt salt again, treat to obtain mixed solution after its dissolving, in mixed solution, add ammoniacal liquor then and stir and obtain precursor solution, wherein, nickel salt in the precursor solution or mantoquita or cadmium salt or cobalt salt, mol ratio between ammoniacal liquor and the water is 1～2:10～30:5000; Step 2, earlier precursor solution being placed temperature is that 120～160 ℃, pressure are to react at least under the autogenous pressure that 8h obtains precipitated product, washes precipitated product again with water to neutral, makes porous silicate nanometer hollow granule.
As the preparation method's of porous silicate nanometer hollow granule further improvement, described magnesium salts is magnesium chloride or sal epsom or magnesium nitrate; Described nickel salt is nickelous chloride or single nickel salt or nickelous nitrate; Described mantoquita is cupric chloride or copper sulfate or cupric nitrate; Described cadmium salt is Cadmium chloride fine powder or Cadmium Sulphate or cadmium nitrate; Described cobalt salt is cobalt chloride or rose vitriol or Xiao Suangu; The water of described preparation dispersion liquid is deionized water or distilled water.
For solving the technical problem that also has of the present invention, the technical scheme that also has that is adopted is: the application of porous silicate nanometer hollow granule comprises the processing to polluted water, particularly porous silicate nanometer hollow granule is placed the water that is subjected to organism dyestuff or heavy-metal pollution to carry out adsorption treatment.
Beneficial effect with respect to prior art is, one, the product that makes is used field emission scanning electron microscope respectively, transmission electron microscope, x-ray diffractometer and specific surface and analysis of porosity instrument carry out form, structure, the sign of composition and specific surface area, from the stereoscan photograph that obtains, transmission electron microscope photo, X-ray diffraction spectrogram and nitrogen adsorption～the desorption graphic representation as can be known, product is dispersed well nanometer hollow granule, the particle diameter of nanometer hollow granule is 0.1～1 μ m, particle is spherical or linear, wherein, the spherical diameter of ball shaped nano hollow bead is 0.1～1 μ m, and the line of linear nanometer hollow granule directly is 50～500nm, line length is 0.1～1 μ m.The shell surface of nanometer hollow granule is a vesicular, and the thickness of shell is 40～200nm, and the aperture is 3～5nm.Nanometer hollow granule is made of Magnesium Silicate q-agent or silicic acid nickel or cupric silicate or cadmium metasilicate or cobaltous silicate.The specific surface area of nanometer hollow granule is 450～550m
2/ g; They are two years old, the formation mechanism of porous silicate nanometer hollow granule is, under the condition of alkaline environment and heating, silica dioxide granule is slowly dissolved and is discharged silicate ion, these silicate ions are in the process of external diffusion, produce reaction and generate silicate granules with near silica dioxide granule metal ion, and deposit to silica particles and formed a layer silicate, the silica dioxide granule of this moment has played the effect of template again.Along with the continuous deposition of silicate granules, this layer silicate is thickening constantly, all is converted into silicate granules until metal ion.The remaining silica particle continues dissolved and discharges silicate ion, and continues to external diffusion, and the silicate shell that is deposited on former silica particles has been retained, and has formed the silicate nano hollow bead at last; Its three, the preparation method utilizes silicon-dioxide to be chemical template, has prepared the silicate nano hollow bead of porous surface shape under alkaline environment, has novelty.This method neither needs to add dispersion agent just can obtain dispersed well product, can regulate and control the pattern of silicate hollow bead again artificially by the pattern of control silica dioxide granule, the quality of metal-salt that also can be by regulating initial adding is controlled the thickness of the silicate layer that silica particles generates, has certain universality especially, can prepare multiple silicate hollow bead material, and whole process of preparation is simple, raw material is cheap, cause does not add other materials such as tensio-active agent in reaction, make aftertreatment convenient yet; They are four years old, the product that makes placed respectively be subjected to organism dyestuff and be subjected to the water of heavy-metal pollution to carry out the test of absorption property, the equipment of test is respectively ultraviolet-visual spectrometer and plasma linking atom emission spectrometer, utilization records adsorption isothermal curve that data draw as can be known, and product all has higher absorption property to organism dyestuff and heavy metal ion.
Further embodiment as beneficial effect, the one, nanometer hollow granule is preferably spherical or linear, wherein, the spherical diameter of ball shaped nano hollow bead is preferably 0.1～1 μ m, the line of linear nanometer hollow granule directly is preferably 50～500nm, line length is preferably 0.1～1 μ m, not only satisfied the needs of due specific surface area when product uses as sorbing material to greatest extent, also made preparation be easy to realize it; The 2nd, magnesium salts is preferably magnesium chloride or sal epsom or magnesium nitrate, nickel salt is preferably nickelous chloride or single nickel salt or nickelous nitrate, mantoquita is preferably cupric chloride or copper sulfate or cupric nitrate, cadmium salt is preferably Cadmium chloride fine powder or Cadmium Sulphate or cadmium nitrate, cobalt salt is preferably cobalt chloride or rose vitriol or Xiao Suangu, make the selection of raw material that bigger leeway be arranged, not only convenient flexibly, also be beneficial to suitability for industrialized production; The 3rd, the water of preparation dispersion liquid is preferably deionized water or distilled water, has avoided the introducing of impurity, has guaranteed the quality of product.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that Sirion200 type scanning electronic microscope (SEM) characterizes to the product that makes, can find out by the SEM photo, and the big and uniform distribution of the output of product, it is shaped as spheroidal particle, and diameter is about 700nm;
Fig. 2 uses one of result that JEM-2010 type transmission electron microscope (TEM) characterizes to product shown in Figure 1, can be found out that by the TEM photo product is a hollow structure, and its shell thickness is about 170nm;
Fig. 3 uses one of result that Phlips X ' Pert type X-ray diffraction (XRD) instrument characterizes to product shown in Figure 1, the X-coordinate in the XRD spectra is a diffraction angle, and ordinate zou is a relative intensity.By XRD spectra as can be known, product is a Magnesium Silicate q-agent talcum structure (JCPDF03-0174);
Fig. 4 be to product shown in Figure 1 use that ASAP2000 type specific surface and analysis of porosity instrument characterize the result---nitrogen adsorption-desorption graphic representation, the X-coordinate among the figure are relative pressure, ordinate zou is absorption volume (cm
3/ g), the illustration in this nitrogen adsorption-desorption graphic representation is the scatter chart in aperture, and its X-coordinate is a micropore size, and ordinate zou is for absorbing volume (cm
3/ g).Can find out that by nitrogen adsorption-desorption graphic representation thermoisopleth has tangible hysteresis loop, belong to the IV type, by the desorption curve calculation as can be known, the specific surface area of product is about 521m
2The distribution in/g, porous aperture is about 4nm;
Fig. 5 uses one of result that JEM-2010 type transmission electron microscope (TEM) characterizes to the product that makes, can be found out that by the TEM photo product is a hollow structure, and its diameter is about 560nm, and shell thickness is about 40nm;
Fig. 6 uses one of result that Phlips X ' Pert type X-ray diffraction (XRD) instrument characterizes to product shown in Figure 5, the X-coordinate in the XRD spectra is a diffraction angle, and ordinate zou is a relative intensity.By XRD spectra as can be known, product is a silicic acid nickel structure (JCPDF20-0790);
Fig. 7 uses one of result that JEM-2010 type transmission electron microscope (TEM) characterizes to the product that makes, can be found out that by the TEM photo product is a hollow structure, and its diameter is about 580nm, and shell thickness is about 50nm;
Fig. 8 uses one of result that Phlips X ' Pert type X-ray diffraction (XRD) instrument characterizes to product shown in Figure 7, the X-coordinate in the XRD spectra is a diffraction angle, and ordinate zou is a relative intensity.By XRD spectra as can be known, product is cupric silicate structure (JCPDF03-0219);
Fig. 9 be to use CARY-5E type ultraviolet-visible spectrum (UV-Vis) instrument to the product shown in Fig. 1 be sorbent material, with the organic dye methylene blue be simulated wastewater adsorb the test resulting result---adsorption isothermal curve figure, the concentration (mg/L) of methylene blue in the solution when X-coordinate in the graphic representation reaches balance for absorption, ordinate zou is the unit adsorptive capacity (mg/g) of product to methylene blue.Curve a among the figure is the adsorption isothermal curve of freshly prepd product to methylene blue, can find out by it, its adsorption rate is up to 207mg/g, curve b is the adsorption isothermal curve of product after a calcination and regeneration, curve c is the adsorption isothermal curve of product after secondary clacining regeneration, and curve d is the adsorption isothermal curve of product after three calcination and regeneration.The absorption test condition that obtains adsorption isothermal curve figure is: be earlier a with 20mg with the product shown in Fig. 1, behind alcohol dampening, respectively that every part of product is different with concentration again methylene blue solution 40mL mix mutually, afterwards every part of mixing solutions are all carried out repeatedly leaving standstill 8 hours behind the ultra-sonic dispersion.Then, earlier respectively with every part of mixing solutions centrifugation, use UV-Vis to characterize respectively to its upper solution again, obtain adsorbing when reaching balance the concentration of methylene blue (mg/L) in the solution, concentration in conjunction with methylene blue in the mixing solutions before the absorption, obtain the adsorptive capacity (mg/g) of product to methylene blue in the solution, the data that last basis records under different concns comprise equilibrium concentration and adsorptive capacity, obtain the adsorption isothermal curve of product to methylene blue.The product that adsorbed methylene blue through 400 ℃ calcining after, again its absorption property is done the as above test of step, can obtain product after calcination and regeneration to the adsorption isothermal curve of methylene blue;
Figure 10 be to use Atomscan Advantage type plasma linking atom emission spectrometer to the product shown in Fig. 1 be sorbent material, with the inorganic heavy metal ion lead ion be simulated wastewater adsorb the test resulting result---adsorption isothermal curve figure, the concentration (mg/L) of lead ion in the solution when X-coordinate in the graphic representation reaches balance for absorption, ordinate zou is the unit adsorptive capacity (mg/g) of product to lead ion.Can find out by the curve among the figure, product to the adsorption rate of lead ion up to 300mg/g.The absorption test condition that obtains adsorption isothermal curve figure is: be earlier a with 20mg with the product shown in Fig. 1, behind alcohol dampening, respectively that every part of product is different with concentration again lead ion solution 10mL mix mutually, afterwards every part of mixing solutions are all carried out repeatedly leaving standstill 8 hours behind the ultra-sonic dispersion.Then, earlier respectively with every part of mixing solutions centrifugation, use plasma linking atom emmission spectrum to characterize respectively to its upper solution again, obtain adsorbing the concentration (mg/L) of lead ion when reaching balance, concentration in conjunction with lead ion in the mixing solutions before the absorption, obtain the adsorptive capacity (mg/g) of product to lead ion in the corresponding mixing solutions, the data that last basis records under different concns comprise equilibrium concentration and adsorptive capacity, obtain the adsorption isothermal curve of product to lead ion.
Embodiment
At first make or buy the silica dioxide granule that particle diameter is 0.1～1 μ m, as magnesium salts, nickel salt, mantoquita, cadmium salt and the cobalt salt of metal-salt, as the ammonium chloride and the ammoniacal liquor of additive, as the deionized water and the distilled water of solvent from market with ordinary method; Wherein, magnesium salts is magnesium chloride, sal epsom and magnesium nitrate, and nickel salt is nickelous chloride, single nickel salt and nickelous nitrate, and mantoquita is cupric chloride, copper sulfate and cupric nitrate, and cadmium salt is Cadmium chloride fine powder, Cadmium Sulphate and cadmium nitrate, and cobalt salt is cobalt chloride, rose vitriol and Xiao Suangu.Then,
Embodiment 1
The concrete steps of preparation are: step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 1g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the magnesium salts in the precursor solution, ammonium chloride, ammoniacal liquor and the water is 1:30:10:5000; Wherein, magnesium salts is a magnesium chloride, and water is deionized water.Perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 1g/L, in dispersion liquid, add nickel salt again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the nickel salt in the precursor solution, ammoniacal liquor and the water is 1:10:5000; Wherein, nickel salt is a nickelous chloride, and water is deionized water.Step 2, earlier precursor solution being placed temperature is that 120 ℃, pressure are to react 40h autogenous pressure under to obtain precipitated product, wash precipitated product again with water to neutral, make be similar to illustrated in figures 1 and 2, and the porous silicate nanometer hollow granule shown in the curve among Fig. 3 and Fig. 4, after it was adsorbed test, its result was shown in the curve among Fig. 9 and Figure 10.Perhaps make be similar to shown in Figure 5, and the porous silicate nanometer hollow granule shown in the curve among Fig. 6, it is adsorbed test after, its result is similar to shown in the curve among Fig. 9 and Figure 10.
Embodiment 2
The concrete steps of preparation are: step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.3 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 2g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the magnesium salts in the precursor solution, ammonium chloride, ammoniacal liquor and the water is 1.3:25:15:5000; Wherein, magnesium salts is a magnesium chloride, and water is deionized water.Perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.3 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 2g/L, in dispersion liquid, add nickel salt again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the nickel salt in the precursor solution, ammoniacal liquor and the water is 1.5:15:5000; Wherein, nickel salt is a nickelous chloride, and water is deionized water.Step 2, earlier precursor solution being placed temperature is that 130 ℃, pressure are to react 32h autogenous pressure under to obtain precipitated product, wash precipitated product again with water to neutral, make be similar to illustrated in figures 1 and 2, and the porous silicate nanometer hollow granule shown in the curve among Fig. 3 and Fig. 4, after it was adsorbed test, its result was shown in the curve among Fig. 9 and Figure 10.Perhaps make be similar to shown in Figure 5, and the porous silicate nanometer hollow granule shown in the curve among Fig. 6, it is adsorbed test after, its result is similar to shown in the curve among Fig. 9 and Figure 10.
Embodiment 3
The concrete steps of preparation are: step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.5 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 2g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the magnesium salts in the precursor solution, ammonium chloride, ammoniacal liquor and the water is 1.5:20:20:5000; Wherein, magnesium salts is a magnesium chloride, and water is deionized water.Perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.5 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 2g/L, in dispersion liquid, add nickel salt again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the nickel salt in the precursor solution, ammoniacal liquor and the water is 1.2:20:5000; Wherein, nickel salt is a nickelous chloride, and water is deionized water.Step 2, earlier precursor solution being placed temperature is that 140 ℃, pressure are to react 24h autogenous pressure under to obtain precipitated product, wash precipitated product again with water to neutral, make be similar to illustrated in figures 1 and 2, and the porous silicate nanometer hollow granule shown in the curve among Fig. 3 and Fig. 4, after it was adsorbed test, its result was shown in the curve among Fig. 9 and Figure 10.Perhaps make as shown in Figure 5, and the porous silicate nanometer hollow granule shown in the curve among Fig. 6, it is adsorbed test after, its result is similar to shown in the curve among Fig. 9 and Figure 10.
Embodiment 4
The concrete steps of preparation are: step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.8 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 3g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the magnesium salts in the precursor solution, ammonium chloride, ammoniacal liquor and the water is 1.8:15:25:5000; Wherein, magnesium salts is a magnesium chloride, and water is deionized water.Perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.8 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 3g/L, in dispersion liquid, add nickel salt again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the nickel salt in the precursor solution, ammoniacal liquor and the water is 1.8:25:5000; Wherein, nickel salt is a nickelous chloride, and water is deionized water.Step 2, earlier precursor solution being placed temperature is that 150 ℃, pressure are to react 16h autogenous pressure under to obtain precipitated product, wash precipitated product again with water to neutral, make as depicted in figs. 1 and 2, and the porous silicate nanometer hollow granule shown in the curve among Fig. 3 and Fig. 4, after it was adsorbed test, its result was shown in the curve among Fig. 9 and Figure 10.Perhaps make be similar to shown in Figure 5, and the porous silicate nanometer hollow granule shown in the curve among Fig. 6, it is adsorbed test after, its result is similar to shown in the curve among Fig. 9 and Figure 10.
Embodiment 5
The concrete steps of preparation are: step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 3g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the magnesium salts in the precursor solution, ammonium chloride, ammoniacal liquor and the water is 2:10:30:5000; Wherein, magnesium salts is a magnesium chloride, and water is deionized water.Perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 3g/L, in dispersion liquid, add nickel salt again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, the mol ratio between the nickel salt in the precursor solution, ammoniacal liquor and the water is 2:30:5000; Wherein, nickel salt is a nickelous chloride, and water is deionized water.Step 2, earlier precursor solution being placed temperature is that 160 ℃, pressure are to react 8h autogenous pressure under to obtain precipitated product, wash precipitated product again with water to neutral, make be similar to illustrated in figures 1 and 2, and the porous silicate nanometer hollow granule shown in the curve among Fig. 3 and Fig. 4, after it was adsorbed test, its result was shown in the curve among Fig. 9 and Figure 10.Perhaps make be similar to shown in Figure 5, and the porous silicate nanometer hollow granule shown in the curve among Fig. 6, it is adsorbed test after, its result is similar to shown in the curve among Fig. 9 and Figure 10.
Select magnesium salts or nickel salt or mantoquita or cadmium salt or cobalt salt more respectively for use, as the ammonium chloride and the ammoniacal liquor of solvent, as the deionized water or the distilled water of water as metal-salt; Wherein, magnesium salts is sal epsom or magnesium nitrate, nickel salt is single nickel salt or nickelous nitrate, mantoquita is cupric chloride or copper sulfate or cupric nitrate, cadmium salt is Cadmium chloride fine powder or Cadmium Sulphate or cadmium nitrate, cobalt salt is cobalt chloride or rose vitriol or Xiao Suangu, repeat the foregoing description 1～5, make equally as or be similar to Fig. 1, Fig. 2, Fig. 5 and shown in Figure 7, and as or be similar to the porous silicate nanometer hollow granule shown in the curve among Fig. 3, Fig. 4, Fig. 6 and Fig. 8, after it is adsorbed test, its result as or be similar to shown in the curve among Fig. 9 and Figure 10.
Obviously, those skilled in the art can carry out various changes and modification to porous silicate nanometer hollow granule of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (6)
1. porous silicate nanometer hollow granule, it is a silicate, it is characterized in that: described silicate is Magnesium Silicate q-agent or silicic acid nickel or cupric silicate or cadmium metasilicate or cobaltous silicate, described Magnesium Silicate q-agent or silicic acid nickel or cupric silicate or cadmium metasilicate or cobaltous silicate are the nanometer hollow granule shape, and the particle diameter of described nanometer hollow granule is that 0.1～1 μ m, shell surface are 450～550m for vesicular, specific surface area
2/ g, the thickness of described shell are 40～200nm, and the aperture in described hole is 3～5nm.
2. porous silicate nanometer hollow granule according to claim 1 is characterized in that nanometer hollow granule is spherical.
3. the preparation method of the described porous silicate nanometer hollow granule of claim 1 adopts hydrothermal method, it is characterized in that completing steps is as follows:
Step 1, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.1～1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 1～3g/L, in dispersion liquid, add magnesium salts and ammonium chloride again, treat to obtain mixed solution after its dissolving, in mixed solution, add ammoniacal liquor then and stir and obtain precursor solution, wherein, mol ratio between magnesium salts in the precursor solution, ammonium chloride, ammoniacal liquor and the water is 1～2: 10～30: 10～30: 5000
Perhaps, the silica dioxide granule ultra-sonic dispersion that with particle diameter is 0.1～1 μ m earlier is in water, obtain the dispersion liquid that concentration is the silica dioxide granule of 1～3g/L, in dispersion liquid, add nickel salt or mantoquita or cadmium salt or cobalt salt again, treat to obtain mixed solution after its dissolving, add ammoniacal liquor then and stir in mixed solution and obtain precursor solution, wherein, the mol ratio between nickel salt in the precursor solution or mantoquita or cadmium salt or cobalt salt, ammoniacal liquor and the water is 1～2: 10～30: 5000;
Step 2, earlier precursor solution being placed temperature is that 120～160 ℃, pressure are to react at least under the autogenous pressure that 8h obtains precipitated product, washes precipitated product again with water to neutral, makes porous silicate nanometer hollow granule.
4. the preparation method of porous silicate nanometer hollow granule according to claim 3 is characterized in that magnesium salts is magnesium chloride or sal epsom or magnesium nitrate.
5. the preparation method of porous silicate nanometer hollow granule according to claim 3 is characterized in that nickel salt is nickelous chloride or single nickel salt or nickelous nitrate.
6. the preparation method of porous silicate nanometer hollow granule according to claim 3 is characterized in that mantoquita is cupric chloride or copper sulfate or cupric nitrate.
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| CN1168860A (en) * | 1996-06-19 | 1997-12-31 | 德古萨股份公司 | Process for prepn. of crystalline microporous and mesoporous metal silicates, products obtainable by said process and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1168860A (en) * | 1996-06-19 | 1997-12-31 | 德古萨股份公司 | Process for prepn. of crystalline microporous and mesoporous metal silicates, products obtainable by said process and their use |
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