CN101791567B - Preparation method of V-SBA-16 mesoporous catalyst - Google Patents
Preparation method of V-SBA-16 mesoporous catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a V-SBA-16 mesoporous catalyst, which relates to a preparation method of a catalyst. The invention solves the problems that vanadium is difficult to enter an SBA-16 mesoporous framework in the process of preparing a V/SBA-16 catalyst by using the traditional method and the obtained catalyst has small specific surface area and low transformation ratio on benzene. The method comprises the steps of: adding a template agent P-123 and a template agent F-127 into deionized water to be stirred in a water bath, adding a hydrochloric acid solution, oscillating ultrasonically, stirring, respectively adding an ammonium metavanadate water solution and tetraethoxysilane, stirring, carrying out hydro-thermal reaction for 2-5 days, cooling, filtering, drying in vacuum after washing filter residue, and roasting to obtain the V-SBA-16 mesoporous catalyst. The method makes a part of V materials to enter the SBA-16 mesoporous framework to enable cell parameters of the V-SBA-16 mesoporous catalyst to be large, increases the surface area of the V-SBA-16 mesoporous catalyst, and further improves the transformation ratio on the benzene.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method.
Background technology
Select and preparation has high catalytic activity and be the matter of utmost importance that the researcher faces to the catalyst of target product high selectivity.The SBA-16 molecular sieve has high specific area, bigger hole dimension, narrow pore-size distribution and regular three-dimensional cage shape pore passage structure, it helps metal active constituent and disperses at its apparent height, helps transmission and the diffusion in the duct of reactant and product again.Vanadium is a kind of element of effective catalytic selective oxidation, how to synthesize have the high-ratio surface that contains vanadium, wide-aperture mesoporous SBA-16 type catalyst is a challenging problem.
Owing to be subjected to various preparation condition restrictions such as ratio, structure directing agent and the preparation time etc. of acidity, Si and V.At present, also do not have a kind of method successfully to synthesize and only contain the orderly three-dimensional meso-hole SBA-16 catalysis material that isolates vanadium oxygen activity center.The preparation method of existing V/SBA-16 mesoporous catalyst, gained V/SBA-16 catalyst is oligomeric V-O-V and high poly-V
2O
5The mixture of crystallite, and vanadium is difficult to enter into the SBA-16 mesoporous framework, gained V/SBA-16 specific surface area of catalyst is less, is applied in the benzene oxidation step system phenol, and the highest turn over number of benzene only is 48.9.
Summary of the invention
Goal of the invention of the present invention is to be difficult to enter into the SBA-16 mesoporous framework for vanadium in the process of the V/SBA-16 catalyst that solves existing method preparation, and the problem that gained V/SBA-16 specific surface area of catalyst is little, low to the conversion ratio of benzene provides a kind of preparation method of V-SBA-16 mesoporous catalyst.
The preparation method of V-SBA-16 mesoporous catalyst of the present invention is as follows: one, take by weighing template agent P-123, template agent F-127, deionized water, concentration is hydrochloric acid, ethyl orthosilicate and the ammonium metavanadate of 2mol/L; Two, 0.0015～0.0020mol template agent P-123 and 0.0035～0.0040mol template agent F-127 are joined back in 14～15mol deionized water at 30 ℃～40 ℃ stirred in water bath 30min, add the hydrochloric acid solution that 0.025～0.11L concentration is 2mol/L again, be ultrasonic concussion 15min under the condition of 100Hz in supersonic frequency then, continue to stir 4h, get mixed liquor; Three, 0.02～0.1mol ammonium metavanadate is joined 55～66mol deionized water for stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 2 gained, again the 1.0mol ethyl orthosilicate is joined in the mixed liquor of step 2 gained, stir 24 h, hydro-thermal reaction 2～5 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 500 ℃～600 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
The V-SBA-16 catalyst of the inventive method preparation is being in the reaction of the direct Selective Oxidation phenol of oxidizer catalytic benzene with hydrogen peroxide and oxygen respectively, shows excellent catalytic performance.When wherein being oxidant with the hydrogen peroxide, the selectivity of phenol is 100%, and yield is 8.7～11.8%; With oxygen is oxidant, and the selectivity of phenol is 86.7～94.8%, and phenol yield is 16.4～35.1%.The inventive method makes the part of V species enter vanadium species isolated in the V-SBA-16 mesoporous catalyst that makes the inventive method gained in the skeleton of SBA-16 to increase, further improved the conversion ratio of benzene, V-SBA-16 catalyst of the present invention can be 248.0 to turn over number (TON value) maximum of the benzene of benzene hydroxylation reaction.
Description of drawings
By Fig. 1 is the small angle X-ray diffraction figure of the specific embodiment 11 gained V-SBA-16 mesoporous catalysts; Fig. 2 is the N of the specific embodiment 11 gained V-SBA-16 mesoporous catalysts
2Adsorption-desorption isothermal curve figure; Fig. 3 is the Raman spectrogram of the specific embodiment 11 gained V-SBA-16 mesoporous catalysts.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method of V-SBA-16 mesoporous catalyst is as follows in the present embodiment: one, take by weighing template agent P-123, template agent F-127, deionized water, concentration is hydrochloric acid, ethyl orthosilicate and the ammonium metavanadate of 2mol/L; Two, 0.0015～0.0020mol template agent P-123 and 0.0035～0.0040mol template agent F-127 are joined back in 14～15mol deionized water at 30 ℃～40 ℃ stirred in water bath 30min, add the hydrochloric acid solution that 0.025～0.11L concentration is 2mol/L again, be ultrasonic concussion 15min under the condition of 100Hz in supersonic frequency then, continue to stir 4h, get mixed liquor; Three, 0.02～0.1mol ammonium metavanadate is joined 55～66mol deionized water for stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 2 gained, again the 1.0mol ethyl orthosilicate is joined in the mixed liquor of step 2 gained, stir 24 h, hydro-thermal reaction 2～5 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 500 ℃～600 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
0.005g～0.015g present embodiment gained V-SBA-16 mesoporous catalyst is joined in the reaction bulb of being furnished with reflux, add 50～200mmol acetonitrile and 3.4～34 mmol benzene then, temperature rises to 50～80 ℃, adds 10～100 mmol H again
2O
2(mass concentration is 30%), back flow reaction 2～8h obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 100%, and phenol yield is 8.7～11.8%.
0.050～0.500g present embodiment gained V-SBA-16 mesoporous catalyst, 4.5～15mmol ascorbic acid, 24～50mL solvent (being made up of by the volume ratio of 2 ﹕ 1 acetate and deionized water) and 5～50mmol benzene joined have in the teflon-lined autoclave, charge into O
2Pressure is 1.5～1.7MPa to the high pressure reactor, is to react 4～10h under 80 ℃ of conditions in temperature then, and cooling obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 86.7～94.8%, and phenol yield is 16.4～35.1%.
The specific embodiment two: present embodiment and the specific embodiment one are different is that the temperature of water-bath in the step 2 is 35 ℃.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different with the specific embodiment one or two be in the step 3 in the outstanding muddy water solution of ammonium metavanadate the content of ammonium metavanadate be that concentration is 0.03～0.09mol/L.Other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different with the specific embodiment one or two be in the step 3 in the outstanding muddy water solution of ammonium metavanadate the content of ammonium metavanadate be that concentration is 0.05～0.08mol/L.Other is identical with the specific embodiment one or two.
The specific embodiment five: present embodiment is different with the specific embodiment one or two be in the step 3 in the outstanding muddy water solution of ammonium metavanadate the content of ammonium metavanadate be that concentration is 0.06 mol/L.Other is identical with the specific embodiment one or two.
The specific embodiment six: present embodiment and the specific embodiment three are different be in the step 3 hydro-thermal reaction time be 4 days.Other is identical with the specific embodiment three.
The specific embodiment seven: present embodiment and the specific embodiment three are different be in the step 3 hydro-thermal reaction time be 3 days.Other is identical with the specific embodiment three.
The specific embodiment eight: present embodiment and the specific embodiment one to eight are different be in the step 3 under 510 ℃～590 ℃ condition roasting 4h.Other is identical with the specific embodiment one to eight.
The specific embodiment nine: present embodiment and the specific embodiment one to eight are different be in the step 3 under 520 ℃～580 ℃ condition roasting 4h.Other is identical with the specific embodiment one to eight.
The specific embodiment ten: present embodiment and the specific embodiment one to eight are different be in the step 3 under 550 ℃ condition roasting 4h.Other is identical with the specific embodiment one to eight.
The specific embodiment 11: the preparation method of V-SBA-16 mesoporous catalyst is as follows in the present embodiment: one, get 1.30g template agent F127 and 0.25g template agent P123 joins among the round-bottomed flask A, add 7.5 g deionized waters then, at 40 ℃ of stirred in water bath 30 min, add 0.75 mL hydrochloric acid solution (concentration is 2mol/L) and 25 g deionized waters again, then flask A is put into ultrasonic concussion 15 min under the condition that Ultrasound Instrument is 100Hz in supersonic frequency, continue to stir 4 h, get mixed liquor; Two, 0.19 g ammonium metavanadate is dissolved in the 5 g deionized waters, after stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 1 gained, ethyl orthosilicate with 6.1mL joins in the mixed liquor of step 1 gained again, stir 24 h, hydro-thermal reaction 4 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 550 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
The V content of present embodiment gained V-SBA-16 mesoporous catalyst is 1.67%.
0.005g present embodiment gained V-SBA-16 mesoporous catalyst is joined in the reaction bulb of being furnished with reflux, add 94.6 mmol acetonitriles and 3.4 mmol benzene then, temperature rises to 70 ℃, adds 14.7 mmol H again
2O
2(mass concentration is 30%), back flow reaction 4h obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 100%, and phenol yield is 11.8%.
0.010g present embodiment gained V-SBA-16 mesoporous catalyst is joined in the reaction bulb of being furnished with reflux, add 94.6 mmol acetonitriles and 3.4 mmol benzene then, temperature rises to 60 ℃, adds 14.7 mmol H again
2O
2(mass concentration is 30%), back flow reaction 8h obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 100%, and phenol yield is 9.7%.
0.015g present embodiment gained V-SBA-16 mesoporous catalyst is joined in the reaction bulb of being furnished with reflux, add 94.6 mmol acetonitriles and 3.4 mmol benzene then, temperature rises to 60 ℃, adds 14.7 mmol H again
2O
2(mass concentration is 30%), back flow reaction 4h obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 100%, and phenol yield is 10.4%.
0.100g present embodiment gained V-SBA-16 mesoporous catalyst, 8.5mmol ascorbic acid, 24mL solvent (being made up of by the volume ratio of 2 ﹕ 1 acetate and deionized water) and 11.3mmol benzene joined have in the teflon-lined autoclave, charge into O
2Pressure is 1.7 MPa to the high pressure reactor, reacts 10h then under temperature is 80 ℃ condition, and cooling obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 90.0%, and phenol yield is 30.4%.
0.500g present embodiment gained V-SBA-16 mesoporous catalyst, 15mmol ascorbic acid, 50mL solvent (being made up of by the volume ratio of 2 ﹕ 1 acetate and deionized water) and 50mmol benzene joined have in the teflon-lined autoclave, charge into O
2Pressure is 1.7 MPa to the high pressure reactor, reacts 10h then under temperature is 80 ℃ condition, and cooling obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 91.1%, and phenol yield is 34.9%.
By Fig. 1 (the small angle X-ray diffraction figure of present embodiment gained V-SBA-16 mesoporous catalyst) and Fig. 2 (N of present embodiment gained V-SBA-16 mesoporous catalyst
2Adsorption-desorption isothermal curve figure) present embodiment gained V-SBA-16 mesoporous catalyst has (200) (211) diffraction maximum a little less than tangible (a 110) diffraction maximum and two as can be known, and this shows that present embodiment gained V-SBA-16 mesoporous catalyst has kept the orderly 3 D stereo mesopore orbit structure of SBA-16.The cell parameter (as table 1) that calculates the V-SBA-16 mesoporous catalyst is 16.22nm, and the cell parameter 15.22nm of synthetic SBA-16 is big down than the same terms, and this is because the part of V species enter in the skeleton of SBA-16 causes.
The structural parameters of table 1 V-SBA-16 and catalytic activity are (with H
2O
2Be oxidant)
As can be seen from Figure 3, at 1044 cm
-1There is a strong Raman vibration peak at the place, and this peak ownership is the VO with isolated four-coordination
4The stretching vibration peak of the two keys of V=O in the construction unit illustrates that vanadium is all with isolated four-coordination VO in the V-SBA-16 catalyst
4Exist.This also is the main cause (as table 1) that this catalyst has high activity (TON=100.1) and high selectivity.
The specific embodiment 12: the preparation method of V-SBA-16 mesoporous catalyst is as follows in the present embodiment: one, get 0.65g template agent F127 and 0.12g template agent P123 joins among the round-bottomed flask A, add 3.5 g deionized waters then, at 30 ℃ of stirred in water bath 30 min, add 0.59 mL hydrochloric acid solution (concentration is 2mol/L) and 8 g deionized waters again, then flask A is put into ultrasonic concussion 15min under the condition that Ultrasound Instrument is 100Hz in supersonic frequency, continue to stir 4h, get mixed liquor; Two, 0.16 g ammonium metavanadate is dissolved in the 7g deionized water, after stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 1 gained, ethyl orthosilicate with 3mL joins in the mixed liquor of step 1 gained again, stir 24 h, hydro-thermal reaction 5 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 500 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
The V content of present embodiment gained V-SBA-16 mesoporous catalyst is 2.42%.
0.010g present embodiment gained V-SBA-16 mesoporous catalyst is joined in the reaction bulb of being furnished with reflux, add 94.6 mmol acetonitriles and 3.4 mmol benzene then, temperature rises to 60 ℃, adds 10 mmol H again
2O
2(mass concentration is 30%), back flow reaction 4h obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 100%, and phenol yield is 11.0%.
0.100g present embodiment gained V-SBA-16 mesoporous catalyst, 12.5mmol ascorbic acid, 24mL solvent (being made up of by the volume ratio of 2 ﹕ 1 acetate and deionized water) and 11.3mmol benzene joined have in the teflon-lined autoclave, charge into O
2Pressure is 1.5 MPa to the high pressure reactor, reacts 6h then under temperature is 80 ℃ condition, and cooling obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 86.7%, and phenol yield is 35.1%.
The specific embodiment 13: the preparation method of V-SBA-16 mesoporous catalyst is as follows in the present embodiment: one, get 1.30g template agent F127 and 0.25g template agent P123 joins among the round-bottomed flask A, add the 7.0g deionized water then, at 40 ℃ of stirred in water bath 30 min, add 0.32 mL hydrochloric acid solution (concentration is 2mol/L) and 25 g deionized waters again, then flask A is put into ultrasonic concussion 15 min under the condition that Ultrasound Instrument is 100Hz in supersonic frequency, continue to stir 4 h, get mixed liquor; Two, the 0.06g ammonium metavanadate is dissolved in the 5 g deionized waters, after stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 1 gained, ethyl orthosilicate with 5.0mL joins in the mixed liquor of step 1 gained again, stir 24 h, hydro-thermal reaction 4 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 550 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
The V content of present embodiment gained V-SBA-16 mesoporous catalyst is 0.74%.
The specific embodiment 14: the preparation method of V-SBA-16 mesoporous catalyst is as follows in the present embodiment: one, get 1.30g template agent F127 and 0.25g template agent P123 joins among the round-bottomed flask A, add 7.5 g deionized waters then, at 40 ℃ of stirred in water bath 30 min, add 0.56 mL hydrochloric acid solution (concentration is 2mol/L) and 25 g deionized waters again, then flask A is put into ultrasonic concussion 15 min under the condition that Ultrasound Instrument is 100Hz in supersonic frequency, continue to stir 4h, get mixed liquor; Two, the 0.13g ammonium metavanadate is dissolved in the 5g deionized water, after stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 1 gained, ethyl orthosilicate with 6.1mL joins in the mixed liquor of step 1 gained again, stir 24 h, hydro-thermal reaction 2 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 550 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
The V content of present embodiment gained V-SBA-16 mesoporous catalyst is 1.03%.
0.010g present embodiment gained V-SBA-16 mesoporous catalyst is joined in the reaction bulb of being furnished with reflux, add 94.6 mmol acetonitriles and 3.4 mmol benzene then, temperature rises to 60 ℃, adds 14.7 mmol H again
2O
2(mass concentration is 30%), back flow reaction 4h obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 100%, and phenol yield is 8.7%.
0.100g present embodiment gained V-SBA-16 mesoporous catalyst, 8.5mmol ascorbic acid, 50mL solvent (being made up of by the volume ratio of 2 ﹕ 1 acetate and deionized water) and 11.3mmol benzene joined have in the teflon-lined autoclave, charge into O
2Pressure is 1.7 MPa to the high pressure reactor, reacts 4h then under temperature is 80 ℃ condition, and cooling obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 90.2%, and phenol yield is 28.3%.
The specific embodiment 15: the preparation method of V-SBA-16 mesoporous catalyst is as follows in the present embodiment: one, get 0.65g template agent F127 and 0.12g template agent P123 joins among the round-bottomed flask A, add 3.5 g deionized waters then, at 35 ℃ of stirred in water bath 30 min, add 1.34 mL hydrochloric acid solutions (concentration is 2mol/L) and 13 g deionized waters again, then flask A is put into ultrasonic concussion 15 min under the condition that Ultrasound Instrument is 100Hz in supersonic frequency, continue to stir 4 h, get mixed liquor; Two, 0.10 g ammonium metavanadate is dissolved in the 2.5 g deionized waters, after stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 1 gained, ethyl orthosilicate with 3.0mL joins in the mixed liquor of step 1 gained again, stir 24 h, hydro-thermal reaction 3 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 550 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
The V content of present embodiment gained V-SBA-16 mesoporous catalyst is 0.38%.
0.050g present embodiment gained V-SBA-16 mesoporous catalyst, 4.5mmol ascorbic acid, 24mL solvent (being made up of by the volume ratio of 2 ﹕ 1 acetate and deionized water) and 5mmol benzene joined have in the teflon-lined autoclave, charge into O
2Pressure is 1.7 MPa to the high pressure reactor, reacts 10h then under temperature is 80 ℃ condition, and cooling obtains phenol.The selectivity that obtains V-SBA-16 mesoporous catalyst Pyrogentisinic Acid by quantitative analysis is 94.8%, and phenol yield is 16.4%.
Claims (10)
1.V-SBA-16 the preparation method of mesoporous catalyst is characterized in that the preparation method of V-SBA-16 mesoporous catalyst is as follows: one, take by weighing template agent P-123, template agent F-127, deionized water, concentration is hydrochloric acid, ethyl orthosilicate and the ammonium metavanadate of 2mol/L; Two, 0.0015～0.0020mol template agent P-123 and 0.0035～0.0040mol template agent F-127 are joined back in 14～15mol deionized water at 30 ℃～40 ℃ stirred in water bath 30min, add the hydrochloric acid solution that 0.025～0.11L concentration is 2mol/L again, be ultrasonic concussion 15min under the condition of 100Hz in supersonic frequency then, continue to stir 4h, get mixed liquor; Three, 0.02～0.1mol ammonium metavanadate is joined 55～66mol deionized water for stirring 15min, obtain the outstanding muddy water solution of ammonium metavanadate, then the outstanding muddy water solution of ammonium metavanadate is joined in the mixed liquor of step 2 gained, again the 1.0mol ethyl orthosilicate is joined in the mixed liquor of step 2 gained, stir 24h, hydro-thermal reaction 2～5 days under 100 ℃ condition then, cooling, filter, with behind the residue washing under 50 ℃ condition vacuum drying 12h, roasting 4h under 500 ℃～600 ℃ condition promptly gets the V-SBA-16 mesoporous catalyst again.
2. the preparation method of V-SBA-16 mesoporous catalyst according to claim 1, the temperature that it is characterized in that water-bath in the step 2 is 35 ℃.
3. the preparation method of V-SBA-16 mesoporous catalyst according to claim 1 and 2 is characterized in that the content of ammonium metavanadate in the outstanding muddy water solution of ammonium metavanadate in the step 3 is 0.03～0.09mol/L.
4. the preparation method of V-SBA-16 mesoporous catalyst according to claim 1 and 2 is characterized in that the content of ammonium metavanadate in the outstanding muddy water solution of ammonium metavanadate in the step 3 is 0.05～0.08mol/L.
5. the preparation method of V-SBA-16 mesoporous catalyst according to claim 1 and 2 is characterized in that the content of ammonium metavanadate in the outstanding muddy water solution of ammonium metavanadate in the step 3 is that concentration is 0.06mol/L.
6. the preparation method of V-SBA-16 mesoporous catalyst according to claim 3 is characterized in that the hydro-thermal reaction time is 4 days in the step 3.
7. the preparation method of V-SBA-16 mesoporous catalyst according to claim 3 is characterized in that the hydro-thermal reaction time is 3 days in the step 3.
8. according to the preparation method of claim 1,2 or 6 described V-SBA-16 mesoporous catalysts, it is characterized in that in the step 3 roasting 4h under 510 ℃～590 ℃ condition.
9. according to the preparation method of claim 1,2 or 6 described V-SBA-16 mesoporous catalysts, it is characterized in that in the step 3 roasting 4h under 520 ℃～580 ℃ condition.
10. according to the preparation method of claim 1,2 or 6 described V-SBA-16 mesoporous catalysts, it is characterized in that in the step 3 roasting 4h under 550 ℃ condition.
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