CN103962185B - The method of one step sol-gal process synthesis phosphotungstic acid-titanium dioxide complex spherical nano material - Google Patents
The method of one step sol-gal process synthesis phosphotungstic acid-titanium dioxide complex spherical nano material Download PDFInfo
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- CN103962185B CN103962185B CN201410205782.2A CN201410205782A CN103962185B CN 103962185 B CN103962185 B CN 103962185B CN 201410205782 A CN201410205782 A CN 201410205782A CN 103962185 B CN103962185 B CN 103962185B
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Abstract
The invention discloses the method for a kind of step sol-gal process synthesis phosphotungstic acid-titanium dioxide complex spherical nano material belonging to function nano technical field of material.This method avoid experimental procedure and the high-energy source consumption of solvent-induced self assembly and hydrothermal method complexity, greatly simplifie experiment flow.The appearance and size of the phosphotungstic acid-titanium dioxide complex spherical nano material prepared is controlled.And this nanometer class spherical structure has high sulfur removal effectiveness, be applied to extraction in conjunction with catalytic oxidation except in reaction of Salmon-Saxl, the DBT simulated oil of sulfur content 350ppm can be degraded to 4.8ppm by the catalyst of use 70mg in 2h.This novel nanocatalyst preparation method is simple, has that thermal stability is good, equipment energy consumption is few, the feature of environmental protection, is expected to practical development application in the industrial production of sulphur removal.
Description
Technical field
The invention belongs to function nano technical field of material, be specifically related to a kind of method with the phosphotungstic acid-titanium dioxide complex spherical nano material of efficient sulphur removal performance of use one step sol-gal process synthesis.
Background technology
Polyoxometallate recent years (abbreviation polyacid) obtain the extensive concern of people as a kind of " green " industrial catalyst, polyacid is due to the adjustability of chemical property, high oxidation selectivity, have stimulated the scientific research in many fields, such as, catalysis, material, structural chemistry and medicine etc.Polyacid obtains deep research as catalyst in catalytic oxidation sulphur removal.Polyacid catalyst shows very high catalytic activity in Oxybenzene bithiophene (BTs) and dibenzothiophenes (DBTs) process, but these homogeneous catalysts are difficult to separation and recycling limits its commercial Application.Someone develops amphiphilic season ammonia multi-acid salt catalyst, and these catalyst considerably improve sulfur removal effectiveness in selective oxidation sulphur removal process, but many carbon chain quaternary ammonium salts limit its practical application in the industrial production owing to having higher cost.Some researchers by phosphotungstic acid (referred to as PW
12) immobilized to cheaper silica, on silica pillared clay and hexagonal mesoporous silicon acid substance carrier, these catalyst prepared show very high catalytic efficiency, and active material only has slight loss in circulation sulphur removal process.But prepare above-mentioned immobilized PW
12need through for a long time reaction, repeatedly calcining and hydro-thermal high energy consumption process except sulfur catalyst, the preparation method therefore needing further exploratory development easier and carrier.
TiO in numerous carrier
2at catalytic field, there is higher activity and selectivity and cause the great interest of people, TiO
2load polyacid obtains deep research as a kind of high performance catalyst at catalytic field.Report is had to use infusion process by PW
12immobilized to mesoporous TiO
2on be prepared into the acid catalyst of load, but the wash-out of polyacid causes catalytic activity to reduce in catalytic reaction.Also report is had to use the method for solvent-induced self assembly to prepare a series of different PW
12the PW of content
12/ TiO
2meso-porous nano material, and the catalytic oxidation sulphur removal these nano-substances being applied to dibenzothiophenes simulated oil, but in these catalyst synthesis processes, need the reaction through 2 days, the aging 673K high-temperature calcination also having 20h of 2 days.Therefore preparation method's complexity and energy consumption problem still do not solve.
Summary of the invention
Object of the present invention is on the material base with excellent catalytic oxidation sulphur removal performance, provides a kind of means for solving material from being prepared into practical application: namely provide that a kind of preparation method is simple, stability is high, less energy consumption and the PW of the regulatable a kind of high catalytic oxidation sulphur removal performance of pattern
12/ TiO
2complex spherical nano material and preparation method thereof.
The phosphotungstic acid-titanium dioxide complex spherical nano material of the present invention's synthesis has spherical tufted structure, and wherein the mass ratio of phosphotungstic acid and titanium dioxide is 1:10-4:10.
The preparation method of a step sol-gal process synthesis phosphotungstic acid-titanium dioxide complex spherical nano material of the present invention: by 0.3-3g butyl titanate instillation 30-70mL absolute ethyl alcohol, vigorous stirring, dropwise instilling 0.5-3mL is the ethanol solution of 0.01-0.5g containing phosphotungstic acid quality, controls the mass ratio of phosphotungstic acid and butyl titanate between 1:42-4:42; Then 0.2-2mL water and alcohol mixed solution is dropwise added in whipping process, the volume ratio of water and ethanol is 1:5-5:1, continue stirring reaction 3-5h at normal temperatures, centrifugally obtain white precipitate, wash respectively with water and ethanol, last 50-80 DEG C of oven dry 3-5h in an oven, in Muffle furnace, 150-200 DEG C is dried 2-4h.
The above-mentioned phosphotungstic acid-titanium dioxide composite Nano sphere material prepared is applied to extraction in conjunction with catalytic oxidation except reaction of Salmon-Saxl.
The present invention utilizes a simple step sol-gel method to prepare phosphotungstic acid-titanium dioxide complex spherical nano material first, this method avoid experimental procedure and the high-energy source consumption of solvent-induced self assembly and hydrothermal method complexity, greatly simplifie experiment flow.The appearance and size of the phosphotungstic acid-titanium dioxide complex spherical nano material prepared can be adjustable with the ratio of phosphotungstic acid and butyl titanate.And this nanometer class spherical structure has high sulfur removal effectiveness, be applied to extraction in conjunction with catalytic oxidation except in reaction of Salmon-Saxl, the DBT simulated oil of sulfur content 350ppm can be degraded to 4.8ppm by the catalyst of use 70mg in 2h.This novel nanocatalyst preparation method is simple, has that thermal stability is good, equipment energy consumption is few, the feature of environmental protection, is expected to practical development application in the industrial production of sulphur removal.
Accompanying drawing explanation
Fig. 1. the SEM figure of phosphotungstic acid-titanium dioxide complex spherical nano material prepared by embodiment 1.
Fig. 2. the grain size distribution of phosphotungstic acid-titanium dioxide complex spherical nano material prepared by embodiment 1.
Fig. 3. phosphotungstic acid-titanium dioxide complex spherical nano material prepared by embodiment 1 is schemed over time as the high performance liquid chromatography peak of catalyst oxidation removal DBT.
Fig. 4. the SEM figure of phosphotungstic acid-titanium dioxide complex spherical nano material prepared by embodiment 2.
Fig. 5. the grain size distribution of phosphotungstic acid-titanium dioxide complex spherical nano material prepared by embodiment 2.
Fig. 6. phosphotungstic acid-titanium dioxide complex spherical nano material prepared by embodiment 2 is schemed over time as the high performance liquid chromatography peak of catalyst oxidation removal DBT.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further details, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1
1) by 0.6g butyl titanate ([C
4h
90]
4ti) instill in 50mL absolute ethyl alcohol, vigorous stirring;
2) ethanol solution of 1mL containing 0.135g phosphotungstic acid is dropwise instilled;
3) continue stir and dropwise add 1ml water and ethanol (v/v=1:5) mixed solution, continue stirring reaction 4h at normal temperatures;
4) centrifugally white precipitate is obtained, 2 times are washed respectively with water and ethanol, dry 4h for 70 DEG C in an oven, then 150 DEG C of baking 3h in Muffle furnace, phosphotungstic acid-titanium dioxide complex spherical nano material, this material has spherical tufted structure, and wherein the mass ratio of phosphotungstic acid and titanium dioxide is 1:10.
Preparation sulfur content is the DBT normal octane solution 20mL of 350ppm, join in 100mL tri-neck round-bottomed flask, add 20ml acetonitrile as extractant, take 70mg above-mentioned prepare phosphotungstic acid-titanium dioxide complex spherical nano material as catalyst, add in oil phase and react, 60 DEG C of heating water baths, certain time interval is at normal octane sampling efficient liquid phase chromatographic analysis mutually, and after reaction 2h, catalytic oxidation desulfurization performance can reach 97.5%.
Embodiment 2
1) by 0.6g butyl titanate ([C
4h
90]
4ti) instill in 50mL absolute ethyl alcohol, vigorous stirring;
2) ethanol solution of 1mL containing 0.653g phosphotungstic acid is dropwise instilled;
3) continue stir and dropwise add 1ml water and ethanol (v/v=1:5) mixed solution, continue stirring reaction 4h at normal temperatures;
4) centrifugally white precipitate is obtained, 2 times are washed respectively with a small amount of water and ethanol, dry 4h for 70 DEG C in an oven, then 150 DEG C of baking 3h in Muffle furnace, phosphotungstic acid-titanium dioxide complex spherical nano material, this material has spherical tufted structure, and wherein the mass ratio of phosphotungstic acid and titanium dioxide is 3:10.
Preparation sulfur content is the DBT normal octane solution 20mL of 350ppm, join in 100mL tri-neck round-bottomed flask, add 20ml acetonitrile as extractant, take 70mg above-mentioned prepare phosphotungstic acid-titanium dioxide complex spherical nano material as catalyst, add in oil phase and react, 60 DEG C of heating water baths, certain time interval is at normal octane sampling efficient liquid phase chromatographic analysis mutually, and after reaction 2h, catalytic oxidation desulfurization performance can reach 99.5%.
Claims (2)
1. a step colloidal sols gelatin synthesizing method of a phosphotungstic acid-titanium dioxide complex spherical nano material, it is characterized in that, its concrete operation step is: by 0.3-3g butyl titanate instillation 30-70mL absolute ethyl alcohol, vigorous stirring, dropwise instilling 0.5-3mL is the ethanol solution of 0.01-0.5g containing phosphotungstic acid quality, controls the mass ratio of phosphotungstic acid and butyl titanate between 1:42-4:42; Then 0.2-2mL water and alcohol mixed solution is dropwise added in whipping process, the volume ratio of water and ethanol is 1:5-5:1, continue stirring reaction 3-5h at normal temperatures, centrifugally obtain white precipitate, wash respectively with water and ethanol, last 50-80 DEG C of oven dry 3-5h in an oven, in Muffle furnace, 150-200 DEG C is dried 2-4h;
Above-mentioned obtained phosphotungstic acid-titanium dioxide complex spherical nano material has spherical tufted structure, and wherein the mass ratio of phosphotungstic acid and titanium dioxide is 1:10-4:10.
2. the phosphotungstic acid-titanium dioxide composite Nano sphere material of a step colloidal sols gelatin synthesizing method synthesis according to claim 1 removes the application in reaction of Salmon-Saxl in extraction in conjunction with catalytic oxidation.
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