CN109731573A - A kind of preparation method and application of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst - Google Patents
A kind of preparation method and application of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst Download PDFInfo
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- CN109731573A CN109731573A CN201811579000.6A CN201811579000A CN109731573A CN 109731573 A CN109731573 A CN 109731573A CN 201811579000 A CN201811579000 A CN 201811579000A CN 109731573 A CN109731573 A CN 109731573A
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Abstract
The invention discloses a kind of preparation method and applications of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst, by including one or more kinds of element doping nano-carbon materials in O, N, S, P, carrier is used as including one of nano-carbon materials such as carbon nanotubes, carbon nano-fiber, Nano diamond, active carbon and graphene or more than one mixing, using colloidal sol anchor titration, load quality score is the gold nano grain of 0.5-5.0wt%.Au/ nanocarbon catalyst provided by the invention converts benzyl alcohol producing benzaldehyde by oxygen or air successive reaction efficient catalytic under normal pressure and lower temperature.Method according to the present invention, in section Example, according to set response parameter, phenmethylol conversion ratio is up to 88.6%, and the selectivity of benzaldehyde is up to 99.0% or more.
Description
Technical field
The present invention relates to a kind of preparation method of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst and answer
With being using element doping nano-carbon materials one or more of in O, N, S, P, and by colloidal sol anchor titration load quality score
The gold nano grain of 0.5-5.0wt%.By successive reaction under oxygen or air conditions, under normal pressure and lower temperature, effectively
Catalyzed conversion benzyl alcohol benzyl alcohol.
Background technique
Load type gold nano material is because of its excellent catalytic activity in heterogeneous catalytic reaction and the Gao Xuan of target product
Selecting property, the favor by researcher.Compared with the Au catalyst of active carrier load, inert carrier (including SiO2、Al2O3, receive
Rice carbon material etc.) due to being difficult to interact between the stronger gold-carrier of gold formation, generally result in size of nanometer gold grain compared with
Greatly, the problems such as being easy to be sintered and inactivate in heat treatment and reaction process.However, inert carrier has rich reserves, at low cost
It is honest and clean and convenient for large-scale production etc. advantages, further increase the Activity and stabill of inert carrier load gold catalyst, be always
By one of the significant problem of extensive concern in gold catalysis.
Nano-carbon material includes the zero dimensions such as Nano diamond, carbon nanotubes, graphene, carbon nano-fiber, active carbon, one
Dimension, two dimension and three-dimensional material, while there is morphology controllable, surface chemical property to be easy to regulation, good electrical and thermal conductivity performance etc.
Excellent property can be applied to include the effective carrier material of the noble metal nano particles such as Pt, Pd, Rh.However, nano-sized carbon
Material as carrier loaded size uniformity and tiny gold nano grain, and show in heterogeneous catalytic reaction high activity,
The correlative study of single selective and stability still rarely has report.
On the other hand, it is synthesis fine chemicals and high added value chemistry that alcohols selectivity oxidation, which generates corresponding aldehydes or ketones,
The important reaction path of intermediate.Wherein, the oxidation of benzyl alcohol is one of most representative important reaction.As one of product
Benzaldehyde be important organic intermediate, can be used for the industries such as medicine, dyestuff, food and pesticide.Select green air or
Oxygen is as oxidant, using high activated catalyst, in the case where by-product only has water and more mild reaction condition, high conversion
Conversion benzyl alcohol prepares benzaldehyde, has important research significance.
Patent CN107805190 has reported a kind of side of air oxidation benzyl alcohol producing benzaldehyde using solvent-free system
Method uses activated carbon supported mass fraction to carry out for the nano cupric oxide of 1%-4% as catalyst in sealing reactor
Atmospheric operation.Post catalyst reaction is easily recycled.However the particle of active component copper oxide is 20nm or so, catalyst is used
Larger (mass parts ratio with benzyl alcohol is 1:9-1:27) is measured, reaction temperature is higher (120-150 DEG C).
A kind of method that patent CN107983412 describes catalytic oxidation of benzyl alcohol producing benzaldehyde catalyst, using La2O3@
COF sol solution is as catalyst, at 45-80 DEG C of reaction temperature, 30-60min is reacted under normal pressure, benzaldehyde yield is reachable
51.4%-94.0%.However this method raw material prepares cumbersome and technological operation and is related to Schiff alkali phosphate, propylene oxide, tetrahydro
Furans etc. is inflammable, toxic organic compounds, does not meet environmentally protective production requirement.
Patent CN108640824 reports a kind of method that catalysis oxidation benzyl alcohol prepares benzaldehyde, using xCu-yZn/
CNTS catalyst, Ni metal mass percentage are 0.01%-20%, and the mass percentage of metal Zn is 0.1%-30%.
Using gas phase successive reaction, catalyst is stable during the reaction and easily-activated regeneration, and benzaldehyde yield is 95% or more.So
And reaction temperature is higher (220-400 DEG C) in catalytic process, does not meet energy-saving and environment-friendly requirement.
In conclusion in view of the limitation of current Preparation of Benzaldehyde, develop a kind of new and effective carbon material supported
Nano catalyst realizes molecular oxygen to catalytic oxidation of benzyl alcohol producing benzaldehyde technique gesture must under normal pressure and lower temperature
Row.How to improve the conversion ratio of benzyl alcohol and controls the highly selective most important of benzaldehyde.
Summary of the invention
The present invention provides a kind of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst and preparation method thereof,
It is 0.5- using element doping nano-carbon materials one or more of in O, N, S, P, and by colloidal sol anchor titration load quality score
The gold nano grain of 5.0wt%.It is effectively urged under normal pressure and lower temperature by the successive reaction under oxygen or air conditions
Change conversion benzyl alcohol benzyl alcohol.
Technical solution of the present invention:
A kind of preparation method of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst, steps are as follows:
It under agitation, is 10 to concentration-4-10-2It is 1- that mass fraction is added in the aqueous solution of chloraurate of mol/L
The polyvinyl alcohol water solution of 10wt%, stirring are no less than 20min, wherein the mass ratio of polyvinyl alcohol and Au are 1:1-10:1；Again
The sodium borohydride solution that molar concentration is 0.1-1.0mol/L is added, stirring is no less than 10min, wherein sodium borohydride and Au's
Molar ratio is 1:1-10:1；The nano-carbon material for adding element doping, continue stirring be no less than 3h, control Au simple substance component with
The mass ratio of nano-carbon material is 0.5-5.0；After being filtered, washed, drying, by powder in tube furnace air atmosphere 200-
600 DEG C of roasting 2-5h obtain benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst.
One or more of described nano-carbon material, including O, N, S, P of element doping element co-doped；
The nano-carbon material includes carbon nanotubes, carbon nano-fiber, Nano diamond, active carbon, one or two kinds of in graphene
The above mixing.
A kind of high activity Au/ nanocarbon catalyst is used for benzyl alcohol oxidation producing benzaldehyde, and steps are as follows:
High activity Au/ nanocarbon catalyst, benzyl alcohol, paraxylene and NaOH are mixed, are passed through 10-100ml/min's
Oxygen or air carry out successive reaction, and control reaction thermostat temperature section is 30-120 DEG C, react 0.5-6h under normal pressure, pass through
Separating-purifying is up to product benzaldehyde.
Wherein, high activity Au/ nanocarbon catalyst, benzyl alcohol, paraxylene and NaOH mass ratio be 0.005~
0.05:0.01~0.5:2~20:0.02~0.2.
Element doping nano-carbon material provided by the invention loads Au catalyst, under lower reaction temperature and normal pressure,
By successive reaction, higher phenmethylol conversion ratio and benzaldehyde selectivity are obtained.Method according to the present invention is implemented in part
In example, according to set response parameter, phenmethylol conversion ratio up to 88.6%, the selectivity of benzaldehyde up to 99.0% with
On.
Detailed description of the invention
Fig. 1 is the transmission electron microscope image of Au/OCNT catalyst.
Fig. 2 is the transmission electron microscope image of O-NCNT catalyst.
X-ray photoelectron spectroscopy image of the Fig. 3 for Au/S-OCNT catalyst, (a) O1s spectrogram, (b) Au4f spectrogram, (c)
S2p spectrogram.
Fig. 4 is high angle annular dark-scanning transmission electron microscope image of Au/S-OCNT catalyst.
Specific embodiment
With following embodiment, the invention will be further described, and following embodiment is served only for summary of the invention furtherly
It is bright, it does not constitute a limitation on the scope of protection of the present invention.
1 colloidal sol anchor titration of embodiment prepares Au/OCNT catalyst
Taking 76mL molar concentration is 10-3The aqueous solution of chloraurate of mol/L, 7.5mL mass fraction is added under stiring is
The polyvinyl alcohol water solution (polyvinyl alcohol/Au mass ratio is 5:1) of 1wt%, is added 3.8mL molar concentration after stirring 20min
For the sodium borohydride solution of 0.1mol/L, 1.0g oxygen doping carbon nanotubes (OCNT) carrier is added ten minutes later, continues to stir for stirring
Mix 16h, after being filtered, washed, drying, by powder in tube furnace 300 DEG C of roasting 3h, obtain OCNT load Au catalyst.Fig. 1
For the transmission electron microscope image of Au/OCNT catalyst.
The preparation of embodiment 2 oxygen doping carbon nanotubes (OCNT) carrier
5g carbon nanotube powder (Shandong great Zhan nano material Co., Ltd) is taken, is washed using the hydrochloric acid solution of 200mL37%
12h is washed, is neutrality by filtration washing to filtrate, obtains the carbon nanotubes of pickling after dry.Using ozone generator, with smelly
Oxygen/air Mixture carries out functionalization to carbon nanotubes, and pump gas velocity degree is 16L/min, and gaseous mixture passes through and carries temperature
Continue functionalization 50min into 40 DEG C of constant temperature of vertical reactors for 30 DEG C of vapor, obtain oxygen doping carbon nanotubes
OCNT。
The preparation of embodiment 3 oxygen nitrogen dual element dopen Nano carbon pipe (O-NCNT) carrier
By chemical vapour deposition technique, using imidazoles as nitrogen source and carbon source, nitrogen-doped nanometer carbon pipe (NCNT) is prepared, use is smelly
Oxygen Generator carries out functionalization to carbon nanotubes with ozone/air Mixture, and pump gas velocity degree is 16L/min, yield of ozone
For 5g/h, gaseous mixture passes through and carries the vapor that temperature is 30 DEG C, into 40 DEG C of constant temperature of vertical reactors, continues function
Change 50min, obtains oxygen nitrogen dual element dopen Nano carbon pipe (O-NCNT).Fig. 2 is the transmission electron microscope of O-NCNT catalyst
Image.
The preparation of embodiment 4 sulphur oxygen dual element dopen Nano carbon pipe (S-OCNT) carrier
3.5g OCNT is taken uniformly to mix with 1g sulphur, in tube furnace under argon atmosphere, using gas velocity 50mL/min, with 2
DEG C/min temperature programming to 150 DEG C of holding 6h, 300 DEG C are continuously heating to, 3h is kept, is cooled to room temperature, obtains sulphur oxygen dual element
The carbon nanotube (S-OCNT) of doping.
Catalysis oxidation benzyl alcohol producing benzaldehyde at 40 DEG C of embodiment 5Au/OCNT catalyst
10mgAu/OCNT, 0.05g benzyl alcohol, 5g paraxylene and 0.08gNaOH are added in three-necked flask, used
The gas velocity of 40ml/min is passed through oxygen and carries out successive reaction, controls 70 DEG C of reaction temperature constant temperature, after reacting 3h, measures benzyl alcohol
Conversion ratio is 88.6%, selectivity > 99.0% of benzaldehyde.
Catalysis oxidation benzyl alcohol producing benzaldehyde at 60 DEG C of embodiment 6Au/OCNT catalyst
10mgAu/OCNT, 0.05g benzyl alcohol, 5g paraxylene and 0.08gNaOH are added in three-necked flask, used
The gas velocity of 40ml/min is passed through oxygen and carries out successive reaction, controls 60 DEG C of reaction temperature constant temperature, after reacting 3h, measures benzyl alcohol
Conversion ratio is 87.4%, selectivity > 99.0% of benzaldehyde.
Embodiment 7OCNT catalyst Oxybenzene methyl alcohol producing benzaldehyde
10mgOCNT, 0.05g benzyl alcohol, 5g paraxylene and 0.08gNaOH are added in three-necked flask, using 40ml/
The gas velocity of min is passed through oxygen and carries out successive reaction, controls 40 DEG C of reaction temperature constant temperature, after reacting 3h, measures the conversion of benzyl alcohol
Rate is 18.7%, selectivity > 99.0% of benzaldehyde.
Embodiment 8Au/CNT catalyst Oxybenzene methyl alcohol producing benzaldehyde
10mgAu/CNT, 0.05g benzyl alcohol, 5g paraxylene and 0.08gNaOH are added in three-necked flask, used
The gas velocity of 40ml/min is passed through oxygen and carries out successive reaction, controls 40 DEG C of reaction temperature constant temperature, after reacting 3h, measures benzyl alcohol
Conversion ratio is 50.4%, selectivity > 99.0% of benzaldehyde.
Embodiment 9Au/S-OCNT catalyst Oxybenzene methyl alcohol producing benzaldehyde
10mgAu/S-OCNT, 0.05g benzyl alcohol, 5g paraxylene and 0.08gNaOH are added in three-necked flask, used
The gas velocity of 40ml/min is passed through oxygen and carries out successive reaction, controls 40 DEG C of reaction temperature constant temperature, after reacting 3h, measures benzyl alcohol
Conversion ratio is 60.3%, selectivity > 99.0% of benzaldehyde.Fig. 3 is the x-ray photoelectron spectroscopy figure of Au/S-OCNT catalyst
Picture.Fig. 4 is high angle annular dark-scanning transmission electron microscope image of Au/S-OCNT catalyst.
Claims (4)
1. a kind of preparation method of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst, which is characterized in that step is such as
Under:
It under agitation, is 10 to concentration-4-10-2It is 1-10wt%'s that mass fraction is added in the aqueous solution of chloraurate of mol/L
Polyvinyl alcohol water solution, stirring are no less than 20min, wherein the mass ratio of polyvinyl alcohol and Au are 1:1-10:1；It adds mole
Concentration is the sodium borohydride solution of 0.1-1.0mol/L, and stirring is no less than 10min, wherein the molar ratio of sodium borohydride and Au is
1:1-10:1；The nano-carbon material for adding element doping continues stirring and is no less than 3h, controls Au simple substance component and nano carbon material
The mass ratio of material is 0.5-5.0；After being filtered, washed, drying, the 200-600 DEG C of roasting in tube furnace air atmosphere by powder
2-5h is burnt, benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst is obtained.
2. preparation method according to claim 1, which is characterized in that the nano-carbon material of the element doping, including
O, one or more of N, S, P element co-doped；The nano-carbon material includes carbon nanotubes, Nano carbon fibers
Dimension, Nano diamond, active carbon, one or more kinds of mixing in graphene.
3. a kind of high activity Au/ nanocarbon catalyst is used for benzyl alcohol oxidation producing benzaldehyde, which is characterized in that steps are as follows:
High activity Au/ nanocarbon catalyst, benzyl alcohol, paraxylene and NaOH are mixed, the oxygen of 10-100ml/min is passed through
Or air carries out successive reaction, control reaction thermostat temperature section is 30-120 DEG C, 0.5-6h is reacted under normal pressure, by separation
It purifies up to product benzaldehyde.
4. high activity Au/ nanocarbon catalyst according to claim 3 is used for benzyl alcohol oxidation producing benzaldehyde, feature exists
In high activity Au/ nanocarbon catalyst, benzyl alcohol, paraxylene and the NaOH mass ratio are 0.005~0.05:
0.01~0.5:2~20:0.02~0.2.
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| CN110124717A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of catalyst and preparation method thereof being converted into benzaldehyde for benzyl alcohol |
| CN111905726A (en) * | 2020-08-03 | 2020-11-10 | 大连理工大学 | Preparation method of Au-C high-selectivity oxidation catalyst with controllable size |
| CN114130413A (en) * | 2021-10-26 | 2022-03-04 | 浙江大学衢州研究院 | Preparation method and application of N, S-double-heterocarbon-supported tungsten-based catalyst |
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| CN110124717A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of catalyst and preparation method thereof being converted into benzaldehyde for benzyl alcohol |
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| CN111905726A (en) * | 2020-08-03 | 2020-11-10 | 大连理工大学 | Preparation method of Au-C high-selectivity oxidation catalyst with controllable size |
| CN111905726B (en) * | 2020-08-03 | 2022-12-20 | 大连理工大学 | Preparation method of Au-C high-selectivity oxidation catalyst with controllable size |
| CN114130413A (en) * | 2021-10-26 | 2022-03-04 | 浙江大学衢州研究院 | Preparation method and application of N, S-double-heterocarbon-supported tungsten-based catalyst |
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Application publication date: 20190510 |