CN108636423A - A kind of preparation method of load type nano gold catalyst and application - Google Patents
A kind of preparation method of load type nano gold catalyst and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
Abstract
The invention discloses a kind of preparation method of load type nano gold catalyst and application, which includes the following steps：Prepare support C u Ce OY；Prepare load type nano gold catalyst.The application is specifically application of the load type nano gold catalyst in preparing vanillic aldehyde, is included the following steps：By the catalyst being prepared and vanillyl alcohol in the liner of autoclave, and paraxylene and tetrahydrofuran is added as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C, reaction kettle is put into oil bath, and with stirring, after reaction, ice-water bath cools down, and opens reaction kettle, takes out liner, it draws reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.The present invention may be implemented vanillyl alcohol dehydrogenation vanillic aldehyde under conditions of anaerobic agent hydrogen-free receptor, and highest yield is up to 99% or more.
Description
Technical field
The invention belongs to the synthesis technical fields of vanillic aldehyde, specifically, being related to a kind of chinese cymbidium based on vanilla alcohol dehydrogenase
The preparation method of element.
Background technology
Vanillic aldehyde (Vanillin) also known as vanillic aldehyde, vanillic aldehyde are the first essence synthesized by the mankind, by the Kazakhstan of Germany
Germania doctor is successful in synthesis in 1874 with safe mambo scholar.Vanillic aldehyde can be found in the seed of vanilla, there is strong milk
Breath.Vanillic aldehyde has a wide range of applications in field of food such as cake, cold drink, chocolate, candy, the fields such as fine chemistry industry also
It can be used for rubber, plastics, cosmetics, pharmaceuticals and health products.
China is vanillic aldehyde big export country of the world, and 2350 tons of domestic demand amount in 2002 accounts for the 30% of yield, remaining 70%
For exporting.China's vanillic aldehyde export volume average growth rate per annum is 12%, is enjoyed well in North America, Europe, the Southeast Asia markets Deng Di
Prestige.Developing country is obviously increasing the demand of vanillic aldehyde so that the aggregate demand of vanillic aldehyde is still in the rise period.Mesh
Before, 99% or more vanillic aldehyde is produced by chemical synthesis.Continue reliable yield although can obtain, it is same
It needs using complicated separation process, the synthesis condition of strong basicity and virose oxidant, and generates in process of production
Other by-products.
Industrial production vanillic aldehyde has more than 100 years history, and people have studied many approaches and methods being synthetically prepared, but
Mainly there are following three kinds of methods applied to large-scale industrial production.
First, lignin route：Using lignosulfonates contained in the lignosulfite of paper industry as raw material,
Through alkaline high temperature and high pressure hydrolysis, be then dehydrated carry out again oxidation be made.Canada and the U.S. mainly use the method to produce vanillic aldehyde,
Its synthetic route is as follows：
With lignin route synthesis of vanillin, needs high temperature and pressure and needs to add a large amount of highly basic, and yield is relatively low,
Only 10%-15%, pollution problem is serious, often produces one ton of vanillic aldehyde and generates nearly 150 tons of waste water.
Second, guaiacol-formaldehyde route：Guaiacol is the most important raw material of synthesis of vanillin, with guaiacol,
Formaldehyde, the synthetic route that nitrosodimethylaniline is raw material, also known as nitroso process.The country such as the former Soviet Union and China is main
Using the method, synthetic route is as follows：
Vanillic aldehyde is prepared with guaiacol-formaldehyde route, the method complex process, reaction efficiency is low, and pollution is big, and foreign countries have washed in a pan
Eliminate, raw material type is more, technological process is long, low yield, discharge waste liquid the deficiencies of being unable to biochemical treatment, especially environmental issue limits
The development of Zhi Liao enterprises.
Third, guaiacol-glyoxalic acid route：Using guaiacol and glyoxalic acid as raw material, through condensation, oxidation, decarboxylation system
At vanillic aldehyde, synthetic route is as follows：
Guaiacol-glyoxalic acid route prepares vanillic aldehyde, and in high-temperature oxydation, a large amount of copper sulphate need to be added as catalysis
Agent, during the reaction copper sulphate itself be reduced to the cuprous oxide of microfine, later stage separation is very difficult.
4th, vanillyl alcohol aoxidizes route, mostly using compound transition metal oxide as catalyst, with oxygen, and air or mistake
Hydrogen oxide is oxidant, and alkali is added simultaneously, and synthetic route is as follows：
Vanillyl alcohol oxidation prepares vanillic aldehyde, and a large amount of inorganic bases and strong oxidizer, such as H need to be added2O2Etc. relatively hazardous oxidisability
Reagent, and react and need to carry out under high pressure, severe reaction conditions, operation is more dangerous, and can generate others
By-product, yield be not high.
5th, vanilla alcohol dehydrogenase route, at present only document report (Green Chemistry, 2016,18,
6136-6142.), using mesoporous silicon oxide (SBA-15) load zero-valent metal Pd0For catalyst, using water as reaction dissolvent,
It is reacted 7 hours under the conditions of 80 DEG C of nitrogen protections, vanillic aldehyde yield is up to 99%.
Wherein, the synthetic route of vanillyl alcohol anaerobic agent hydrogen-free receptor dehydrogenation generation vanillic aldehyde is as follows：
The preparation route of catalyst is as follows：
As can be seen that using metallic catalyst in the vanilla fabricated by dehydrogenating alcohol vanillic aldehyde for being added without any oxidant and hydrogen acceptor
Synthetic route, will be unquestionably a safer, environmentally friendly, easily-controllable process.Vanilla alcohol dehydrogenase prepares vanillic aldehyde, at present only
Some pertinent literature reports use zeroth order palladium and other carrier components although realizing anaerobic agent hydrogen-free receptor dehydrogenation
The catalyst prepared is assembled, catalyst synthesis processes are complicated, and cost is higher, needed in addition using organic amine and itrogenous organic substance etc.
To the serious reagent of water pollution, and palladium catalyst Metal Palladium component during recycling is easy to happen loss.
Invention content
In view of this, the present invention provides a kind of preparation method of load type nano gold catalyst and applications.
In order to solve the above-mentioned technical problem, the invention discloses a kind of preparation sides of the vanillic aldehyde based on vanilla alcohol dehydrogenase
Method includes the following steps：
Step 1 prepares support C u-Ce-OY：
Step 2 prepares load type nano gold catalyst.
Optionally, the preparation support C u-Ce-O in the step 1YSpecially：
Step 1.1, by CuN2O6·3H2O and CeN3O9·6H2O is dissolved in methanol, is configured to solution I；
Under magneton stirring with dropping funel triethylamine is added dropwise in step 1.2 dropwise, until pH value of solution=9, then in constant temperature
Oil bath in be aged；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filtration cakes torrefaction after grinding, roasts under air atmosphere；Carrier is made
Cu-Ce-OY, store to be used.
Optionally, the CuN in step 1.12O6·3H2O and CeN3O9·6H2The molar ratio of O is 1:0.2-2:3；CuN2O6·
3H2The molal volume of O and methanol ratio (mmol/ml) is 16:155-26.7:100.
Optionally, the rotating speed of the magneton stirring in step 1.2 is 400-700rpm；Aging Temperature is 60-80 DEG C of constant temperature, old
The change time is 12-24h.
Optionally, the drying temperature in step 1.3 is 100-120 DEG C, drying time 10-14h；Calcination temperature is 290-
610 DEG C, roasting time 4-6h.
Optionally, the vanillic aldehyde for preparing in the step 2 is specially：
Step 2.1 prepares aqueous solution of chloraurate, pipettes chlorauric acid solution and is diluted in water, is configured to solution II；
Polyvinylpyrrolidone is dissolved in the water by step 2.2；Under agitation, by polyvinylpyrrolidonesolution solution
It is added dropwise in solution II, Cu-Ce-O is added after persistently stirring 15minYIn above-mentioned solution, 0.5h is persistently stirred；
Step 2.3, end to be mixed, sodium borohydride is dissolved in suitable quantity of water, is added dropwise in above-mentioned solution, is dripped
Continue to stir 2h after finishing；After stirring, above-mentioned solution is filtered, filter cake is washed with deionized to neutrality；After washing,
Gained filtration cakes torrefaction is stayed overnight, and storage is protected from light after grinding, and Au/Cu-Ce-O is madeY。
Optionally, a concentration of 0.002-0.01g/ml of the aqueous solution of chloraurate in the step 2.1, chlorauric acid solution with
The volume ratio of water is 1:40-1:100.
Optionally, the mass volume ratio (mg/ml) of the polyvinylpyrrolidone in step 2.2 and water is 10:1-20:1；
Cu-Ce-OYMass ratio (mg/mg) with polyvinylpyrrolidone is 500:12.
Optionally, the deionized water temperature in step 2.3 is 75-95 DEG C；Drying temperature is 75-85 DEG C；Sodium borohydride with
The mass volume ratio (mg/ml) of water is 18:1-18:3.
The invention also discloses a kind of application of load type nano gold catalyst in preparing vanillic aldehyde, including following step
Suddenly：The vanillyl alcohol of 100mg catalyst and 1mmol are weighed in the liner of autoclave, and 14ml paraxylene and 6ml is added
Tetrahydrofuran is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, is made
Ar pressure is maintained at 10bar in kettle；It is 120 DEG C to adjust oil bath pot temperature, by temperature control in reaction preset temperature T ± 1 DEG C
Afterwards, reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down
20min opens reaction kettle, takes out liner, draws reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Compared with prior art, the present invention can be obtained including following technique effect：
1) it is directed to and prepares vanillic aldehyde industrial reaction, prepare a kind of new catalyst, and use anaerobic agent, without hydrogen acceptor
Reaction condition replaces the existing oxidation reaction that a large amount of highly basic are added, and keep reaction condition more mild easy to control and reduce should
Harm and environmental pollution of the industrial system to health.
2) it utilizes vanilla alcohol dehydrogenase to generate vanillic aldehyde, the selectivity to product vanillic aldehyde is improved on reaction path, makes perfume (or spice)
Alcoholic extract hydroxyl group 100% in careless alcohol is converted into carbonyl, while inhibiting the generation of by-product, while improving raw material availability and target production
Object yield.
3) implement catalytic dehydrogenation processes under the conditions of lower temperature (120 DEG C), reduce reaction cost, reduce security risk.
4) report that Au catalyst prepares the system of vanillic aldehyde as vanilla alcohol dehydrogenase for the first time, vanillyl alcohol can be measured (>
99%) it is converted into vanillic aldehyde.
Certainly, it implements any of the products of the present invention it is not absolutely required to while reaching all the above technique effect.
Description of the drawings
Attached drawing described herein is used to provide further understanding of the present invention, and constitutes the part of the present invention, this hair
Bright illustrative embodiments and their description are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 is vanilla alcohol conversion and vanillic aldehyde selectivity disclosed by the invention；
Fig. 2 is Au/Cu-Ce-O disclosed by the inventionYCatalyst recycling result.
Specific implementation mode
Carry out the embodiment that the present invention will be described in detail below in conjunction with embodiment, thereby to the present invention how application technology hand
Section solves technical problem and reaches the realization process of technical effect to fully understand and implement.
The invention discloses a kind of preparation methods of load type nano gold catalyst, include the following steps：
Step 1 prepares support C u-Ce-OY：
Step 1.1, by CuN2O6·3H2O and CeN3O9·6H2O is dissolved in methanol, is configured to solution I；Wherein, CuN2O6·
3H2O and CeN3O9·6H2The molar ratio of O is 1:0.2-2:3；CuN2O6·3H2The molal volume of O and methanol ratio (mmol/ml) is
16:155-26.7:100；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 400-700rpm) is added dropwise dropwise with dropping funel, until molten
Then liquid pH=9 is aged 12-24h in the oil bath of 60-80 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 100-120 DEG C of dry 10-14h, after grinding, in air atmosphere
Enclose lower 290-610 DEG C of roasting 4-6h；Support C u-Ce-O is madeY, Y represents oxygen atom stoichiometric number, preferably 1.25-2, and storage waits for
It uses；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.002-0.01g/ml, pipette chlorauric acid solution and are diluted in water, match
Solution II is made；Wherein, the volume ratio of chlorauric acid solution and water is 1:40-1:100；
Polyvinylpyrrolidone is dissolved in the water by step 2.2；Under agitation, by polyvinylpyrrolidonesolution solution
It is added dropwise in solution II, Cu-Ce-O is added after persistently stirring 15minYIn above-mentioned solution, 0.5h is persistently stirred；Wherein, gather
The mass volume ratio (mg/ml) of vinylpyrrolidone and water is 10:1-20:1；Cu-Ce-OYWith the quality of polyvinylpyrrolidone
It is 500 than (mg/mg):12；
Step 2.3, end to be mixed, weigh sodium borohydride, are dissolved in the water, the mass volume ratio of sodium borohydride and water
(mg/ml) it is 18:1-18:3；It is added dropwise in above-mentioned solution, continues to stir 2h after being added dropwise.It, will be above-mentioned after stirring
Solution filters, and filter cake is washed to neutrality with 75-95 DEG C of deionized water.After washing, gained filter cake is dried in 75-85 DEG C
Night is protected from light storage after grinding, load type nano gold catalyst Au/Cu-Ce-O is madeY。
The invention also discloses a kind of application of load type nano gold catalyst in preparing vanillic aldehyde, including following step
Suddenly：The vanillyl alcohol of 100mg catalyst and 1mmol are weighed in the liner of autoclave, and 14ml paraxylene and 6ml is added
Tetrahydrofuran is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, is made
Ar pressure is maintained at 10bar in kettle.It is 120 DEG C to adjust oil bath pot temperature, by temperature control in reaction preset temperature T ± 1 DEG C
Afterwards, reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down
20min opens reaction kettle, takes out liner, draws reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 1
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce0.5OY：
Step 1.1 weighs 6.43g (26.7mmol) CuN2O6·3H2O and 5.77g (13.3mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 150ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 600rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 18h is aged in the oil bath of 65 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 110 DEG C of dry 12h, after grinding, 500 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce0.5OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 50ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 1ml water.Under agitation, by polyethylene pyrrole
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce0.5OYIn above-mentioned solution, continue
Stir 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 1ml water, are added dropwise in above-mentioned solution,
Continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed into 80 DEG C of deionized water
Property.After washing, gained filter cake is dried overnight in 80 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce0.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 2
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce0.2OY：
Step 1.1 weighs 8.05g (33.3mmol) CuN2O6·3H2O and 2.91g (6.7mmol) CeN3O9·6H2O dissolves
In 130ml methanol, it is configured to solution I；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 500rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 15h is aged in the oil bath of 60 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 100 DEG C of dry 10h, after grinding, 500 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce0.2OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 75ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 1.2ml water.Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce0.2OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 1.5ml water, and above-mentioned solution is added dropwise
In, continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed extremely with 95 DEG C of deionized water
It is neutral.After washing, gained filter cake is dried overnight in 75 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce0.2OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.2OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 3
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce0.7OY：
Step 1.1 weighs 5.68g (23.5mmol) CuN2O6·3H2O and 7.16g (16.5mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 140ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 550rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 16h is aged in the oil bath of 70 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 105 DEG C of dry 11h, after grinding, 500 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce0.7OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 70ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 0.7ml water.Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce0.7OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 2.0ml water, and above-mentioned solution is added dropwise
In, continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed extremely with 90 DEG C of deionized water
It is neutral.After washing, gained filter cake is dried overnight in 80 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce0.7OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.7OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 4
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce1OY：
Step 1.1 weighs 4.83g (20.0mmol) CuN2O6·3H2O and 8.68g (20.0mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 160ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 650rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 19h is aged in the oil bath of 63 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 103 DEG C of dry 12h, after grinding, 500 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce1OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 55ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 1.1ml water.Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce1OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 2.5ml water, and above-mentioned solution is added dropwise
In, continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed extremely with 93 DEG C of deionized water
It is neutral.After washing, gained filter cake is dried overnight in 78 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce1OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce1OY14ml paraxylene and 6ml tetrahydrochysenes is added in the liner of autoclave in vanillyl alcohol with 1mmol
Furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, is made in kettle
Ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, will by temperature control behind reaction preset temperature T ± 1 DEG C
Reaction kettle is put into oil bath, and with stirring, and duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, opens
Reaction kettle takes out liner, draws reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 5
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce1.5OY：
Step 1.1 weighs 3.87g (16.0mmol) CuN2O6·3H2O and 10.42g (24.0mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 155ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 570rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 17h is aged in the oil bath of 66 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 104 DEG C of dry 14h, after grinding, 500 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce1.5OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 80ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 0.9ml water；Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce1.5OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 2.0ml water, and above-mentioned solution is added dropwise
In, continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed extremely with 90 DEG C of deionized water
It is neutral.After washing, gained filter cake is dried overnight in 85 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce1.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce1.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 6
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce0.5OY：
Step 1.1 weighs 6.43g (26.7mmol) CuN2O6·3H2O and 5.77g (13.3mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 110ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 450rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 21h is aged in the oil bath of 60 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 110 DEG C of dry 11h, after grinding, 300 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce0.5OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 80ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 0.9ml water.Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce0.5OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 1ml water, are added dropwise in above-mentioned solution,
Continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed into 75 DEG C of deionized water
Property.After washing, gained filter cake is dried overnight in 75 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce0.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 7
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce0.5OY：
Step 1.1 weighs 6.43g (26.7mmol) CuN2O6·3H2O and 5.77g (13.3mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 100ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 700rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 22h is aged in the oil bath of 70 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 100 DEG C of dry 11h, after grinding, 400 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce0.5OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 90ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 1.2ml water；Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce0.5OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 2.5ml water, and above-mentioned solution is added dropwise
In, continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed extremely with 85 DEG C of deionized water
It is neutral.After washing, gained filter cake is dried overnight in 85 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce0.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 8
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u1Ce0.5OY：
Step 1.1 weighs 6.43g (26.7mmol) CuN2O6·3H2O and 5.77g (13.3mmol) CeN3O9·6H2O is molten
Solution is configured to solution I in 150ml methanol；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 550rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 20h is aged in the oil bath of 75 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 100 DEG C of dry 12h, after grinding, 600 under air atmosphere
DEG C roasting 4h；Support C u is made1Ce0.5OY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.005g/ml, pipette 1.00ml chlorauric acid solutions and are diluted to 65ml water
In, it is configured to solution II；
Step 2.2 weighs 12mg polyvinylpyrrolidones, is dissolved in 1.2ml water.Under agitation, by polyethylene
Pyrrolidone solution is added dropwise in solution II, and 0.50g Cu are added after persistently stirring 15min1Ce0.5OYIn above-mentioned solution, hold
Continuous stirring 0.5h；
Step 2.3, end to be mixed, weigh 18mg sodium borohydrides, are dissolved in 2.2ml water, and above-mentioned solution is added dropwise
In, continue to stir 2h after being added dropwise.After stirring, above-mentioned solution is filtered, filter cake is washed extremely with 85 DEG C of deionized water
It is neutral.After washing, gained filter cake is dried overnight in 80 DEG C, and storage is protected from light after grinding, and Au/Cu is made1Ce0.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 9
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u-Ce-OY：
Step 1.1, by CuN2O6·3H2O and CeN3O9·6H2O is dissolved in methanol, is configured to solution I；Wherein, CuN2O6·
3H2O and CeN3O9·6H2The molar ratio of O is 1:0.5；CuN2O6·3H2The molal volume of O and methanol ratio (mmol/ml) is 100:
150；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 400rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then it is aged for 24 hours in the oil bath of 80 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 120 DEG C of dry 10h, after grinding, 610 under air atmosphere
DEG C roasting 6h；Support C u-Ce-O is madeY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.002g/ml, pipette chlorauric acid solution and are diluted in water, be configured to molten
Liquid II；Wherein, the volume ratio of chlorauric acid solution and water is 1:100；
Polyvinylpyrrolidone is dissolved in the water by step 2.2；Under agitation, by polyvinylpyrrolidonesolution solution
It is added dropwise in solution II, Cu is added after persistently stirring 15min1Ce0.5OYIn above-mentioned solution, 0.5h is persistently stirred；Wherein, gather
The mass volume ratio (mg/ml) of vinylpyrrolidone and water is 20:1；Cu1Ce0.5OYWith the mass ratio of polyvinylpyrrolidone
(mg/mg) it is 500:12；
Step 2.3, end to be mixed, weigh sodium borohydride, are dissolved in the water, the mass volume ratio of sodium borohydride and water
(mg/ml) it is 18:3；It is added dropwise in above-mentioned solution, continues to stir 2h after being added dropwise.After stirring, by above-mentioned solution mistake
Filter, filter cake is washed to neutrality with 75 DEG C of deionized water.After washing, gained filter cake is dried overnight in 85 DEG C, is kept away after grinding
Light stores, and load type nano gold catalyst Au/Cu is made1Ce0.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
Embodiment 10
A kind of preparation method of load type nano gold catalyst, includes the following steps：
Step 1 prepares support C u-Ce-OY：
Step 1.1, by CuN2O6·3H2O and CeN3O9·6H2O is dissolved in methanol, is configured to solution I；Wherein, CuN2O6·
3H2O and CeN3O9·6H2The molar ratio of O is 1:0.5；CuN2O6·3H2The molal volume of O and methanol ratio (mmol/ml) is 20:
150；
The step 1.2, (rotating speed under magneton stirring：Triethylamine 700rpm) is added dropwise dropwise with dropping funel, until pH value of solution
=9, then 12-24h is aged in the oil bath of 60 DEG C of constant temperature；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed into deionized water
Property, then washed with absolute ethyl alcohol；After washing, gained filter cake is in 100 DEG C of dry 10h, after grinding, 290 under air atmosphere
DEG C roasting 4-6h；Support C u-Ce-O is madeY, store to be used；
Step 2 prepares catalyst：
Step 2.1, the aqueous solution of chloraurate for preparing 0.01g/ml, pipette chlorauric acid solution and are diluted in water, be configured to molten
Liquid II；Wherein, the volume ratio of chlorauric acid solution and water is 1:40；
Polyvinylpyrrolidone is dissolved in the water by step 2.2；Under agitation, by polyvinylpyrrolidonesolution solution
It is added dropwise in solution II, Cu is added after persistently stirring 15min1Ce0.5OYIn above-mentioned solution, 0.5h is persistently stirred；Wherein, gather
The mass volume ratio (mg/ml) of vinylpyrrolidone and water is 10:1；Cu1Ce0.5OYWith the mass ratio of polyvinylpyrrolidone
(mg/mg) it is 500:12；
Step 2.3, end to be mixed, weigh sodium borohydride, are dissolved in the water, the mass volume ratio of sodium borohydride and water
(mg/ml) it is 18:1；It is added dropwise in above-mentioned solution, continues to stir 2h after being added dropwise.After stirring, by above-mentioned solution mistake
Filter, filter cake is washed to neutrality with 95 DEG C of deionized water.After washing, gained filter cake is dried overnight in 75 DEG C, is kept away after grinding
Light stores, and load type nano gold catalyst Au/Cu is made1Ce0.5OY。
Application of the above-mentioned load type nano gold catalyst in preparing vanillic aldehyde, includes the following steps：100mg is weighed to urge
Agent Au/Cu1Ce0.5OY14ml paraxylene and 6ml tetra- is added in the liner of autoclave in vanillyl alcohol with 1mmol
Hydrogen furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, makes kettle
Interior ar pressure is maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control behind reaction preset temperature T ± 1 DEG C,
Reaction kettle is put into oil bath, and with stirring, duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, beats
Reaction kettle is opened, liner is taken out, draw reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
The technique effect of the present invention is illustrated with reference to specific experimental data：
One, catalyst reaction performance is tested：
The vanillyl alcohol of 100mg catalyst and 1mmol (0.154g) are weighed in the liner of autoclave, and 14ml is added
PX and 6ml THF are as mixed solvent.Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor,
Ar pressure in kettle is set to be maintained at 10bar.It is 120 DEG C to adjust oil bath pot temperature, by temperature control in reaction preset temperature T ± 1
After DEG C, reaction kettle is put into oil bath, and with stirring, the record moment is reaction initial time, and duration of the reaction is for 24 hours.
After reaction, ice-water bath cools down 20min, opens reaction kettle, takes out liner, draws reaction solution and is filtered with nanometer filter, filter
Liquid is using the silent winged generation that 1310 type gas chromatograph quantitative analyses of Trace of match, by fid detector after TR-5 capillary column separations
Detection.Testing result includes the conversion ratio of vanillyl alcohol, the selectivity of vanillic aldehyde and the yield of vanillic aldehyde；
Calculation formula is as follows：
Vanillic aldehyde yield (%)=vanilla alcohol conversion × vanillic aldehyde selectivity
Two, catalytic performance test result：
The present invention has invented a kind of load type nano gold catalyst, and carrier is cu-ce composite oxidation, and vanilla may be implemented
Alcohol dehydrogenation vanillic aldehyde under conditions of anaerobic agent hydrogen-free receptor, highest yield is up to 99% or more.
1, the allotment of carrier metal ratio：
As can be seen from Table 1, the molar ratio of copper cerium significantly affects turning for vanillyl alcohol in cu-ce composite oxidation carrier
Rate, but the selectivity of vanillic aldehyde is not influenced.Work as Cu:Ce molar ratios are 1:When 0.5, load gold catalyst performance is best.When
When reducing or increasing the content of Ce in catalyst carrier, the conversion ratio of vanillyl alcohol declines.
The allotment of 1 carrier metal ratio of table
2, the optimization of carrier calcination temperature
As can be seen from Table 2, the calcination temperature of carrier can influence the conversion ratio of vanillyl alcohol, but not influence vanillic aldehyde
Selectivity.Work as Cu1Ce0.5OYWhen carrier roasts at 300 DEG C, load gold catalyst performance is best, and vanilla alcohol conversion reaches
100%, vanillic aldehyde yield is up to 99% or more.When the calcination temperature for further decreasing or increasing carrier, vanilla alcohol conversion
Reduce.
As shown in Figure 1, Au/Cu1Ce0.5OYIt is a kind of excellent catalysts based on vanilla fabricated by dehydrogenating alcohol vanillic aldehyde, with anti-
Extension between seasonable, vanillic aldehyde selectively remains at 99% or more, and vanilla alcohol conversion is continuously increased, small in reaction 24
When after vanillyl alcohol 100% be converted into vanillic aldehyde.
The optimization of 2 carrier calcination temperature of table
3, the recycling of catalyst
Catalyst can be easily separated recycling, repeatedly continuous to recycle, and not have deactivation phenomenom.Catalyst recycling is real
It tests in Au/Cu1Ce0.5OYIt is carried out on catalyst, carrier calcination temperature is 300 DEG C.Concrete operations are as follows：After reaction, it is catalyzed
High speed centrifugation (rotating speed is passed through in agent：10,000rmp, the time：It 10min) is separated from reaction solution, then 20ml PX is used alternatingly
With 20ml THF washing catalysts 2 times, catalyst is fully finally eluted with deionized water again, washing, which finishes, every time all uses high speed
Centrifugation comes out separation and recovery of catalyst.Finally catalyst is dried overnight in 80 DEG C, for catalysis reaction next time after grinding.
Catalyst recycling result is as shown in Figure 2.From reaction result, it can be seen that the Au/ that the present embodiment 6 is prepared
Cu1Ce0.5OYCatalyst keeps excellent stability, vanilla alcohol conversion to remain during continuous recycle 8 times
100%, vanillic aldehyde yield also remains at 99% or more.
Above description has shown and described several preferred embodiments of invention, but as previously described, it should be understood that invention is not
It is confined to form disclosed herein, is not to be taken as excluding other embodiments, and can be used for various other combinations, modification
And environment, and can be carried out by the above teachings or related fields of technology or knowledge in the scope of the invention is set forth herein
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of invention, then should all be weighed appended by invention
In the protection domain that profit requires.
Claims (10)
1. a kind of preparation method of load type nano gold catalyst, which is characterized in that include the following steps：
Step 1 prepares support C u-Ce-OY：
Step 2 prepares load type nano gold catalyst.
2. the preparation method of load type nano gold catalyst according to claim 1, which is characterized in that in the step 1
Preparation support C u-Ce-OYSpecially：
Step 1.1, by CuN2O6·3H2O and CeN3O9·6H2O is dissolved in methanol, is configured to solution I；
Under magneton stirring with dropping funel triethylamine is added dropwise in step 1.2 dropwise, until pH value of solution=9, then in the oil of constant temperature
It is aged in bath；
Suspension after ageing is poured into sand core funnel and filters by step 1.3, is fully washed to neutrality with deionized water, then
It is washed with absolute ethyl alcohol；After washing, gained filtration cakes torrefaction after grinding, roasts under air atmosphere；Support C u-Ce- is made
OY, store to be used.
3. the preparation method of load type nano gold catalyst according to claim 2, which is characterized in that in step 1.1
CuN2O6·3H2O and CeN3O9·6H2The molar ratio of O is 1:0.2-2:3；CuN2O6·3H2The molal volume of O and methanol ratio
(mmol/ml) it is 16:155-26.7:100.
4. the preparation method of load type nano gold catalyst according to claim 2, which is characterized in that in step 1.2
The rotating speed of magneton stirring is 400-700rpm；Aging Temperature is 60-80 DEG C of constant temperature, digestion time 12-24h.
5. the preparation method of load type nano gold catalyst according to claim 2, which is characterized in that in step 1.3
Drying temperature is 100-120 DEG C, drying time 10-14h；Calcination temperature is 290-610 DEG C, roasting time 4-6h.
6. the preparation method of load type nano gold catalyst according to claim 1, which is characterized in that in the step 2
The vanillic aldehyde for preparing be specially：
Step 2.1 prepares aqueous solution of chloraurate, pipettes chlorauric acid solution and is diluted in water, is configured to solution II；
Polyvinylpyrrolidone is dissolved in the water by step 2.2；Under agitation, dropwise by polyvinylpyrrolidonesolution solution
It is added in solution II, Cu-Ce-O is added after persistently stirring 15minYIn above-mentioned solution, 0.5h is persistently stirred；
Step 2.3, end to be mixed, sodium borohydride is dissolved in suitable quantity of water, is added dropwise in above-mentioned solution, after being added dropwise
Continue to stir 2h；After stirring, above-mentioned solution is filtered, filter cake is washed with deionized to neutrality；After washing, gained
Filtration cakes torrefaction is stayed overnight, and storage is protected from light after grinding, and Au/Cu-Ce-O is madeY。
7. the preparation method of load type nano gold catalyst according to claim 6, which is characterized in that the step 2.1
In aqueous solution of chloraurate a concentration of 0.002-0.01g/ml, the volume ratio of chlorauric acid solution and water is 1:40-1:100.
8. the preparation method of load type nano gold catalyst according to claim 6, which is characterized in that in step 2.2
The mass volume ratio (mg/ml) of polyvinylpyrrolidone and water is 10:1-20:1；Cu-Ce-OYWith the matter of polyvinylpyrrolidone
Amount is 500 than (mg/mg):12.
9. the preparation method of load type nano gold catalyst according to claim 6, which is characterized in that in step 2.3
Deionized water temperature is 75-95 DEG C；Drying temperature is 75-85 DEG C；The mass volume ratio (mg/ml) of sodium borohydride and water is 18:
1-18:3。
10. a kind of application of load type nano gold catalyst in preparing vanillic aldehyde, which is characterized in that include the following steps：Claim
It takes the vanillyl alcohol of 100mg catalyst and 1mmol in the liner of autoclave, and 14ml paraxylene and 6ml tetrahydrochysenes is added
Furans is as mixed solvent；Autoclave is connect with argon gas steel cylinder, is passed through argon gas, after excluding the air in reactor, is made in kettle
Ar pressure is maintained at 10bar；It is 120 DEG C to adjust oil bath pot temperature, will by temperature control behind reaction preset temperature T ± 1 DEG C
Reaction kettle is put into oil bath, and with stirring, and duration of the reaction is for 24 hours；After reaction, ice-water bath cools down 20min, opens
Reaction kettle takes out liner, draws reaction solution and is filtered with nanometer filter, vanillic aldehyde is prepared.
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| CN109351984A (en) * | 2018-12-24 | 2019-02-19 | 北京光禾生物科技有限公司 | The method for preparing liquid nano silver as reducing agent using vanillic aldehyde |
| CN113101929A (en) * | 2021-04-26 | 2021-07-13 | 云南大学 | Supported high-dispersion nanogold catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109351984A (en) * | 2018-12-24 | 2019-02-19 | 北京光禾生物科技有限公司 | The method for preparing liquid nano silver as reducing agent using vanillic aldehyde |
| CN113101929A (en) * | 2021-04-26 | 2021-07-13 | 云南大学 | Supported high-dispersion nanogold catalyst and preparation method and application thereof |
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| CN108636423B (en) | 2021-01-15 |
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