CN102492957A - Method for preparing aldehydes or acids by selectively performing catalytic oxidation on alcohols by electro-catalysis membrane - Google Patents
Method for preparing aldehydes or acids by selectively performing catalytic oxidation on alcohols by electro-catalysis membrane Download PDFInfo
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Abstract
The invention relates to the technical field of electro-catalysis selective oxidation synthesis, in particular to a method for preparing corresponding aldehydes or acids by performing catalytic oxidation on alcohols by an electro-catalysis membrane effectively at high selectivity. Electro-catalytic oxidation and a membrane separation technology are coupled, a system that aldehydes or acids are synthesized by using alcohols is used as a research system, and the electro-catalysis membrane used as an anode and an auxiliary electrode are connected through a guide line and a direct-current stabilized power supply to form an electro-catalysis membrane reactor. In an aqueous solution containing alcohol reactants and electrolyte, operation parameters comprising working voltage and current density in the membrane reactor are controlled and adjusted, and the surface of the membrane is introduced to generate reactive oxygen species such as hydroxyl radicals and the like under the action of a low-voltage electric field (1-6V), so the aldehydes or acids can be controllably and efficiently prepared by using the alcohols. Compared with the conventional process, the method has the advantages of low energy consumption, high selectivity, controllable process and the like, is easy to operate, can be industrially implemented, and can be widely used for catalytic oxidation controllable preparation in an organic synthesis field.
Description
Technical field
The present invention relates to electrocatalysis selective oxidation synthesis technical field, particularly a kind of method of utilizing electrocatalysis film high-level efficiency, high-selectivity oxidation alcohols to prepare corresponding aldehyde or acid.
Background technology
Organic synthesis all has irreplaceable importance such as each fields such as food, medicine, material, chemical industry.Being oxidized to corresponding aldehyde, ketone or carboxylic acid by alcohol is purposes one of functional group's conversion reaction the most widely in the organic synthesis.Annual through the carbonyl compound of pure metering oxidation production in the world above 1,000,000 tons.The tradition organic synthesis is to prepare through the method that is metered into oxygenant, but its cost is expensive, and the many poisonous and harmfuls of reagent, and by product is many, is difficult to from product, separate.Along with the concern to the environment and the energy increases day by day, people begin one's study development environment close friend, highly selective and pure efficiently method for oxidation.
2006 311 volumes of " science " magazine have been reported a kind of Au-Pd/TiO with nucleocapsid structure for the 362nd page
2Catalyzer, its under condition of no solvent to the inversion frequency (TOF) of pure oxidation up to 2.7 * 10
5h
-1, but its scope of application is narrower." american chemical " 2004 126 volumes have been reported a kind of efficient different-phase catalyst that is carried on the palladium nanometer bundle on the Win 40350 for the 10657th page, and such catalyzer can effectively utilize oxygen to come selective oxidation alcohol." German applied chemistry " 2006 45 volumes have been reported a kind of Au/MgAl for the 4648th page
2O
4Catalyst system, it is oxygenant with the air, is acetate with the aqueous ethanolic solution selective oxidation, for biological alcoholic acid high value added utilization provides new application prospect.Though more than several types of reaction effects pretty good, all need under heating condition, carry out, some also needs high pressure, severe reaction conditions, and higher as the catalyzer cost with precious metal.
In recent years, photocatalysis technology was developed on a large scale as a kind of nontoxic and research that oxidation capacity is strong very much." american chemical " 2008 130 volumes have been reported for the 1568th page and have been utilized rutile phase TiO
2The research for preparing aldehyde at aqueous phase selective oxidation aromatic alcohol.Chinese patent CN101531575A discloses a kind of method of utilizing photocatalysis to selectively oxidize primary alcohol or secondary alcohol to prepare aldehydes or ketones.But photocatalyst also exists problems such as Separation and Recovery difficulty and solar energy utilization ratio be low.
Membrane sepn has been widely used in every field such as oil, chemical industry, medicine, biology, food and water treatment as a kind of energy-efficient, eco-friendly new separation technology." German applied chemistry " 2011 50 volumes 2148-2150 page or leaf has been reported a kind of novel electro-catalytic film and electro-catalytic membrane reactor technology; It is characterized in that effective integration and coupling through low voltage electric field-catalysis-membrane sepn, realize the mould material catalyzed oxidation with separate difunctional.The electrocatalysis film has aspect Industrial Wastewater Treatment efficiently, fast, energy-conserving and environment-protective, characteristics such as non-secondary pollution.Above-mentioned work is the inventor's international initiative achievement; 4 of patents in the applicant country comprise a kind of novel electro-catalytic composite membrane material and preparation method thereof (Chinese invention patent, publication number CN101559332A); A kind of electro-catalytic membrane reactor device (Chinese invention patent; Publication number CN101597096A), and a kind of electro-catalytic membrane reactor device that is used for wastewater treatment (Chinese utility model patent, ZL200920097687.X); And nano load titanium base electrocatalysis film and preparation method thereof (Chinese invention patent, application number: 201110193777.0).The research that electrocatalytic reaction and film separation coupling technique-alcohols prepare aldehyde or acid has been proposed again on the basis of the above.
The present invention is a research system with synthetic aldehyde of alcohols or acids, as anode, plays catalyzed oxidation and centrifugation with the electrocatalysis film, and (1-6V) induces its surface to produce OH, O under the low voltage electric field effect
2 -, HO
2And H
2O
2Isoreactivity oxygen species realize that alcohols is controlled, efficient oxidation prepares aldehyde or acid.The electrocatalysis film integrates efficient selective, environmental protection and less energy-consumption advantage, and it will have huge research potential and application prospects in the organic synthesis field.
Summary of the invention
To the deficiency of prior art, the technical problem that quasi-solution of the present invention is determined is to provide a kind of high-level efficiency, high-selectivity oxidation alcohols to prepare the method for corresponding aldehyde or acid.And it is low, simple to operate that the present invention has energy consumption, and advantages such as selectivity height, controllable process are suitable for industrializing implementation, can be widely used in the controlled preparation of catalyzed oxidation in organic synthesis field.
The technical scheme that the present invention solves said problem is: utilize electrocatalysis film selective catalytic oxidation alcohols to prepare aldehyde or acid; It is characterized in that with the electrocatalysis film being connected to form electro-catalytic membrane reactor through lead and D.C. regulated power supply respectively with supporting electrode as anode; In comprising alcohols reactant and electrolytical solution, comprise WV and current density through operating parameters in the regulation and control membrane reactor, obtain product aldehyde or acid, realize controllable high-efficiency oxidation to alcohols.
But the mould material of said electrocatalysis film for constituting by catalyzer and conductive base film.
But said D.C. regulated power supply is the power supply of constant voltage or continuous current control.
Saidly comprise that the alcohols reactant concn is 0.01-1.0mol/L in alcohols reactant and the electrolytical solution, said alcohols reactant is monohydroxy-alcohol or divalent alcohol, and described monohydroxy-alcohol is a kind of in ethanol, propyl alcohol, the butanols, and described divalent alcohol is a terepthaloyl moietie.
Saidly comprise that electrolyte concentration is 0.5-10.0g/L in alcohols reactant and the electrolytical solution, said ionogen is Na
2SO
4, NaCl, Na
2CO
3, NaHCO
3, at least a among the NaOH.
Said WV is 1.0-6.0V, and current density is 0.1-10.0mA/cm
2
Compared with prior art, advantage of the present invention is: 1) the present invention need not add strong oxidizers such as potassium permanganate or ydrogen peroxide 50, more meets environment protection requirement; 2) the present invention can carry out at normal temperatures and pressures, need not traditional technology in to the equipment requirements of temperature of reaction and pressure, equipment and technological process are simpler; 3) technology of the present invention integrates catalyzed oxidation and separation function, can the title product that obtain in time be separated from reaction solution, effectively keeps the lasting high efficiency of electrocatalysis film, avoids the generation of side reaction, improves the selectivity of title product.
Description of drawings
Fig. 1 prepares aldehyde or sour schematic diagram of device for electrocatalysis film selective catalytic oxidation alcohols;
Fig. 2 utilizes electrocatalysis film selective catalytic oxidation propyl alcohol to prepare the propionic acid gas chromatogram among the embodiment 2.
Embodiment
Below further describe the present invention through embodiment and accompanying drawing thereof.
Is negative electrode with the electrocatalysis film as anode, supporting electrode, is connected with D.C. regulated power supply through lead respectively, constitutes electrocatalysis film synthetic system (Fig. 1).The electrocatalysis film plays catalyzed oxidation and centrifugation in this process; In comprising alcohols reactant and electrolytical solution; Comprise WV and current density through operating parameters in the regulation and control membrane reactor, (1-6V) induces the film surface to produce OH, O under the low voltage electric field effect
2 -, HO
2And H
2O
2Isoreactivity oxygen species, alcohols material is oxidized to aldehyde or acids in seeing through the process of film, thereby realizes the controllable high-efficiency oxidation to alcohols.
Embodiment 1
Present embodiment is by ethanol preparation acetate: the aqueous ethanolic solution of preparation 0.05mol/L places membrane reactor, adds 7g/L NaOH as ionogen.Under the normal temperature and pressure, be that 1.5V and current density are 0.9mA/cm in WV
2Under the condition, utilize electrocatalysis film catalytic oxidation of alcohol synthesis of acetic acid.With gas chromatograph-mass spectrometer reactor drum is seen through liquid and carry out qualitative and quantitative detection, draw the transformation efficiency and the productive rate of reactant.This experiment reaches 96.2% to ethanol conversion, and the acetate productive rate is 88.7%.
Embodiment 2
Present embodiment prepares propionic acid by propyl alcohol: the aqueous propanol solution of preparation 0.03mol/L places membrane reactor, adds 5g/L NaHCO
3As ionogen.Under the normal temperature and pressure, be that 2.3V and current density are 0.95mA/cm in WV
2Under the condition, electricity consumption catalytic film catalyzed oxidation propyl alcohol is propionic acid synthesized.With gas chromatograph-mass spectrometer reactor drum is seen through liquid and carry out qualitative and quantitative detection, draw the transformation efficiency and the productive rate of reactant.The transformation efficiency of this experiment propyl alcohol reaches 92.95%, and the productive rate of propionic acid reaches 79.83% (like Fig. 2).
Embodiment 3
Present embodiment prepares butyric acid by butanols: the butanols aqueous solution of preparation 0.1mol/L places reactor drum, adds 10g/LNa
2CO
3As ionogen.Under the normal temperature and pressure, be that 3.5V and current density are 10.0mA/cm in WV
2Under the condition, electricity consumption catalytic film catalyzed oxidation butanols synthetic butyric acid.With gas chromatograph-mass spectrometer reactor drum is seen through liquid and carry out qualitative and quantitative detection, draw the transformation efficiency and the productive rate of reactant.The transformation efficiency of this experiment butanols reaches 98.84%, and the butyric acid productive rate is 21.7%.
Embodiment 4
Present embodiment is by the ethylene glycol oxalic acid: the aqueous glycol solution of preparation 0.01mol/L places reactor drum, adds 0.5g/L NaCl as ionogen.Under the normal temperature and pressure, be that 6.0V and current density are 0.3mA/cm at electrolysis voltage
2Under the condition, electricity consumption catalytic film catalyzed oxidation terepthaloyl moietie synthesizes oxalic acid.With gas chromatograph-mass spectrometer reactor drum is seen through liquid and carry out qualitative and quantitative detection, draw the transformation efficiency and the productive rate of reactant.The transformation efficiency of this experiment terepthaloyl moietie reaches 95.21%, and the oxalic acid productive rate is 10.2%.
Embodiment 5
Present embodiment is by ethanol preparation acetaldehyde: the aqueous ethanolic solution of preparation 1.0mol/L places reactor drum, adds 3g/L Na
2SO
4As ionogen.Under the normal temperature and pressure, be that 1.0V and current density are 0.1mA/cm in WV
2Under the condition, electricity consumption catalytic film catalytic oxidation of alcohol synthesizes acetaldehyde.With gas chromatograph-mass spectrometer reactor drum is seen through liquid and carry out qualitative and quantitative detection, draw the transformation efficiency and the productive rate of reactant.This experiment ethanol conversion reaches 89.6%, and the acetaldehyde productive rate is 60.5%.
Claims (7)
1. a method of utilizing electrocatalysis film selective oxidation alcohols to prepare aldehyde or acid is characterized in that with the electrocatalysis film being connected to form electro-catalytic membrane reactor through lead and D.C. regulated power supply as anode respectively with supporting electrode; In comprising alcohols reactant and electrolytical solution, comprise WV and current density through operating parameters in the regulation and control membrane reactor, obtain product aldehyde or acid, realize controllable high-efficiency oxidation to alcohols.
2. by the described method of claim 1, but it is characterized in that the mould material of said electrocatalysis film for constituting by catalyzer and conductive base film.
3. by the described method of claim 1, but it is characterized in that the power supply of said D.C. regulated power supply for constant voltage or continuous current control.
4. by the described method of claim 1; It is characterized in that saidly comprising that the alcohols reactant concn is 0.01-1.0mol/L in alcohols reactant and the electrolytical solution; Said alcohols reactant is monohydroxy-alcohol or divalent alcohol; Described monohydroxy-alcohol is a kind of in ethanol, propyl alcohol, the butanols, and described divalent alcohol is a terepthaloyl moietie.
5. by the described method of claim 1, it is characterized in that saidly comprising that electrolyte concentration is 0.5-10.0g/L in alcohols reactant and the electrolytical solution, said ionogen is Na
2SO
4, NaCl, Na
2CO
3, NaHCO
3, at least a among the NaOH.
6. by the described method of claim 1, it is characterized in that said WV is 1.0-6.0V.
7. by the described method of claim 1, it is characterized in that said current density is 0.1-10.0mA/cm
2
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Cited By (6)
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|---|---|---|---|---|
| CN103436910A (en) * | 2013-08-02 | 2013-12-11 | 天津工业大学 | Preparation method of gluconic acid and glucaric acid |
| CN105200448A (en) * | 2015-09-30 | 2015-12-30 | 大连理工大学 | Electrochemistry hydrogen pump dual reactor for organic matter dehydrogenation and hydrogenation coupling |
| CN107779907A (en) * | 2017-10-10 | 2018-03-09 | 凯莱英医药集团（天津）股份有限公司 | The method of electrochemistry formated carbonyls |
| CN111592024A (en) * | 2020-04-24 | 2020-08-28 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
| CN114166834A (en) * | 2021-12-08 | 2022-03-11 | 桂林医学院 | Method for analyzing photo-decomposition degree of medicine by tracing auxiliary agent |
| CN114855192A (en) * | 2022-03-31 | 2022-08-05 | 浙江大学杭州国际科创中心 | Method for preparing benzyl ketone/aldehyde compound by electrochemical oxidation of transition metal oxide catalyst |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436910A (en) * | 2013-08-02 | 2013-12-11 | 天津工业大学 | Preparation method of gluconic acid and glucaric acid |
| CN103436910B (en) * | 2013-08-02 | 2015-12-02 | 天津工业大学 | The preparation method of a kind of gluconic acid and glucaric acid |
| CN105200448A (en) * | 2015-09-30 | 2015-12-30 | 大连理工大学 | Electrochemistry hydrogen pump dual reactor for organic matter dehydrogenation and hydrogenation coupling |
| CN105200448B (en) * | 2015-09-30 | 2017-08-22 | 大连理工大学 | A kind of organic matter dehydrogenation and hydrogenation coupled electrochemistry hydrogen pump double-reactor |
| CN107779907A (en) * | 2017-10-10 | 2018-03-09 | 凯莱英医药集团（天津）股份有限公司 | The method of electrochemistry formated carbonyls |
| CN111592024A (en) * | 2020-04-24 | 2020-08-28 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
| CN111592024B (en) * | 2020-04-24 | 2022-09-06 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
| CN114166834A (en) * | 2021-12-08 | 2022-03-11 | 桂林医学院 | Method for analyzing photo-decomposition degree of medicine by tracing auxiliary agent |
| CN114166834B (en) * | 2021-12-08 | 2024-04-02 | 桂林医学院 | Method for analyzing photodecomposition degree of medicine by tracing auxiliary agent |
| CN114855192A (en) * | 2022-03-31 | 2022-08-05 | 浙江大学杭州国际科创中心 | Method for preparing benzyl ketone/aldehyde compound by electrochemical oxidation of transition metal oxide catalyst |
| CN114855192B (en) * | 2022-03-31 | 2023-12-08 | 浙江大学杭州国际科创中心 | Method for preparing benzyl ketone/aldehyde compound by electrochemical oxidation of transition metal oxide catalyst |
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