CN108677210A - A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor - Google Patents
A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor Download PDFInfo
- Publication number
- CN108677210A CN108677210A CN201810375920.XA CN201810375920A CN108677210A CN 108677210 A CN108677210 A CN 108677210A CN 201810375920 A CN201810375920 A CN 201810375920A CN 108677210 A CN108677210 A CN 108677210A
- Authority
- CN
- China
- Prior art keywords
- esterification
- ketone
- carboxylic acid
- cathode
- hydrogen pump
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to Electrochemical Engineering technical fields, are related to a kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor.In electrochemical hydrogen pump reactor, when additional electric energy, utilize the extremely low electrochemical window of hydrogen, it dissociates in anode and is transmitted to cathode catalysis layer and generate absorption hydrogen in situ, hydrogenation reaction directly occurs with the ketone in cathode circulation liquid for absorption hydrogen in situ, and further with the carboxylic acid in cathode circulation liquid esterification occurs for the alcohol being hydrogenated to.It realizes plus hydrogen couples progress, synergy in atmospheric conditions, in same reactor with esterification.
Description
Technical field
The invention belongs to Electrochemical Engineering technical field, it is related to a kind of ketone and carboxylic acid step in electrochemical hydrogen pump reactor
The method of hydrogenation and esterification.
Background technology
The energy is the material base of mankind's activity, restricts socio-economic development.Bio oil is referred to as " green (pollution free) petro ", its source
It is rich reserves, environmental-friendly, mutually compatible with infrastructure in photosynthesis of plant, while also acting as the original of many chemicals
Material, therefore receive more and more attention.Bio oil is oxygen-containing mixed by the complexity that alcohol, ether, aldehyde, ketone, acid and its derivative form
Object is closed, needs plus hydrogen removes its unsaturated component, esterification removes organic carboxyl acid, to improve the stability and flammability of oil product
Can, reduce its corrosivity.Bio oil plus hydrogen and be esterified the chemical reaction that be two classes different, usually in different types of reactor
Middle progress, wherein hydrogenation reaction step in order to control.
Bio oil adds hydrogen to be non-homogeneous catalytic hydrogenation process, hydrogen dissolving in the liquid phase, diffusion and in solid catalysis
The resistance to mass tranfers such as the Dissociative on agent surface are the ratedeterming step of hydrogenation reaction.Conventional phase reactor, such as slurry reactor
Or fixed bed, tubular reactor, it needs to carry out under high pressure, equipment is complicated, energy consumption increases.Electrochemical hydrogenation can be in the moon
Electrode catalyst surface in situ generates Hydrogen Proton, eliminates the mass transfer and limit of hydrogen, realizes and adds hydrogen under room temperature, normal pressure.But traditional liquid
The problems such as phase three-electrode electro Chemical hydrogenation reactor is polluted there are solution leakage, burn into.Electrochemical hydrogen pump reactor is a kind of
Model electrochemical reactor, structure is identical as polymer electrolyte fuel cells, and difference is to need to power up outside to push
Lower realization electrochemical reaction.As shown in Figure of description 1, the Hydrogen Proton that hydrogen is dissociated into anode passes through solid polymer electricity
Plasma membrane is solved, cathode catalysis layer is reached and generates absorption hydrogen in situ, directly participation liquid-phase hydrogenatin reaction, it can be achieved that atmospheric operation, and nothing
Solution leakage.In ChemSusChem 8 (2015) 288, cathode butanone is supplied as hydrogen source using hydrogen and adds the hydrogen, hydrogenation rate to be
6 times of conventional high-tension reactor.Patent ZL201510641954.5 reports electrochemistry hydrogen pump double-reactor, using isopropanol as hydrogen
Source supplies cathode phenol hydrogenation in anode dehydrogenation.And electrochemical hydrogen pump reactor is used, realize cathode hydrogenation products in reactor
Interior another reaction of further generation, generates the research of other target products, has not been reported.
Conventional liquid-phase reflux reactor can be used in the esterification of organic acid and alcohol, and by constantly removing product water
Reaction forward is promoted to carry out.The catalyst of esterification is Bronsted acid, is divided into liquid acids homogeneous catalyst and solid acids is non-
Homogeneous catalyst.Using the components such as ketone, acid are contained in bio oil simultaneously, using ketone plus hydrogen as alcohol source, carries out one step of ketone acid and add hydrogen
Esterification, be bio oil complex system upgrading reaction coupling merger a kind of important models reaction, can simplify reaction unit,
Cooperative reinforcing reacts.The research emphasis of a current one-step hydrogenation esterification reaction is the catalysis that exploitation has plus hydrogen is difunctional with esterification
Agent, as described in document Energy＆Fuel22 (2008) 3484.But an one-step hydrogenation esterification reaction of document report is still needed in high-pressure section
It is operated under part, has no report of the electrochemical hydrogen pump reactor for one step hydrogenation and esterification of ketone acid.
Invention content
To solve the above problems, the present invention provides a kind of ketone and carboxylic acid step in electrochemical hydrogen pump reactor to add hydrogen ester
The method of change.In electrochemical hydrogen pump reactor, when additional electric energy, using the extremely low electrochemical window of hydrogen, dissociated in anode
And be transmitted to cathode catalysis layer and generate absorption hydrogen in situ, hydrogenation reaction directly occurs with the ketone in cathode circulation liquid, is hydrogenated to
Alcohol further in cathode circulation liquid carboxylic acid occur esterification.Realize plus hydrogen with esterification in atmospheric conditions, it is same anti-
Coupling in device is answered to carry out, is synergistic.
The concrete scheme of the present invention is as follows：
A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor, in electrochemical hydrogen pump reactor
In, additional electric energy；Hydrogen is dissociated into Hydrogen Proton in anode, passes through solid polymer dielectric film, is hydrogenated in cathode and ketone
Alcohol, alcohol occur esterification with the carboxylic acid in cathode circulation liquid again, prepare carboxylate；It is specific as follows：
Solid polymer dielectric film is clipped in two single sides to be coated in the carbon paper diffusion layer of catalyst, is coated with catalyst
Side is contacted with solid polymer dielectric film, and membrane electrode is made in hot pressing 90-150s under the conditions of 120-140 DEG C, 3-5MPa；So
Membrane electrode assembly is carved with mounted in two pieces among the graphite electrode plate of serpentine flow path afterwards, formation cathode and anode, on two pieces of graphite electrode plates
Serpentine flow path be arranged symmetrically；When normal pressure, additional electric energy, an one-step hydrogenation esterification reaction, temperature occur for the reactant of cathode and anode
Degree control is at 30-70 DEG C；The catalyst is Pt/C, and wherein the loading of Pt is 0.5mg/cm2。
The additional electric energy refers to constant current operation mode, current density 4-30mA/cm2。
The hydrogen is dissociated in anode, refers to hydrogen from anode feed, flow 10-30sccm, urging on anode
Under agent effect, it is dissociated into Hydrogen Proton.
The ketone of the cathode adds hydrogen, refers to that the Hydrogen Proton of anode dissociation passes through solid polymer dielectric film, in cathode
On catalyst surface generate absorption hydrogen in situ, hydrogenation reaction directly occurs with the ketone in cathode circulation liquid for the hydrogen in situ that adsorbs, raw
At alcohol.
The esterification refers under the catalytic action of sulfuric acid, in the alcohol that ketone is hydrogenated to and cathode circulation liquid
Carboxylic acid reacts, and generates carboxylate.
The cathode circulation liquid is the mixed liquor of ketone and carboxylic acid, and the volume ratio of the two is 1:1-1:16.4, with sulfuric acid tune
Section pH value is 1.0-3.0, and cathode circulation liquid is in cathode circulation, flow 10-30mL/min.
The one step hydrogenation and esterification, refers on the cathode of electrochemical hydrogen pump reactor, ketone adds hydrogen, alcohol and carboxylic esterification
Two reaction couplings, prepare carboxylate.
The solid polymer dielectric film is perfluorosulfonic acid proton exchange film Nafion117, ion exchange capacity
For 0.91mmol/g.
Ketone in the cathode circulation liquid is butanone, and hydroxy acid is acetic acid.
The beneficial effects of the invention are as follows：(1) electrochemical window for utilizing hydrogen extremely low generates catalyst absorption hydrogen in situ,
The high-pressure hydrogenation reaction routinely used is avoided, the step hydrogenation and esterification under normal pressure is realized；(2) alkyd in cathode circulation liquid
Esterification promotes desorption and diffusion of the hydrogenation products alcohol of ketone from catalyst surface, can significantly improve ketone and add the anti-of hydrogen
Answer rate, current efficiency and conversion ratio；(3) ketone and carboxylic acid in cathode circulation liquid passes through the micron order duct of carbon paper diffusion layer
Be distributed to cathod catalyst surface, improve reactant cathod catalyst surface the degree that is uniformly dispersed；(4) cathode Pt/C is urged
Agent has high-specific surface area, increases the reaction interface of alcoholic acid esterification, improves the reaction rate and conversion ratio of alcoholic acid esterification.
Description of the drawings
Fig. 1 is the flow diagram of the ketone and acid step hydrogenation and esterification in electrochemical hydrogen pump reactor of the present invention.
Fig. 2 is in the electrochemical hydrogen pump reactor of the present invention, and cathode occurs one step hydrogenation and esterification of ketone acid and adds with only generation ketone
The comparison diagram of hydrogen reaction.Fig. 2 (A) is the comparison diagram of conversion ratio, and Fig. 2 (B) is the comparison diagram of applied voltage.Wherein, operation temperature
Be 40 DEG C, anode hydrogen gas flow is 20sccm, and cathode reaction liquid recycle stream amount is 10mL/min, pH value 1.8, wherein butanone with
The volume ratio of acetic acid is 1:1, current density 4-24mA/cm2.The fourth in an one-step hydrogenation esterification reaction it can be seen from Fig. 2 (A)
Conversion ratio, reaction rate and the current efficiency of ketone are above cathode, and only there is a situation where butanone, and hydrogen, butanone conversion ratio to be added to be promoted about
20%, hydrogenation rate and current efficiency promote about 30%.Esterification in an one-step hydrogenation esterification reaction it can be seen from Fig. 2 (B) is anti-
It should not be related to electrochemical process, so the applied voltage needed for the two is almost the same.What Fig. 2 showed to occur in cathode circulation liquid
Esterification reaction promotes desorption and diffusion of the hydrogenation products alcohol of ketone from catalyst surface, enhances butanone hydrogenation reaction.
Fig. 3 is in the electrochemical hydrogen pump reactor of the present invention, and cathode occurs one step hydrogenation and esterification of ketone acid and alkyd only occurs
Esterification, and the comparison diagram using conventional liquid phase refluxing reactor progress one step hydrogenation and esterification of ketone acid.Wherein, anode hydrogen gas
Flow is 20sccm, and cathode circulation liquid is butanone and acetate mixture, and ketone acid volume ratio is 1:1, circular flow 10mL/min,
PH value is 1.8, and reaction temperature is 40 DEG C.As seen from Figure 3, one step of ketone acid is carried out in electrochemical hydrogen pump reactor add hydrogen ester
The conversion rate of esterification of change, higher than only in cathode generation esterification reaction and conventional liquid phase refluxing reactor.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
Table 1 is the design parameter of the ketone and carboxylic acid one-step hydrogenation esterification reaction in electrochemical hydrogen pump reactor of the present invention.
Wherein, the loading of positive and negative the two poles of the earth catalyst Pt is 0.5mg/cm2, anode hydrogen gas flow is 20sccm, cathode circulation liquid stream
Amount is 10mL/min, and circulation fluid pH value is 1.8.Table 1 statistics indicate that, in electrochemical hydrogen pump reactor, a step hydrogenation and esterification is anti-
Should can carry out.
The design parameter of 1. ketone of table and carboxylic acid one-step hydrogenation esterification reaction in electrochemical hydrogen pump reactor
Embodiment 1：
In electrochemical hydrogen pump reactor, anode hydrogen gas charging, inlet amount 20sccm；Cathode butanone and acetic acid mixture
Charging, feed temperature is 40 DEG C, circular flow 10ml/min, pH value 1.8, and wherein the volume ratio of butanone and acetic acid is 1:1.
When electrochemical hydrogen pump reactor is with constant current 18.9mA/cm2, after 40 DEG C of operation 3h, reactor voltage is 0.47V, and butanone adds hydrogen
The reaction rate for generating butanol is 117.6mmol/ (cm s), current efficiency 96.1%.Butanone the hydrogenation phase only occurs with cathode
Than butanone conversion ratio promotes about 25%, and hydrogenation rate and current efficiency promote about 30%.Butanol and acetic acidreaction generation acetic acid are secondary
The conversion ratio of butyl ester is 85.6%, is about not added with electric energy and merely 1.09 times when cathode carries out esterification reaction, about
1.06 times of a step hydrogenation and esterification in conventional liquid phase refluxing reactor.
Embodiment 2：
In electrochemical hydrogen pump reactor, anode hydrogen gas charging, inlet amount 10sccm；Cathode butanone and acetic acid mixture
Charging, feed temperature is 60 DEG C, circular flow 20mL/min, pH value 1.0, and wherein the volume ratio of butanone and acetic acid is 1:1.
When electrochemical hydrogen pump reactor is with constant current 18.9mA/cm2, after 60 DEG C of operation 3h, reactor voltage is 0.55V, and butanone adds hydrogen
The reaction rate for generating butanol is 82.9mmol/ (cm s), current efficiency 83.6%.Butanone the hydrogenation phase only occurs with cathode
Than butanone conversion ratio promotes about 20%, and hydrogenation rate and current efficiency promote about 30%.Butanol and acetic acidreaction generation acetic acid are secondary
The conversion ratio of butyl ester is 82.3%.
Embodiment 3：
In electrochemical hydrogen pump reactor, anode hydrogen gas charging, inlet amount 25sccm；Cathode butanone and acetic acid mixture
Charging, feed temperature is 40 DEG C, circular flow 30mL/min, pH value 3.0, and wherein the volume ratio of butanone and acetic acid is 1:1.
When electrochemical hydrogen pump reactor is with constant current 18.9mA/cm2, after 40 DEG C of operation 10h, reactor voltage is 0.66V, and butanone adds hydrogen
The reaction rate for generating butanol is 51.3mmol/ (cm s), and current efficiency 52.4%, butanol and acetic acidreaction generation acetic acid are secondary
The conversion ratio of butyl ester is 75.0%.
Embodiment 4：
In electrochemical hydrogen pump reactor, anode hydrogen gas charging, inlet amount 20sccm；Cathode butanone and acetic acid mixture
Charging, feed temperature is 40 DEG C, circular flow 10mL/min, pH value 1.8, and wherein the volume ratio of butanone and acetic acid is 1:
3.4.When electrochemical hydrogen pump reactor is with constant current 18.9mA/cm2, after 40 DEG C of operation 3h, reactor voltage is 0.38V, butanone
The reaction rate for being hydrogenated to butanol is 90.5nmol/ (s cm2), current efficiency 92.4%, butanol is generated with acetic acidreaction
The conversion ratio of sec-butyl acetate is 76.4%.
Claims (10)
1. a kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor, which is characterized in that in electrochemistry
In hydrogen pump reactor, additional electric energy；Hydrogen is dissociated into Hydrogen Proton in anode, pass through solid polymer dielectric film, cathode with
Ketone is hydrogenated to alcohol, and alcohol occurs esterification with the carboxylic acid in cathode circulation liquid again, prepares carboxylate；It is specific as follows：
Solid polymer dielectric film is clipped in two single sides to be coated in the carbon paper diffusion layer of catalyst, is coated with the side of catalyst
It is contacted with solid polymer dielectric film, membrane electrode is made in hot pressing 90-150s under the conditions of 120-140 DEG C, 3-5MPa；Then will
Membrane electrode assembly is carved with mounted in two pieces among the graphite electrode plate of serpentine flow path, forms cathode and anode, the snake on two pieces of graphite electrode plates
Shape runner is arranged symmetrically；When normal pressure, additional electric energy, an one-step hydrogenation esterification reaction, temperature control occur for the reactant of cathode and anode
System is at 30-70 DEG C；The catalyst is Pt/C, and wherein the loading of Pt is 0.5mg/cm2。
2. the method for a kind of ketone according to claim 1 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor,
It is characterized in that, the additional electric energy, refers to constant current operation mode, current density 4-30mA/cm2。
3. the side of a kind of ketone according to claim 1 or 2 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor
Method, which is characterized in that the hydrogen is dissociated in anode, refers to hydrogen from anode feed, flow 10-30sccm.
4. the side of a kind of ketone according to claim 1 or 2 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor
Method, which is characterized in that the cathode circulation liquid is the mixed liquor of ketone and carboxylic acid, and the volume ratio of the two is 1:1-1:16.4 using
Sulphur acid for adjusting pH value is 1.0-3.0, and cathode circulation liquid is in cathode circulation, flow 10-30mL/min.
5. the method for a kind of ketone according to claim 3 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor,
It is characterized in that, the cathode circulation liquid is the mixed liquor of ketone and carboxylic acid, the volume ratio of the two is 1:1-1:16.4, use sulfuric acid
Adjusting pH value is 1.0-3.0, and cathode circulation liquid is in cathode circulation, flow 10-30mL/min.
6. a kind of ketone according to claim 1,2 or 5 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor
Method, which is characterized in that the solid polymer dielectric film is perfluorosulfonic acid proton exchange film Nafion117, ion
Exchange capacity is 0.91mmol/g.
7. the method for a kind of ketone according to claim 3 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor,
It is characterized in that, the solid polymer dielectric film, is perfluorosulfonic acid proton exchange film Nafion117, ion exchange
Capacity is 0.91mmol/g.
8. the method for a kind of ketone according to claim 4 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor,
It is characterized in that, the solid polymer dielectric film, is perfluorosulfonic acid proton exchange film Nafion117, ion exchange
Capacity is 0.91mmol/g.
9. a kind of ketone and carboxylic acid step in electrochemical hydrogen pump reactor according to claim 1,2,5,7 or 8 add hydrogen ester
The method of change, which is characterized in that the ketone in the cathode circulation liquid is butanone, and hydroxy acid is acetic acid.
10. the method for a kind of ketone according to claim 6 and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor,
It is characterized in that, the ketone in the cathode circulation liquid is butanone, hydroxy acid is acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810375920.XA CN108677210B (en) | 2018-04-17 | 2018-04-17 | A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810375920.XA CN108677210B (en) | 2018-04-17 | 2018-04-17 | A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108677210A true CN108677210A (en) | 2018-10-19 |
| CN108677210B CN108677210B (en) | 2019-10-29 |
Family
ID=63801629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810375920.XA Active CN108677210B (en) | 2018-04-17 | 2018-04-17 | A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108677210B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101146A (en) * | 2019-12-28 | 2020-05-05 | 大连理工大学 | H2/CO2Separation from CO2Hydrogenation self-coupling method |
| CN111909736A (en) * | 2020-07-29 | 2020-11-10 | 华中科技大学 | Electrochemical upgrading method for bio-oil |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117192A (en) * | 1975-04-07 | 1976-10-15 | Agency Of Ind Science & Technol | Highly selective catalyst for manufacture of esters of carboxylic acid s |
| WO2003010361A3 (en) * | 2001-07-25 | 2003-08-07 | Ylektra Inc | Nitrogen atom transfer |
| CN1476491A (en) * | 2000-11-24 | 2004-02-18 | �����ɷ� | Method for producing alcoxylated carbonyl compounds by anodic oxidation method using cathodic coupled reaction for organic synthesis |
| JP2004262823A (en) * | 2003-02-28 | 2004-09-24 | Otsuka Chemical Co Ltd | Water-soluble n-oxyl compound, oxidation catalyst, and production method of oxide using the catalyst |
| 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 |
| CN107699917A (en) * | 2017-10-14 | 2018-02-16 | 南阳师范学院 | A kind of method of electrochemistry formated lactone |
-
2018
- 2018-04-17 CN CN201810375920.XA patent/CN108677210B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117192A (en) * | 1975-04-07 | 1976-10-15 | Agency Of Ind Science & Technol | Highly selective catalyst for manufacture of esters of carboxylic acid s |
| CN1476491A (en) * | 2000-11-24 | 2004-02-18 | �����ɷ� | Method for producing alcoxylated carbonyl compounds by anodic oxidation method using cathodic coupled reaction for organic synthesis |
| WO2003010361A3 (en) * | 2001-07-25 | 2003-08-07 | Ylektra Inc | Nitrogen atom transfer |
| JP2004262823A (en) * | 2003-02-28 | 2004-09-24 | Otsuka Chemical Co Ltd | Water-soluble n-oxyl compound, oxidation catalyst, and production method of oxide using the catalyst |
| 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 |
| CN107699917A (en) * | 2017-10-14 | 2018-02-16 | 南阳师范学院 | A kind of method of electrochemistry formated lactone |
Non-Patent Citations (1)
| Title |
|---|
| 王涛: "电化学氢泵反应器用于生物质基酮加氢的研究", 《大连理工硕士学位论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101146A (en) * | 2019-12-28 | 2020-05-05 | 大连理工大学 | H2/CO2Separation from CO2Hydrogenation self-coupling method |
| CN111101146B (en) * | 2019-12-28 | 2022-01-04 | 大连理工大学 | H2/CO2Separation from CO2Hydrogenation self-coupling method |
| CN111909736A (en) * | 2020-07-29 | 2020-11-10 | 华中科技大学 | Electrochemical upgrading method for bio-oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108677210B (en) | 2019-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| An et al. | Performance of an alkaline-acid direct ethanol fuel cell | |
| Qiu et al. | Integrated electrocatalytic processing of levulinic acid and formic acid to produce biofuel intermediate valeric acid | |
| CN105200448B (en) | A kind of organic matter dehydrogenation and hydrogenation coupled electrochemistry hydrogen pump double-reactor | |
| Kwok et al. | A dual fuel microfluidic fuel cell utilizing solar energy and methanol | |
| CN108677210B (en) | A kind of method of ketone and carboxylic acid step hydrogenation and esterification in electrochemical hydrogen pump reactor | |
| CN113913846A (en) | Water electrolysis hydrogen production oxygen generation reaction device | |
| CN113774416A (en) | Gas diffusion cathode and electrochemical reactor for in-situ production of hydrogen peroxide | |
| Huang et al. | A bilateral electrochemical hydrogen pump reactor for 2-propanol dehydrogenation and phenol hydrogenation | |
| CN101702435B (en) | Air cathode without metal catalyst and preparation method thereof | |
| Yang et al. | Effects of ethanol in methanol fuel on the performance of membrane electrode assemblies for direct methanol fuel cells | |
| CN101800325B (en) | Alkaline direct dimethyl ether fuel cell | |
| WO2023082884A1 (en) | New electrocatalytic membrane reactor and use thereof in preparation of high-purity hydrogen | |
| CN115069269B (en) | CoMoS x O y Electrocatalyst, preparation method thereof and application thereof in electro-active persulfate system degradation of organic pollutants | |
| CN218561635U (en) | Solar-driven microbial electrolysis hydrogen production synchronous organic sewage treatment system | |
| CN102315464B (en) | Anode binary-channel charging direct dimethyl ether fuel cell and power generation method thereof | |
| Tsujiguchi et al. | Effect of the impurities in crude bio-methanol on the performance of the direct methanol fuel cell | |
| CN201956423U (en) | Spraying heating vacuum sucker for membrane electrodes of proton exchange membrane fuel cells | |
| CN103120960B (en) | Pt-Nafion/C catalyst and preparation method and application for same | |
| CN115537861A (en) | Constant-speed gas diffusion electrode for generating hydrogen peroxide and application method thereof | |
| Huang et al. | Electrocatalytic dehydrogenation of 2-propanol in electrochemical hydrogen pump reactor | |
| Cui et al. | Integration of a well-designed biomass pair in electrochemical hydrogen pump reactor: ethylene glycol dehydrogenation and levulinic acid hydrogenation | |
| CN112830467A (en) | Method for preparing MOF carbon material with porous structure and catalyst slurry of proton exchange membrane fuel cell comprising carbon material | |
| CN108808041A (en) | Biomass direct generation of electricity fuel cell and CO2Utilize system and method | |
| CN101707257B (en) | Direct dimethyl ether fuel battery | |
| CN110735150A (en) | large-scale high-efficiency electrocatalysis H production2O2Double-chamber assembled reactor system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |