CN1172394C - Electrochemical synthesis of propanol in protein exchange film fuel cell - Google Patents
Electrochemical synthesis of propanol in protein exchange film fuel cell Download PDFInfo
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- CN1172394C CN1172394C CNB021371717A CN02137171A CN1172394C CN 1172394 C CN1172394 C CN 1172394C CN B021371717 A CNB021371717 A CN B021371717A CN 02137171 A CN02137171 A CN 02137171A CN 1172394 C CN1172394 C CN 1172394C
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- exchange membrane
- proton exchange
- membrane fuel
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- propanol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to a propanol electrochemical synthesizing method in a proton exchange membrane fuel cell, which utilizes a proton exchange membrane fuel cell for electrochemically synthesizing allyl alcohol into propanol and electric energy symbiosis. The proton exchange membrane fuel cell is accessed into a test system and control the temperature of the cell. A cathode chamber is pretreated by nitrogen gas before cathodic reaction materials are pumped into the cathode chamber, and then the cell is initially polarized, namely that a circuit is switched on after hydrogen gas is led into an anode to make residual oxygen in the cathode chamber sufficiently react. At the reaction time, the flow quantity of hydrogen led into the an anode chamber and the flow quantity of allyl alcohol water solution pumped into the cathode chamber are controlled, and normal propanol with different purities can be obtained after the hydrogen and the allyl alcohol water solution react for one to eight hours without load by regulating a variable resistor to control reaction current. The proton exchange membrane fuel cell of the present invention adopts a porous gas diffusion triad film electrode. The present invention has the advantages of simple technology process, little pollution and low energy consumption, and can generate electric energy while the product is synthesized; thus, the present invention has an important significance for producing a small quantity of high-quality chemical products.
Description
Technical field:
The present invention relates to electrochemical synthesis of propanol in the proton exchanging film fuel battery, with the Proton Exchange Membrane Fuel Cells is reactor, in the Proton Exchange Membrane Fuel Cells working range, carry out the electrochemical hydrogenation reaction of propenyl, synthetic propyl alcohol and generation electric energy.Belong to Electrochemical Engineering and catalysis technical field.
Background technology:
Propenyl has another name called allyl alcohol, owing to contain two keys and two kinds of functional groups of hydroxyl in the propenyl structure, can participate in various organic reactions such as oxidation, reduction, esterification and addition, make it have purposes widely at aspects such as organic synthesis, agricultural chemicals, medicine and spices intermediates.Utilize propenyl can produce multiple organic chemicals,, have even more important meaning especially for the traditional handicraft of some product, as propenyl method synthesizing epoxy chloropropane, propenyl synthetic glycerine, propenyl synthetic 1,4 butadiene, the synthetic normal propyl alcohol of propenyl etc.The synthetic normal propyl alcohol of tradition propenyl often adopts electrolytic reduction, and severe reaction conditions is polluted greatly, and energy consumption is serious.
Fuel cell is a kind ofly by the electrode catalyst course of reaction chemical energy to be converted into the electrochemical reaction appts of electric energy, and wherein Proton Exchange Membrane Fuel Cells (PEMFC) has shown the applications well prospect on electric automobile, small-sized portable power source.At present, people are promoting the business-like while of PEMFC, are also considering the application of PEMFC in wide spectrum more, and utilizing Proton Exchange Membrane Fuel Cells is one of its application direction as synthesis reactor.Utilize the fuel cell reaction device not only can generate chemicals, produce electric energy simultaneously, can also control reaction process easily by the load of control external circuit, pollute for a short time, meet the direction of environmental friendliness chemical technology research, the more important thing is, it can generate electricity, the resource utilization height.
In the past few decades, people's the research oxidation reaction in fuel cell that focuses mostly on, as ethene one-step method system acetaldehyde, benzene one-step method system phenol, cyclohexane oxidation, toluene oxidations etc. have synthesized important organic substance such as acetaldehyde, phenol etc.In Proton Exchange Membrane Fuel Cells, Kiyoshi Otsuka etc. has studied a step of hydrogen peroxide and has synthesized, negative electrode and anode are separated by the Nafion117 film, and Pt is deposited on the anode film surface, and Pt, Pd, Au use the same method and be deposited on negative electrode, the target chamber, oxygen imports in the 0.1NHCl solution, and in the anode chamber, hydrogen is also imported by helium, in order to obtain product as much as possible, external circuit does not add any load.But (apparent area is 2.5cm to have had to 10-30mA in the process of synthesize hydrogen peroxide
2) electric current.In same device, people such as Kiyoshi Otsuka have also studied oxidation step (the Otsuka K of benzene, Hosokawa K, Yamanaka I, et al.One-step oxidation of benzene to phenol applying afuel cell system, Electrochimica Acta, 1989,34 (10): 1485-1488), and almost nobody shows any interest in this field of hydrogenation reaction that seldom has research to relate in the reduction reaction, particularly Proton Exchange Membrane Fuel Cells.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, break through the thought of traditional electrolysis hydrogenating reduction and fuel cell reaction device technology, electrochemical synthesis of propanol in one proton exchanging film fuel battery is proposed, in Proton Exchange Membrane Fuel Cells, carry out synthetic propyl alcohol of propenyl electrochemistry and electric energy symbiosis, solve severe reaction conditions in the existing synthetic technology, problem that energy consumption is serious, simultaneously, for hydrogenation reaction provides a new reacting environment, for Proton Exchange Membrane Fuel Cells is expanded new application.
For realizing such purpose, the present invention utilizes Proton Exchange Membrane Fuel Cells to carry out synthetic propyl alcohol of propenyl electrochemistry and electric energy symbiosis, because Proton Exchange Membrane Fuel Cells is an electrochemical reactor that integrates oxidation reaction and reduction reaction, hydrogen enters the anode chamber, at anode generation dissociation reaction, the H that anode reaction produces
+Conduction by proton exchange membrane migrates to cathode surface, and catholyte (propenyl) pumps into cathode chamber by peristaltic pump, at cathode chamber and H
+Hydrogenation reaction taking place and generate propyl alcohol, simultaneously, obtains electric current at external circuit.The present invention has realized synthetic propyl alcohol of propenyl electrochemistry and electric energy symbiosis in Proton Exchange Membrane Fuel Cells, promptly obtain electric energy when generating the product propyl alcohol.Concrete steps are as follows:
(1) Proton Exchange Membrane Fuel Cells is inserted test macro, promptly the cathode and anode collector plate by fuel cell inserts DVM to measure open circuit voltage, connects the output of variable resistance and galvanometer Control current simultaneously.
Proton Exchange Membrane Fuel Cells adopts typical porous gas diffusion three in one membreane electrode, perhaps self-control.The self-control method is as follows: catalyst is 20%Pt/C (Johnson Matthey), and the Pt carrying capacity is 0.5-2mg/cm
2, solid polymer membrane be Nafion 117, Nafion 115 or Nafion 112 (Dupont, Fayetteville, PA).Catalyst oar material is coated on the carbon paper by the method for brushing, and the Nafion film is hot pressed into three in one membreane electrode (MEA) with electrode after preliminary treatment.
(2) temperature of control Proton Exchange Membrane Fuel Cells is in 20-75 ℃ of scope.
(3) for eliminating the influence of oxygen and impurity, purge with nitrogen target chamber before the aqueous solution of cathode reactant ally alcohol pumps into, then battery is carried out initial polarization, further eliminate the influence of oxygen and impurity kinetic current.During initial polarization, anode is connected circuit after feeding hydrogen, and oxygen remaining in the cathode chamber is fully reacted, and electric current is by regulating variable resistance control, and the kinetic current that galvanometer can measure when external resistance is zero is less than 1mA.
(4) hydrogen (99.99%) is fed the anode chamber, the control flow is at 10-60ml/min.
(5) the propenyl aqueous solution of 0.2-5mol/L pumps into cathode chamber by peristaltic pump, and the control flow is at 1-6ml/min.
(6) will be reflected at and carry out under the situation that does not have load 1-8 hour, obtain the product normal propyl alcohol of different purity.
The present invention is reactor with the Proton Exchange Membrane Fuel Cells, in the Proton Exchange Membrane Fuel Cells working range, carries out the electrochemical hydrogenation reaction of propenyl, synthetic normal propyl alcohol and generation electric energy.Technical process of the present invention is simple, has good competitiveness; Though the conversion ratio of reaction is also not too high, the electric current of gained is higher, does not have accessory substance; The reaction condition gentleness, propenyl is hydrogenated to liquid phase reactor, and the device lifting load is convenient; Not only pollute for a short time, energy consumption is low, can also produce electric energy in sintetics.The present invention is for producing a small amount of high quality chemical product, and is significant, especially China's chemical industry development had far reaching significance.
Proposition of the present invention provides a new reacting environment for hydrogenation reaction, and simultaneously, it has also expanded new application for Proton Exchange Membrane Fuel Cells.
Description of drawings:
Fig. 1 is experimental provision of the present invention and process flow diagram.
As shown in Figure 1, the present invention realizes that the synthetic normal propyl alcohol of propenyl electrochemistry and electric energy symbiosis are at PEM Carry out in the fuel cell. The end plate of Proton Exchange Membrane Fuel Cells C and carbon plate all have port be connected negative electrode and The anode pipeline passes in and out for reactant. Hydrogen is through pressure-reducing valveFlowmeter F and humidifierRear water entrainment steam enters the anode chamber, by the effect generation dissociation reaction of catalyst, generates H in the anode chamber+, then with The form of proton hydrate is passed PEM, enters cathode chamber. Unreacted hydrogen and steam are from anode The other end of chamber is discharged. For eliminating oxygen and impurity to the impact of kinetic current, cathode reactant pumps into front usefulness Nitrogen target chamber purges, and as shown in the figure, nitrogen is through pressure-reducing valve
With flowmeter F, pass through triple valve Enter cathode chamber, preliminary treatment is carried out in the target chamber, discharges from the cathode chamber other end after purging. Reactant is third The aqueous solution of enol (AA) is contained in container C ' in, available peristaltic pump P passes through valve with catholyte from container V and threeway pump into the cell cathode chamber, at cathode chamber and H+Reaction is discharged from another outlet after generating propyl alcohol. Logical The cathode and anode collector plate of crossing fuel cell can meet the external circuit system, and the external circuit system can connect DVMIn order to measure open-circuit voltage, also can connect variable resistance L and galvanometer
The output of control electric current.
Specific implementation method:
The present invention adopts typical Proton Exchange Membrane Fuel Cells porous gas diffusion three in one membreane electrode or self-control membrane electrode, and with the membrane electrode battery of packing into.Press accompanying drawing 1 connected mode, connect negative electrode pipeline and the anode pipeline and the external circuit test macro of battery.The temperature of control Proton Exchange Membrane Fuel Cells is in 20-75 ℃ of scope.For eliminating the influence of oxygen and impurity to kinetic current, before pumping into, cathode reactant purges with nitrogen target chamber, then battery is carried out initial polarization, further eliminate the influence of oxygen and impurity.Hydrogen (99.99%) is fed the anode chamber, and the control flow is at 10-60ml/min.0.2-5mol/L the propenyl aqueous solution pump into cathode chamber by peristaltic pump, control flow at 1-6ml/min.Carried out under the situation that does not have load 1-8 hour being reflected at, obtain the product normal propyl alcohol of different purity.
Embodiment 1: preparation platinum carrying capacity 0.5mg/cm
2Membrane electrode, and with the membrane electrode battery of packing into.The propenyl aqueous solution 30ml of configuration 0.5mol/L presses accompanying drawing 1 jockey system, and the control battery temperature is at 30 ℃.Behind the initial polarization, feed hydrogen (hydrogen flowing quantity is controlled at 10ml/min), open peristaltic pump (catholyte flow velocity 1mL/min), can obtain normal propyl alcohol 6.8mmol in 2 hours, conversion ratio 16%, maximum power density are 4.9mW/cm
2, the current density of this moment is 51mA/cm
2
Embodiment 2: preparation platinum carrying capacity 2mg/cm
2Membrane electrode, and with the membrane electrode battery of packing into.The propenyl aqueous solution 30ml of configuration 5mol/L presses accompanying drawing 1 jockey system, and the control battery temperature is at 70 ℃.Behind the initial polarization, feed hydrogen (hydrogen flowing quantity is controlled at 60ml/min), open peristaltic pump (catholyte flow velocity 6ml/min), can obtain normal propyl alcohol 7.4mmol in 2 hours, conversion ratio 18%, maximum power density are 5.8mW/cm
2, the current density of this moment is 60mA/cm
2
Embodiment 3: adopt typical Proton Exchange Membrane Fuel Cells porous gas diffusion three in one membreane electrode, and with the membrane electrode battery of packing into.The propenyl aqueous solution 30ml of configuration 2mol/L presses accompanying drawing 1 jockey system, and the control battery temperature is at 50 ℃.Behind the initial polarization, feed hydrogen (hydrogen flowing quantity is controlled at 10ml/min), open peristaltic pump (catholyte flow velocity 3ml/min), can obtain normal propyl alcohol 8.8mmol in 2 hours, conversion ratio 21%, maximum power density are 6.2mW/cm
2, the current density of this moment is 66mA/cm
2
Claims (2)
1, electrochemical synthesis of propanol in the proton exchanging film fuel battery is characterized in that comprising following concrete steps:
1) Proton Exchange Membrane Fuel Cells is inserted test macro, promptly the cathode and anode collector plate by fuel cell inserts DVM to measure open circuit voltage, connects the output of variable resistance and galvanometer Control current simultaneously;
2) temperature of control Proton Exchange Membrane Fuel Cells is in 20-75 ℃ of scope;
3) purge with nitrogen target chamber before the aqueous solution of cathode reactant ally alcohol pumps into, then battery is carried out initial polarization, during initial polarization, anode is connected circuit after feeding hydrogen, oxygen remaining in the cathode chamber is fully reacted, regulate the variable resistance Control current, the kinetic current that galvanometer can measure when external resistance is zero is less than 1mA;
4) be that 99.99% hydrogen feeds the anode chamber with concentration, the control flow is at 10-60ml/min;
5) the propenyl aqueous solution of 0.2-5mol/L pumps into cathode chamber by peristaltic pump, and the control flow is at 1-6ml/min;
6) will be reflected at and carry out under the situation that does not have load 1-8 hour, obtain the product normal propyl alcohol of different purity.
2,, it is characterized in that Proton Exchange Membrane Fuel Cells adopts porous gas diffusion three in one membreane electrode as electrochemical synthesis of propanol in the said Proton Exchange Membrane Fuel Cells of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371717A CN1172394C (en) | 2002-09-26 | 2002-09-26 | Electrochemical synthesis of propanol in protein exchange film fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371717A CN1172394C (en) | 2002-09-26 | 2002-09-26 | Electrochemical synthesis of propanol in protein exchange film fuel cell |
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| CN1404181A CN1404181A (en) | 2003-03-19 |
| CN1172394C true CN1172394C (en) | 2004-10-20 |
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| CNB021371717A Expired - Fee Related CN1172394C (en) | 2002-09-26 | 2002-09-26 | Electrochemical synthesis of propanol in protein exchange film fuel cell |
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| CN1893162B (en) * | 2005-07-08 | 2012-03-28 | 中国人民解放军63971部队 | Liquid accumulator cell with double functions of accumulating and electrochemical synthesizing |
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