CN103069051A - Device for manufacturing organic hydride - Google Patents

Device for manufacturing organic hydride Download PDF

Info

Publication number
CN103069051A
CN103069051A CN2011800400333A CN201180040033A CN103069051A CN 103069051 A CN103069051 A CN 103069051A CN 2011800400333 A CN2011800400333 A CN 2011800400333A CN 201180040033 A CN201180040033 A CN 201180040033A CN 103069051 A CN103069051 A CN 103069051A
Authority
CN
China
Prior art keywords
organic hydride
catalyst layer
producing device
water
material producing
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.)
Pending
Application number
CN2011800400333A
Other languages
Chinese (zh)
Inventor
平重贵之
石川敬郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Publication of CN103069051A publication Critical patent/CN103069051A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

This device for electrochemically manufacturing an organic hydride is characterized by the electrode structure thereof being a structure that forms a matrix in which a metal catalyst supporting carbon or a metal catalyst is suitably intermingled with a proton conductive solid polymer electrolyte, and catalyst layers (13, 14) thereof are formed on the front and back of a proton conductive solid polymer electrolyte film (12) on which a layer that blocks water from passing through is formed. When water or water vapor is supplied to the anode side of this electrode and a hydrogenated substance is supplied to the cathode side, application of a voltage across the anode and cathode causes an electrolysis reaction to occur at the anode and a hydrogenation reaction to the hydrogenated substance to occur at the cathode, producing the organic hydride.

Description

The organic hydride material producing device
Technical field
The present invention relates to the organic hydride material producing device of electrochemical fabrication organic hydride.
Background technology
The greenhouse effects of the earth that causes at carbonic acid gas etc. becomes in the deep problem, replaces fossil oil, and as undertaking the lower centurial energy, hydrogen receives much concern.With regard to hydrogen fuel, the material that is discharged from when rate of fuel consumption only has water, does not discharge carbonic acid gas, and is therefore, little to the load of environment.On the other hand, because hydrogen is gas at normal temperatures and pressures, therefore, conveying, storage, plenum system become large problem.
In recent years, as the hydrogen storage practice of security, transporting and storage capacity excellence, use hexanaphthene and methylcyclohexane are arranged, the organic hydride system of hydrocarbon that naphthane is such receives much concern.Because these hydrocarbon are liquid at normal temperatures, therefore, transporting is excellent.For example, toluene is the cyclic hydrocarbon with identical carbon number with methylcyclohexane, and toluene is that hydrocarbon key each other is the unsaturated hydrocarbons of two keys, and relative therewith, methylcyclohexane is not for having the saturation of double bonds hydrocarbon.Addition reaction of hydrogen by toluene obtains methylcyclohexane, and the dehydrogenation reaction by methylcyclohexane obtains toluene.That is, by addition reaction of hydrogen and the dehydrogenation reaction of utilizing these hydrocarbon, can carry out storage and the supply thereof of hydrogen.
In order to make the organic hydrides such as methylcyclohexane, need at first make hydrogen, this hydrogen and toluene are reacted at catalyzer.That is, the technique of present situation is the two-stage technique that makes hydrogen produce, make hydrogen and toluene reaction and organic hydride is generated in apparatus for electrolyzing etc. in the addition reaction of hydrogen device.
Therefore, the manufacturing to organic hydride needs a plurality of devices, the complicated problem of generation device.In addition and since make behind the hydrogen to addition reaction of hydrogen be gasiform hydrogen, therefore, about storage, carry, have problems.If build in abutting connection with hydrogen producing apparatus and hydrogen addition device, then can address the above problem, but have the problem of building and using cost, comprehensive energy efficiency also reduces.In addition, because device maximizes, therefore, it is limited that the place is set.
In recent years, disclose the technology (for example patent documentation 1) of using single device to make organic hydride at one-phase.These technology are the technology of electrochemical fabrication organic hydride.For example, in patent documentation 1, dispose respectively metal catalyst in the both sides that optionally see through hydrionic hydrogen ion perviousness solid polyelectrolyte membrane, one side is supplied feedwater or water vapour, the opposing party's supply is hydrogenated thing, the hydrogen ion that electricity by the water in the anode side or water vapour is decomposed generates cathode side be hydrogenated thing generation addition reaction of hydrogen, the manufacturing organic hydride.
The prior art document
Patent documentation
Patent documentation 1: JP 2003-45449 communique
Summary of the invention
Invent problem to be solved
But it is difficult that these organic hydride manufacture method obtain high energy efficiency.As its reason, can consider it is the impact that sees through water.That is, can think that the water that is used for anodic reaction sees through hydrogen ion perviousness solid polyelectrolyte membrane and arrives negative electrode, should see through the reaction of water anticathode and produce baneful influence.It is insoluble each other that water and toluene etc. are hydrogenated phase, do not mix.Therefore, water is present in the situation of cathode catalyst layer, hinders by this water resistance the toluene of catalyzer is supplied with.Its result thinks that organic hydride does not generate, the energy efficiency step-down because cause at the catalyzer of not supplying with toluene etc. and be hydrogenated thing and not occur hydrogen generation etc. to being hydrogenated the addition reaction of hydrogen of thing.In addition, when mixing through the organic hydride behind water and the addition reaction of hydrogen, need except the technique of anhydrating especially.When the simplification of considering device etc., should be not preferred.
The object of the invention is to, the organic hydride manufacturing installation is provided, described device is to generate in the device of organic hydride in electrochemistry, is device small-sized and that efficient is good.
Be used for solving the means of problem
In view of described practical situation, the inventor concentrates on studies, and found that: by form the layer that sees through water that stops from anode to negative electrode in solid polyelectrolyte membrane surface or solid polyelectrolyte membrane, can obtain high efficiency electrode.In electrode of the present invention, catalyst layer is set as metal catalyst and supports the structure that carbon or metal catalyst become the matrix of suitably mixing with the proton-conducting solid macromolecule electrolyte, and these catalyst layers form on the two sides in being formed with through the table of the proton-conducting solid polyelectrolyte membrane on water blocking layer.
In organic hydride material producing device of the present invention, have: be formed with the membrane-electrode assembly that mode through the solid polyelectrolyte membrane of the proton conductive on water blocking layer disposes the anode catalyst layer of cathode catalyst layer that reduction is hydrogenated thing and oxidizing water with clamping, the supply of anticathode catalyst layer is hydrogenated the parts of thing and the parts that the antianode catalyst layer supplies feedwater or water vapour, described cathode catalyst layer comprises that reduction is hydrogenated thing and with the catalyst metal of hydride reaction with support the carrier of described catalyst metal and the solid macromolecule electrolyte of proton conductive, and described anode catalyst layer comprises oxidizing water and with the catalyst metal of alpha proton reaction with support the carrier of described catalyst metal and the solid macromolecule of proton conductive.
The invention effect
According to the present invention, the organic hydride manufacturing installation can be provided, described device is that electrochemistry generates in the device of organic hydride, is device small-sized and that efficient is good.
Description of drawings
Fig. 1 is the figure of an embodiment of expression organic hydride material producing device of the present invention or fuel cell.
Fig. 2 is the figure of expression membrane-electrode assembly of the present invention.
Fig. 3 is the figure of the membrane-electrode assembly of expression prior art.
Fig. 4 is the figure of an embodiment of expression organic hydride material producing device of the present invention.
Fig. 5 is the figure of an embodiment of expression organic hydride material producing device of the present invention.
Fig. 6 is the figure of an embodiment of the organic hydride material producing device of expression prior art.
Fig. 7 is the figure of an embodiment of the organic hydride material producing device of expression prior art.
Embodiment
The present invention is the device of electrochemical fabrication organic hydride, it is characterized in that having in being formed with through the table of the proton-conducting solid polyelectrolyte membrane on water blocking layer two sides and be formed with proton-conducting solid macromolecule electrolyte and metal catalyst and support the electrode structure of catalyst layer that carbon or metal catalyst become the structure of the matrix of suitably mixing.In this electrode, it is characterized in that, apply voltage by supply feedwater or water vapour, anticathode side to supply with between the state antianode-negative electrode that is hydrogenated thing with the antianode side, the electric decomposition reaction of water occurs in anode, in negative electrode, occur being hydrogenated the addition reaction of hydrogen of thing, organic hydride is generated.
Use accompanying drawing at length to narrate to embodiments of the present invention.
Fig. 1 represents an example of organic hydride material producing device of the present invention.The organic hydride material producing device of present embodiment is clamped in a pair of gas diffusion layers 15 and the dividing plate 11 that is formed with gas flow path and engages anode catalyst layer 13 on the face that is formed with through the solid polyelectrolyte membrane 12 on water blocking layer, engages cathode catalyst layer 14 and integrated membrane-electrode assembly (MEA:Membrane Electrode Assembly) and consist of at another face.In addition, between a pair of dividing plate 11, insert the gasket 16 that is used for air seal.
Dividing plate 11 has electroconductibility, the preferred solid graphite plate of its material, the carbon materials such as graphite and carbon black is utilized the metallic substance of the corrosion resistance excellents such as carbon plate, stainless steel and titanium that resin forms.In addition, also preferably the surface of dividing plate 11 is carried out the conductive coating paint of precious metal plating or coated corrosion resistant, excellent heat resistance and carried out surface treatment.Become the ditch of the stream of reactant gases or liquid at the face with the anode catalyst layer 13 of dividing plate 11 and cathode catalyst layer 14 subtends.The stream ditch of the dividing plate 11 of antianode side is for feedwater or water vapour.Water or the water vapour of stream ditch of flowing through is supplied to anode catalyst layer via gas diffusion layers 15.In addition, the side dividing plate 11 of anticathode side is supplied with and is hydrogenated thing.The thing that is hydrogenated of stream ditch of flowing through is supplied to cathod catalyst via gas diffusion layers 15.As the supply method that is hydrogenated thing, both directly the feeding liquid shape be hydrogenated thing, also can be for giving He gas and N 2Gas be carrier vaporous be hydrogenated thing.
Gas diffusion layers 15 is to arrange for the reactive material of the stream that will be supplied to dividing plate 11 (gas or liquid) supplies with equably in the face of catalyst layer, uses carbon paper or carbon cloth etc. to have the matrix of air permeability.Particularly preferably these matrixes being carried out preventing hydration processes.
Gasket 16 is insulativity, particularly with respect to hydrogen or be hydrogenated thing, organic hydride has patience, as long as be the material that sees through less and keep stopping property of these materials, can enumerate such as isoprene-isobutylene rubber, Viton, EPDM rubber etc.
To supply with state as the toluene that is hydrogenated thing between anode-cathode during on load voltage in the antianode side for feedwater or water vapour, anticathode side, the electric decomposition reaction of the water of generation (1) formula in anode.The proton that electric decomposition reaction by (1) formula produces moves to negative electrode 14 via solid polyelectrolyte membrane 12, and the addition reaction of hydrogen of (2) formula occurs in negative electrode, generates the methylcyclohexane as organic hydride.
H 2O→2H ＋＋1/2O 2＋2e - (1)
C 7H 8＋6H ＋＋6e -→C 7H 14 (2)
In the organic hydride device of present embodiment, see through the water resistance gear owing in solid polyelectrolyte membrane, form, therefore, the water of anode can not see through to negative electrode.Therefore, can generate organic hydride with high-level efficiency.
Fig. 2 represents the electrode part of the organic hydride material producing device of present embodiment.Fig. 2 represents that observing in being formed with through the table of the solid polyelectrolyte membrane 21 on water blocking layer 27 two sides from cathode side is formed with the orthographic plan of the MEA of cathode catalyst layer 22, anode catalyst layer 23, sectional view and the enlarged view of D-E part the orthographic plan.
Shown in the D-E sectional view, the negative electrode of MEA and anode as the catalyst layer of densification in the up and down formation that is formed with through the solid polyelectrolyte membrane 21 on water blocking layer 27.Shown in enlarged view F, cathode catalyst layer 22 has supported catalyst metal 24 in support of the catalyst 25, and support of the catalyst 25 utilizes solid macromolecule electrolyte 26 bonding each other.Catalyst metal 24 has via support of the catalyst 25 interconnective network structures, forms the electron channel that needs in the reaction of (2).In addition, the solid macromolecule electrolyte 26 in the catalyst layer has the network structure of connection similarly, forms the proton channel that needs in the reaction of (2).
The enterprising column electrode reaction of the three phase boundary that metal catalyst 24 on support of the catalyst 25 contacts with ionogen and reactive material.In the electrode of present embodiment, utilize solid macromolecule electrolyte 26 to form proton channel, so, with in the solid polyelectrolyte membrane 21 direct-connected metal catalysts 24 also do not forming three phase boundary, therefore, many metal catalysts become the structure that can help electrode reaction.
In the electrode of the organic hydride material producing device of present embodiment, form at solid polyelectrolyte membrane and to see through water blocking layer 27, can prevent that therefore the water of anode from seeing through to negative electrode.Therefore, can generate organic hydride with high-level efficiency.
Fig. 3 represents the structure of the electrode of prior art.In electrode shown in Figure 3, directly form the support of the catalyst 35 that supports metal catalyst 34 on the surface of solid polyelectrolyte membrane 31.In the electrode structure of prior art, the metal catalyst 34 that helps electrode reaction only for and the direct-connected part of dielectric film, three phase boundary is few, helps the catalyzer that reacts restricted.In addition, can think that the formation of the network structure of catalyzer is also few, resistance raises.
In addition, Fig. 3 represents the structure of the electrode of prior art.In electrode shown in Figure 3, for the surface at solid polyelectrolyte membrane 31 supports the support of the catalyst 35 of catalyst metal 34 and the structure that solid macromolecule electrolyte 36 mixes.In the prior art, the water of anode sees through has the water 37 that sees through of solid polyelectrolyte membrane 31 to be present in cathode catalyst layer.Water and toluene etc. are hydrogenated thing for mutually insoluble, do not mix.Therefore, water is present in the situation of cathode catalyst layer 32, utilizes this water resistance to hinder to the toluene of catalyzer and supplies with.Its result can think that not supplying with toluene etc. and be hydrogenated on the catalyst metal 38 of thing be not addition reaction of hydrogen, occurs but produce hydrogen by following (3) formula.
2H ＋＋2e -→H 2 (3)
Therefore, in the electrode of prior art, owing to do not occur to exist to the catalyzer of the addition reaction of hydrogen that is hydrogenated thing, therefore limit organic hydride and generate, its result thinks, the energy efficiency step-down.
About MEA of the present invention, can make of following method.At first, make the solvent and the well-mixed cathod catalyst slurry that add the carrier, solid macromolecule electrolyte and the dissolved solids polymer electrolyte that support catalyst metal, and the solvent and the well-mixed anode catalyst slurry that add catalyst metal, solid macromolecule electrolyte and dissolved solids polymer electrolyte.Utilize spray-drying process etc. to spray at stripping films such as fluorinated ethylene propylene (PTFE) films respectively in these slurries, carry out drying and make solvent evaporation at 80 ℃, form negative electrode and anode catalyst layer.Then, these negative electrodes and anode catalyst layer are formed with through the solid polyelectrolyte membrane on water blocking layer and utilize pressure sintering to engage in the center clamping, peel stripping film (PTFE), thus, can make MEA of the present invention.
In addition, other example as MEA making of the present invention, by utilizing spray-drying process etc. being formed with the solid polyelectrolyte membrane that directly sees through the water blocking layer catalyst pulp of spraying, these catalyst pulps are solvent and the well-mixed anode catalyst slurries that add solvent and the well-mixed cathod catalyst slurry of the carrier, solid macromolecule electrolyte and the dissolved solids polymer electrolyte that support above-mentioned catalyst metal and add catalyst metal, solid macromolecule electrolyte and dissolved solids polymer electrolyte.
As the organic polymer that consists of solid polyelectrolyte membrane, can use in perfluorocarbon sulfonic acid or polystyrene and polyetherketone, polyether-ether-ketone, polysulfones, polyethersulfone, other engineering plastic materials, mix or chemically the protons such as bonding sulfonic group, phosphonate group, carboxyl supply with bodies and immobilized materials.In addition, in above-mentioned materials, also preferably by making crosslinking structure or the partially fluorinated stability of material that improves.In addition, also can use the composite electrolyte membrane of organic polymer and metal oxide hydrate etc.
In addition, as stopping the layer that sees through water, the layer of block water gets final product so long as make hydrogen ion see through also.For example, can consider the inorganicss such as palladium or palldium alloy.As carrying out alloyed metal (AM) with palladium, can enumerate: the transition metal such as Rh, Cu, Co, Ir, Ag.In addition, rare earth metals such as the alkaline-earth metal such as Mg, Ca, La, Nd etc. can be considered have various with the Pd alloyed metal (AM).In addition, as stopping the layer that sees through water, can enumerate hydrogen storage alloy.As this hydrogen storage alloy, can enumerate: Ti-Fe is that metal, V are that metal, Mg system close, Ca is alloy.In addition, also can enumerate take the alloy of the transition element such as Ti, Mn, Zr, the Ni AB2 shaped metal as the basis.Perhaps enumerate with LaNi 5, ReNi 5Contain the alloy of transition element (Ni, Co, Al etc.) 5 atoms with catalytic effect in rare earth element, with respect to Nb, Zr1 atom and be the AB5 type on basis.In addition, also can use the protons such as sulfonic group, phosphonate group, carboxyl to supply with the few organic polymer of body.Supply with the few organic polymer of body as proton, the ion exchange capacity of preferred every dry weight is the following organic polymer of 0.75meq/g.
See through the water blocking layer and both can form on the solid polyelectrolyte membrane surface, in addition, also can in solid polyelectrolyte membrane, form.The present invention stops that by formation the layer that sees through water limits the transit dose of water.Move owing to seeing through the water associated proton, therefore, according to the current value that flows, it measures different.As containing the membrane-electrode assembly that sees through the water blocking layer of the present invention, at current density value 60mA/cm 2The time, the transit dose of water is preferably 30 μ g/cm 2Below the sec.Use the aforesaid water blocking layer that sees through in the mode that satisfies this condition.
The solid macromolecule electrolyte that contains in catalyst layer can be enumerated: to use the macromolecular material, for example perfluorocarbon that show proton conductive be sulfonate resin and be that sulfonate resin is as the sulfonated of representative or carried out the Sulfonated fluorine based polymer of alkylidene group and polystyrene type with poly-perfluoro styrene.In addition, can be set forth in the material that imports the protons such as sulfonic group is arranged supply body in polysulfones, polyether sulfone, polyether ethersulfone class, polyetheretherketone, the hydrocarbon system polymkeric substance.
On the other hand, in the catalyst metal that uses in the present invention, can use the catalystic material with hydrogen addition, the alloy catalyst that uses metals such as Ni, Pd, Pt, Rh, Ir, Re, Ru, Mo, W, V, Os, Cr, Co, Fe and these metals.With regard to the hydrogen addition catalyst, because therefore the cost degradation that the minimizing of catalyst metal causes and the increase of reaction table area preferably carry out corpusculed.In addition, in order to prevent the minimizing of the specific surface area that atomic cohesion causes, can support in carrier.The manufacture method of catalyzer is that coprecipitation method, thermal decomposition method, electroless plating cover method etc., is not particularly limited.
As the cathod catalyst Substrates, can use alumina silicates such as the carbon materials such as gac, carbon nanotube, graphite and silicon-dioxide, aluminum oxide, zeolite etc.On the other hand, when having carbon material in anode, possible carbon is oxidized, not preferred.Therefore, as the anode catalyst Substrates, can use the non-carbon materials such as alumina silicate such as silicon-dioxide, aluminum oxide, zeolite.Perhaps, in anode, can not use Substrates and only use catalyst metal.
As being hydrogenated thing, can use benzene,toluene,xylene, sym-trimethylbenzene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthroline and their alkyl to replace any or a plurality of material that is mixed into of body.By addition hydrogen on these carbon two keys each other, can storage of hydrogen.
Below, use embodiment at length to describe to the present invention.In addition, the present invention is not limited to following embodiment.
Embodiment 1
As solid polyelectrolyte membrane, use the surface physics of Nafion (society of Du Pont system) be bonded with the film of the palladium film of 25 μ m.The palladium film is adhered to anode-side surface.
Cathode catalyst layer use spraying machine directly on above-mentioned solid polyelectrolyte membrane the coating catalyst slurries form.By following order coating cathode catalyst layer on above-mentioned solid polyelectrolyte membrane.
Place on the hot plate of substrate by the Nafion that will be bonded with the palladium film and attract to fix.At this, the Temperature Setting of hot plate is 50 ℃.
Then, shelter from it, with spraying machine (promise letter society system) coating cathode catalyst slurry.As the cathod catalyst slurries, use platinum is supported C catalyst TEC10E70TPM (Tanaka's precious metal system) and water, 5wt%Nafion solution, 221 solution (1-propyl alcohol: the solution that the solution of 2-propyl alcohol: water=2:2:1) is mixed into by the weight ratio of 2:1.2:5.4:10.6.The coating condition is set as hydraulic pressure 0.01MPa, eddy current and presses 0.15MPa, atomizing to press 50 ℃ of 0.15MPa, rifle/substrate distance 60mm, substrate temperature.Cathode catalysis dosage is set as 0.4mgPtcm -2
Form cathode catalyst layer on the Nafion surface that is bonded with the palladium film.In addition, form anode catalyst layer at the back side of Nafion.Anode catalyst layer utilizes transfer printing to form.At first, make the anode catalyst slurries.As the anode catalyst slurries, use the solution that platinum black HiSPEC1000 (ten thousand rich systems are believed in the village) and 5wt%Nafion solution, 221 solution are mixed into by the weight ratio of 1:1.11:2.22.Utilize applicator to apply at the sheet material of Teflon (registered trademark) it.Form the anode catalyst layer of the sheet material that is coated on Teflon (registered trademark) on the Nafion surface that is bonded with the palladium film with the hot transfer printing that utilizes hot pressing (the テ ス タ ー industry SA-401-M processed of society).Hot pressing pressure is set as 37.2kgfcm -2, hot pressing temperature is set as 120 ℃, and hot pressing time is set as 2 minutes.Anode-catalyzed dosage is set as 4.8mgPtcm -2
In the organic hydride material producing device of Fig. 1, insert the MEA that makes.Cell resistance is 200m Ω.
Supply with under the toluene that is hydrogenated thing, antianode is supplied with pure water with 5ml/min the state with 0.03ml/min and 0.1ml/min at anticathode, between anode-cathode, apply voltage 2.2V.With regard to battery temperature, carry out at 25,40,60,80 ℃.
Fig. 4 represents the current value with respect to battery temperature.Battery temperature more raises, and current density is larger.It can be thought because temperature more raises, and gets over respect to the reactive behavior of the electrode catalyst that reacts to raise.In addition, be in the situation of 0.03ml/min and 0.1ml/min in the feed rate of toluene, become the result of the current flowing of roughly the same degree.
Reclaim negative electrode liquid behind the addition reaction of hydrogen, when analyzing with vapor-phase chromatography, under any condition, all see the generation as the methylcyclohexane of organic hydride.Show: utilize electrode of the present invention, in the addition reaction of hydrogen of toluene, generate methylcyclohexane.In addition, in the recovery liquid from negative electrode, do not contain water.Can think, utilize the palladium film that is formed at the Nafion surface, can prevent that the water of anode from seeing through.
Toluene when Fig. 5 represents by addition reaction of hydrogen is to the transformation efficiency of methylcyclohexane.Transformation efficiency utilizes following formula to be calculated by the peak area of vapor-phase chromatography.
The peak area of transformation efficiency=methylcyclohexane/(peak area of the peak area+methylcyclohexane of toluene) * 100 (4)
Detect methylcyclohexane under 25 ℃ of battery temperatures, 40 ℃, 60 ℃, 80 ℃ arbitrary temperature, battery temperature more raises, and transformation efficiency more increases.In addition, compare with the feed rate 0.1ml/min of toluene, the side of 0.03ml/min becomes the high result of transformation efficiency.It can think because, the feed speed of toluene is less, the chance that toluene contact with electrode catalyst is got over increase.Transformation efficiency is the highest under this condition, and in 80 ℃ of toluene flux 0.03ml/min of battery temperature, transformation efficiency is 68%.
[comparative example 1]
As solid polyelectrolyte membrane, use Nafion to make MEA.Other manufacturing conditions is set as identical.
Insert the MEA that makes in the organic hydride material producing device of Fig. 1, measure cell resistance, the result is 250m Ω.
Under condition similarly to Example 1, carry out the addition reaction of hydrogen test to toluene.Battery temperature 25,40,60,80 ℃, on load voltage 2.2V between anode-cathode.Fig. 6 represents the current value with respect to battery temperature.Battery temperature more raises, and electric current is more mobile, but compares with embodiment 1, is the low result of current density.
Negative electrode liquid behind the recovery addition reaction of hydrogen when analyzing with vapor-phase chromatography, is all seen the generation as the methylcyclohexane of organic hydride under any condition.But the liquid effluent that reclaims from negative electrode all is separated into 2 phases under arbitrary battery temperature.Think that upper phase section is toluene and methylcyclohexane, lower phase section is water.Temperature more raises, and the ratio of the water of lower phase section more increases.This water thinks that the water of anode arrives the water of negative electrode through dielectric film.Can think that particularly battery temperature more raises and electric current more increases, the proton from anode to negative electrode moves more and increases, and the movement of the water that accompanies with it also more increases.
Fig. 7 represents the transformation efficiency from toluene to methylcyclohexane.Battery temperature more raises, and transformation efficiency more raises, but compares with embodiment 1, becomes little result.And can think, see through water and be present in cathode catalyst layer, utilize this water resistance to hinder to the toluene of catalyzer and supply with.Its result causes hydrogen generation etc. at the catalyzer of not supplying with toluene, does not cause the generation of methylcyclohexane, the transformation efficiency step-down.
Embodiment 2
Use Nafion as dielectric film, at the S-PES of its surface bonding 10 μ m (Sulfonated-Poly Ether Sulfone).S-PES has sulfonic organic polymer for importing at polyethersulfone.Use the loading capacity of every dry weight to be the organic polymer of 0.6meq/g.With regard to other MEA manufacturing conditions, with embodiment 1 the same terms under carry out.
Insert the MEA that makes in the organic hydride material producing device of Fig. 1, measure cell resistance, the result is 350m Ω.Under condition similarly to Example 1, carry out the addition reaction of hydrogen test to toluene.Battery temperature 25,40,60,80 ℃, between anode-cathode on load voltage 2.2V.
Negative electrode liquid behind the recovery addition reaction of hydrogen when analyzing with vapor-phase chromatography, is all seen the generation as the methylcyclohexane of organic hydride under any condition.In addition, although the negative electrode discharge opeing is few with comparative example 1 phase specific water,, all be separated into 2 phases.This can think that in S-PES, fully not anti-sealing sees through.But when comparing with the situation that the Nafion monomer of comparative example 1 is used for dielectric film, water sees through and tails off, and therefore, becomes the high result of transformation efficiency.The highest transformation efficiency is transformation efficiency 58% in 80 ℃ of battery temperatures, toluene flux 0.03ml/min.
The explanation of symbol
11 ... dividing plate, 12,21,31 ... solid polyelectrolyte membrane, 13,23,33 ... anode catalyst layer, 14 ... cathode catalyst layer, 15 ... gas diffusion layers, 16 ... gasket, 22,32 ... cathode catalyst layer, 24,34 ... catalyst metal, 25,35 ... support of the catalyst, 26,36 ... solid macromolecule electrolyte, 27 ... see through the water blocking layer, 37 ... see through water, 38 ... the catalyst metal that is helpless to react

Claims (12)

1. the organic hydride material producing device is characterized in that,
Have: with the mode of the solid polyelectrolyte membrane of clamping proton conductive dispose the anode catalyst layer of cathode catalyst layer that reduction is hydrogenated thing and oxidizing water membrane-electrode assembly, described cathode catalyst layer is supplied with the parts that are hydrogenated thing and to the parts of described anode catalyst layer for feedwater or water vapour
Surface or the inner layer that is formed with block water at described solid polyelectrolyte membrane.
2. organic hydride material producing device as claimed in claim 1 is characterized in that, the layer of described block water is palladium or palldium alloy.
3. organic hydride material producing device as claimed in claim 1 is characterized in that, the layer of described block water is the following organic polymer of 0.75meq/g for the ion exchange capacity of every dry weight.
4. organic hydride material producing device as claimed in claim 1 is characterized in that, described cathode catalyst layer comprises catalyst metal and supports the carrier of described catalyst metal,
Described anode catalyst layer only comprises catalyst metal or comprises catalyst metal and support the non-carbon support of described catalyst metal.
5. organic hydride material producing device as claimed in claim 1 is characterized in that, the described thing that is hydrogenated is benzene,toluene,xylene, sym-trimethylbenzene, naphthalene, methylnaphthalene or anthracene.
6. organic hydride material producing device as claimed in claim 1, it is characterized in that, described cathode catalyst layer comprises catalyst metal and supports the carrier of described catalyst metal, and described catalyst metal comprises platinum, ruthenium, rhodium, palladium, iridium, molybdenum, rhenium, tungsten and contains the alloy of at least a portion of these metals.
7. organic hydride material producing device, it has:
With the mode of the solid polyelectrolyte membrane of clamping proton conductive dispose the anode catalyst layer of cathode catalyst layer that reduction is hydrogenated thing and oxidizing water membrane-electrode assembly,
Be disposed at the surface of described cathode catalyst layer and described anode catalyst layer gas diffusion layers,
With the surface that is connected described gas diffusion layers, be formed with the dividing plate of stream ditch at the face that is connected with described gas diffusion layers,
It is characterized in that, at the surperficial or inner layer that is formed with block water of described solid polyelectrolyte membrane.
8. organic hydride material producing device as claimed in claim 7 is characterized in that, the layer of described block water is palladium or palldium alloy.
9. organic hydride material producing device as claimed in claim 7 is characterized in that, the layer of described block water is the following organic polymer of 0.75meq/g for the ion exchange capacity of every dry weight.
10. organic hydride material producing device as claimed in claim 7 is characterized in that, supply with from the stream ditch of the dividing plate of described cathode catalyst layer side and be hydrogenated thing, from the stream ditch of the dividing plate of described anode catalyst layer side for feedwater or water vapour.
11. organic hydride material producing device as claimed in claim 7 is characterized in that, the described thing that is hydrogenated is benzene,toluene,xylene, sym-trimethylbenzene, naphthalene, methylnaphthalene or anthracene.
12. organic hydride material producing device as claimed in claim 7, it is characterized in that, described cathode catalyst layer comprises catalyst metal and supports the carrier of described catalyst metal, and described catalyst metal comprises platinum, ruthenium, rhodium, palladium, iridium, molybdenum, rhenium, tungsten and contains the alloy of at least a portion of these metals.
CN2011800400333A 2010-09-30 2011-08-18 Device for manufacturing organic hydride Pending CN103069051A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010-220254 2010-09-30
JP2010220254A JP2012072477A (en) 2010-09-30 2010-09-30 Device for manufacturing organic hydride
PCT/JP2011/068660 WO2012043086A1 (en) 2010-09-30 2011-08-18 Device for manufacturing organic hydride

Publications (1)

Publication Number Publication Date
CN103069051A true CN103069051A (en) 2013-04-24

Family

ID=45892561

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800400333A Pending CN103069051A (en) 2010-09-30 2011-08-18 Device for manufacturing organic hydride

Country Status (4)

Country Link
US (1) US20140144774A1 (en)
JP (1) JP2012072477A (en)
CN (1) CN103069051A (en)
WO (1) WO2012043086A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107002262A (en) * 2014-11-10 2017-08-01 国立大学法人横浜国立大学 Oxygen anode
CN107075700A (en) * 2014-11-21 2017-08-18 国立大学法人横浜国立大学 Organic hydride material producing device and the manufacture method using its organic hydride
CN109996905A (en) * 2016-11-15 2019-07-09 国立大学法人横浜国立大学 The manufacturing method of organic hydride material producing device and organic hydride

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013084360A (en) * 2011-10-06 2013-05-09 Hitachi Ltd Membrane-electrode assembly, and device for organic hydride production
WO2014156125A1 (en) 2013-03-29 2014-10-02 Ｊｘ日鉱日石エネルギー株式会社 Electrochemical reduction device and production method for hydrogenated product of aromatic compound
EP2980276B1 (en) * 2013-03-29 2019-05-08 JX Nippon Oil & Energy Corporation Electrochemical reduction device and production method for hydrogenated product of aromatic compound
FR3009834B1 (en) * 2013-08-23 2015-08-28 Commissariat Energie Atomique ACTIVE LAYER / MEMBRANE ASSEMBLY FOR HYDROGEN PRODUCTION DEVICE AND ASSEMBLY COMPRISING SAID ASSEMBLY ADAPTED TO A POROUS CURRENT COLLECTOR AND METHOD FOR MANUFACTURING THE ASSEMBLY
EP3040449B1 (en) * 2013-08-30 2018-03-21 JX Nippon Oil & Energy Corporation Electrochemical reduction device
ES2727152T3 (en) 2014-03-28 2019-10-14 Yokohama National Univ Device for manufacturing organic hydride
JP6400410B2 (en) * 2014-09-25 2018-10-03 国立大学法人横浜国立大学 Electrolysis cell for organic chemical hydride production
KR101773969B1 (en) * 2016-11-11 2017-09-04 한국과학기술연구원 Electrochemical reaction cell enhancing reduction reaction
JP7115728B2 (en) * 2017-02-03 2022-08-09 国立大学法人 東京大学 Membrane electrode assembly
JP6882676B2 (en) * 2017-06-29 2021-06-02 富士通株式会社 Carbon dioxide reduction film, its manufacturing method, and carbon dioxide reduction device
CN107913653B (en) * 2017-12-26 2023-08-15 大连理工大学盘锦产业技术研究院 Electrochemical hydrogenation device and method
JPWO2022118695A1 (en) * 2020-12-03 2022-06-09
CN113135614A (en) * 2021-03-10 2021-07-20 中国工程物理研究院材料研究所 Organic pollutant anodic oxidation treatment device based on proton exchange membrane

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789488A (en) * 1980-11-25 1982-06-03 Tokuyama Soda Co Ltd Electrolysis of organic compound
JPH02262543A (en) * 1988-02-29 1990-10-25 Nippon Shokubai Kagaku Kogyo Co Ltd Production of 1-aminoanthraquinones
JPH10195686A (en) * 1997-01-07 1998-07-28 Permelec Electrode Ltd Hydrogenating method and electrolytic cell
JP2003045449A (en) * 2001-08-01 2003-02-14 Masaru Ichikawa Chemical power generation/device for manufacturing organic hydride and chemical power generation/ manufacturing method for organic hydride
CN1731617A (en) * 2004-08-05 2006-02-08 株式会社日立制作所 Catalyst for fuel cell, membrane-electrode assembly, method of manufacturing the assembly, and fuel cell using the assembly
JP2009007647A (en) * 2007-06-29 2009-01-15 Hitachi Ltd Organic hydride manufacturing apparatus and distributed power supply and automobile using the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4223619B2 (en) * 1999-02-15 2009-02-12 ペルメレック電極株式会社 Electrolytic cathode and electrolytic cell equipped with the cathode
US6949178B2 (en) * 2002-07-09 2005-09-27 Lynntech, Inc. Electrochemical method for preparing peroxy acids
EP1788654B1 (en) * 2004-09-09 2011-11-16 Asahi Kasei Chemicals Corporation Solid polymer electrolyte membrane and method for producing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789488A (en) * 1980-11-25 1982-06-03 Tokuyama Soda Co Ltd Electrolysis of organic compound
JPH02262543A (en) * 1988-02-29 1990-10-25 Nippon Shokubai Kagaku Kogyo Co Ltd Production of 1-aminoanthraquinones
JPH10195686A (en) * 1997-01-07 1998-07-28 Permelec Electrode Ltd Hydrogenating method and electrolytic cell
JP2003045449A (en) * 2001-08-01 2003-02-14 Masaru Ichikawa Chemical power generation/device for manufacturing organic hydride and chemical power generation/ manufacturing method for organic hydride
CN1731617A (en) * 2004-08-05 2006-02-08 株式会社日立制作所 Catalyst for fuel cell, membrane-electrode assembly, method of manufacturing the assembly, and fuel cell using the assembly
JP2009007647A (en) * 2007-06-29 2009-01-15 Hitachi Ltd Organic hydride manufacturing apparatus and distributed power supply and automobile using the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107002262A (en) * 2014-11-10 2017-08-01 国立大学法人横浜国立大学 Oxygen anode
US10889903B2 (en) 2014-11-10 2021-01-12 National University Corporation Yokohama National University Oxygen-generating anode
CN107075700A (en) * 2014-11-21 2017-08-18 国立大学法人横浜国立大学 Organic hydride material producing device and the manufacture method using its organic hydride
CN107075700B (en) * 2014-11-21 2019-04-19 国立大学法人横浜国立大学 The manufacturing method of organic hydride material producing device and the organic hydride using it
US11035045B2 (en) 2014-11-21 2021-06-15 National University Corporation Yokohama National University Apparatus for producing organic hydride and method for producing organic hydride using same
CN109996905A (en) * 2016-11-15 2019-07-09 国立大学法人横浜国立大学 The manufacturing method of organic hydride material producing device and organic hydride
CN109996905B (en) * 2016-11-15 2021-05-11 国立大学法人横浜国立大学 Organic hydride manufacturing device and organic hydride manufacturing method
US11519082B2 (en) 2016-11-15 2022-12-06 National University Corporation Yokohama National University Organic hydride production apparatus and method for producing organic hydride

Also Published As

Publication number Publication date
US20140144774A1 (en) 2014-05-29
JP2012072477A (en) 2012-04-12
WO2012043086A1 (en) 2012-04-05

Similar Documents

Publication Publication Date Title
CN103069051A (en) Device for manufacturing organic hydride
JP5705214B2 (en) Organic hydride production equipment
EP3031955B1 (en) Hydrogen refining pressure-boosting device
EP1171384B1 (en) Proton conducting membrane using a solid acid
KR101417354B1 (en) Film electrode-bond and organic hydride manufacturing apparatus
EP2660356A1 (en) Organic compound hydrogenation device and hydrogenation method
KR20170085591A (en) Apparatus for producing organic hydride and method for producing organic hydride using same
JP7410724B2 (en) Organic hydride production equipment and organic hydride production method
JP6799368B2 (en) Equipment and methods combined with fuel cells without reformer
WO2018037774A1 (en) Cathode, electrolysis cell for producing organic hydride, and organic hydride production method
US20220333257A1 (en) Organic hydride production device
WO2023239426A2 (en) Systems and methods for ethylene production
Ju et al. Methanol-water co-electrolysis for sustainable hydrogen production with PtRu/C-SnO 2 electro-catalyst
CN101578726A (en) Fuel cell catalyst, fuel cell cathode and polymer electrolyte fuel cell including the same
WO2014192089A1 (en) Device for producing organic hydride
WO2003065490A2 (en) A co-catalyst proton exchange membrane fuel cell utilizing borohydride fuels
Aykut et al. The role of the EHC system in the transition to a sustainable energy future: A review
Uhm et al. Effective Electrode Structure for the Stability of Alkaline Hydrazine Fuel Cells
WO2022091360A1 (en) Device for manufacturing organic hydride
KR20190125885A (en) Electrochemical dehydrogen reactor and method of dehydrogenation using the same
WO2022091361A1 (en) Organic hydride production apparatus, and method for forming cathode catalyst layer
WO2024048340A1 (en) Apparatus for producing organic hydride and method for producing organic hydride
TWI682068B (en) Liquid-gas cycling system and multifunctional water electrolysis device
JP7105421B2 (en) Epoxy Derivative Production Apparatus, Epoxy Derivative Production Method, and Epoxy Derivative Production Apparatus Production Method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130424