CN104204304A - Electrochemical reduction device, and method for producing hydrogenated product of aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound - Google Patents
Electrochemical reduction device, and method for producing hydrogenated product of aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound Download PDFInfo
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- CN104204304A CN104204304A CN201380017673.1A CN201380017673A CN104204304A CN 104204304 A CN104204304 A CN 104204304A CN 201380017673 A CN201380017673 A CN 201380017673A CN 104204304 A CN104204304 A CN 104204304A
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Abstract
This electrochemical reduction device (10) is provided with an electrode unit (100), a power control unit (20), an organic matter storage tank (30), a water storage tank (40), a steam separator (50) and a control unit (60). This electrode unit (100) has an electrolyte film (110), a reduction electrode (120) and an oxygen-generating electrode (130). The electrolyte film (110) is formed from ionomers. The reduction catalyst used in the reduction electrode (120) contains at least one of Pt and Pd. This oxygen-generating electrode (130) contains a noble metal oxide catalyst such as RuO2, IrO2, etc. Representing the potential in the reversible hydrogen electrode as VHER, the standard redox potential of an aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound as VTRR, and the potential of the reduction electrode (120) as VCA, the control unit (60) controls the power control unit (20) such that the relation VHER-20mV <= VCA<= VTRR is satisfied.
Description
Technical field
The present invention relates to the apparatus and method that arene compound or nitrogen heterocyclic ring aromatics are carried out to electrochemically hydrogenation.
Background technology
The cyclic organic compounds of known hexanaphthene, perhydronaphthalene and so on can obtain efficiently by using hydrogen that corresponding arene compound (benzene, naphthalene) is carried out to core hydrogenation.Reaction conditions for this reaction high temperature and high pressure is necessary, is therefore unaccommodated with little～middle scale manufacture.On the other hand, the electrochemical reaction of known employing electrolyzer, owing to can making water as hydrogen source, therefore there is no need to process gasiform hydrogen, and also under gentleer (DEG C left and right, normal temperature～200, normal pressure), carries out at reaction conditions.
(prior art document)
(patent documentation)
Patent documentation 1: TOHKEMY 2003-045449 communique
Patent documentation 2: TOHKEMY 2005-126288 communique
Patent documentation 3: TOHKEMY 2005-239479 communique
(non-patent literature)
(non-patent literature 1) river, city victory, J.Jpn.Inst.Energy, 85 volumes, 517 (2006)
Summary of the invention
As the example that the arene compound of toluene etc. is carried out to electrochemically hydrogenation, report that will be gasificated into gasiform toluene delivers to reducing electrode side, with with the similar structure of water electrolysis, do not obtain technology (with reference to non-patent literature 1), the electrode area amount that can transform per hour (current density) as the methylcyclohexane of core hydride through hydrogen state little, be therefore difficult to, industrial, arene compound is carried out to core hydrogenation.
The present invention completes in view of the foregoing problems, and its object is to provide the technology that arene compound or nitrogen heterocyclic ring aromatics can be carried out to the hydrogenation of electrochemistry core efficiently.
A mode of the present invention is electrochemical reduction device.This electrochemical reduction device, is characterized in that possessing: comprise dielectric film, reducing electrode and oxygen the electrode unit forming with electrode occurs; Between occurring with electrode, reducing electrode and oxygen applies the electric power control part of voltage Va; And control part, wherein, described dielectric film has ionic conductivity, described reducing electrode is arranged on a side of dielectric film and contains and is useful on the reducing catalyst of arene compound core hydrogenation, there is to be arranged on electrode the opposite side of dielectric film in described oxygen, the current potential of reversible hydrogen electrode is being labeled as V by described control part
hER, arene compound standard oxidationreduction potential be labeled as V
tRR, reducing electrode current potential be labeled as V
cAtime, to meet V
hER-arbitrarily selectedly allow current potential≤V
cA≤ V
tRRthe mode of relation is controlled electric power control part.Current potential of the present invention refers to the true electropotential with respect to reference electrode current potential.Therefore, for example, in the time that existence comes from resistance, the ohmic loss of various electrical connections etc. of dielectric film resistance, electrode catalyst layer, as described later in this wise, consider these factors, be necessary true electropotential to calculate correction.
In the electrochemical reduction device of aforesaid way, the selected current potential of allowing can be 20mV arbitrarily.In addition also possess: contact with dielectric film and remain reference electrode current potential V with reducing electrode and oxygen occur to configure isolator with electrode electricity
refreference electrode, the potential difference Δ V to reference electrode and reducing electrode
cAthe voltage detection department detecting, control part can be based on potential difference Δ V
cAwith reference electrode current potential V
ref, obtain the current potential V of reducing electrode
cA.Control part can be controlled, and voltage Va is changed, and makes the current potential V of reducing electrode
cAbecome the current potential of specialized range.Oxygen generation equilibrium potential when by the electrolysis of water is labeled as V
oERtime, control part is to meet Va>=(V
oER-V
cA) mode described electric power control part is controlled.Reference electrode can be configured in that side that is provided with described reducing electrode of dielectric film.
Other modes of the present invention are electrochemical reduction devices.This electrochemical reduction device, it is characterized in that, possess: comprise dielectric film, there is the multiple electrode units electrode unit aggregate that reciprocally electricity is connected in series forming with electrode in reducing electrode and oxygen, electric power control part and control part, described dielectric film has ionic conductivity, described reducing electrode is arranged on a side of dielectric film and contains and is useful on the reducing catalyst of arene compound core hydrogenation, there is to be arranged on electrode the opposite side of dielectric film in described oxygen, described electric power control part applies voltage VA between the positive terminal of electrode unit aggregate and negative terminal, the current potential of reversible hydrogen electrode is being labeled as V by described control part
hER, described arene compound standard oxidationreduction potential be labeled as V
tRR, each electrode unit the current potential of described reducing electrode be labeled as V
cAtime, to meet V
hER-arbitrarily selectedly allow current potential≤V
cA≤ V
tRRthe mode of relation is controlled described electric power control part.
In the electrochemical reduction device of aforesaid way, the selected current potential of allowing can be 20mV arbitrarily.Also possess: contact and with reducing electrode and oxygen, the reference electrode configuring isolator with electrode electricity occur with the dielectric film of any electrolyte layers contained in electrode unit aggregate; With the potential difference Δ V that detects reference electrode and reducing electrode
cAvoltage detection department, control part is based on potential difference Δ V
cAwith reference electrode current potential V
ref, can obtain the current potential V of described reducing electrode
cA.Control part can make voltage Va change, so that the current potential V of the reducing electrode of each electrode unit
cAbe controlled at the current potential of specialized range.In addition, the oxygen generation equilibrium potential when by the electrolysis of water is labeled as V
oERtime, control part is to meet VA>=(V
oER-V
cA) × N[N (more than 2) is the number of the electrode unit that is connected in series] mode electric power control part is controlled.What reference electrode can be configured in dielectric film is provided with that side of reducing electrode.Reference electrode can be in that side configuration that is provided with described reducing electrode of dielectric film.
Other modes of the present invention are preparation methods of the hydride of arene compound or nitrogen heterocyclic ring aromatics.The preparation method of the hydride of this arene compound or nitrogen heterocyclic ring aromatics, it is characterized in that, use the electrochemical reduction device of above-mentioned any mode, reducing electrode side at electrode unit imports arene compound or nitrogen heterocyclic ring aromatics, occur to pass into water or the gas of humidification by electrode side at oxygen, arene compound or the nitrogen heterocyclic ring aromatics of importing reducing electrode side are carried out to core hydrogenation.In the preparation method of which, the arene compound or the nitrogen heterocyclic ring aromatics that import reducing electrode side can be imported to reducing electrode side in temperature of reaction with liquid state.
It should be noted that, the invention of appropriately combined above-mentioned each key element is also contained in the invention scope that requires to protect through the patent application of this part.
invention effect
According to the present invention, arene compound or nitrogen heterocyclic ring aromatics can be carried out to the hydrogenation of the electrochemistry earth's core efficiently.
Brief description of the drawings
Fig. 1 is the mode chart that represents the schematic construction of the electrochemical reduction device of embodiment 1.
Fig. 2 is the figure of the schematic construction of the electrode unit that represents that the electrochemical reduction device of embodiment 1 has.
Fig. 3 is the schema that represents an example of the control of Electric potentials of the reducing electrode that adopts control part.
Fig. 4 is the chart that represents the current potential of reducing electrode and the relation of various current densities.
Fig. 5 is the mode chart that represents the schematic construction of the electrochemical reduction device of embodiment 2.
Fig. 6 is the mode chart that represents the schematic construction of the electrochemical reduction device of embodiment 3.
Embodiment
Referring to brief description of the drawings embodiments of the present invention.It should be noted that, in institute's drawings attached, to the additional same symbol of same structural element, suitably description thereof is omitted.
(embodiment 1)
Fig. 1 is the mode chart of the schematic construction of the electrochemical reduction device 10 of embodiment.Fig. 2 is the figure of the schematic construction of the electrode unit that represents that the electrochemical reduction device 10 of embodiment has.As shown in Figure 1, electrochemical reduction device 10 possesses electrode unit 100, electric power control part 20, organism store groove 30, water store groove 40, gas-water separation portion 50 and control part 60.
Electric power control part 20 is for example the DC/DC transmodulator that the output voltage of power supply is converted to assigned voltage.Cathode output end of electric power control part 20 is connected with the positive pole of electrode unit 100.Cathode output end of electric power control part 20 is connected with the negative pole of electrode unit 100.Thus, between occurring by electrode (positive pole) 130 and reducing electrode (negative pole) 120, the oxygen of electrode unit 100 applies the voltage of regulation.It should be noted that, the reference electrode input terminal of electric power control part 20 is connected with the reference electrode 112 arranging on dielectric film 110 described later, according to the instruction of control part 60, taking the current potential of reference electrode 112 as benchmark, determine the current potential of cathode output end and the current potential of cathode output end.It should be noted that, as power supply, can use the electricity from natural energy of sunlight, wind-force etc.The mode of cathode output end of control part 60 and the control of Electric potentials of cathode output end as described later.
Organism store groove 30 has been preserved aromatics.The aromatics using in present embodiment, be arene compound or the nitrogen heterocyclic ring aromatics that at least contains an aromatic nucleus, can enumerate benzene, naphthalene, anthracene, diphenylethane, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline 99.9, N-alkyl pyrroles (N-alkylpyrrole), N-alkyl indoles (N-alkylindole), N-alkyl diphenyl pyrroles (N-alkyldibenzopyrrole) etc.In addition, 1～4 hydrogen atom in the aromatic nucleus of above-mentioned aromatic hydrocarbon and nitrogen heterocyclic ring aromatics can be replaced by alkyl.Wherein, " alkyl " in above-mentioned aromatics is straight chained alkyl or the branched-chain alkyl of carbonatoms 1～6.For example, as alkylbenzene, can enumerate toluene, ethylbenzene etc., can enumerate dimethylbenzene, diethylbenzene etc. as dialkyl benzene, can enumerate sym-trimethylbenzene etc. as trialkyl benzene.As alkylnaphthalene, can enumerate methylnaphthalene.In addition, the aromatic nucleus of above-mentioned aromatic hydrocarbon and nitrogen heterocyclic ring aromatics can have 1～3 substituting group.It should be noted that, in the following description, sometimes the arene compound using in the present invention and nitrogen heterocyclic ring aromatics are called to " aromatics ".Aromatics is preferably liquid at normal temperatures.In addition, when mix in above-mentioned aromatics multiple use time, if as mixture liquid.According to this situation, can not heat, aromatics be supplied with to electrode unit 100 under liquid state to the processing of pressurization etc., therefore can realize the easy of electrochemical reduction device 10 structures.The concentration of the aromatic series carbide compound of liquid state is more than 0.1%, preferably more than 0.3%, more preferably more than 0.5%.
Be housed in aromatics in organism store groove 30 and supply with the reducing electrode 120 of electrode unit 100 by the 1st fluid Supplying apparatus 32.The 1st fluid Supplying apparatus 32, for example, can use various pumps or the natural downward flow type device etc. of toothed gear pump or cylinder formula pump etc.It should be noted that, can use the N-replacement of above-mentioned aromatics to replace aromatics.Between organism store groove 30 and the reducing electrode of electrode unit 100, circulating path is set, utilizes the aromatics of electrode unit 100 core hydrogenations and unreacted aromatics to be stored in organism store groove 30 via circulating path.The main reaction of carrying out in the reducing electrode 120 of electrode unit 100 does not produce gas, in the time producing hydrogen by product, at circulating path, gas-liquid separation mechanism can be set midway.
Ion exchanged water, pure water etc. (being designated hereinafter simply as " water ") in water store groove 40, are preserved.The oxygen that the water of storage is supplied with electrode unit 100 by the 2nd fluid Supplying apparatus 42 in water store groove 40 occurs with electrode 130.The 2nd fluid Supplying apparatus 42, with the 1st fluid Supplying apparatus 32 similarly, for example can use various pumps or the natural downward flow type device etc. of toothed gear pump or cylinder formula pump etc.Between the oxygen of water store groove 40 and electrode unit 100 occurs with electrode, be provided with circulating path, in electrode unit 100, unreacted water is housed in water store groove 40 via circulating path.It should be noted that, unreacted water is being sent back to the gas-water separation portion 50 that is provided with in path of water store groove 40 from electrode unit 100 midway.Utilize gas-water separation portion 50, the oxygen that the electrolysis of water produces in electrode unit 100 separates and is discharged to system from water.
As shown in Figure 2, electrode unit 100 has dielectric film 110, reducing electrode 120, oxygen generation electrode 130, fluid diffusion layer 140a, 140b and barrier film 150a, 150b.It should be noted that, in Fig. 1, illustrated briefly electrode unit 100, omitted fluid diffusion layer 140a, 140b and barrier film 150a, 150.
Dielectric film 110 is formed by the material (ionomer) with proton-conducting, requires optionally proton conducting on the one hand, is suppressed on the other hand reducing electrode 120 and oxygen mixing or the diffusion with material between electrode 130 occurs.The thickness of dielectric film 110 is 5～300 μ m preferably, more preferably 10～150 μ m, most preferably 20～100 μ m.If the thickness of dielectric film 110 lower than 5 μ m, exists the barrier of dielectric film 110 to decline, easily produce to intersect and leak (crossleak).In addition, thicker than 300 μ m if the thickness of dielectric film 110 becomes, ion migration resistance becomes excessive, therefore not preferred.
The area resistance of dielectric film 110, the i.e. preferred 2000m Ω of the ion migration resistance cm of per unit geometric area
2below, more preferably 1000m Ω cm
2below, 500m Ω cm most preferably
2below.If the area resistance of dielectric film 110 is higher than 2000m Ω cm
2, proton-conducting deficiency.As the material (ionomer of cationic exchange type) with proton-conducting, can enumerate the perfluorinated sulfonic acid polymer of Nafion (registered trademark), Flemion (registered trademark) etc.Preferably 0.7～2meq/g of the ionomeric loading capacity of cationic exchange type (IEC), more preferably 1～1.2meq/g.When the ionomeric loading capacity of cationic exchange type is during lower than 0.7meq/g, it is not enough that ionic conductivity becomes.On the other hand, in the time that the ionomeric loading capacity of cationic exchange type is higher than 2meq/g, ionomer increases the solubleness of water, and therefore the intensity of dielectric film 110 becomes insufficient.
It should be noted that, occur to be provided with reference electrode 112 with the region of electrode 130 in the mode contacting with dielectric film 110 with oxygen in the reducing electrode 120 of leaving of dielectric film 110., reference electrode 112 occurs with electrode 130 electricity isolation with reducing electrode 120 and oxygen.Reference electrode 112 remains reference electrode current potential V
ref.As reference electrode 112, can enumerate standard hydrogen reducing electrode (reference electrode current potential V
ref=0V), Ag/AgCl electrode (reference electrode current potential V
ref=0.199V), and reference electrode 112 is not limited to these.It should be noted that, reference electrode 112 is preferably arranged on the surface of the dielectric film 110 of reducing electrode 120 sides.
Potential difference Δ V between reference electrode 112 and reducing electrode 120
cAdetected by voltage detection department 114.The potential difference Δ V being detected by voltage detection department 114
cAvalue input to control part 60.
Reducing electrode 120 is arranged on a side of dielectric film 110.Reducing electrode 120 is the reduction electrode catalyst layers that comprise the reducing catalyst for aromatics being carried out to core hydrogenation.In reducing electrode 120 use reducing catalyst be not particularly limited, for example by contain comprise in Pt, Pd at least one the 1st catalyst metal (precious metal) and be selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Sn, W, Re, Pb, Bi one or more the 2nd catalyst metal composition form.The form of this metal composites, be by the alloy of the 1st catalyst metal and the 2nd catalyst metal or, the intermetallic compound that formed by the 1st catalyst metal and the 2nd catalyst metal.The 1st catalyst metal is with respect to the preferably 10～95wt% of ratio of the total mass of the 1st catalyst metal and the 2nd catalyst metal, more preferably 20～90wt%, most preferably 25～80wt%.If the ratio of the 1st catalyst metal, lower than 10wt%,, from the angle of dissolubility resistent etc., may cause the decline of weather resistance.On the other hand, if the ratio of the 1st catalyst metal higher than 95wt%, the character of reducing catalyst is close to the independent character of precious metal, therefore electrode activity becomes insufficient.In the following description, sometimes the 1st catalyst metal and the 2nd catalyst metal are always called to " catalyst metal ".
Above-mentioned catalyst metal can be supported by conductive material (carrier).The specific conductivity of conductive material preferably 1.0 × 10
-2more than S/cm, more preferably 3.0 × 10
-2more than S/cm, most preferably 1.0 × 10
-1more than S/cm.When the specific conductivity of conductive material is lower than 1.0 × 10
-2when S/cm, cannot give enough electroconductibility.As this conductive material, can enumerate any one conductive material as principal constituent containing in porous carbon, porous metal, porous metal oxide compound.As porous carbon, can enumerate the carbon blacks such as Ketjen black (registered trademark), acetylene black, VULCAN (registered trademark).Through the preferred 100m of BET specific surface area of the porous carbon of determination of nitrogen adsorption
2more than/g, more preferably 150m
2more than/g, most preferably 200m
2more than/g.If the BET specific surface area of porous carbon is less than 100m
2/ g, becomes and is difficult to catalyst-loaded metal equably.For this reason, the utilization ratio on catalyst metal surface declines, and causes the decline of catalyst performance.As porous metal, for example, can enumerate platinum black, palladium black, separate out platinum into shred etc.As porous metal oxide compound, can enumerate the oxide compound of Ti, Zr, Nb, Mo, Hf, Ta, W.In addition, as the porousness conductive material for catalyst-loaded metal, can enumerate nitride, carbide, oxynitride, the carbonitride of the metals such as Ti, Zr, Nb, Mo, Hf, Ta, W, the carbonitride (following, to be generically and collectively referred to as porous metal carbonitride etc.) of partial oxidation.Through the preferred 1m of BET specific surface area of porous metal, porous metal oxide compound and the porous metal carbonitride etc. of determination of nitrogen adsorption
2more than/g, more preferably 3m
2more than/g, most preferably 10m
2more than/g.If the BET specific surface area of porous metal, porous metal oxide compound and porous metal carbonitride etc. is less than 1m
2/ g, becomes and is difficult to catalyst-loaded metal equably.Therefore, the utilization ratio on catalyst metal surface declines, and causes the decline of catalyst performance.
Catalyst metal is supported to the method on carrier, although according to the kind of the 1st catalyst metal, the 2nd catalyst metal, form different, but can adopt below make the 1st catalyst metal and the 2nd catalyst metal impregnated in carrier simultaneously time pickling process or the 1st catalyst metal be impregnated in after carrier, make the 2nd catalyst metal impregnated in the order pickling process of carrier.In the time of employing order pickling process, can make the 1st catalyst metal support after carrier, impose temporary transient thermal treatment etc., then make the 2nd catalyst metal support in carrier.After the dipping of the 1st catalyst metal and the 2nd catalyst metal completes, by heat treatment step carry out the alloying of the 1st catalyst metal and the 2nd catalyst metal, the forming of the intermetallic compound that formed by the 1st catalyst metal and the 2nd catalyst metal.
In reducing electrode 120, can add the material that the aforementioned electroconductive oxide, the carbon black etc. that are different from the conductive compound that has supported catalyst metal have electroconductibility.Thus, can increase the interparticle electrical conductance path of reducing catalyst, sometimes also can reduce the resistance of the unit geometric area of reducing catalyst layer.
In reducing electrode 120, can also contain the fluorine resin of tetrafluoroethylene (PTFE) as additive etc.
Reducing electrode 120 can contain and has proton-conducting ionomer.Reducing electrode 120, preferably contains the ionic conductivity material (ionomer) with above-mentioned dielectric film 110 with identical or similar structures with the mass ratio of regulation.Utilize this material, can make the ionic conductivity of reducing electrode 120 improve.Especially, in the time that support of the catalyst is porousness, reducing electrode 120 contains the ionomer with proton-conducting, can go far towards thus the raising of ionic conductivity.As the ionomer (cationic exchange type ionomer) with proton-conducting, can enumerate the perfluorinated sulfonic acid polymer such as Nafion (registered trademark), Flemion (registered trademark).Preferably 0.7～3meq/g of the ionomeric loading capacity of cationic exchange type (IEC), more preferably 1～2.5meq/g, most preferably 1.2～2meq/g.When catalyst metal was supported on porous carbon (carbon support) when upper, the mass ratio I/C of cationic exchange type ionomer (I)/carbon support (C) preferably 0.1～2, more preferably 0.2～1.5, most preferably 0.3～1.1.If, lower than 0.1, becoming, mass ratio I/C is difficult to obtain enough ionic conductivities.On the other hand, if mass ratio I/C is greater than 2, ionomer increases the cladding thickness of catalyst metal, is hindered thus as the aromatics of reactive material with contacting of catalyst activity site, or electronic conductivity reduces, thereby electrode activity declines.
In addition, in reducing electrode 120, contained ionomer preferably partly covers reducing catalyst.Thus, can be by the 3 required electrochemical reaction of reducing electrode 120 key elements (aromatics, proton, electronics) supply response field effectively.
Fluid diffusion layer 140a is layered on the face of reducing electrode 120 of dielectric film 110 opposition sides.Fluid diffusion layer 140a plays the aromatic liquid compounds of group of being supplied with by barrier film 150a described later is diffused into the function in reducing electrode 120 equably.As fluid diffusion layer 140a, for example, can use carbon paper, carbon cloth.
Barrier film 150a is layered on the face of fluid diffusion layer 140a of dielectric film 110 opposition sides.Barrier film 150a is formed by the erosion resistance alloy of carbon resin, Cr-Ni-Fe system, Cr-Ni-Mo-Fe system, Cr-Mo-Nb-Ni system, Cr-Mo-Fe-W-Ni system etc.At the face of the fluid diffusion layer 140a of barrier film 150a side and established the stream 152a of single or multiple ditch shapes.In stream 152a, pass into the aromatic liquid compounds of group of being supplied with by organism store groove 30, aromatic liquid compounds of group is from stream 152a infiltrate body diffused layer 140a.The form of stream 152a is not particularly limited, for example, can adopt linearity stream, bending stream.In addition, in the time that barrier film 150a is used for to metallic substance, barrier film 150a can be by structure spherical, that granular metal micropowder sintering forms.
There is to be arranged on electrode 130 opposite side of dielectric film 110 in oxygen.Oxygen occurs preferably to use and contain RuO with electrode 130
2, IrO
2at the electrode of metal oxide containing precious metals series catalysts.These catalyzer can be the metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ta, W, or dispersion supports or is coated in the metal base of metal wire, the silk screens etc. such as the alloy taking these metals as principal constituent.Especially, IrO
2be at high price, therefore work as IrO
2while use as catalyzer, metal base is carried out to thin film coated, can reduce thus manufacturing cost.
The oxygen that fluid diffusion layer 140b is layered in dielectric film 110 opposition sides occurs with on the face of electrode 130.Fluid diffusion layer 140b plays the water of being supplied with by barrier film 150b described later is diffused into the function of oxygen generation in electrode 130 equably.As fluid diffusion layer 140b, for example, can use carbon paper, carbon cloth.
Barrier film 150b is layered on the face of fluid diffusion layer 140b of dielectric film 110 opposition sides.Barrier film 150b is formed by erosion resistance alloys such as Cr/Ni/Fe system, Cr/Ni/Mo/Fe system, Cr/Mo/Nb/Ni system, Cr/Mo/Fe/W/Ni systems, or the material that these metallic surfaces are covered by oxide skin forms.At the face of the fluid diffusion layer 140b of barrier film 150b side and established single or multiple ditch shape stream 152b.In stream 152b, pass into the water of being supplied with by water store groove 40, water is from stream 152b infiltrate body diffused layer 140b.The form of stream 152b is not particularly limited, for example, can use linearity stream, bending stream.In addition, in the time that metallic substance is used for to barrier film 150b, barrier film 150b can be by structure spherical, that granular metal micropowder sintering forms.
In the present embodiment, can occur to supply with liquid water with electrode 130 to oxygen, but can use the gas (for example air) of humidification to replace liquid water.In this case, preferred room temperature～100 DEG C of the dew-point temperature of humidified gases, more preferably 50～100 DEG C.
The reaction of the electrode unit 100 while using toluene as aromatics is as follows.
There is the electrode reaction > with electrode in < oxygen
3H
2O→1.5O
2+6H
++6e
-：E
0＝1.23V
The electrode reaction > of < reducing electrode
Toluene+6H
++ 6e
-→ methylcyclohexane: E
0=0.153V (vsRHE)
; carrying out concurrently oxygen occurs by the electrode reaction of electrode and the electrode reaction of reducing electrode; occur to make proton Jie who produces through the electrolysis of water supply with reducing electrode by dielectric film 110 by the electrode reaction of electrode by oxygen, the electrode reaction of reducing electrode can be used in the core hydrogenation of aromatics.
Return to Fig. 1, control part 60 is when the current potential of reversible hydrogen electrode is labeled as to V
hER, aromatics standard oxidationreduction potential be labeled as V
tRR, reducing electrode 120 current potential be labeled as V
cAtime, to meet V
hER-20mV≤V
cA≤ V
tRRthe mode of relation is controlled electric power control part 20.If current potential V
cAlower than V
hER-20mV, the competition reacting with hydrogen, the reduction selectivity of aromatics becomes insufficient, therefore not preferred.On the other hand, if current potential V
cAhigher than standard oxidationreduction potential V
tRR, can not carry out with speed of response enough in practicality the core hydrogenation of aromatics, therefore not preferred.In other words, by by current potential V
cAbe set in the scope that meets above-mentioned relation formula, can make electrochemical reaction carry out at the two poles of the earth, can be in the core hydrogenation of industrial enforcement aromatics.
In addition, the reaction conditions when using electrochemical reduction device 10 by the hydrogenation of aromatics core can be enumerated condition below.Preferred room temperature～100 DEG C of temperature of electrode unit 100, more preferably 40～80 DEG C.If the temperature of electrode unit 100 is lower than room temperature, the carrying out of electrolytic reaction may be slack-off or need to be by the very macro-energy of the heat extraction of following this reaction to carry out and to produce, therefore preferred.On the other hand, if the temperature of electrode unit 100 is higher than 100 DEG C, occur with the boiling that produces water in electrode 130 at oxygen, in reducing electrode 120, organic vapour pressure uprises, and it is not preferred therefore all carrying out liquid reactive electrochemical reduction device 10 as the two poles of the earth.It should be noted that reduction electrode potential V
cAbe true electropotential, therefore exist and be different from the current potential V that actual observation arrives
cA_actualpossibility.In the various resistance components that exist in the electrolyzer using in the present invention, in the time that existence is equivalent to the part of ohmic resistance, using the resistance value of these overall per unit electrode areas as total ohmic resistance R
ohmic, utilize following formula to calculate true electropotential V
cA.
V
cA=V
cA_actual+ R
ohmic× J (current density)
As ohmic resistance, the electronics that the proton that can enumerate such as dielectric film moves resistance, electrode catalyst layer moves contact resistance on resistance, other circuit etc.
Herein, R
ohmiccan use the alternating current resistance mensuration of alternating current resistance method, fixed frequency to try to achieve as the actual resistance composition on equivalent circuit, if depend on the structure of electrolyzer, material system used, be almost used as the method for steady state value use in following control and also preferably obtain.
Fig. 3 is the schema that represents control of Electric potentials one example of the reducing electrode 120 of control part 60.Following as reference electrode 112, to adopt Ag/AgCl electrode (reference electrode current potential V
ref=0.199V) situation be example, the control of Electric potentials form of reducing electrode 120 is described.
First, set and meet V
hER-20mV≤V
cA≤ V
tRRv
cA(target value) (S10).In a mode, current potential V
cA(target value) is the value that is stored in advance the storeies such as ROM.In other modes, current potential V
cA(target value) set by user.
Then, utilize the potential difference Δ V of voltage detection department 114 to reference electrode 112 and reducing electrode 120
cAdetect (S20).
Next, control part 60 uses (formula) V
cA=Δ V
cA-V
ref=Δ V
cAthe current potential V of-0.199V to reducing electrode 120
cA(measured value) calculates (S30).
Then, judge current potential V
cAwhether (measured value) meets following formula (1) and following formula (2) (S40).
| current potential V
cA(measured value)-current potential V
cA(target value) |≤permissible value (1)
V
hER-20mV≤V
cA(measured value)≤V
tRR(2)
In above formula, permissible value is for example 1mV.
As current potential V
cAwhen (measured value) meets formula (1) and formula (2), the "Yes" that enters S40, finishes processing herein.On the other hand, as current potential V
cA(measured value) do not meet formula (1) and formula (2) both time, the "No" that enters S40, regulates (S50) to the voltage Va applying between reducing electrode 120 and oxygen occur with electrode 130.After regulating voltage Va, return to above-mentioned (S10) and process.
Herein, example voltage Va being regulated describes.For example,
As current potential V
cA(measured value)-current potential V
cAwhen (target value) > permissible value, the mode of control part 60 1mV so that voltage Va only rises transmits instruction to electric power control part 20.It should be noted that, improve voltage Va, result, even meet | current potential V
cA(measured value)-current potential V
cA(target value) | when≤permissible value, become V
cA(measured value) <V
hER-V
allow, now owing to not meeting formula (2), therefore, in processing below, control part 60 makes voltage Va decline 1mV.
On the other hand, as current potential V
cA(measured value)-current potential V
cAwhen (target value) <-permissible value,
Electric power control part 20 is sent in instruction by the mode of control part 60 1mV so that voltage Va only declines.It should be noted that, reduce voltage Va, even result meets | current potential V
cA(measured value)-current potential V
cA(target value) | the situation of≤permissible value, becomes V
cA(measured value) >V
tRR, now do not meet formula (2) yet, therefore, in processing below, voltage Va is improved 1mV by control part 60.In this wise, control part 60 the most at last voltage Va be adjusted to and meet formula (1) and formula (2).
It should be noted that, make the upper and lower value of voltage Va (regulation range) be not limited to 1mV.For example, in primary voltage Va regulates, make the regulation range of voltage Va and above-mentioned permissible value equal, in later for the second time voltage Va regulates, the regulation range of voltage Va can be set as to 1/4 of for example above-mentioned permissible value.Thus, can be by current potential V
cA(measured value) is more promptly adjusted into the scope that meets formula (1) and formula (2).
Control part 60, when by the electrolysis of water, oxygen generation equilibrium potential is labeled as V
oERtime, to meet Va>=(V
oER-V
cA) mode electric power control part 20 is controlled.Thus, there is the current potential V with electrode 130 in oxygen
aNremain on oxygen generation equilibrium potential V
oERabove.
(relation between toluene reduction characteristic and the current potential of reducing electrode)
Use the electrode battery of structure shown in table 1, the current potential that changes reducing electrode carries out the core hydrogenation of toluene.Fig. 4 represents the current potential of reducing electrode and the chart of various current density relations.It should be noted that, the quality of reducing catalyst metal is 0.5mg/cm
2.
(table 1)
Current density A shown in Fig. 4, current density B and current density C are as follows respectively.
Current density A: the overall current density that flows into electrode battery
Current density B: the growing amount backstepping by the quantitative methylcyclohexane such as gas-chromatography is calculated, the current density using in toluene reduction
Current density C: current density A-current density B (not for the reduction of toluene, being mainly used in the current density that hydrogen occurs)
In addition, the faradic efficiency shown in Fig. 4 is calculated by current density B/ current density A × 100 (%).
Confirmed as shown in Figure 4, the current potential of reducing electrode becomes current potential V
hER-20mV,, ratio-20mV is low, hydrogen generation increases, faradic efficiency declines 50%, therefore not preferred.
(embodiment 2)
Fig. 5 is the mode chart that represents the schematic construction of the electrochemical reduction device of embodiment 2.As shown in Figure 5, electrochemical reduction device 10 possesses electrode unit aggregate 200, electric power control part 20, organism store groove 30, water store groove 40, gas-water separation portion 50 and control part 60.Electrode unit aggregate 200 has multiple electrode units 100 and is connected in series the stepped construction forming.In present embodiment, the number N of electrode unit 100 is 5.It should be noted that, the structure of each electrode unit 100 is same with embodiment 1.In Fig. 5, electrode unit 100 omits diagram, has omitted fluid diffusion layer 140a, 140b and barrier film 150a, 150.
Cathode output end of the electric power control part 20 of present embodiment is connected with the positive terminal of electrode unit aggregate 200.On the other hand, the cathode output end of electric power control part 20 is connected with the negative terminal of electrode unit aggregate 200.Thus, between the positive terminal of electrode unit aggregate 200 and negative terminal, apply assigned voltage VA.It should be noted that, the reference utmost point input terminal of electric power control part 20 is connected with the reference electrode 112 arranging on the dielectric film 110 of aftermentioned specific electrode unit 100, taking the current potential of reference electrode 112 as benchmark, determine the current potential of cathode output end and the current potential of cathode output end.
Between organism store groove 30 and the reducing electrode 120 of each electrode unit 100, be provided with the 1st circulating path.In organism store groove 30, the aromatics of storage utilizes the 1st fluid Supplying apparatus 32 to supply with the reducing electrode 120 of each electrode unit 100.Specifically, form the pipe arrangement branch of the 1st circulating path in the downstream side of the 1st fluid Supplying apparatus 32, distribute and supply with aromatics to the reducing electrode 120 of each electrode unit 100.Through aromatics and the unreacted aromatics of each electrode unit 100 core hydrogenations, behind the pipe arrangement being communicated with organism store groove 30 interflow, be housed in organism store groove 30 via this pipe arrangement.
Between occurring with electrode 130, the oxygen of water store groove 40 and each electrode unit 100 is provided with the 2nd circulating path.The oxygen that the water of storage is supplied with each electrode unit 100 via the 2nd fluid Supplying apparatus 42 in water store groove 4 occurs with electrode 130.Specifically, in the downstream side of the 2nd fluid Supplying apparatus 42, form the pipe arrangement branch of the 2nd circulating path, the oxygen that water dispenser is supplied with each electrode unit 100 occurs with electrode 130.In each electrode unit 100, behind the pipe arrangement interflow that unreacted water is communicated with water store groove 40, be housed in water store groove 40 via this pipe arrangement.
At the dielectric film 110 of specific electrode unit 100, with embodiment 1 similarly, there is from reducing electrode 120 and oxygen the region separating with electrode 130, be provided with reference electrode 112 in the mode contacting with dielectric film 110.Specific electrode unit 100 can be any one in multiple electrode units 100.
Potential difference Δ V between reference electrode 112 and reducing electrode 120
cAdetected by voltage detection department 114.The potential difference Δ V being detected by voltage detection department 114
cAvalue input control portion 60.
Control part 60, when the current potential of reversible hydrogen electrode is labeled as to V
hER, aromatics standard oxidationreduction potential be labeled as V
tRR, each electrode unit 100 the current potential of reducing electrode 120 be labeled as V
cAtime, to meet V
hER-20mV≤V
cA≤ V
tRRthe mode control electric power control part 20 of relation.
The current potential mode of the reducing electrode 120 of control part 60 is same with embodiment 1.Wherein, in embodiment 1, utilize control part 60 to regulate and apply voltage Va, on the other hand, utilize in the present embodiment control part 60 to regulate the voltage VA applying between the positive terminal at electrode unit aggregate 200 and negative terminal.
Control part 60 is to meet VA>=(V
oER-V
cA) × N[N (more than 2) is the number of electrode unit: be 5 in the present embodiment] mode electric power control part 20 is controlled.Thus, make current potential V
aNremain on oxygen generation equilibrium potential V
oERabove.
According to present embodiment, in multiple electrode units, can carry out concurrently the core hydrogenation of aromatics, therefore can increase the core amount of hydrogenation of the aromatics of time per unit tremendously.Therefore, can be in the core hydrogenation of industrial enforcement aromatics.
(embodiment 3)
Fig. 6 is the mode chart that represents the schematic construction of the electrochemical reduction device of embodiment 3.The basic structure of the electrochemical reduction device 10 of present embodiment is same with embodiment 2.In the present embodiment, electrode unit aggregate 200 is accommodated in electrolyzer 300.Between electrolyzer 300 and water store groove 40, be provided with the 2nd circulating path, in electrolyzer 300, be full of the water of supplying with from water store groove 40.The oxygen of each electrode unit 100 occurs with electrode 130, and the water that is full of electrolyzer 300 can circulate.
The electrochemical reduction device 10 of present embodiment, the effect that can obtain except embodiment 2, there is the thermal capacity by increasing the tank in electrolyzer, increase oxygen and occur by the temperature head between temperature head, electrode unit and the such advantage of interpolar temperature head of reducing electrode 120 in the face of electrode 130.
The invention is not restricted to above-mentioned embodiment, knowledge various design alterations in addition that also can be based on those skilled in the art, the embodiment that imposes such distortion also can comprise within the scope of the invention.For example, in the respective embodiments described above, be aromatics and the water structure at circulating path internal recycle, but can arrange be respectively connected with the inlet side of electrolysis cells retain groove, be connected with the outlet side of electrolysis cells retain groove.
In the respective embodiments described above, reducing electrode 120 contains the ionomer with proton-conducting, but reducing electrode 120 can contain and has the conductive ionomer of hydroxyl ion.
In embodiment 2,3, reference electrode 112 is arranged on the dielectric film 110 of an electrode unit 100, but reference electrode 112 can be arranged on to the dielectric film 110 of multiple electrode units 100.In this case, utilize voltage detection department 114 to detect each reference electrode 112 and the potential difference Δ V between corresponding reducing electrode 120 with it
cA, with the multiple potential difference Δ V that detect
cAmean value, carry out current potential V
cAcalculating.Thus, when in 100 fluctuations that produce current potential of electrode unit, voltage VA can be adjusted to more suitable scope.
(label declaration)
10 electrochemical reduction devices, 20 electric power control parts, 30 organism store grooves, 40 water store grooves, 50 gas-water separation portions, 100 electrode units, 112, reference electrode, 114 voltage detection departments, 110 dielectric films, 120 reducing electrodes, 130 oxygen occur with electrode, 140a, 140b fluid diffusion layer, 150a, 150b barrier film, 200 electrode unit aggregates, 300 electrolyzers
(industrial utilizability)
The present invention can utilize arene compound or nitrogen heterocyclic ring aromatics are carried out in the technology of electrochemically hydrogenation.
Claims (14)
1. an electrochemical reduction device, is characterized in that, possesses:
Electrode unit, comprising dielectric film, reducing electrode and oxygen occurs to form with electrode, described dielectric film has ionic conductivity, described reducing electrode is arranged on a side of described dielectric film and containing being useful on the reducing catalyst of arene compound or the hydrogenation of nitrogen heterocyclic ring aromatics core, the opposite side of described dielectric film occurs to be arranged on electrode described oxygen;
Electric power control part, described electric power control part applies voltage Va between described reducing electrode and described oxygen occur with electrode; With
Control part, the current potential of reversible hydrogen electrode is being labeled as V by described control part
hER, described arene compound or nitrogen heterocyclic ring aromatics standard oxidationreduction potential be labeled as V
tRR, described reducing electrode current potential be labeled as V
cAtime, to meet V
hER-arbitrarily selectedly allow current potential≤V
cA≤ V
tRRthe mode of relation is controlled described electric power control part.
2. electrochemical reduction device according to claim 1, wherein, the described current potential of allowing of selecting is arbitrarily 20mV.
3. electrochemical reduction device according to claim 1 and 2, is characterized in that also possessing:
Reference electrode, contacts with described dielectric film and occurs to configure isolator with electrode electricity with described reducing electrode and described oxygen, remains on reference electrode current potential V
ref; With
Voltage detection department, to the potential difference Δ V of described reference electrode and described reducing electrode
cAdetect,
Described control part is based on potential difference Δ V
cAwith reference electrode current potential V
ref, obtain the current potential V of described reducing electrode
cA.
4. electrochemical reduction device according to claim 3, is characterized in that, described control part is controlled, and voltage Va is changed, and makes the current potential V of described reducing electrode
cAbecome the current potential of specialized range.
5. electrochemical reduction device according to claim 4, wherein, the oxygen generation equilibrium potential of described control part when by water electrolysis is labeled as V
oERtime, to meet Va>=(V
oER-V
cA) mode described electric power control part is controlled.
6. according to the electrochemical reduction device described in any one in claim 3 to 5, it is characterized in that, described reference electrode is configured in that side that is provided with described reducing electrode of described dielectric film.
7. an electrochemical reduction device, is characterized in that, possesses:
Electrode unit aggregate, by contain dielectric film, reducing electrode and oxygen occur multiple electrode units of forming with electrode reciprocally electricity be connected in series, described dielectric film has ionic conductivity, described reducing electrode is arranged on a side of described dielectric film and containing being useful on the reducing catalyst of arene compound or the hydrogenation of nitrogen heterocyclic ring aromatics core, the opposite side of described dielectric film occurs to be arranged on electrode described oxygen;
Electric power control part applies voltage Va between the positive terminal of described electrode unit aggregate and negative terminal; With
Control part, when the current potential of reversible hydrogen electrode is labeled as to V
hER, described arene compound or nitrogen heterocyclic ring aromatics standard oxidationreduction potential be labeled as V
tRR, each electrode unit the current potential of described reducing electrode be labeled as V
cAtime, to meet V
hER-arbitrarily selectedly allow current potential≤V
cA≤ V
tRRthe mode of relation is controlled described electric power control part.
8. electrochemical reduction device according to claim 7, wherein, the described current potential of allowing of selecting is arbitrarily 20mV.
9. according to the electrochemical reduction device described in claim 7 or 8, it is characterized in that also possessing:
Reference electrode, contacts with the dielectric film of any electrolyte layers contained in described electrode unit aggregate and occurs to configure isolator with electrode electricity with described reducing electrode and described oxygen,
Voltage detection department, to the potential difference Δ V of described reference electrode and described reducing electrode
cAdetect;
Described control part is based on potential difference Δ V
cAwith reference electrode current potential V
ref, obtain the current potential V of described reducing electrode
cA.
10. electrochemical reduction device according to claim 9, is characterized in that,
Described control part is controlled, and voltage VA is changed, and makes the current potential V of the described reducing electrode of each electrode unit
cAbecome the current potential of specialized range.
11. electrochemical reduction devices according to claim 10, wherein, the oxygen generation equilibrium potential when by water electrolysis is labeled as V
oERtime, described control part is to meet VA>=(V
oER-V
cAthe mode of) × N is controlled described electric power control part, and wherein N, more than 2, is the number of the electrode unit that is connected in series.
12. according to the electrochemical reduction device described in any one in claim 9 to 11, it is characterized in that, described reference electrode is configured in that side that is provided with described reducing electrode of described dielectric film.
The preparation method of the hydride of 13. 1 kinds of arene compounds or nitrogen heterocyclic ring aromatics, is characterized in that,
Right to use requires the electrochemical reduction device described in any one in 1 to 12,
Described reducing electrode side at described electrode unit imports arene compound or nitrogen heterocyclic ring aromatics, there is to pass into water or the gas of humidification by electrode side arene compound or the hydrogenation of nitrogen heterocyclic ring aromatics core that will the described reducing electrode side of importing at described oxygen.
The preparation method of the hydride of 14. arene compounds according to claim 13 or nitrogen heterocyclic ring aromatics, wherein, the arene compound or the nitrogen heterocyclic ring aromatics that import to described reducing electrode side import described reducing electrode side with liquid state under temperature of reaction.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-075635 | 2012-03-29 | ||
| JP2012075635 | 2012-03-29 | ||
| PCT/JP2013/002187 WO2013145782A1 (en) | 2012-03-29 | 2013-03-29 | Electrochemical reduction device, and method for producing hydrogenated product of aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound |
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| Publication Number | Publication Date |
|---|---|
| CN104204304A true CN104204304A (en) | 2014-12-10 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380017673.1A Pending CN104204304A (en) | 2012-03-29 | 2013-03-29 | Electrochemical reduction device, and method for producing hydrogenated product of aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20150008138A1 (en) |
| EP (1) | EP2837712A4 (en) |
| JP (1) | JP6113715B2 (en) |
| CN (1) | CN104204304A (en) |
| AR (1) | AR090576A1 (en) |
| AU (1) | AU2013238682A1 (en) |
| CA (1) | CA2868594A1 (en) |
| WO (1) | WO2013145782A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| 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 |
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| AR091406A1 (en) * | 2012-06-12 | 2015-02-04 | Jx Nippon Oil & Energy Corp | ELECTROCHEMICAL REDUCTION DEVICE AND METHOD FOR MANUFACTURING HYDROCARBON HYDROCARBON OR AROMATIC HYDROCARBON COMPOUND OR AROMATIC COMPOUND WITH NITROGEN CONTENT |
| 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 |
| JP6343602B2 (en) | 2013-03-29 | 2018-06-13 | Ｊｘｔｇエネルギー株式会社 | Electrochemical reduction apparatus and method for producing hydrogenated aromatic compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4145264A (en) * | 1977-03-14 | 1979-03-20 | Basf Aktiengesellschaft | Preparation of metal-free phthalocyanines |
| US4588484A (en) * | 1985-02-28 | 1986-05-13 | Eli Lilly And Company | Electrochemical reduction of 3-chlorobenzo[b]thiophenes |
| WO2011122155A1 (en) * | 2010-03-31 | 2011-10-06 | 株式会社日立製作所 | Device for manufacturing organic hydride |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072584A (en) * | 1976-12-21 | 1978-02-07 | Allied Chemical Corporation | Electrochemical production of organic thiols |
| 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 |
| JP3452140B1 (en) * | 2003-01-08 | 2003-09-29 | スガ試験機株式会社 | Water electrolysis device |
| JP2005126288A (en) | 2003-10-24 | 2005-05-19 | Toyota Motor Corp | Hydrogen storage and release apparatus |
| JP2005239479A (en) | 2004-02-26 | 2005-09-08 | Toyota Motor Corp | Hydrogen gas separating equipment and hydrogen gas generation equipment |
| JP2009215647A (en) * | 2008-02-13 | 2009-09-24 | Tokyo Institute Of Technology | Method for producing carbonic acid diester |
| JP2011053478A (en) * | 2009-09-02 | 2011-03-17 | Oki Data Corp | Image forming apparatus |
| US8524066B2 (en) * | 2010-07-29 | 2013-09-03 | Liquid Light, Inc. | Electrochemical production of urea from NOx and carbon dioxide |
-
2013
- 2013-03-29 EP EP13767471.9A patent/EP2837712A4/en not_active Withdrawn
- 2013-03-29 CN CN201380017673.1A patent/CN104204304A/en active Pending
- 2013-03-29 WO PCT/JP2013/002187 patent/WO2013145782A1/en active Application Filing
- 2013-03-29 AU AU2013238682A patent/AU2013238682A1/en not_active Abandoned
- 2013-03-29 CA CA2868594A patent/CA2868594A1/en not_active Abandoned
- 2013-03-29 JP JP2014507451A patent/JP6113715B2/en active Active
- 2013-04-03 AR ARP130101071A patent/AR090576A1/en unknown
-
2014
- 2014-09-23 US US14/493,396 patent/US20150008138A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4145264A (en) * | 1977-03-14 | 1979-03-20 | Basf Aktiengesellschaft | Preparation of metal-free phthalocyanines |
| US4588484A (en) * | 1985-02-28 | 1986-05-13 | Eli Lilly And Company | Electrochemical reduction of 3-chlorobenzo[b]thiophenes |
| WO2011122155A1 (en) * | 2010-03-31 | 2011-10-06 | 株式会社日立製作所 | Device for manufacturing organic hydride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| Publication number | Publication date |
|---|---|
| AU2013238682A1 (en) | 2014-09-25 |
| EP2837712A1 (en) | 2015-02-18 |
| CA2868594A1 (en) | 2013-10-03 |
| US20150008138A1 (en) | 2015-01-08 |
| EP2837712A4 (en) | 2015-12-02 |
| JP6113715B2 (en) | 2017-04-12 |
| AR090576A1 (en) | 2014-11-19 |
| WO2013145782A1 (en) | 2013-10-03 |
| JPWO2013145782A1 (en) | 2015-12-10 |
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