CN101103140A - Method and apparatus for producing hydrogen - Google Patents
Method and apparatus for producing hydrogen Download PDFInfo
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- CN101103140A CN101103140A CNA2005800054335A CN200580005433A CN101103140A CN 101103140 A CN101103140 A CN 101103140A CN A2005800054335 A CNA2005800054335 A CN A2005800054335A CN 200580005433 A CN200580005433 A CN 200580005433A CN 101103140 A CN101103140 A CN 101103140A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 90
- 239000001257 hydrogen Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 169
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 61
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 61
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 61
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 144
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 31
- 150000002431 hydrogen Chemical class 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 27
- 230000004888 barrier function Effects 0.000 claims description 25
- 235000011089 carbon dioxide Nutrition 0.000 claims description 23
- -1 oxonium ion Chemical class 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000010512 thermal transition Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 15
- 239000011195 cermet Substances 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 238000005245 sintering Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 235000009508 confectionery Nutrition 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 210000004907 gland Anatomy 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 1
- FQNGRYARVHJPPC-UHFFFAOYSA-L [La].[Cr](=O)(=O)(O)O Chemical compound [La].[Cr](=O)(=O)(O)O FQNGRYARVHJPPC-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
An electrolyzer structure is provided that is suitable for use in a method that produces hydrogen by steam electrolysis by feeding reducing gas to an anode side and feeding steam to a cathode side of an electrolyzer that is partitioned into the anode side and the cathode side by a diaphragm of solid oxide electrolyte, and feeding power to the anode and cathode of the electrolyzer. One embodiment of the present invention relates to an apparatus that produces hydrogen by high temperature steam electrolysis and that comprises an electrolyzer partitioned into an anode side and a cathode side by a solid oxide electrolyte diaphragm, a conduit that feeds reducing gas to the anode side of the electrolyzer, and a conduit that feeds steam to the cathode of the electrolyzer, in which a metal cermet stable in a reducing atmosphere is used as the material of the anode and the cathode. Another embodiment of the present invention relates to a method of producing hydrogen by high temperature steam electrolysis for reducing electrolysis voltage by feeding steam to a cathode side and feeding hydrocarbon-containing gas to an anode side for reaction with oxygen ion, the cathode side and the anode side being provided in a high temperature steam electrolytic apparatus in which an electrolyzer is partitioned into the anode side and the cathode side using a solid oxide electrolyte as the diaphragm, wherein offgas discharged from the anode side of the electrolytic apparatus is admixed into the hydrocarbon-containing gas that is fed to the anode side of the electrolytic apparatus.
Description
Technical field
The present invention relates to high-temperature water vapour electrolytic and prepare hydrogen methods and device, especially: relate to the cathode side supply water vapor, the anode side that are suitable for to utilizing the solid oxide electrolyte barrier film electrolyzer to be separated into the electrolyzer of anode side and cathode side and supply with reducing gas, reduce the electrolyzer that uses in the electrolysis process of electrolysis electric power by carrying out electrolysis.
Technical background
With preparation hydrogen is that the electrolytic process of the water of purpose has the buck electrolysis, solid macromolecule water electrolysis, high-temperature water vapour electrolytic etc., but because buck electrolysis, must make electrolysis voltage during the solid macromolecule water electrolysis is more than the 1.8V, so electrical efficiency 80% or lower, it is big to prepare the required electric power amount of hydrogen.On the contrary, use solid oxide electrolyte electrolyzer to be separated into anode side and cathode side as barrier film, by supplying with the pyritous water vapor to cathode side, the high-temperature water vapour electrolytic method of electrolysis of water steam under the high temperature about 800 ℃, owing to can utilize heat energy further to suppress electrode overvoltage or resistance superpotential when being high reviewing knowledge already acquired water decomposition more low-level, so can expect the electrical efficiency more than 90%, can make electrolysis voltage little below 1.5V, can reduce the required electric power amount of preparation hydrogen.In addition, proposed recently by supplying with Sweet natural gas to the anode electrolytic cell side, make from cathode side and pass oxonium ion that solid oxide electrolyte barrier film anode side moves in anode reaction, can reduce the electrolytic process (United States Patent (USP) 6 of power consumption significantly by the chemical potential energy that uses reaction when the water decomposition, 051,125).
The method that proposes in the above-mentioned United States Patent (USP) is directly to supply with Sweet natural gas to the anode side of electrolyzer, makes it and the oxonium ion reaction that is present in anode side, its reaction can be applied at the method for the water decomposition of cathode side.This occasion, on principle because the depolarisation of methane reduces the electrolysis voltage of water, so theoretical electrolysis voltage is almost 0.Apparatus for electrolyzing in the practicality must apply superpotential voltage to device, and above-mentioned United States Patent (USP) advocates that total voltage then can water electrolysis at about 0.5V.
The electrolyzer that common high-temperature water vapour electrolytic uses, identical with the battery of Solid Oxide Fuel Cell (SOFC) and material and structure, pretend electrode for the cathode side that imports water vapor generation hydrogen, use is applicable to the Ni sintering metal of reducing environment atmosphere, and conduct produces the electrode of the anode side of oxygen, use electroconductive oxide, lanthanum cobalt ore for example, lanthanum manganate etc.Fig. 1 represents the notion of common high-temperature water vapour electrolytic device.The device that Fig. 1 represents, electrolyzer (electrolyzer) utilizes the solid oxide electrolyte barrier film to be separated into cathode side and anode side, anticathode electrode and anode electrode supply capability are carried out the electrolysis of water vapor at cathode side by supplying with the pyritous water vapor to cathode side, obtain highly purified hydrogen.The oxonium ion O that the water vapor electrolysis produces
2-Move on to anode side by the solid oxide electrolyte barrier film.
On the contrary, to the anode side importing reducing gas of the electrolyzer that produces oxygen, the limit reduces electrolysis electric power limit and carries out in the electrolytic method of water vapor, and negative electrode, anode all are exposed in the gas of reductibility.But at the water vapor of anode side importing as raw material, the generation up to hydrogen takes place might cause steam oxidation under the high temperature of metal.Anode side is separated out and is imported water vapor sometimes in order to suppress carbon, and, because electrode reaction generates the sour gas of water etc., thus similarly must consider high temperature water vapor oxidation, but also not have the electrolyzer and the processing condition of the suitable this situation of proposition.
Summary of the invention
The object of the invention is to supply with reducing gas by upwards stating the bright anode side of utilizing the solid oxide electrolyte barrier film to be separated into the electrolyzer of anode side and cathode side, supply with water vapor to cathode side, antianode electrode and cathode electrode supply capability are found to be applicable to that the water steam electrolytic prepares the formation of the electrolyzer of hydrogen methods.
As the method that solves above-mentioned problem, a kind of mode of the present invention provide adopt possess utilize the solid oxide electrolyte barrier film be divided into anode side and cathode side electrolyzer, supply with the pipeline of reducing gas, supply with the preparation hydrogen production device of high-temperature water vapour electrolytic method of the pipeline of water vapor to the cathode side of electrolyzer to the anode side of electrolyzer, this device characteristic is the material as anode electrode and cathode electrode, the sintering metal that uses pottery stable in the reductibility ambiance of 400～1000 ℃ of temperature and metal to constitute.
In addition, the anode side to electrolyzer is supplied with reducing gas among the present invention.Here, so-called reducing gas, mean the gas that in water vapor electrolyzer of the present invention, reacts the oxygen concn that can reduce anode side, comprise the appropriate hydrocarbon gas of Sweet natural gas or methane etc. with the oxygen that penetrates into the anode side of electrolyzer by the solid oxide electrolyte film.
The accompanying drawing simple declaration
Fig. 1 is the figure of the common high-temperature water vapour electrolytic device notion of expression.
Fig. 2 is the figure of expression high-temperature water vapour electrolytic device notion of the present invention.
Fig. 3 is the figure of expression interconnection structure of the present invention.
Fig. 4 is the mode chart of the high-temperature water vapour electrolytic device that uses of expression the present invention the 2nd mode.
Fig. 5 is the model process figure of an example of the described preparation hydrogen methods of expression the present invention's the 2nd mode.
Fig. 6 is the mode chart of the preparation hydrogen production device of use among the expression embodiment 1.
Fig. 7 is the figure of the preparation hydrogen experimental installation structure of expression embodiments of the invention 2 uses.
Fig. 8 is the result's of expression embodiments of the invention 2 a graphic representation.
Fig. 2 represents the pattern of a kind of mode of preparation hydrogen production device of the present invention. Of the present invention The preparation hydrogen production device owing to utilize hydrogen that the cathode side of electrolysis unit (electrolytic cell) generates, also Supply with reducibility gas in anode-side, so all become the ambiance of reproducibility. Therefore, because Anode electrode and cathode electrode all are exposed in the gas of reproducibility, so it is characterized in that as this The material of a little electrodes is used stable pottery in the reproducibility ambiance of 400～1000 ℃ of temperature The cermet that porcelain and metal consist of.
In addition, at the cathode side of electrolytic cell, because the water vapour electrolysis that imports generates hydrogen, so electricity Separate the gas composition in the groove, change towards outlet side from entrance side. The entrance hydrogen concentration is minimum, The outlet hydrogen concentration is the highest. Only supply with the occasion of water vapour, the gold of Ni etc. to the cathode side of electrolytic cell Genus causes steam oxidation for high temperature. Prevent steam oxidation, effectively sneak into reproducibility Gas, and the cathode side of electrolytic cell of the present invention because purpose is the hydrogen of preparing high-purity, so Be fit to sneak into hydrogen as reducibility gas. The widely used Ni electrode of electrolytic cell is owing to expose ring The mol ratio of hydrogen and water vapour: H in the atmosphere of border2/H
2O is more than 0.01, and is preferred more than 0.04 The time, do not cause steam oxidation, so this concentration is as the hydrogen dividing potential drop of necessary minimum.
Decomposition voltage increases PO as best one can according to the partial pressure of oxygen of the anode-side of electrolytic cell and cathode side and change2(cathode side)/PO2(anode-side) is to reduce the effective ways of decomposition voltage.
Yet, if improve mixed hydrogen concentration to the electric tank cathode side, because the oxygen of cathode side Dividing potential drop reduces, and becomes the main cause that voltage rises, so the hydrogen that preferred as best one can inhibition is sneaked into is dense Degree is at reduced levels.
Especially, make the anode side of electrolyzer export near the reducing gas and the mol ratio of sour gas: reducing gas/sour gas is below 0.4, reduces the electrolysis voltage effect in order to bring into play, can be with the H of cathode side inlet
2/ H
2O is suppressed at below 0.4, preferably is suppressed at below 0.2.
The hydrogen of sneaking into is if a part of hydrogen that the water vapor electrolysis is generated is recycled to inlet, then because simplified system and preferred.
The anode side of electrolyzer, the concentration of reducing gas are up to outlet at inlet and are tending towards reducing.Therefore, oxygen partial pressure is minimum at inlet, and outlet is maximum.On the other hand, the cathode side of electrolyzer, owing to generate hydrogen, so hydrogen concentration rises towards outlet, oxygen partial pressure reduces towards outlet thereupon.The identical occasion of flow direction of the reducing gas of the mobile and anode side of the water vapor of the cathode side of electrolyzer is at inlet P
O2(cathode side/P
O2(anode side) is big, and it is minimum that the exit becomes, so the ununiformity of current density increases, becomes the reason of generation thermal stresses etc.Therefore, the water vapor of the cathode side of electrolyzer is flowed and the reducing gas of anode side mobile becomes flow (convection current) respect to one another.
In addition, in the reducing gas of the anode side of supplying with electrolyzer, add water vapor and can suppress separating out of carbon.This occasion, the mol ratio of water and reducing gas are below 0.4, to be preferably below 0.2.
Anode electrode and cathode electrode must have the diffustivity of gas, have electronic conduction with as the activity of electrode catalyst.
Preferred preferred atmosphere H in the electrolyzer of above-mentioned explanation
2/ H
2The metallic substance that does not form oxide compound under the envrionment conditions of O＜0.4 is main constitute anode and negative electrode.The metal of electronic conduction and catalytic activity is arranged as do not form oxide compound under such condition, can enumerate Ni, Fe, Co, Cu, Pt, Ag, Pd, Ru or these mixture or alloy etc.
In addition, as electrode materials,, be made generally in ceramic powder blended sintering metal and use, and, can consider at H as the blended pottery in order to suppress the sintering under the high temperature
2/ H
2Stable under the condition of O＜0.4, select with the approximation of the reactivity of electrolyte, associativity coefficient of thermal expansion and oxygen-ion conductive or oxonium ion, electronic conductivity.
Device of the present invention preferably uses ZrO
2, CeO
2, LaCrO
3, LaTiO
3, LaGaO
3Deng carrying out the part element substitution, improve the material of the material of oxygen-ion conductive or electronic conductivity as anode electrode and cathode electrode.Especially, when using the conductive material that electronics and oxonium ion are arranged, as the occasion of electrode because reactive site increases, or the area that oxonium ion can spread also increases, so it is effective that superpotential is reacted in reduction.
In addition, in the water vapor electrolyzer, the occasion of a plurality of electrolyzer multistageizations that are connected in series, needs connect the communicating vessels of anode electrode and cathode electrode, and the gas both sides of the anode side of this communicating vessels and electrolyzer and cathode side are joined, and also play the effect of separation (sealing gland).When common SOFC pond or high-temperature water vapour electrolytic pond, because a side is a reducing environment atmosphere, the opposing party is a well-oxygenated environment atmosphere, thus the difficult selected material that is applicable to these ambiances, and the manufacturing in pond is also difficult.Particularly, at present,, only found the limited Dingtao porcelain of chromic acid lanthanum etc., be difficult to make fine and close structure by this material as the material of the communicating vessels that is applicable to reducing environment atmosphere and well-oxygenated environment atmosphere both sides.Therefore, with the communicating vessels that this material is made, difficulty makes the sealing gland at junction surface of electrode firm.
In present method, owing to anode side and cathode side both as electrolyzer are the reductibility ambiances, as the communicating vessels material, can use metal, the easy moulding of metal engages, and the while is proof stress also, but the high electrolyzer of fabrication reliability.As using the communicating vessels material among the present invention, can enumerate Ni or Ni base alloy, Fe base alloy, Co base alloy, Cu base alloy, Ag base alloy etc.
Fig. 3 represents the notion of communicating vessels structure of the present invention.Electrolyzer 5 is divided into the anode side 12 in the outside and the cathode side 11 of inboard by the film 3 of the solid oxide electrolyte of tubular, at the outside of solid oxide electrolyte configuration anode electrode 4, and at inboard configuration cathode electrode 2.In the device that Fig. 3 represents, 2 columnar electrodes, solid oxide electrolyte complex bodys utilize isolator 21 to engage up and down, and anode and negative electrode utilize communicating vessels 22 to be connected in series.Therefore, by direct supply is linked to each other with negative electrode with anode, can guarantee just that with few electric current the required voltage of electrolysis carries out electrolytic reaction.Supply with high-temperature water vapor by the cathode side 11 to electrolyzer, anode side 12 is supplied with reducing gas (as CH
4Illustrate), to two electrode supply capabilities, cause that at cathode side the electrolysis of water vapor generates hydrogen.And the oxonium ion that generates moves on to cathode side by solid oxide electrolyte.In anode side, move the oxonium ion and the reducing gas reaction of coming and generate CO
2And H
2O.In the device of the present invention,, pretend to the communicating vessels material and can use above-mentioned metallic substance because the anode side and cathode side two Fang Jun of electrolyzer are the reductibility ambiances.
In addition, to studying, find that the anode side to electrolyzer that proposes in the above-mentioned United States Patent (USP) only supplies with the method for Sweet natural gas following defective is arranged before the inventor with above-mentioned 6,051, No. 125 roughly the same technology of United States Patent (USP).That is, the electrolyzer entry into service can obtain and the roughly the same data of condition shown in the above-mentioned United States Patent (USP) at first, but if the current value that remains in operation reduces gradually, just can not remain in operation soon.Result to the reason that can not remain in operation is investigated distinguishes when the anode side of electrolyzer is directly supplied with methane, causes methane decomposition in the pyritous anode side, owing to be membranaceous covering electrodes so produce the cause that electrode stops up as the carbon of decomposition product.
The 2nd mode of the present invention adopts simple method to prevent that the generation carbon of above-mentioned explanation from causing stopping up the method for electrode problems as problem so that little increase cost to be provided.
The inventor is in order to find to solve the method for above-mentioned problem, the result who concentrates on studies repeatedly, discovery is blended into in the Sweet natural gas (gas containing hydrocarbon) of anode side that gives electrolyzer by making water vapor or carbonic acid gas, and then gas containing hydrocarbon decomposes the carbon that generates in anode side and becomes CO or CO with water vapor and carbon dioxide reaction immediately
2So, can prevent to separate out solid carbon at electrode surface.In addition, utilize the membranous high-temperature water vapour electrolytic device of solid oxide electrolyte, though utilization also can make oxidation of coal by the oxonium ion that the solid oxide electrolyte barrier film is present in the anode side of electrolyzer, but because the amount of reducing gas is more than the amount of oxonium ion, so only utilize this reaction can not prevent separating out of solid carbon.And, because the CO of carbon and water vapor or carbon dioxide reaction generation and hydrogen reacts as the oxonium ion of reducing gas and anode side, so help to reduce the electrolysis voltage of electrolyzer.
In addition, the inventor finds upwards to state the bright cathode side that utilizes solid oxide electrolyte electrolyzer to be separated into the high-temperature water vapour electrolytic device of anode side and cathode side as barrier film again and supplies with water vapor, anode side is supplied with gas containing hydrocarbon by making in the high-temperature water vapour electrolytic method of electrolysis voltage reduction with the oxonium ion reaction, be conceived to from the exhaust that the anode side of electrolyzer is discharged, contain hydrocarbon in the supply gas etc. and the water vapor and the carbonic acid gas that generate by the membranous oxygen reaction of solid oxide electrolyte from cathode side, by sneaking into water vapor and/or carbonic acid gas simply in the gas containing hydrocarbon that this anode side exhaust is blended into the anode side of supplying with electrolyzer.
Promptly, the 2nd mode of the present invention relates to the preparation hydrogen methods, it is characterized in that supplying with water vapor to the cathode side that utilizes solid oxide electrolyte electrolyzer to be separated into the high-temperature water vapour electrolytic device of anode side and cathode side as barrier film, anode side is supplied with gas containing hydrocarbon by with the oxonium ion reaction high-temperature water vapour electrolytic of electrolysis voltage reduction being prepared in the hydrogen methods, and the exhaust that the anode side of electrolyzer is discharged is blended in the gas containing hydrocarbon of the anode side of supplying with electrolyzer.
In addition, the 2nd mode of the present invention relates to the device that the described method of enforcement is used.Therefore, another other modes of the present invention relate to the preparation hydrogen production device, it is characterized in that having the barrier film that utilizes solid oxide electrolyte be separated into anode side and cathode side electrolyzer, to the anode side of electrolyzer supply with gas containing hydrocarbon pipeline, supply with the pipeline of water vapor to the cathode side of electrolyzer, also have the exhaust of discharging from the anode side of electrolyzer be blended into pipeline to the gas containing hydrocarbon that the anode side of electrolyzer is supplied with.
In addition, in the inventive method, supply with gas containing hydrocarbon to the anode side of electrolyzer.Here, so-called gas containing hydrocarbon means Sweet natural gas or contains the gas of the hydrocarbon of methane etc.In addition, the expression of " reducing gas " that uses in this specification sheets means and the oxygen reaction that moves on to the anode side of electrolyzer in water vapor electrolyzer of the present invention by the solid oxide electrolyte film, can make the gas of the oxygen concn reduction of anode side.
The ultimate principle that the high-temperature water vapour electrolytic that utilizes the employed solid oxide electrolyte film of the present invention's the 2nd mode is prepared hydrogen production device describes with reference to Fig. 4.
High-temperature water vapour electrolytic groove 113 utilizes the barrier film 114 of solid oxide electrolyte to be separated into anode side 115 and cathode side 116.Cathode side 116 to electrolyzer is supplied with high-temperature water vapor 119, anode side 115 to electrolyzer is supplied with gas containing hydrocarbon 110, use AC-DC transformer 118 that electric power 117 is transformed into direct current when electrolyzer is switched on, the high-temperature water vapor 119 that anticathode side 116 is supplied with resolves into hydrogen and oxygen under electrolytic action.The hydrogen that generates 120 is recovered as high-purity hydrogen.And the oxygen 121 that generates becomes oxonium ion, and optionally the barrier film 114 by solid oxide electrolyte moves on to anode side 115.At this, when anode side 115 was supplied with gas containing hydrocarbon 110, oxonium ion 121 was consumed with the gas containing hydrocarbon reaction, owing to help to form the concentration gradient of oxonium ion, so the required loss of voltage of water electrolysis, current consumption reduces significantly.
The 2nd mode of the present invention is characterized in that making the waste gas of discharging from the anode side of electrolyzer to be blended into the gas containing hydrocarbon that the anode side of high-temperature water vapour electrolytic groove is supplied with.With reference to Fig. 5 method of the present invention is described.Moreover below suitably to get methane be that example describes as appropriate hydrocarbon gas, but the present invention is not subjected to described qualification, also applicable to other appropriate hydrocarbon gas.
In the system that Fig. 5 represents, upwards state the anode side of bright high-temperature water vapour electrolytic groove and supply with gas containing hydrocarbon, meanwhile supply with high-temperature water vapor to the cathode side of electrolyzer, supply capability is carried out the electrolysis of high-temperature water vapor.Generate the pyritous exhaust from the anode side of electrolyzer, generate pyritous hydrogen-containing gas (comprising hydrogen and water vapor) from cathode side.System of the present invention, the high-temperature exhaust air discharging from the anode side of this electrolyzer is blended in the gas containing hydrocarbon that the anode electrolytic cell side is supplied with.
As described above, the described method of the 2nd mode of the present invention is characterized in that the exhaust that handle is discharged from the anode side of electrolyzer, is blended in the gas containing hydrocarbon that the anode side of electrolyzer is supplied with, and supplies with the anode electrolytic cell side.Thus, water vapor that contains in the exhaust of being sneaked into and carbonic acid gas, the carbon immediate response that generates with the hydrocarbon thermolysis of the anode side methane of electrolyzer etc. becomes CO or CO
2So, prevent that the anode electrolytic cell side from producing solid carbon, can prevent the pollution of the electrode that blocking causes.
Yet, even this occasion when the addition of water vapor is not enough, generates carbon coating and produces obstacle on electrode.In theory in order to prevent to generate carbon coating, the total addition of water vapor or carbonic acid gas, if with the carbon amount (carbon atom conversion mole number) in the gas containing hydrocarbon that the anode electrolytic cell side is supplied be equimolar amount, then because the carbon of gas containing hydrocarbon is the amount that all changes into CO, so difficulty causes separating out of carbon.Yet, separate out in order to ensure anti-blocking, the total addition that is blended into water vapor in the gas containing hydrocarbon or carbonic acid gas preferably with the gas containing hydrocarbon of supplying with the anode electrolytic cell side in carbon amount (carbon atom conversion mole number) be more than the equimolar amount.Compare the occasion that adds water vapor with the molar excess ground such as carbon amount of hydrocarbon, the carbon of methane is up to being oxidized to carbonic acid gas, and when reaching 2 times of molar weights, produces hydrogen along with the generation of carbonic acid gas, because this hydrogen reacts as reductive agent and oxonium ion, so energy-producing hardly waste.CO+H
2O → CO
2+ H
2Reaction be thermopositive reaction, carrying out this reaction does not need energize.CH as total reaction of methane and water
4+ 2H
2O → CO
2+ 4H
2And CH
4+ CO
2→ 2CO+2H
2Reaction owing to be slightly thermo-negative reaction, must supply with heat so will carry out total overall reaction, but because this heat energy is little as the electric energy of superpotential adding during than electrolysis, so do not need to heat from the outside.
Because it is quite big to add the required energy of the water vapor of 2 times of mole of methane, must use high efficiency interchanger so will suppress energy consumption, the pyritous that utilizes electrolyzer to discharge is discharged the heat of gas (waste gas).In addition, the water that generates for the composition methane oxidation of waste gas exists by 2: 1 with carbonic acid gas, and contains the reducing gas composition (hydrocarbon of methane etc.) that does not fire.Therefore, according to the present invention, if adding to supply with, the waste gas that the anode electrolytic cell side is discharged replaces adding water vapor in the gas containing hydrocarbon from the outside, then do not need heat exchange by direct use high-temp waste gas, water vapor and carbonic acid gas contained in the waste gas all have the effect that carbon is separated out that suppresses, and reducing gas composition and the methane owing to not combustion all plays unpolarizing so can more effectively utilize energy in addition.
The gas mixture of methane and water vapor and carbonic acid gas under the temperature of using in high-temperature water vapour electrolytic of the present invention (about 650 ℃～1000 ℃), uses catalyzer to be reacted into CO and hydrogen or CO easily
2And hydrogen.If utilize this reaction energetically and since methane with all change into CO, CO before electrode contacts
2, H
2So methane decomposition is contaminated electrode not.Therefore, optimal way of the present invention, also relate in above-mentioned described method, at the gas containing hydrocarbon that will supply with the anode side of electrolyzer and the mixed gas of anode side exhaust gases, before the anode of electrolyzer contacts, change into the method that contacts with anode again behind the mixed gas that hydrogen and carbon monoxide are main component to feature by thermal response.In order to realize this method, if in the mixed gas of the methane of supplying with electrolyzer and water vapor and carbonic acid gas and the structure of formation before electrode contact by catalyst layer, the then direct purpose that just can fully realize preventing electrode fouling that do not contact with electrode of methane.Promptly, electrolyzer of the present invention, more preferably become on the pipeline of the gas mixture of the anode side exhaust gases of the anode side of electrolyzer being supplied with water vapor and electrolyzer and dispose catalyst layer, with before the anode of electrolyzer contacts, changing into hydrogen and carbon monoxide by thermal response is the such formation of gas mixture of main component at the mixed gas of gas containing hydrocarbon and anode side exhaust gases.
As above-mentioned illustrated, be slightly thermo-negative reaction because the reaction of methane and water generates hydrogen, and high-temperature water vapour electrolytic device of the present invention must keep 650～1000 ℃ high temperature, so the energy shortage sometimes of the superpotential about use 0.5V.Particularly when adopting thin YSZ (yttria-stabilized zirconia) film to reduce superpotential occasion etc., must inject energy in order to keep the required temperature of water vapor electrolytic reaction as the solid oxide electrolyte barrier film.Because using the electric energy supplementing energy is not very wise move, so preferably utilize the ignition energy of methane.This occasion is supplied with electrolyzer by add oxygen in methane after, make it to cause the partial oxidation reaction of methane, and utilizing this reaction heat is simple and the highest method of thermo-efficiency.Because the amount of the oxygen that this reaction is required is not many, so almost do not sneak into the danger that oxygen causes.Even use air to replace oxygen, but nitrogen causes the increase of used heat also can not become big volume.In addition, because the water vapor of this reaction generation and CO are used to prevent that electrode from separating out carbon and more preferably.
Therefore, other mode of the present invention, also relate in above-mentioned described preparation hydrogen methods, oxygen or air mixed in the anode side exhaust gases of electrolyzer, the mixed gas that obtains is blended in the gas containing hydrocarbon that the anode side of electrolyzer is supplied with, and utilizing the partial oxidation reaction thermal transition of gas containing hydrocarbon to become with hydrogen and carbon monoxide is that the mixed gas of main component is the method for feature.
The experimental installation 1 that uses Fig. 6 to represent carries out the preparation hydrogen experiment of high-temperature water vapour electrolytic.The columnar scandium stabilized zirconia (SSZ) of end sealing as solid oxide electrolyte barrier film 3, at the Ni-zirconia cermet electrode of membranous both sides configuration as anode 2 and negative electrode 4.It is configured in the electrolyzer 5, electrolyzer 5 is separated into anode side 12 and cathode side 11.The vapor pipe 6 of the hydrogen that discharge to generate and the gas mixture of water vapor is set at cathode side 11, (is expressed as CH and form the importing reducing gas in the anode side 12 of electrolyzer
4) gas introduction port 7.
Supply with methane from gas introduction port 7 to the cathode side 12 of electrolyzer, supply with water vapors by cathode side inlet 8, at 700 ℃ by carrying out high-temperature water vapour electrolytic by direct supply 13 antianodes 2 and negative electrode 4 supply capabilities.Confirm to generate hydrogen by the outlet 9 that generates gas exhaust pipe 6.
Experimental example 2
The high-temperature water vapour electrolytic device that uses Fig. 7 to represent carries out the experiment that the described high-temperature water vapour electrolytic of the 2nd mode of the present invention prepares hydrogen.The high-temperature water vapour electrolytic device 1 that Fig. 7 represents, at one end the both sides installing electrodes of the barrier film 3 of the solid oxide electrolyte of Feng Bi cylindrical shape (anode 2 and negative electrode 4) is separated into anode side 12 and cathode side 11 to electrolyzer 5.The vapor pipe 6 of the mixed gas of the hydrogen that discharge to generate and water vapor is set at cathode side 11.And form the gas introduction port 7 that imports gas containing hydrocarbon in the anode side 12 of electrolyzer.This structure is roughly identical with the pond of Solid Oxide Fuel Cell (SOFC), and its manufacture method and SOFC pond there are not variation basically.Present embodiment uses the film (thickness 100 μ m) as the YSZ (yttria-stabilized zirconia) of solid oxide electrolyte barrier film 3, and the electrode 2,4 of nickel cermet all is installed in the both sides of YSZ film 3, and the electrode 2 in the outside is an anode, and inboard electrode 4 is a negative electrode.
Electrolyzer 5 is configured in the electric furnace, temperature is remained on 1000 ℃ volts DS 13 is supplied with at the two poles of the earth carried out electrolytic trial.The inventive method, 11 of cathode sides to electrolyzer under normal pressure feed water vapor, and anode side 12 feeds and is mixed with the gas mixture of discharging gas with respect to the simulation of 2 times of methane gas volume ratios.Discharge gas as simulation, supply with mixed water vapor, carbonic acid gas, the mixed gas of methane by 4: 2: 1.Actual anode is discharged gas, is not the methane as unburned gas, but contains hydrogen and CO that methane reaction generates, but substitutes with methane here.Suppose that fuel availability is about 85% to decide the ratio of sneaking into of methane.Moreover the outside that makes electrolyzer is that anode side is for observing the cause of the state of the carbon of separating out on the anode easily.
In addition, experiment as a comparison, the mode according to No. 6,051,125, above-mentioned United States Patent (USP) feeds water vapor in the anticathode side 11 under normal pressure, and 12 of antianode sides feed methane and experimentize.In addition, use open anode side 12 not feed the condition of methane, that is, use the condition of common high-temperature water vapour electrolytic method to compare experiment.The experiment counter electrode is supplied with volts DS observation balance of voltage electric current, carries out simultaneously observing the anodic state after the electrolysis of reasonable time.
By the minimizing of electrolysis voltage 1.3V is continued for a long time time observation current value, can recognize water vapor and carbonic acid gas are blended into the electrode fouling effect that prevents in the gas containing hydrocarbon of supply anode electrolytic cell side.12 occasions of supplying with methane of anode side to electrolyzer, discharge the variation of Faradaic current value of occasion of the anode side 12 that resupplies electrolyzer behind the gas for the simulation anode of 2 times of volumes of methane shown in the curve of Fig. 8 with mixed phase, the occasion current value of only supplying with methane constantly descends, and is steady state value basically and simulation anode discharge gas is blended in the occasion current value of supplying with in the methane.In addition, during visual observation electrode (anode), to 12 occasions of supplying with methane of the anode side of electrolyzer, it is quite a lot of to confirm after 1 hour that anode is separated out carbon, and methane is mixed the occasion that the back is supplied with the anode side 12 of electrolyzer with simulated exhaust, after 10 hours, also keep clean surface.
Show by this test-results, the anode side of electrolyzer is supplied with in the high-temperature water vapour electrolytic method of gas containing hydrocarbon (methane), the anode side of electrolyzer is only supplied with the method for methane, because the obstruction that begins to produce electrode by the electrolysis of a few hours, so difficult continuous operation.And after being added to the anode of moisture vapor and carbonic acid gas discharge gas in the methane, the occasion of supplying with to the anode side of electrolyzer, if discharging the mixed volume of gas is about 2 times of volume ratios of methane, then produces carbon hardly and separate out the influence that brings, but the long-time running of practicality is described.Experiment in addition, the ratio of the water vapor that is blended in the methane that the anode side 12 of electrolyzer is supplied with and carbonic acid gas is changed when experimentizing, even 2 times of the amount methane of the water vapor of sneaking into below the volume ratio, also do not produce the obstruction of electrode immediately, and the ratio that the water vapor in methane and the discharge gas and carbonic acid gas add up to such as is at the occasion of mol ratio, confirms that the relatively shorter time begins to stop up.In the test so far, make the water vapor that adds in the methane and carbonic acid gas add up to 2 times of mol ratios of methane the time, owing to do not observe separating out of carbon fully, estimation contains the water vapor of 2 times of mol ratios and being mixed into of gas of anode side discharge of carbonic acid gas prevents that electrode from stopping up most preferred amount.Mixing is greater than the discharge gas of this amount, and this is also preferred to preventing that electrode from stopping up, but because the methane concentration that the anode side of electrolyzer is supplied with is low, can not adopt big Faradaic current value so can not be referred to as preferred.
By the way, the method that replaces anode side to discharge gas from the external mix water vapor can prevent that anode from stopping up, but generating water vapor by water need be for the energy that electrolyzer operating temperature (about 650 ℃～1000 ℃) is risen, so electrolysis superpotential consumption energy especially hour then.But the inventive method, contained unburned gas (residual methane) is re-used in the gas because anode is discharged, so compare with the water vapor of sneaking into 2 times of mole of methane, can make the minimizing about 40% of unburned gas.
Variety of way of the present invention is as follows.
1. preparation hydrogen methods, it is characterized in that supplying with water vapor to the cathode side that utilizes solid oxide electrolyte electrolyzer to be separated into the high-temperature water vapour electrolytic device of anode side and cathode side as barrier film, anode side is supplied with gas containing hydrocarbon by reacting in the preparation hydrogen methods of the high-temperature water vapour electrolytic that makes the electrolysis voltage reduction with oxonium ion, and the discharge gas (waste gas) of discharging from the anode side of electrolyzer is blended into the gas containing hydrocarbon that the anode side of electrolyzer is supplied with.
2. above-mentioned the 1st described preparation hydrogen methods is characterized in that the mole number that the carbon atom with respect to the gas containing hydrocarbon of supplying with to the anode side of electrolyzer converts, and sneaks into that discharge gas from anode side makes water vapor and carbonic acid gas and is etc. more than the mol ratio.
3. above-mentioned the 1st described preparation hydrogen methods is characterized in that the mole number that the carbon atom with respect to the gas containing hydrocarbon of supplying with to the anode side of electrolyzer converts, sneak into discharge gas from anode side make water vapor and carbonic acid gas and be about 2 times of mol ratios.
4. any one above-mentioned the 1st～the 3rd described preparation hydrogen methods, it is characterized in that to gas mixture that the anode side of electrolyzer is supplied with gas containing hydrocarbon and anode side discharge gas with before the anode of electrolyzer contacts, contact with anode again after changing into the gas mixture that hydrogen and carbon monoxide are main component by thermal response.
5. any one above-mentioned the 1st～the 4th described preparation hydrogen methods, it is characterized in that in the anode side discharge gas of electrolyzer, sneaking into oxygen or air, the gas mixture that obtains is blended in the gas containing hydrocarbon that the anode side of electrolyzer is supplied with, utilizes the partial oxidation reaction thermal transition Cheng Qing of gas containing hydrocarbon and carbon monoxide mixed gas for main component.
6. preparation hydrogen production device, it is characterized in that having the barrier film that utilizes solid oxide electrolyte and be separated into the electrolyzer of anode side and cathode side, supply with the pipeline of gas containing hydrocarbon to the anode side of electrolyzer, supply with the pipeline of water vapor to the cathode side of electrolyzer, also have the discharge gas of the anode side of electrolyzer discharge is blended into pipeline in the gas containing hydrocarbon that the anode side of electrolyzer is supplied with.
7. above-mentioned the 6th described preparation hydrogen production device, it is characterized in that disposing catalyst layer in the pipeline according to the gas mixture of discharging gas in anode side from electrolyzer to the anode side of electrolyzer that supply with water vapor and, with before the anode of electrolyzer contacts, changing into hydrogen and carbon monoxide by thermal response is that the gas mixture mode of main component constitutes at gas mixture that gas containing hydrocarbon and anode side are discharged gas.
8. device, it is characterized in that be have the barrier film that utilizes solid oxide electrolyte be separated into anode side and cathode side electrolyzer, to the anode side of electrolyzer supply with the pipeline of reducing gas, supply with to the cathode side of electrolyzer water vapor pipeline, utilize the high-temperature water vapour electrolytic legal system to be equipped with the device of hydrogen, as the material of anode electrode and cathode electrode, use the sintering metal that contains pottery and metal stable in the reductibility ambiance of 400～1000 ℃ of temperature.
9. above-mentioned the 8th described device is characterized in that as electrode materials, the sintering metal of use, use temperature at 400～1000 ℃, and hydrogen with respect to the mol ratio of the water vapor in the ambiance: H
2/ H
2O, or water is under the ambiance condition below 0.4, not form the sintering metal of the metal of oxide compound as balanced reaction for the mol ratio of reducing gas.
10. above-mentioned the 8th described device is characterized in that using the Ni sintering metal as the sintering metal as electrode materials.
11. any one above-mentioned the 8th～the 10th described device is characterized in that as the sintering metal of electrode materials, using the main body that is blended in the pottery in the metal is the material of oxygen ion conduction body or oxonium ion, electronic conduction body.
12. any one above-mentioned the 8th～the 10th described device wherein as solid oxide electrolyte, uses scandium stabilizing zirconia (SSZ) or yttrium stable zirconium oxide (YSZ).
13. any one above-mentioned the 8th～the 12nd described device, a part that it is characterized in that also having the hydrogen that the cathode side that makes electrolyzer generates is blended into the pipeline in the water vapor that the cathode side of electrolyzer is supplied with.
14. any one above-mentioned the 8th～the 13rd described device is characterized in that making the mobile formation that becomes convection current each other with the reducing gas of anode electrolytic cell side of flowing of the water vapor of electric tank cathode side.
15. any one above-mentioned the 8th～the 14th described device, wherein a plurality of anode electrodes and cathode electrode utilize metal communicating vessels series connection to engage.
16. method, it is characterized in that it being the anode side supply reducing gas that is separated into the electrolyzer of anode side and cathode side to the barrier film that utilizes solid oxide electrolyte, supply with water vapor to cathode side, by antianode and negative electrode supply capability, adopt the method for water vapor electrolytic preparation hydrogen, hydrogen is blended in the water vapor of supplying with the electric tank cathode side.
17. above-mentioned the 16th described method is characterized in that according to the mol ratio of hydrogen with respect to water vapor: H
2/ H
2O is that 0.01～0.4 amount is blended in the water vapor of supplying with the electric tank cathode side hydrogen.
18. above-mentioned the 16th or the 17th described method is characterized in that the mobile mode that becomes mutual convection current with the reducing gas of the anode side of electrolyzer of flowing according to the water vapor of the cathode side that makes electrolyzer, supply with water vapor and reducing gas.
The possibility of utilizing on the industry
According to the present invention, the present invention relates to the method and the dress that utilize high-temperature water vapour electrolytic to prepare hydrogen Put, especially provide by to utilizing the solid oxide electrolyte barrier film that electrolytic cell is separated into sun The cathode side of the electrolysis unit of utmost point side and cathode side is supplied with water vapour, and anode side is supplied with reproducibility Gas, carry out electrolysis, be suitable for reducing the electrolysis dress that uses in the electrolytic method of electrolysis electric power Put and best method of operation.
In addition, according to the 2nd mode of the present invention, to utilizing solid oxide electrolyte barrier film handle Electrolytic cell is separated into the anode-side of the electrolysis unit of anode-side and cathode side and supplies with gas containing hydrocarbon, to Cathode side is supplied with high-temperature water vapor by carrying out the method for water vapour electrolytic preparation hydrogen, can prevent The electrode that the solid carbon that the hydrocarbon thermal decomposition is separated out causes stops up, and can effectively utilize reacted simultaneously The unburned gas composition that contains in the heat that the anode-side Exhaust Gas has and the anode-side Exhaust Gas can To prepare expeditiously hydrogen.
Claims (7)
1. preparation hydrogen methods, it is characterized in that, be by following: supplying with water vapor to the cathode side that utilizes solid oxide electrolyte electrolyzer to be separated into the high-temperature water vapour electrolytic device of anode side and cathode side as barrier film, anode side is supplied with gas containing hydrocarbon, by reacting the preparation hydrogen methods that makes the high-temperature water vapour electrolytic that electrolysis voltage reduces, the discharge gas from the anode side discharge of electrolyzer is blended into the gas containing hydrocarbon that the anode side of electrolyzer is supplied with oxonium ion.
2. the described preparation hydrogen methods of claim 1, it is characterized in that, sneak into discharge gas from anode side, with respect to the mole number that the carbon atom of the gas containing hydrocarbon of supplying with to the anode side of electrolyzer converts, make water vapor and carbonic acid gas and be etc. more than the mol ratio.
3. the described preparation hydrogen methods of claim 1, it is characterized in that, sneak into discharge gas from anode side, with respect to the mole number that the carbon atom of the gas containing hydrocarbon of supplying with to the anode side of electrolyzer converts, make water vapor and carbonic acid gas and be about 2 times of mol ratios.
4. the described preparation hydrogen methods of any one of claim 1～3, it is characterized in that, will be to the mixed gas of gas containing hydrocarbon that the anode side of electrolyzer is supplied with and anode side discharge gas with before the anode of electrolyzer contact, changing into hydrogen and carbon monoxide by thermal response is to contact with anode behind the mixed gas of main component again.
5. the described preparation hydrogen methods of any one of claim 1～4, it is characterized in that, to discharge in the gas to the anode side of electrolyzer and sneak into oxygen or air, the mixed gas that obtains is blended in the gas containing hydrocarbon that the anode side of electrolyzer is supplied with, and it is the mixed gas of main component that the partial oxidation reaction thermal transition by gas containing hydrocarbon becomes with hydrogen and carbon monoxide.
6. preparation hydrogen production device, it is characterized in that, has the pipeline that the barrier film that utilizes solid oxide electrolyte is separated into the electrolyzer of anode side and cathode side, supplies with gas containing hydrocarbon to the anode side of electrolyzer, supply with the pipeline of water vapor to the cathode side of electrolyzer, also have the discharge gas of being discharged by the anode side of electrolyzer is blended into pipeline in the gas containing hydrocarbon that the anode side of electrolyzer is supplied with.
7. the described preparation hydrogen production device of claim 6, it is characterized in that, constitute by following mode: dispose catalyst layer supplying with to the anode side of electrolyzer in the pipeline of water vapor and the mixed gas of the anode side discharge gas of electrolyzer, with before the anode of electrolyzer contacts, changing into hydrogen and carbon monoxide by thermal response is the gas mixture mode of main component at mixed gas that gas containing hydrocarbon and anode side are discharged gas.
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|---|---|---|---|
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| JP042040/2004 | 2004-02-18 | ||
| JP2004042040A JP4512788B2 (en) | 2004-02-18 | 2004-02-18 | High temperature steam electrolyzer |
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| CN102181878A (en) * | 2011-04-22 | 2011-09-14 | 北京航空航天大学 | Static water supply proton exchange membrane brine electrolysis device |
| CN106115620A (en) * | 2016-06-20 | 2016-11-16 | 武汉大学 | A kind of hydro powered cogeneration of hydrogen and electricity system |
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| JP2008260971A (en) * | 2007-04-10 | 2008-10-30 | Toshiba Corp | Steam electrolyzer and steam electrolyzing method |
| AU2009277956B2 (en) * | 2008-07-29 | 2014-10-02 | Yeda Research And Development Company Ltd. | System and method for hydrogen or syngas production |
| FR2969179B1 (en) | 2010-12-20 | 2013-02-08 | Commissariat Energie Atomique | HYDROGEN PRODUCTION CELL COMPRISING A HIGH TEMPERATURE WATER VAPOR ELECTROLYSER CELL |
| KR20120097196A (en) * | 2011-02-24 | 2012-09-03 | 한국에너지기술연구원 | Mnaifold for flat-tubular solid oxide cell stack |
| JP5514266B2 (en) * | 2012-06-25 | 2014-06-04 | 株式会社東芝 | Steam electrolysis apparatus and steam electrolysis method |
| CN106661741B (en) | 2015-03-13 | 2019-06-04 | H2Sg能源私人有限公司 | Electrolysis system |
| US10458027B2 (en) * | 2015-10-08 | 2019-10-29 | Low Emission Resources Corporation | Electrode-supported tubular solid-oxide electrochemical cell |
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| JP3369192B2 (en) * | 1991-02-14 | 2003-01-20 | 日本原子力研究所 | Countercurrent electrolytic reactor |
| JPH10172578A (en) * | 1996-12-13 | 1998-06-26 | Mitsubishi Heavy Ind Ltd | Fuel electrode material of solid electrolyte type electrochemical cell |
| JPH11241195A (en) * | 1998-02-27 | 1999-09-07 | Mitsubishi Heavy Ind Ltd | Solid electrolyte type electrochemical cell and production of hydrogen |
| JP3581011B2 (en) * | 1998-03-20 | 2004-10-27 | 日本原子力研究所 | Electrochemical reactor |
| US6051125A (en) * | 1998-09-21 | 2000-04-18 | The Regents Of The University Of California | Natural gas-assisted steam electrolyzer |
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| CN102181878A (en) * | 2011-04-22 | 2011-09-14 | 北京航空航天大学 | Static water supply proton exchange membrane brine electrolysis device |
| CN102181878B (en) * | 2011-04-22 | 2013-11-13 | 北京航空航天大学 | Static water supply proton exchange membrane brine electrolysis device |
| CN106115620A (en) * | 2016-06-20 | 2016-11-16 | 武汉大学 | A kind of hydro powered cogeneration of hydrogen and electricity system |
| CN106115620B (en) * | 2016-06-20 | 2018-03-13 | 武汉大学 | A kind of hydro powered cogeneration of hydrogen and electricity system |
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