CN102056866A - Process for producing compounds of the CxHyO2 type by reduction of carbon dioxide (CO2) and/or carbon monoxide (CO) - Google Patents
Process for producing compounds of the CxHyO2 type by reduction of carbon dioxide (CO2) and/or carbon monoxide (CO) Download PDFInfo
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- CN102056866A CN102056866A CN2009801219418A CN200980121941A CN102056866A CN 102056866 A CN102056866 A CN 102056866A CN 2009801219418 A CN2009801219418 A CN 2009801219418A CN 200980121941 A CN200980121941 A CN 200980121941A CN 102056866 A CN102056866 A CN 102056866A
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 13
- 230000009467 reduction Effects 0.000 title claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000007769 metal material Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000002950 deficient Effects 0.000 claims description 9
- 230000005588 protonation Effects 0.000 claims description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000280 densification Methods 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 229910052586 apatite Inorganic materials 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010436 fluorite Substances 0.000 claims description 3
- 150000004715 keto acids Chemical class 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 abstract description 6
- 239000007924 injection Substances 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 150000001722 carbon compounds Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- -1 carbon monoxide compound Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012078 proton-conducting electrolyte Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a process for electrolysing steam introduced under pressure into an anode compartment (32) of an electrolyser (30) provided with a proton-conducting membrane (31) made of a material that allows protonated species to be incorporated into this membrane under steam, water injected in steam form being oxidized at the anode (32) so as to generate protonated species in the membrane that migrate within this same membrane and are reduced at the surface of the cathode (33) in the form of reactive hydrogen atoms capable of reducing carbon dioxide and/or carbon monoxide, said process comprising the following steps: injection of CO2 and/or CO under pressure into the cathode compartment (33) of the electrolyser (30); - reduction of the CO2 and/or CO injected into the cathode compartment (33) by said reactive hydrogen atoms generated, in such a way that the CO2 and/or the CO form compounds of the CxHyOz type where x>1, y is between 0 and 2x+2 and z is between 0 and 2x.
Description
Technical Field
The invention relates to the reduction of carbon dioxide (CO)2) And/or carbon monoxide (CO), in particular x > 1, y between 0 and 2x +2 and z between 0 and 2x, in particular highly active hydrogen species generated by electrolysis of water.
Background
At present, ceramic conductive membranes (conductive membranes) are the subject of much research to improve their properties. These films find particularly interesting application in the following fields:
-water electrolysis at high temperature to produce hydrogen,
treatment of carbon-containing gases (CO) by electrochemical hydrogenation2CO) to give a compound of the CxHyOz type (x > 1, y between 0 and 2x +2 and z between 0 and 2 x).
Currently hydrogen (H)2) Seems to be a very interesting energy carrier, inOther substances among petroleum, oils and lubricating oils, the treatment of hydrogen is becoming increasingly important and may eventually advantageously replace petroleum and fossil energy, whose reserves will decrease drastically in the coming decades. However, from this viewpoint, development of an efficient hydrogen production method is required.
Admittedly, numerous sources of information have described numerous methods for the production of hydrogen, but many of these methods have proven to be unsuitable for the large-scale industrial production of hydrogen.
In this context, for example, the synthesis of hydrogen from steam reforming hydrocarbons may be cited. One of the major problems with this synthetic route is that it produces a large amount of CO as a by-product2A greenhouse-like gas. In fact, the production of 1 ton of hydrogen releases 8 to 10 tons of CO2。
Thus, two challenges exist in the next few years: new energy carriers (such as hydrogen) are sought that are available and do not pose a threat to the environment, as well as reducing the amount of carbon dioxide.
The technical economic evaluation of industrial processes now takes into account the latter data. However, it is essentially closed, especially in subsurface fractures that do not necessarily correspond to old reservoirs, which in the end may not be without danger.
It seems advisable to reuse this carbon dioxide in the form of compounds useful in the chemical field or in the field of energy production. The energy required for this conversion is electricity, for example from a nuclear source, in particular from a reactor such as a nuclear reactor of the HTR "high temperature reactor" type or an EPR (registered trade mark) european pressurized water reactor.
A promising industrial hydrogen production route is the technique known as steam electrolysis, e.g. at high temperatures (EHT), at intermediate temperatures, typically above 200 ℃, or even at intermediate temperatures between 200 ℃ and 1000 ℃.
Two steam electrolysis production methods are currently known: according to a first method, illustrated in FIG. 1, O is carried2-Electric operated by ions and at temperatures typically between 750 ℃ and 1000 ℃And (4) decomposing the materials.
More specifically, fig. 1 schematically shows an electrolyzer 1 comprising a ceramic membrane 2, O separating an anode 3 and a cathode 4 ensuring the action of an electrolyte2-An ion conductor.
The application of a potential difference between the anode 3 and the cathode 4 causes H on the cathode 4 side2And (4) reducing O steam. This reduction forms hydrogen H on the surface of the cathode 4 according to the following reaction2And O2-Ions (in the Kroen-Weck notation)
)：
According to the following oxidation reaction, O2-Ionic, more precisely, oxygen vacancy (vacacy)
Migrate through the electrolyte 2 to form oxygen O on the surface of the anode 32And, electron e is released:
thus, the first method allows the output from the electrolyzer 1: the anode compartment is made to produce oxygen and the cathode compartment is made to produce hydrogen mixed with steam.
According to a second method, illustrated in figure 2, an electrolyte is used which is capable of carrying protons and which operates at a temperature lower than that required for the first method described above, generally between 200 ℃ and 800 ℃.
More specifically, this figure 2 schematically shows an electrolyser 10 comprising a proton-conducting ceramic membrane 11 separating an anode 12 and a cathode 13 ensuring the action of the electrolyte.
The application of a potential difference between the anode 12 and the cathode 13 causes H on the anode 12 side2And (4) oxidizing O steam. The steam injected into the anode 12 is thus oxidized to form oxygen O2And H+Ions (or in the Kroen-Weck notation)
) The reaction releases electrons e according to the following equation-：
According to the formula, the formula H+Ions (or in the Kroen-Weck notation)
) Migrate through the electrolyte 11 to form hydrogen H on the surface of the cathode 132：
Thus, the method provides an output from the electrolyzer 10: the cathode compartment supplies pure hydrogen gas-the anode compartment supplies oxygen mixed with steam.
More specifically, H is caused by the formation of an intermediate compound2The intermediate compound is a hydrogen atom and/or radical hydrogen atom H adsorbed on the surface of a cathode with variable energy and degree of interaction*(or H in Kroen-Weck notationX Electrode for electrochemical cell). Since these substances have high activity, they generally recombine to form hydrogen H according to the following equation2：
The aim of the invention is to reduce the amount of carbon dioxide present, for example by reusing it in the form of compounds usable in the chemical field or in the field of energy production.
To achieve this object, the invention proposes a method of electrolyzing water vapour injected under pressure into the anode compartment of an electrolyser having a proton-conducting membrane made of a material into which a substance capable of protonating under steam is introduced, the water injected in the form of steam being oxidized at the anode to produce a protonated substance in the membrane, which migrates within the membrane and is reduced at the cathode surface to a substance capable of reducing carbon dioxide, CO2And/or the active hydrogen atoms of carbon monoxide CO, said process comprising the steps of:
-reacting CO under pressure2And/or CO is injected into the cathode compartment of the electrolyzer;
-CO to be injected into the cathodic compartment by means of the active hydrogen atoms produced2And/or CO reduction, whereby CO2And/or CO form CxHyOz type compounds, where x > 1, y is between 0 and 2x +2, and z is between 0 and 2 x.
As mentioned above, it is understood that active hydrogen atoms refer to hydrogen atoms and/or radical hydrogen atoms H adsorbed on the surface of the cathode with variable energy and degree of interaction*(or H in the Kroen-Weck notation)X Electrode for electrochemical cell)。
The present invention results from the observation that the second method described above produces highly active hydrogen at the cathode of the electrolyzer (in particular hydrogen atoms and/or radical hydrogen atoms adsorbed on the surface of the electrodes).
These highly active hydrogen atoms HX Electrode for electrochemical cellThe reaction on the surface of the cathode is as follows:
in fact, CO on the cathode side2And/or CO, high active hydrogen HX Electrode for electrochemical cellReacting with a carbon compound at the electrode to produce a reduced carbon dioxide and/or carbon monoxide compound of the CxHyOz type, wherein x > 1, y is between 0 and 2x +2, and z is between 0 and 2 x.
Illustratively, these compounds are paraffins CnH2n+2C olefin2nH2nAlcohol CnH2n+2OH or CnH2n-1OH, aldehydes and ketones CnH2nO, acid Cn-1H2n+1COOH, wherein n > 1.
Thus, as will be described below, the present invention enables electrolysis of steam and simultaneous electroreduction of carbon dioxide and/or carbon monoxide.
The process of the invention may also have one or more of the following characteristics, considered alone or in all technically possible combinations:
the method comprises a step of controlling the nature of the formed compound of the CxHyOz type according to the voltage-current pair applied on the cathode;
the method comprises the step of using a proton-conducting membrane for oxygen O2And hydrogen H2Is impermeable and enables the protonated species to be injected into the membrane at vapor pressure;
the method comprises the step of using a proton conducting membrane of the type: perovskite vacancy (perovskite), non-stoichiometric perovskite and/or doped with a compound of formula ABO3Perovskite, fluorite, pyrochlore A of2B2X7Apatite Me10(XO4)6Y2Hydroxyapatite Me10(XO4)6O2Structure, hydroxyapatite Me10(XO4)6(OH)2A structure, a silicate, an aluminosilicate (layered silicate or zeolite) structure, an oxoacid (oxyacid) grafted silicate or a phosphate grafted silicate;
the method comprises the step of using an electrolyte supported by the cathode or by the anode to reduce its thickness and thus to improve its mechanical strength;
-the method comprises a step of exploiting a relative partial pressure of steam greater than or equal to 1 bar and less than or equal to the burst pressure of the assembly, the latter being greater than or equal to at least 100 bar;
the relative partial pressure of steam is advantageously greater than or equal to 50 bar;
-CO2and/or the relative pressure of the CO is greater than or equal to 1 bar and less than or equal to the burst pressure of the assembly, the latter being greater than or equal to at least 100 bar;
-electrolysis temperature greater than or equal to 200 ℃ and less than or equal to 800 ℃, advantageously between 350 ℃ and 650 ℃;
the electrode with porous structure can be a ceramic-metal material or a "ceramic" electrode with both electronic and ionic conductivity;
the ceramic-metal material of the cathode is a ceramic compatible with the electrolyte, wherein the nature of the dispersed metal is advantageously a metal or metal alloy, wherein the metal can be, for example, cobalt, copper, molybdenum, silver, iron, zinc, noble metals (gold, platinum, palladium) and/or transition elements;
the ceramic-metal material of the anode is a ceramic compatible with the electrolyte, wherein the dispersed metal is advantageously a metal alloy or a passivatable metal.
The invention also relates to a steam electrolysis device for the electrolysis of water vapour introduced under pressure into the anode chamber of an electrolyser having a proton-conducting membrane made of a material which, after oxidation under steam, enables protonation of substances to be injected into the membrane, comprising:
-an electrolyte in the form of an ion-conducting membrane made of a material capable of allowing the injection of a protonated substance into the membrane under the action of water pressure;
-an anode
-cathode
-a generator (generator) capable of generating an electric current and applying a potential difference between the anode and the cathode;
characterized in that said generator comprises:
-means for introducing steam under pressure into said electrolyte through said anode;
-reacting CO under pressure2And/or CO injection into the cathode compartment of the electrolyzer; and
-injecting CO into the cathodic compartment according to the method of one of the preceding embodiments2And/or equipment for CO reduction.
The device of the invention may also have one or more of the following features, considered alone or in all technically possible combinations:
material capable of causing the protonated species to be injected towards O2And H2The gas is impermeable;
-the material capable of allowing the injection of the protonated species has a densification level (densification level) exceeding 88%, preferably equal to at least 94%;
the material capable of causing the protonated substance to be implanted is an oxygen atom-deficient oxide that functions as a protonated conductor, such as an oxygen-deficient perovskite; in this case, the oxygen atom deficient oxide may exhibit stoichiometric intervals (stoichiometric intervals) and/or may be doped.
Drawings
Other characteristics and advantages of the invention will appear more clearly from the following description, made with reference to the accompanying drawings, which are given by way of illustration and are not to be construed as limiting the invention in any way. Wherein,
FIGS. 1 and 2 already described describe steam in a simple schematic way, and
FIG. 3 depicts schematically and in a simplified manner the CO2And/or a steam electrolyzer in which CO is simultaneously electrically reduced.
FIG. 3 shows, schematically and in a simple manner, an embodiment of the electrolysis device according to the invention for the production of hydrogen and simultaneous CO2And/or electro-reduction of CO.
Detailed Description
The electrolysis apparatus has a structure similar to that of the apparatus of FIG. 2. Thus, the device comprises:
-an anode 32;
-a cathode 33;
-an electrolyte 31;
a generator 34 ensuring a potential difference between said anode 32 and said cathode 33;
-allowing pH at steam pressure2Means 35 for introducing steam into the membrane 31 through the cathode 33 (the relative partial pressure of the steam being greater than or equal to 1 bar and less than or equal to the burst pressure of the assembly, the latter being greater than or equal to at least 100 bar).
According to the invention, the device also comprises means allowing the pressure of the gas (pCO)2And/or CO) by reacting CO2And/or means 36 for introducing CO into the cathode compartment 33.
At the level of the anode 32, the injection of steam is carried out through the device 35, while at the level of the cathode 33, CO2And/or the CO gas is injected through the device 36In (1).
At the anode 32, water is oxidized by releasing electrons, while H+Ion (in)
Format) was produced according to a method similar to that described for fig. 2.
These H+Ion transport through electrolyte 31, CO2And/or CO type carbon compound in cathode 33 and these H+The ions react at the cathode to form a CxHyOz type compound (x > 1, y between 0 and 2x +2, z between 0 and 2 x) and water.
In particular, the chemical formula of the various reactions can be described as:
since the nature of the compound formed depends on the process conditions, the complete CxHyOz formation reaction can be described as:
the properties of the CxHyOz compound synthesized at the cathode depend on many process parameters such as gas pressure, operating temperature T1 and the voltage-current pair applied to the cathode:
with respect to gas pressure, CO2And/or the relative pressure of the CO is greater than or equal to 1 bar and less than or equal to the burst pressure of the assembly, the latter being greater than or equal to at least 100 bar.
It should be noted that the term relative pressure herein refers to the introduced pressure relative to atmospheric pressure.
It should be noted that it is possible to use a gas stream containing only steam, but also a gas stream containing part of the steam. Thus, based on this, the term "partial pressure" will refer to the total pressure of the gas stream when the gas stream consists only of steam, but may also be the partial pressure of steam when the gas stream contains gases other than steam.
The total pressure applied to the cathode or anode chamber can be counteracted by the other chamber to have a pressure differential between the two chambers to prevent cracking of the membrane, and if the membrane's resistance to cracking is too low, the electrode support assembly.
As regards the operating temperature T1 of the device, the latter depends on the type of material used for the membrane 31; in any case, the temperature is above 200 ℃ and generally below 800 ℃ or even below 600 ℃. The operating temperature is in accordance with the formula H+Proton assured conductivity.
The operating temperature T1 of the device also depends on the desired properties of the CxHyOz carbon compound, in the range of 200-800 ℃.
In fact, a wide variety of compounds are available, such as methane, methanol, formaldehyde, carboxylic acids (formic acid, etc.) and other compounds with longer chains, which can go all the way to the formation of synthetic fuels.
For example, at the cathode the following reactions can be performed:
with respect to the voltage-current pair applied to the cathode, it should be noted that the nature of the carbon compounds formed also depends on the voltage. In fact, the more reducing the cathode medium (low redox potential E), the more carbon compounds are hydrogenated, as shown in the following figure (R, for example, is an alkyl group).
For an advantageous embodiment of these reactions, electrodes with many three contact points, i.e. points or contact surfaces between the ion conductor, the electron conductor and the gas phase, have to be used.
For example, contemplated electrodes are preferably ceramic-metal materials formed from a mixture of ionically conductive ceramics and electronically conductive metals.
However, it is also contemplated to use "all-ceramic" electron conducting electrodes instead of ceramic-metal materials.
It should be noted that a given electrolyte may be O depending on the temperature and pressure of the steam used2-Proton or ion conductors.
However, the use of proton-conducting membranes generates hydrogen (in the form of hydrogen atoms more or less adsorbed on the cathode surface) which is compared to hydrogen H2(or dihydro) is much more active and therefore more active than the conventional hydrogenation process (in H)2 ofIn the presence) of CO is better able to make CO2And CO hydrogenation.
Also, H operating at moderate temperatures is used+Ion-conducting membranes are capable of synthesizing CxHyOz-type complex compounds (x, y and z greater than 1) while using O operating at much higher temperatures2-Conductive membranes preferentially produce CO, which is a product that is stable at high temperatures.
The aim of the invention is to obtain hydrogen generation and/or CO2And/or maximum yield of hydrogenation of CO. For this reason, most of the current used has to intervene in the faraday process, i.e. for the reduction of water and thus the production of highly active hydrogen.
Therefore, the voltage for polarization must be influenced by at least the following factors
Overvoltage at the electrode
Contact resistance at electrode/electrolyte interface
Resistance voltage drop in the material and in particular in the electrolyte
Standard thermodynamic reaction voltage at the electrodes
Herein, the invention proposes the use of proton conducting electrolytes to electrolyze water at high temperature under steam pressure for hydrogen production and CO at the cathode2And/or electro-reduction of CO.
The method comprises the following steps:
-introducing a protonated species into the membrane under the pressure of a gas stream comprising steam;
electrolysis of steam and reduction of gas (CO) in the cathodic compartment2And/or CO).
The protonation of the membrane is promoted by steam under pressure by means of a steam-containing gas stream, and this pressure is advantageously used to obtain the desired conductivity at a given temperature. Such a method is described, for example, in the following documents: french patent application No. 07/55418 filed on 6/1 of 2007.
As described in this application, the applicant observed that an increase in the relative partial pressure of steam resulted in an increase in the ionic conductivity of the membrane.
The correlation between the increase in relative partial pressure and the increase in conductivity enables suitable materials to operate at lower temperatures. In other words, the decrease in conductivity caused by operating at lower temperatures is compensated by an increase in the relative partial pressure of steam.
According to the invention, "highly active" hydrogen is produced at the cathode, which can produce hydrogen (H) in the absence of reducible compounds2) Or in CO2And/or CO (x > 1, y is between 0 and 2x +2, z is between 0 and 2 x).
The proton-conducting membrane is made of a material (e.g. having the general formula AB) that promotes water incorporation1-xDxO3-x/2Doped perovskite material of (a). The material for the anode and cathode is preferably a ceramic-metal material (a mixture of a metal and a perovskite material for the electrolyte). The membrane is preferably selected for O2And H2The gas is impermeable.
In general, the membrane may be of the following type: perovskite vacancies, non-stoichiometric perovskites and/or doped with a compound of the general formula ABO3Perovskite, fluorite, pyrochlore A of2B2X7Apatite Me10(XO4)6Y2Hydroxyapatite Me10(XO4)6O2Structure, hydroxyapatite Me10(XO4)6(OH)2Structure, silicate structure, aluminosilicate (layered silicate or zeolite), silicate grafted with an oxo acid or silicate grafted with a phosphate.
More generally, electrolytes can advantageously be all compounds which act as proton conductors at high or intermediate temperatures, due to their channel or flake structure and/or by the presence of vacancies capable of introducing protonated species of small molecular weight.
Many variations of the invention are possible. The material which is capable of introducing a protonated species in particular may be for O2And H2The gas is impermeable and/or the protonated species may be introduced at a densification level of more than 88%, preferably equal to at least 94%.
In fact, a good compromise must be found between the level of densification which must be as high as possible (in particular with respect to the mechanical strength of the electrolyte and the gas permeation) and the ability of the material to be able to introduce the protonated species. Increasing the partial vapor pressure that promotes incorporation of the protonated species into the film compensates for the increased level of densification.
According to a variant, the material capable of water injection is an oxygen atom-deficient oxide acting as a proton conductor, such as an oxygen atom-vacancy perovskite. Additionally, the oxygen atom deficient oxide may be present at stoichiometric intervals and/or may be doped.
In fact, the non-stoichiometry and/or doping results in the creation of oxygen atom vacancies. Thus, in the case of proton conduction, exposure of the perovskite, which has a stoichiometric spacing and/or is doped (and therefore oxygen deficient) to steam under pressure, induces protonation species to be incorporated into the structure. According to the reaction, a water molecule fills an oxygen vacancy and splits into two hydroxyl groups (or H on an oxide site)+Proton):
it should be noted that materials other than non-stoichiometric and/or doped perovskites may also be used as materials that facilitate the introduction of water and its decomposition in the form of protonated species and/or hydroxyl groups.
For example, there may be mentioned crystallographic structures, such as fluorite structure, pyrochlore A2B2X7Structure, apatite Me10(XO4)6Y2Structure, hydroxyapatite Me10(XO4)6O2Structure, hydroxyapatite Me10(XO4)6(OH)2Structure, silicate, aluminosilicate, layered silicate or phosphate.
It is possible for these structures to be grafted via oxo groups. In fact, all structures with high affinity for water and/or protons can be considered.
Claims (17)
1. A method of electrolyzing steam injected under pressure into an anode chamber (32) of an electrolyzer (30), said electrolyzer (30) having a proton-conducting membrane (31) made of a material that under steam enables protonation species to be introduced into said membrane, water injected in the form of steam being oxidized at said anode (32) to generate protonation species in the membrane, which migrate within said membrane and are reduced at the surface of a cathode (33) to form species capable of reducing carbon dioxide CO2And/or the active hydrogen atoms of carbon monoxide CO, said process comprising the steps of:
-carbon dioxide CO under pressure2And/or carbon monoxide CO is introduced into the cathode compartment (33) of the electrolyzer (30);
-reducing the CO introduced into the cathodic compartment (33) by means of the active hydrogen atoms produced2And/or CO, such that the CO2And/or CO form CxHyOz type compounds, where x ≧ 1, y ranges from 0 to 2x +2, and z ranges from 0 to 2 x.
2. The electrolytic process of claim 1, comprising the step of controlling the nature of the formed CxHyOz-type compound as a function of the voltage-current pair applied to the cathode.
3. The electrolytic process according to claim 1 or 2, characterized in that it comprises a step of using a proton-conducting membrane (31), said proton-conducting membrane (31) being oxygen, O2And H2Is impermeable and enables the introduction of the protonated species into the membrane (31) under vapour pressure.
4. The electrolytic process according to claim 3, characterized in that it comprises a step of using a proton-conducting membrane (31) of the following kind: perovskite vacancies, non-stoichiometric perovskites and/or doped with a compound of the general formula ABO3Perovskite, fluorite, pyrochlore A of2B2X7Apatite Me10(XO4)6Y2Hydroxyapatite Me10(XO4)6O2Structure, hydroxyapatite Me10(XO4)6(OH)2Structure, silicate structure, aluminosilicate, layered silicate, zeolite, silicate grafted with an oxo acid, or silicate grafted with a phosphate.
5. The electrolytic process according to claim 4, characterized in that it comprises a step of using as proton-conducting membrane (31) an electrolyte supported by the cathode (33) or by the anode (32) to reduce its thickness and thus to improve its mechanical strength.
6. The electrolytic process of any one of the preceding claims, comprising the step of using a relative partial pressure of steam greater than or equal to 1 bar and less than or equal to the burst pressure of the assembly, the latter being greater than or equal to at least 100 bar.
7. The electrolytic process of any one of the preceding claims, wherein the relative partial pressure of the steam is advantageously greater than or equal to 50 bar.
8. The electrolysis process according to any preceding claim, wherein the CO is2And/or the relative pressure of the CO is greater than or equal to 1 bar and less than or equal to the burst pressure of the assembly, the latter being greater than or equal to at least 100 bar.
9. The method of any one of the preceding claims, wherein the electrolysis temperature is greater than or equal to 200 ℃ and less than or equal to 800 ℃, advantageously between 350 ℃ and 650 ℃.
10. The electrolytic process according to any one of the preceding claims, characterized in that the electrodes (32, 33) with a porous structure are ceramic-metal materials or "ceramic" electrodes with both electronic and ionic conductivity.
11. The electrolytic method according to claim 10, characterized in that the ceramic-metal material of the cathode (33) is a ceramic-metal material in which the ceramic is compatible with the electrolyte forming the membrane (31) and in which the nature of the metal dispersed is advantageously a metal and/or a metal alloy, in which the metal can be, for example, cobalt, copper, molybdenum, silver, iron, zinc, noble metals (gold, platinum, palladium) and/or transition elements.
12. The electrolytic method according to claim 10 or 11, characterized in that the ceramic-metal material of the anode (32) is a ceramic-metal material in which the ceramic is compatible with the electrolyte forming the membrane (31) and in which the properties of the metal dispersed are advantageously a metal alloy or a passivatable metal.
13. A steam electrolysis apparatus (30) for electrolyzing steam introduced under pressure into an anode chamber of an electrolyzer having a proton-conducting membrane made of a material that, after oxidation under steam, enables protonation of species injected into the membrane, the apparatus comprising:
-an electrolyte (31) in the form of an ion-conducting membrane made of said material enabling a protonated substance to be injected into said membrane under the effect of water pressure;
-an anode (32);
-a cathode (33);
-a generator (34) able to generate an electric current and to apply a potential difference between the anode (32) and the cathode (33);
characterized in that the steam electrolysis device comprises:
-means (35) for introducing steam under pressure into the electrolyte (31) through the anode (32);
-reacting CO under pressure2And/or CO into the cathode compartment of the electrolyzer (36);
-CO to be introduced into the cathodic compartment according to the process of one of the preceding embodiments2And/or equipment for CO reduction.
14. The apparatus of claim 13, wherein the material capable of causing the protonation species to be injected is for O2And H2The gas is impermeable.
15. The device according to claim 13 or 14, characterized in that the material capable of causing protonation to be injected has a densification level exceeding 88%, preferably equal to at least 94%.
16. The apparatus according to any of claims 13 to 15, wherein the material capable of causing protonation is an oxygen atom deficient oxide acting as a proton conductor, such as an oxygen atom deficient perovskite.
17. The device of claim 16, wherein the oxygen atom deficient oxide is stoichiometrically spaced and/or doped.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0853161 | 2008-05-15 | ||
| FR0853161A FR2931168B1 (en) | 2008-05-15 | 2008-05-15 | PROCESS FOR PRODUCING CXHYOZ COMPOUNDS BY REDUCING CARBON DIOXIDE (CO2) AND / OR CARBON MONOXIDE (CO) |
| PCT/FR2009/050909 WO2009150352A2 (en) | 2008-05-15 | 2009-05-15 | Process for producing compounds of the c<sb>x</sb>h<sb>y</sb>o<sb>2</sb> type by reduction of carbon dioxide (co<sb>2</sb>) and/or carbon monoxide (co) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102056866A true CN102056866A (en) | 2011-05-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801219418A Pending CN102056866A (en) | 2008-05-15 | 2009-05-15 | Process for producing compounds of the CxHyO2 type by reduction of carbon dioxide (CO2) and/or carbon monoxide (CO) |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20110132770A1 (en) |
| EP (1) | EP2282983A2 (en) |
| JP (1) | JP2011521104A (en) |
| CN (1) | CN102056866A (en) |
| BR (1) | BRPI0912654A2 (en) |
| FR (1) | FR2931168B1 (en) |
| RU (1) | RU2493293C2 (en) |
| WO (1) | WO2009150352A2 (en) |
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| CN103987878A (en) * | 2011-10-12 | 2014-08-13 | 阿海珐 | Method for generating hydrogen and oxygen by steam electrolysis |
| CN104024479A (en) * | 2011-10-12 | 2014-09-03 | 阿海珐 | Method and system for treating carbon gases by electrochemical hydrogenation in order to obtain a cxhyoz compound |
| CN108570690A (en) * | 2017-03-14 | 2018-09-25 | 株式会社东芝 | Carbon dioxide electrolysis unit |
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| FR3004179B1 (en) | 2013-04-08 | 2015-05-01 | Commissariat Energie Atomique | METHODS FOR OBTAINING COMBUSTIBLE GAS FROM WATER ELECTROLYSIS (EHT) OR CO-ELECTROLYSIS WITH H2O / CO2 WITHIN THE SAME ENCLOSURE, CATALYTIC REACTOR AND SYSTEM THEREOF |
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- 2009-05-15 WO PCT/FR2009/050909 patent/WO2009150352A2/en active Application Filing
- 2009-05-15 EP EP09761903A patent/EP2282983A2/en not_active Withdrawn
- 2009-05-15 US US12/992,740 patent/US20110132770A1/en not_active Abandoned
- 2009-05-15 BR BRPI0912654A patent/BRPI0912654A2/en not_active Application Discontinuation
- 2009-05-15 CN CN2009801219418A patent/CN102056866A/en active Pending
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| CN104024479A (en) * | 2011-10-12 | 2014-09-03 | 阿海珐 | Method and system for treating carbon gases by electrochemical hydrogenation in order to obtain a cxhyoz compound |
| CN108570690A (en) * | 2017-03-14 | 2018-09-25 | 株式会社东芝 | Carbon dioxide electrolysis unit |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2931168A1 (en) | 2009-11-20 |
| RU2493293C2 (en) | 2013-09-20 |
| WO2009150352A3 (en) | 2010-02-18 |
| BRPI0912654A2 (en) | 2016-07-05 |
| JP2011521104A (en) | 2011-07-21 |
| US20110132770A1 (en) | 2011-06-09 |
| WO2009150352A2 (en) | 2009-12-17 |
| FR2931168B1 (en) | 2010-07-30 |
| EP2282983A2 (en) | 2011-02-16 |
| RU2010151465A (en) | 2012-06-20 |
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