U.S. patent application number 14/350837 was filed with the patent office on 2014-10-02 for method and system for treating carbon gases by electrochemical hydrogenation in order to obtain a cxhyoz compound.
The applicant listed for this patent is AREVA. Invention is credited to Frederic Grasset, Olivier Lacroix, Joel Mazoyer, Kamal Rahmouni, Beatrice Sala, Abdelkader Sirat, Elodie Tetard.
Application Number | 20140291162 14/350837 |
Document ID | / |
Family ID | 47116072 |
Filed Date | 2014-10-02 |
United States Patent
Application |
20140291162 |
Kind Code |
A1 |
Sala; Beatrice ; et
al. |
October 2, 2014 |
METHOD AND SYSTEM FOR TREATING CARBON GASES BY ELECTROCHEMICAL
HYDROGENATION IN ORDER TO OBTAIN A CxHyOz COMPOUND
Abstract
The present invention relates to a method for treating CO.sub.2
by electrochemical hydrogenation, said method comprising: a step of
transferring heat from a heating means (160) towards a
proton-conductive electrolyser (110) such that said electrolyser
(110) reaches an operating temperature suitable for electrolysing
steam; a step of feeding the CO.sub.2 produced by said heating
means (160) at the cathode of the electrolyser; a step of feeding
the steam at the anode; a step of oxidising the steam at the anode;
a step of generating protonated species in the membrane with proton
conduction; a step of migrating said protonated species into said
proton-conductive membrane; a step of reducing said protonated
species on the surface of the cathode into reactive hydrogen atoms;
and a step of hydrogenating the CO.sub.2 on the surface of the
cathode of the electrolyser (110) by means of said reactive
hydrogen atoms, said hydrogenation step enabling the formation of
C.sub.xH.sub.yO.sub.z compounds, where x.gtoreq.1;
0<y.ltoreq.(2x+2) and 0.ltoreq.z.ltoreq.2x.
Inventors: |
Sala; Beatrice; (Saint Gely
Du Fesc, FR) ; Grasset; Frederic; (Montpellier,
FR) ; Lacroix; Olivier; (Montpellier, FR) ;
Sirat; Abdelkader; (Montpellier, FR) ; Tetard;
Elodie; (Montpellier, FR) ; Rahmouni; Kamal;
(Montpellier, FR) ; Mazoyer; Joel; (Saint-Gilles,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
AREVA |
Paris |
|
FR |
|
|
Family ID: |
47116072 |
Appl. No.: |
14/350837 |
Filed: |
October 11, 2012 |
PCT Filed: |
October 11, 2012 |
PCT NO: |
PCT/FR2012/052319 |
371 Date: |
April 10, 2014 |
Current U.S.
Class: |
205/446 ;
204/262; 205/448; 205/450; 205/455 |
Current CPC
Class: |
B01D 2257/502 20130101;
Y02E 60/36 20130101; C25B 3/04 20130101; B01D 53/326 20130101; C25B
1/04 20130101; Y02P 20/151 20151101; B01D 2251/202 20130101; B01D
2257/504 20130101; C25B 15/08 20130101; Y02P 20/152 20151101; Y02E
60/366 20130101; C25B 15/00 20130101 |
Class at
Publication: |
205/446 ;
205/455; 205/450; 205/448; 204/262 |
International
Class: |
C25B 3/04 20060101
C25B003/04 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 12, 2011 |
FR |
1159223 |
Claims
1. A Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation in order to obtain a C.sub.xH.sub.yO.sub.z type
compound, where x.gtoreq.1; 0<y.ltoreq.(2x+2) and z is comprised
between 0 and 2x, said CO.sub.2 and/or CO being obtained by the
combustion of carbon products via heating means, said method
comprising: a step of transferring heat from the heating means to a
proton-conducting electrolyser such that said electrolyser reaches
an operating temperature (T1) suitable for electrolysing steam,
said proton-conducting electrolyser comprising a proton-conducting
membrane arranged between an anode and a cathode; a step of feeding
the CO.sub.2 and/or CO produced by said heating means at the
cathode of the proton-conducting electrolyser, a step of feeding
steam at the anode of said electrolyser; a step of oxidising the
steam at the anode; a step of generating protonated species in the
proton-conducting membrane after said step of oxidation; a step of
migrating said protonated species in said proton-conducting
membrane; a step of reducing said protonated species on the surface
of the cathode in the form of reactive hydrogen atoms; a step of
hydrogenating CO.sub.2 and/or CO on the surface of the cathode of
the electrolyser by means of said reactive hydrogen atoms, said
hydrogenation step making it possible to form C.sub.XH.sub.yO.sub.Z
type compounds where x.gtoreq.1; 0<y.ltoreq.(2x+2) and
0.ltoreq.z.ltoreq.2x.
2. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1 wherein said method comprises a
step of using C.sub.XH.sub.yO.sub.Z type compounds produced by
hydrogenation as fuel for said heating means.
3. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein prior to the use of
C.sub.XH.sub.yO.sub.Z type compounds as fuel for said heating
means, said method comprises a step of phase separation making it
possible to inject into the heating means uniquely gaseous
C.sub.XH.sub.yO.sub.z type compounds:
4. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein prior to said step of
introducing the CO.sub.2 and/or the CO produced by said heating
means at the cathode of the electrolyser, said method comprises a
step of purifying the CO.sub.2 and/or the CO produced by said
heating means so as to obtain pure CO.sub.2 and/or CO.
5. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein said step of oxidising
the steam at the anode generates oxygen at the outlet of the
electrolyser.
6. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 5 wherein said method comprises a
step of phase separation of the oxygen produced by said
electrolyser.
7. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein said method comprises a
step of re-injecting gaseous oxygen into said heating means.
8. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein the method comprises a
step of controlling the nature of the C.sub.XH.sub.yO.sub.Z type
compounds formed as a function of the potential and/or the current
applied at the cathode (33) or at the terminals of the
electrolyser.
9. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein the
C.sub.XH.sub.yO.sub.Z type compounds formed belong to the family of
alkanes or alkenes or alkynes, substituted or not, being able to
include one or more alcohol or aldehyde or ketone or acetal or
ether or peroxide or ester or anhydride functions.
10. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein the
C.sub.XH.sub.yO.sub.Z type compounds formed are carbon compound
fuels.
11. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein said step of heat
transfer from the heating means to said electrolyser is carried out
by means of a heat exchanger.
12. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein said step of heat
transfer from the heating means to said electrolyser is carried out
by direct heat transfer, said electrolyser being positioned in a
heat area in the vicinity of said heating means.
13. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein said heat transfer from
the heating means to a proton-conducting electrolyser is carried
out such that said electrolyser reaches a temperature (T1) not less
than 200.degree. C. and not more than 800.degree. C.,
advantageously comprised between 350.degree. C. and 650.degree.
C.
14. The Method for treating CO.sub.2 and/or CO by electrochemical
hydrogenation according to claim 1, wherein said heat transfer from
the heating means to a proton-conducting electrolyser is carried
out such that said electrolyser reaches a temperature (T1)
comprised between 500.degree. C. and 600.degree. C.
15. A System for treating carbon gases by electrochemical
hydrogenation for the implementation of the method according to
claim 1, said system comprising: heating means emitting CO.sub.2
and/or CO through the combustion of carbon products; a
proton-conducting electrolyser comprising an electrolyte in the
form of a proton-conducting membrane, an anode and a cathode; said
electrolyser being positioned in the vicinity of the heating means;
means for inserting under pressure steam into said electrolyte via
said anode; means for feeding under pressure the CO.sub.2 and/or
the CO produced by the heating means on the surface of the cathode
of the electrolyser; means for evacuating the C.sub.XH.sub.yO.sub.Z
type compounds formed by hydrogenation on the surface of the
cathode of the electrolyser; means for evacuating the oxygen and
water generated at the anode by the steam electrolysis
reaction.
16. The System for treating carbon gases by electrochemical
hydrogenation according to claim 15 wherein the heating means are
formed of a boiler.
Description
[0001] The present invention relates to a method and a system for
treating carbon gases--carbon dioxide (CO.sub.2) and/or carbon
monoxide (CO)--from very reactive hydrogen generated by
electrolysis of water in order to obtain a CxH.sub.yO.sub.z type
compound, particularly where x.gtoreq.1; 0<y.ltoreq.(2x+2) and
0.ltoreq.z.ltoreq.2x.
[0002] Conductive ceramic membranes are today the subject of
wide-spread research to enhance their performances; notably, said
membranes find particularly interesting applications in the fields:
[0003] of the electrolysis of water at high temperature for the
production of hydrogen, [0004] of the treatment of carbon gases
(CO.sub.2, CO) by electrochemical hydrogenation in order to obtain
CxH.sub.yOz type compounds (x.gtoreq.1; 0<y.ltoreq.(2x+2) and
0.ltoreq.z.ltoreq.2x), the patent application WO2009150352
describes an example of such a method.
[0005] At the present time, two steam electrolysis production
methods are known: [0006] electrolysis using O.sup.2- anionic
conductors and operating at temperatures generally comprised
between 750.degree. C. and 1000.degree. C.; [0007] electrolysis
using the protonic conductors that are involved in this patent.
[0008] The production method, illustrated in FIG. 1, uses an
electrolyte capable of conducting protons and operating at
temperatures generally comprised between 200.degree. C. and
800.degree. C.
[0009] More specifically, this FIG. 1 schematically represents an
electrolyser 10 comprising a proton-conducting ceramic membrane 11
assuring the function of electrolyte separating an anode 12 and a
cathode 13.
[0010] The application of a potential difference between the anode
12 and the cathode 13 leads to an oxidation of the steam H.sub.2O
on the side of the anode 12. The steam fed into the anode 12 is
thus oxidised to form oxygen O.sub.2 and H.sup.+ ions (or OH.sub.o.
in the Kroger-Vink notation), said reaction releasing electrons
e.sup.- according to the equation:
H.sub.2O+2O.sub.o.sup.X.fwdarw.2OH.sub.o.+1/2O.sub.2+2e'
[0011] The H.sup.+ ions (or OH.sub.o. in the Kroger-Vink notation)
migrate through the electrolyte 11, to form hydrogen H.sub.2 on the
surface of the cathode 13 according to the equation:
2e'+2OH.sub.o..fwdarw.2O.sub.o.sup.X+H.sub.2
[0012] Thus, this method provides at the outlet of the electrolyser
10 pure hydrogen-cathodic compartment--and oxygen mixed with
steam-anodic compartment.
[0013] More specifically, the formation of H.sub.2 goes through the
formation of intermediate compounds which are hydrogen atoms
adsorbed on the surface of the cathode with variable energies and
degrees of interaction and/or radical hydrogen atoms H. (or
H.sub.Electrode.sup.X in the Kroger-Vink notation). These species
being highly reactive, they normally recombine to form hydrogen
H.sub.2 according to the equation:
2H.sub.Electrode.sup.X.fwdarw.H.sub.2
[0014] These highly reactive species are used to carry out the
treatment of carbon gases (CO.sub.2, CO) by electrochemical
hydrogenation so as to obtain at the outlet of the electrolyser 10
CxH.sub.yOz type compounds (x.gtoreq.1; 0<y.ltoreq.(2x+2) and
0.ltoreq.z.ltoreq.2x, according to the following relationship:
(4x-2z+y)H.sub.Electrode.sup.X+xCO.sub.2.fwdarw.C.sub.xH.sub.yO.sub.z+(2-
x-z)H.sub.2O
[0015] The aim of the invention is to reclaim the carbon gases
resulting for example from the production of heating from carbon
products (coal, wood, oil), or the incineration of waste, and to
reduce in an optimal manner the production of greenhouse gases for
carrying out the treatment by hydrogenation.
[0016] To this end, the invention proposes a method for treating
CO.sub.2 and/or CO by electrochemical hydrogenation in order to
obtain a C.sub.xH.sub.yO.sub.z type compound, where x.gtoreq.1;
0<y.ltoreq.(2x+2) and z is comprised between 0 and 2x, said
CO.sub.2 and/or CO being obtained by the combustion of carbon
products via heating means (160), said method comprising: [0017] a
step of transferring heat from heating means to a proton-conducting
electrolyser such that said electrolyser reaches an operating
temperature T1 suitable for electrolysing steam, said
proton-conducting electrolyser comprising a proton-conducting
membrane arranged between an anode and a cathode; [0018] a step of
feeding the CO.sub.2 and/or the CO produced by said heating means
at the cathode of the proton-conducting electrolyser; [0019] a step
of feeding the steam at the anode of said electrolyser; [0020] a
step of oxidising steam at the anode; [0021] a step of generating
protonated species in the proton-conducting membrane after said
step of oxidation; [0022] a step of migrating said protonated
species in said proton-conducting membrane; [0023] a step of
reducing said protonated species on the surface of the cathode in
the form of reactive hydrogen atoms; [0024] a step of hydrogenating
CO.sub.2 and/or CO on the surface of the cathode of the
electrolyser by means of said reactive hydrogen atoms, said
hydrogenation step making it possible to form CxH.sub.yOz type
compounds, where x.gtoreq.1; 0<y.ltoreq.(2x+2) and
0.ltoreq.z.ltoreq.2x.
[0025] Reactive hydrogen atoms are taken to mean atoms absorbed on
the surface of the cathode and/or radical hydrogen atoms H (or
H.sub.Electrode.sup.X in the Kroger-Vink notation).
[0026] Thus, the method according to the invention makes it
possible to recycle the carbon gases produced by heating means
resulting from the combustion of carbon products by using jointly
the electrolysis of steam, which generates highly reactive hydrogen
at the cathode of the electrolyser, with an electrocatalysed
hydrogenation of the carbon products injected at the cathode of the
electrolyser by reaction with highly reactive hydrogen.
[0027] As an example, said CxH.sub.yOz type compounds are paraffins
C.sub.nH.sub.2n+2, olefins C.sub.2nH.sub.2n, alcohols
C.sub.nH.sub.2n+2OH or C.sub.nH.sub.2n-1OH, aldehydes and ketones
C.sub.nH.sub.2nO.
[0028] Advantageously, the CxH.sub.yOz compounds produced are
compounds making it possible to supply the combustion of heating
means so as to reduce the external input of carbon products.
Advantageously, the compounds formed are carbon product fuels, such
as for example aliphatics or aromatics belonging to the family of
alkanes, alkenes or alkynes, substituted or not, being able to
include one or more alcohol, aldehyde, ketone, acetal, ether,
peroxide, ester, anhydride functions.
[0029] The invention also makes it possible to use advantageously
the heat produced by the heating means (resulting from the
combustion of carbon products) to heat the proton-conducting
electrolyser, the heating of the electrolyser being required to
carry out the electrolysis reaction and the electrocatalysed
hydrogenation reaction. Thus, the electrolyser does not require the
use of specific costly heating means, generating greenhouse
gases.
[0030] The method according to the invention may also have one or
more of the characteristics below, considered individually or
according to any technically possible combinations thereof: [0031]
the method comprises a step of using the CxH.sub.yOz type compounds
produced by hydrogenation as fuel of said heating means; [0032]
prior to the use of the CxH.sub.yOz type compounds as fuel of said
heating means, said method comprises a step of phase separation
making it possible to inject into the heating means the
CxH.sub.yO.sub.z type compounds uniquely in gaseous form; [0033]
prior to said step of feeding the CO.sub.2 and/or the CO produced
by said heating means into the cathodic compartment of the
electrolyser, said method comprises a step of purifying the
CO.sub.2 and/or the CO produced by said heating means so as to
obtain pure CO.sub.2 and/or CO; [0034] said step of oxidising the
steam at the anode generates oxygen at the outlet of the anodic
compartment; [0035] said method comprises a step of phase
separation of the oxygen produced by said electrolyser, [0036] said
method comprises a step of re-injecting the oxygen in gaseous form
into said heating means; [0037] the method comprises a step of
controlling the nature of the CxH.sub.yOz type compounds formed as
a function of the potential and/or the current applied at the
cathode or at the terminals of the electrolyser; [0038] the
CxH.sub.yOz type compounds formed belong to the family of alkanes
or alkenes or alkynes, substituted or not, being able to include
one or more alcohol or aldehyde or ketone or acetal or ether or
peroxide or ester or anhydride functions; [0039] the CxH.sub.yOz
type compounds formed are carbon compound fuels; [0040] said step
of heat transfer from the heating means to said electrolyser is
carried out by means of a heat exchanger: [0041] said step of heat
transfer from the heating means to said electrolyser is carried out
by direct heat transfer, said electrolyser being positioned in a
heat area in the vicinity of said heating means; [0042] the heat
transfer from the heating means to a proton-conducting electrolyser
is carried out such that said electrolyser reaches a temperature
not less than 200.degree. C. and not more than 800.degree. C.,
advantageously comprised between 350.degree. C. and 650.degree. C.;
[0043] the heat transfer from the heating means to a
proton-conducting electrolyser is carried out such that said
electrolyser reaches a temperature comprised between 500.degree. C.
and 600.degree. C.
[0044] The subject matter of the invention is also a system for
treating carbon gases by electrochemical hydrogenation for the
implementation of the method according to the invention, said
system comprising: [0045] heating means emitting CO.sub.2 and/or CO
through the combustion of carbon products; [0046] a
proton-conducting electrolyser comprising an electrolyte in the
form of a proton-conducting membrane, an anode and a cathode; said
electrolyser being positioned in the vicinity of the heating means;
[0047] means for inserting under pressure steam into said
electrolyte via said anode: [0048] means for feeding under pressure
the CO.sub.2 and/or the CO produced by the heating means on the
surface of the cathode of the electrolyser; [0049] means for
evacuating the CxH.sub.yOz type compounds formed by hydrogenation
on the surface of the cathode of the electrolyser; [0050] means for
evacuating the oxygen and the water generated at the anode by the
steam electrolysis reaction.
[0051] According to an advantageous embodiment of the invention,
the heating means are formed of a boiler.
[0052] Other characteristics and advantages of the invention will
become clear from the description that is given thereof below, by
way of indication and in no way limiting, with reference to the
appended figures, among which:
[0053] FIG. 1, already described, is a simplified schematic
representation of a proton-conducting steam electrolyser,
[0054] FIG. 2 is a schematic representation of a system for
treating carbon gases produced by a boiler during the combustion of
carbon products;
[0055] FIG. 3 is a general simplified schematic representation of
an electrolysis cell for the implementation of the method according
to the invention.
[0056] FIG. 2 schematically represents a system for treating carbon
gases 100 enabling the implementation of the method according to
the invention.
[0057] The treatment system 100 comprises: [0058] heating means
160, such as a boiler, discharging CO.sub.2 and/or CO as well as
other gases resulting from the combustion of carbon products used
for the production of heat; [0059] a purifier 120 making it
possible to purify the gases discharged by the boiler 160 so as to
isolate the CO.sub.2 and/or the CO; [0060] a proton-conducting
electrolyser 110 comprising an electrolyte 31 in the form of a
proton-conducting membrane, an anode 32 and a cathode 33 (FIG. 3);
[0061] means 34 (FIG. 3) for inducing a current circulating between
the anode 32 and the cathode 34 of the electrolyser 110; [0062]
means 41 making it possible to insert, advantageously under
pressure, steam pH.sub.20 into the electrolyte via the anode 32;
[0063] means 42 for feeding, advantageously under pressure, the
pCO.sub.2 and/or the pCO purified on the surface of the cathode 33
of the electrolyser 110; [0064] means for evacuating the
CxH.sub.yOz type compounds formed by hydrogenation on the surface
of the cathode 33 of the electrolyser 110; [0065] means for
evacuating the oxygen generated at the anode 32 by the steam
electrolysis reaction.
[0066] The means 34 for inducing a current circulating between the
anode 32 and the cathode 34 may be a voltage, current generator or
a potentiostat (in this case, the cell will also comprise at least
one reference cathodic or anodic electrode).
[0067] FIG. 3 illustrated in a more detailed manner an embodiment
example of an electrolysis cell 30 of the electrolyser 110 used to
form CxH.sub.yOz type compounds (where x.gtoreq.1,
0<y.ltoreq.(2x+2) and 0.ltoreq.z.ltoreq.2x) after the reduction
of the CO.sub.2 and/or the CO.
[0068] At the anode 32, the water is oxidised while releasing
electrons while H.sup.+ ions (in OH.sub.o. form) are generated.
[0069] These H.sup.+ ions migrate through the electrolyte 31 and
are thus capable of reacting with different compounds that could be
injected at the cathode 33, carbon compounds of CO.sub.2 and/or CO
type reacting at the cathode 33 with said H.sup.+ ions to form
C.sub.xH.sub.yO.sub.z type compounds (where x.gtoreq.1,
0<y.ltoreq.(2x+2) and 0.ltoreq.z.ltoreq.2x) and water at the
cathode 33.
[0070] The chemical equations of the different reactions may
notably be written:
(6n+2)H.sub.Electrode.sup.X+nCO.sub.2.fwdarw.C.sub.nH.sub.2n+2+2nH.sub.2-
O
6nH.sub.Electrode.sup.X+nCO.sub.2.fwdarw.C.sub.nH.sub.2n+2nH.sub.2O
6nH.sub.Electrode.sup.X+nCO.sub.2.fwdarw.C.sub.nH.sub.2n+2O+(2n-1)H.sub.-
2O
(6n-2)H.sub.Electrode.sup.X+nCO.sub.2.fwdarw.C.sub.nH.sub.2nO+(2n-1)H.su-
b.2O
[0071] The nature of the compound formed depending on the operating
conditions, the overall reaction of formation of CxH.sub.yO.sub.z
may thus be written:
(4x-2z+y)H.sub.Electrode.sup.X+xCO.sub.2.fwdarw.C.sub.xH.sub.yO.sub.z+(2-
x-z)H.sub.2O
[0072] The nature of the CxH.sub.yO.sub.z compounds synthesized at
the cathode 33 depends on numerous operating parameters such as,
for example, the pressure of the cathodic compartment, the partial
pressure of the gases, the operating temperature T1, the couple
potential/current/voltage applied at the cathode 33 or at the
terminals of the electrolyser, the dwell time of the gas and the
nature of the electrodes.
[0073] The operating temperature T1 of the electrolyser is
comprised in the range between 200 and 800.degree. C.,
advantageously between 350.degree. C. and 650.degree. C. The
operating temperature T1 in this range of temperature is also going
to depend on the nature of the CxH.sub.yOz carbon compounds that it
is wished to generate.
[0074] These operating parameters are defined so as to form at the
outlet of the cathode 33 of the electrolyser 110 a fuel compound,
able to supply the combustion of the boiler 160.
[0075] It is also advantageous that these operating parameters are
defined so as to produce hydrogen at the same time as the
CxH.sub.yOz compound. The hydrogen/CxH.sub.yOz compound mixture has
the advantage of aiding the combustion of the CxH.sub.yO.sub.z
compound in the heating means.
[0076] According to an embodiment example, the operating parameters
are defined so as to obtain a mixture formed of 90% CxH.sub.yOz
compound and 10% hydrogen.
[0077] According to a first embodiment, the anode 32 and the
cathode 33 are preferentially formed of a cermet constituted of the
mixture of a proton-conducting ceramic and an electron-conducting
passivable alloy that is able to form a protective oxide layer so
as to protect it in an oxidising environment (i.e. at the anode of
an electrolyser). Said passivable alloy is preferentially a metal
alloy.
[0078] The passivable alloy comprises for example chromium (and
preferentially at least 40% of chromium) so as to have a cermet
having the particularly of not oxidising at temperature. The
chromium content of the alloy is determined such that the melting
point of the alloy is above the sintering temperature of the
ceramic. Sintering temperature is taken to mean the sintering
temperature required to sinter the electrolyte membrane so as to
make it leak tight to gas.
[0079] The chromium alloy may also comprise a transition metal so
as to retain an electron-conducting character of the passive layer.
Thus the chromium alloy is an alloy of chromium and one of the
following transition metals: cobalt, nickel, iron, titanium,
niobium, molybdenum, tantalum, tungsten, etc.
[0080] The ceramic of the anodic and cathodic 32 and 33 electrodes
is advantageously the same ceramic as that used by the formation of
the electrolytic membrane of the electrolyte 31.
[0081] According to an advantageous embodiment of the invention,
the proton-conducting ceramic used by the formation of the cermet
of the electrodes 32 and 33 and the electrolyte 31 is a perovskite
of zirconate type of generic formula AZrO.sub.3 being able to be
doped advantageously by an element A selected from lanthanides.
[0082] The use of this type of ceramic for the formation of the
membrane thus requires the use of a high sintering temperature in
order to obtain a sufficient densification to be leak tight to gas.
The sintering temperature of the electrolyte 31 is more
particularly defined as a function of the nature of the ceramic but
also as a function of the desired porosity level. Conventionally,
it is estimated that to be leak tight to gas, the electrolyte 31
has to have a porosity level below 6% (or a density above 94%).
[0083] Advantageously, the sintering of the ceramic is carried out
under a reducing atmosphere so as to avoid the oxidation of the
metal at high temperature, i.e. under an atmosphere of hydrogen
(H.sub.2) and argon (Ar), or even carbon monoxide (CO) if there is
no risk of carburation.
[0084] The electrodes 32 and 33 of the cell 30 are also sintered at
a temperature above 1500.degree. C. (according to the example of
sintering of a ceramic of zirconate type).
[0085] According to a second embodiment, the anode 32 and the
cathode 33 may also be formed of a ceramic material which is a
perovskite doped with a lanthanide. The perovskite may be a
zirconate of formula AZrO.sub.3. The zirconate is doped with a
lanthanide, which is for example erbium. Moreover, the perovskite
doped with lanthanide is doped with a doping element taken from the
following group: niobium, tantalum, vanadium, phosphorous, arsenic,
antimony, bismuth. These doping elements are chosen to dope the
ceramic because they can go from a degree of oxidation equal to 5
to a degree of oxidation of 3, which makes it possible to release
oxygen during sintering. More specifically, the doping element is
preferably niobium or tantalum. Each electrode may also comprise a
metal mixed with the ceramic so as to form a cermet. The ceramic
comprises for example between 0.1% and 0.5% by weight of niobium,
between 4 and 4.5% by weight of erbium and the remainder zirconate.
The fact of doping the ceramic with niobium, tantalum, vanadium,
phosphorous, arsenic, antimony or bismuth makes it possible to
render the ceramic conductive to electrons. The ceramic is then a
ceramic with mixed conduction; in other words, it is conducting
both to electrons and protons whereas in the absence of said doping
elements, perovskite doped with a lanthanide with a single degree
of oxidation is not conducting to electrons. Such a configuration
makes it possible to have electrodes made of a material of same
nature as the solid electrolyte, which has good conductivity of
both protons and electrons, and this is so even when the ceramic is
not mixed with a metal (as is the case of the first
embodiment).
[0086] The system 100 further comprises a condenser 130 receiving
at the inlet the CxH.sub.yO.sub.z compound synthesized at the
cathode 33 of the electrolyser 110. The condenser 130 makes it
possible to separate the CxH.sub.yO.sub.z compound in the gaseous
state and the water that are produced by the hydrogenation
reaction. Thus, the condenser 130 traps the water in liquid form
making it possible to obtain at the outlet of the condenser 130
uniquely the synthesized CxH.sub.yO.sub.z compound in the gaseous
state (carbon compound fuel in the embodiment example illustrated
in FIG. 2). The CxH.sub.yO.sub.z compound is then injected into the
carbon product supply circuit of the boiler 160 after dehydration
in a desiccant cartridge 170. The input of the synthesized
CxH.sub.yO.sub.z compound makes it possible to reduce the specific
input of carbon products. The system according to the invention
thus makes it possible to operate in semi-closed circuit, the
external input of fuel being reduced by the supply of the boiler
with synthesized CxH.sub.yO.sub.z compound.
[0087] The water recovered in the condenser 130 is then re-injected
into the water supply circuit so as to limit external inputs of
water.
[0088] In a similar manner to the preceding paragraph, the system
100 also comprises a condenser 140 receiving at the inlet the
oxygen produced by electrolysis of steam at the anode 31. The
oxygen being mixed with water at the outlet of the electrolyser
110, the condenser 140 makes it possible to separate oxygen from
water. The oxygen is then re-injected into the boiler 160 to supply
the combustion of the carbon products, and the water is re-injected
into the water supply circuit. The oxygen thereby injected makes it
possible to carry out an oxycombustion using directly the oxygen
coming out of the electrolyser as oxidant instead of air.
[0089] The condensers 130 and 140 also have the function of cooling
the compounds entering into the condensers so as to re-inject into
the different circuits of the system 100 compounds cooled to a
temperature comprised between 80 and 85.degree. C.
[0090] The heating of the electrolyser 110 is carried out by heat
transfer from the boiler 160 to the electrolyser 110 such that the
electrolyser reaches the temperature T1 not less than 200.degree.
C. and not more than 800.degree. C., advantageously comprised
between 350.degree. C. and 650.degree. C.
[0091] To obtain hydrogenated organic compounds, the temperature T1
of the electrolyser must be advantageously comprised between
500.degree. C. and 600.degree. C.
[0092] According to a first embodiment example, the heat transfer
is achieved by positioning the electrolyser 110 in a heat area 150
around the boiler 160.
[0093] According to a second embodiment example, the heat transfer
is achieved by means of a heat exchanger (not represented) making
it possible to transfer the thermal energy produced by the boiler
to the electrolyser.
[0094] According to a particular non-limiting embodiment, the
system further comprises a turbine positioned at the outlet of the
electrolyser, and more specifically at the anodic (steam) and/or
cathodic outlet of the electrolyser. In FIG. 2, such a turbine is
illustrated as an example in dotted line by the reference 50. In
this example, the turbine is positioned in the path of the gaseous
flux coming out at the anode of the electrolyser. Such a turbine is
adapted to generate electricity by the passage of the gaseous flux.
According to an advantageous embodiment of the invention, the
electricity produced then makes it possible to electrically supply
the electrolyser. Thus, this particular embodiment makes it
possible to reduce the electrical consumption of a specific
generator to generate a potential difference at the terminals of
the electrolyser.
[0095] According to a particular non-limiting embodiment, the
system according to the invention comprises thermo-electrical
devices advantageously placed so as to recover the heat from the
products formed by the water electrolysis reaction.
[0096] According to a particular non-limiting embodiment, the
system comprises a heat exchanger adapted to cool the oxygen/water
mixture generated at the anode by the electrolysis reaction and to
heat the water at the inlet of the electrolyser so as to form steam
able to be inserted into the electrolyte via the anode.
[0097] The invention finds a particularly interesting application
for reclaiming carbon gases resulting for example from the
production of heating from carbon products (coal, wood, oil), or
the incineration of wastes.
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