HEIREDAL-CLAUSEN THOMAS (DK)
RASS-HANSEN JEPPE (DK)
BLENNOW BENGT PETER GUSTAV (DK)
NØRBY TOBIAS HOLT (DK)
WO2018206235A1 | 2018-11-15 | |||
WO2016091636A1 | 2016-06-16 | |||
WO2018228723A1 | 2018-12-20 | |||
WO2018206235A1 | 2018-11-15 | |||
WO2018228716A1 | 2018-12-20 | |||
WO2016091636A1 | 2016-06-16 | |||
WO2015014527A1 | 2015-02-05 | |||
WO2014154253A1 | 2014-10-02 | |||
WO2018206235A1 | 2018-11-15 | |||
WO2018228716A1 | 2018-12-20 |
US20040081875A1 | 2004-04-29 | |||
US20080169449A1 | 2008-07-17 |
CLAIMS: 1. A method for converting carbon dioxide into carbon monoxide in high-temperature, dry, solid oxide electrolysis, the method comprising the following steps: 1) providing a fuel gas stream comprising 70-100 vol% CO2 and 0-30 vol% CO, wherein the molar fraction of CO (xCO) is in the range of from 0 to 0.3; 2) providing a flush gas stream; 3) providing a solid oxide electrolysis cell (SOEC) having a fuel side and an oxy side; 4) heating the fuel gas stream and the flush gas stream to a gas stream inlet temperature, T, in the range of from 600 to 1000 °C, such as from 700°C to 850°C; 5) supplying the fuel gas stream to the fuel side of the SOEC at a space velocity, SVfuel, in the range of from 2 to 30 s-1; 6) supplying the flush gas stream to the oxy side of the SOEC at a space velocity, SVflush, in the range of from 0.1 to 20 s-1; 7) applying an electrolysis current with a current density, i, in the range of from -0.2 A/cm2 to -1 A/cm2 across the solid electrolyte to electrolytically convert a fraction of the CO2 into CO on the fuel side of the SOEC and to produce an O2 enriched flush gas on the oxy side of the SOEC. 2. The process according to claim 1, wherein xCO, T, SVfuel, SVflush, and i are selected such that the coking potential, CP ≤ -15, where CP is given by the formula (I): CP = -351.3 + 1.3828*T + 10.249*SVflush – 15.570*SVfuel + 845*xCO + 103.67*i – 0.001210*T2 + 1.2418*SVfuel2 – 6677* xCO2 – 68.38*i2 – 0.017976*T*SVflush – 0.017279*T*SVfuel + 0.1987*T* xCO – 0.54114*T*i + (I) 0.04299*SVflush*SVfuel + 0.884*SVflush* xCO – 2.4723*SVflush*i + 10.11*SVfuel*xCO + 11.021*SVfuel*i + 51.0*xCO*i 3. The method according to any one of the preceding claims, wherein the coking potential CP of formula (I) during operation of the SOEC, is in the range of from -100 to -15, such as -80 to -15 or -60 to -15. 4. The method according to any one of the preceding claims, wherein the product gas stream comprises in the range of from 15-95 vol% CO, such as from 15-90, 20-80, 20-70, 20- 60, 20 to 50 vol% CO, or from 30 to 50 vol% CO. 5. The method according to any one of the preceding claims, wherein the fuel gas stream consists of 80-100 vol% CO2, 0- 20 vol% CO, 0-1 vol% H2O and 0-1 vol% H2, the remainder being inert, wherein the molar fraction of CO (xCO) is in the range of from 0 to 0.2. 6. The method according to any one of the preceding claims, wherein the fuel gas stream consists of 88-98 vol% CO2, 1- 12 vol% CO, 0-1 vol% H2O and 0-1 vol% H2, the remainder being inert, wherein the molar fraction of CO (xCO) is in the range of from 0 to 0.2. 7. The method according to any one of the preceding claims, wherein the flush gas comprises air, dry air, O2, CO2, N2, steam or a mixture thereof. 8. The method according to any one of the preceding claims, wherein the solid oxide electrolysis cell comprises a fuel gas inlet to the fuel side of the SOEC and a fuel product gas outlet from the fuel side of the SOEC. 9. The method according to any one of the preceding claims, wherein the solid oxide electrolysis cell comprises a flush gas inlet to the oxy side of the SOEC and a flush gas outlet from the oxy side of the SOEC. 10. The method according to any one of the preceding claims, wherein an oxygen enriched flush gas stream is collected from the oxy-side of the SOEC. 11. The method according to any one of the preceding claims, wherein a CO enriched product gas stream is collected from the fuel side of the SOEC. 12. The method according to claim 11, comprising a further step of dividing the product gas stream into a first, CO enriched gas stream and a second, CO2 enriched gas stream. 13. The method according to claim 12, wherein the second, CO2 enriched stream is recycled to the fuel side of the SOEC. 14. The method according to any one of the preceding claims, wherein the fuel side of the SOEC comprises metallic nickel which is electrically connected to a power supply. 15. A method for selecting the operating conditions for high-temperature, dry CO2 electrolysis in a solid oxide electrolysis cell (SOEC) having a fuel side and an oxy side in ionic contact through a solid electrolyte, the method comprising the steps of: i. supplying a fuel gas stream at a space velocity, SVfuel, in the range of from 2 to 30 s- 1, where the fuel gas stream comprises 70-100 vol% CO2 and 0-30 vol% CO, wherein the molar fraction of CO (xCO) is in the range of from 0 to 0.3 to the fuel side of the SOEC; ii. supplying a flush gas stream at a space velocity, SVflush, to the oxy side of the SOEC in the range of from 0.1 to 20 s-1 iii. supplying heat to the SOEC by heating the fuel and flush gas streams to a gas stream inlet temperature T, in the range of from 600 to 1000 °C and then iv. applying an electrolysis current i across the electrolyte of the SOEC at a current density in the range of from -0.2 A/cm2 to -1 A/cm2, wherein the values for T, SVfuel, SVflush, and i are selected by an iterative process as follows: a) setting the operating conditions for T, SVfuel, SVflush, and i to initial values; b) determining local temperatures and local gas compositions for a number of diversely distributed locations in the cell; c) on the basis of the local gas compositions, estimating the local temperatures below which carbon formation via the Boudouard reaction is thermodynamically favorable (the local Boudouard temperature) for each of the locations, d) subtracting the local Boudouard temperature from the measured local temperature thereby obtaining the Boudouard margin, and 0 e) varying the gas flow rates, inlet temperature(s) and/or electrolysis current density until the Boudouard margin is larger than zero for each of the locations. |
The term "molar fraction" (x CO ) of a gas species in a gas refers in the present context to the the number of moles of a gas species in a gas mixture, divided by the total number of moles in the gas mixture.. For example, when the molar fraction of CO in the fuel gas is 5 mol%, then x CO 0.05.
The term "electrolysis current density" is defined as the total electrolysis current running through the cell or stack, divided by the SOEC active area. "SOEC active area" refers to the geometric area of the SOEC that is electrochemically active, i.e. that participates in the electrochemical reactions. For an SOEC with a rectangular active area, the active area can be estimated by multiplying W with L. In the context of the invention, the term “inert” refers to a gas species that does not participate in chemical or electrochemical reactions in the SOEC at the relevant temperatures. Inert species typically include nitrogen, argon, helium, etc. Under some circumstances, for example when the inert gas is used as a flush gas, the inert gases can also include CO 2 , air, steam, etc. In the present context “local” is meant to refer to a volume that is smaller than 12 x 12 x 12 cm 3 , preferably smaller than 1 x 1 x 1 cm 3 and more preferably smaller than 0.1 x 0.1 x 0.1 cm 3 . The typical operating temperature of SOECs is between approximately 600°C and 1000°C: high temperatures are required in order to reach sufficient oxide ion conductivities in the ceramic membranes that are used as electrolytes. Commonly used electrolyte materials include stabilized zirconias, such as yttria-stabilized zirconia (YSZ), doped cerias, doped lanthanum gallates, and others. Commonly used oxy-electrode materials include perovskite materials, such as Sr-doped LaMnO3 (LSM), Sr-doped LaFeO3 (LSF), Sr-doped LaCoO 3 (LSC), Sr-doped La(Co,Fe)O 3 (LSCF), Sr-doped SmCoO 3 and many others. Perovskite materials are further commonly mixed with doped cerias to form composite oxy electrodes (SOEC anodes). Dopants other than Sr, e.g. Ca, Ba are known, as are materials other than perovskites, e.g. Ruddlesden-Popper phases. Commonly used fuel electrode materials include composites of metallic Ni and stabilized zirconia, e.g. Ni-YSZ, or metallic Ni and doped ceria. The inventors have now found an operating window for SOEC stacks in CO 2 electrolysis, which allows for safe operation of SOEC stacks at the highest possible CO/CO 2 ratios. In particular, the present inventors have defined a coking potential (CP) for a stack, and they further found that the coking potential (CP) may be estimated as a function of T, SV flush , SV fuel , x CO , and i, and is defined by: CP = -351.3 + 1.3828*T + 10.249*SV flush – 15.570*SV fuel + 845*x CO + 103.67*i – 0.001210*T 2 + 1.2418*SV fuel 2 – 6677* x CO 2 – 68.38*i 2 – 0.017976*T*SV flush – (I) 0.017279*T*SVfuel + 0.1987*T* xCO – 0.54114*T*i + 0.04299*SV flush *SV fuel + 0.884*SV flush * x CO – 2.4723*SV flush *i + 10.11*SV fuel *x CO + 11.021*SV fuel *i + 51.0*x CO *i In an embodiment, the SOEC or SOEC stack is operated under conditions where CP ≤ -50. This provides for high conversion of CO 2 into CO and a long lifetime of the SOEC exceeding one year. Simultaneously, economic profitability is maximized when the SOEC stack is operated such that CP ≤ -15. This provides for high conversion of CO 2 into CO and a long lifetime of the SOEC exceeding one year and at the same time high profitability. In an embodiment of the invention, The CP is in the range of from -75 to -15. There is not an actual lower range for CP. However, lower ranges of CP cold be -100, -80, or -75. Formula (I) was empirically determined at atmospheric pressure. Accordingly, the empirical formula (I) is applicable at pressures near atmospheric pressure, at least at absolute pressures of 0.5 to 2 bar, such as of 0.7 to 1.8 bar. In an embodiment, the fuel gas stream comprises 80-100, such as 88-98, vol% CO2. In an embodiment, the fuel gas stream comprises 0-20 vol%, such as 1-12 vol%, CO. In an embodiment, the fuel gas stream comprises 80-100, such as 88-98, vol% CO2 and 0-20 vol%, such as 1-12 vol%, CO. In an embodiment, the molar fraction of CO (x CO ) of the fuel gas stream is in the range of from 0 to 0.2, such as from 0.01 to 0.15 or 0.05 to 0.1. In an embodiment, the product gas stream comprises in the range of from 15-95 vol% CO, such as from 15-90, 20-80, 20-70, 20-60, 20 to 50 vol% CO, or from 30 to 50 vol% CO. In an embodiment, any remainder of gases present in the fuel gas stream are inert gases (e.g. N 2 or noble gases). In a particular embodiment, the fuel gas stream consists of 80-100 vol% CO 2 , 0-20 vol% CO, 0-1 vol% H 2 O and 0-1 vol% H 2 , the remainder being inert, wherein the molar fraction of CO (x CO ) is in the range of from 0 to 0.2, such as from 0.01 to 0.15 or 0.05 to 0.1. Such a fuel gas stream has the advantage that a product gas stream may be obtained, which comprises in the range of from 20 to 50 vol% CO and a low content of H 2 O and H 2 . In another particular embodiment, the fuel gas stream consists of 88-98 vol% CO2, 1-12 vol% CO, 0-1 vol% H2O and 0-1 vol% H 2 , the remainder being inert, wherein the molar fraction of CO (x CO ) is in the range of from 0 to 0.2. Such a fuel gas stream has the advantage that a product gas stream may be obtained, which comprises in the range of from 20 to 50 vol% CO and a low content of H 2 O and H 2 . In another embodiment, a method for selecting the operating conditions for a certain SOEC stack design is initiated by selecting an initial set of T, SV fuel , SV flush , X CO and i using formula (I) fulfilling CP= _15 then proceeding according to the guidance for selecting operating parameters as claimed in claim 15.
DETAILED DESCRIPTION OF THE FIGURES Fig 1 is a schematic view of an SOEC. The SOEC (1) comprises a fuel side (11), an oxygen-ion conducting electrolyte (12) and an oxy side (13). Fuel gas (101) is fed to the fuel side (11), where a fraction of the CO2 present in the gas stream is electrochemically converted into CO. The driving force for the electrochemical reaction is provided by the electric potential that is supplied by the power supply unit (20). The resulting product gas stream (102) has a higher CO content than the fuel gas (i.e. is enriched in CO) this CO enriched product gas stream is collected from the fuel side of the SOEC. A current of oxygen ions passes through the electrolyte and (103) onto the oxy side of the SOEC (13). On the oxy-side of the SOEC, an anode reaction takes place to oxidise the ionic oxygen. Flush gas (104) is used to transport oxygen, formed in the anode reaction, out of the SOEC. As a result of the electrochemical reaction on the oxy side, the flush gas stream (104) becomes enriched in oxygen. The oxygen enriched flush gas stream (105) is collected from the oxy- side of the SOEC. Fig 2 is a block diagram showing an embodiment of a system comprising the SOEC (2). A gas stream (201) is optionally mixed with a CO 2 enriched gas stream (203) and the resulting fuel gas stream (101) is fed onto the fuel-side (11) of the SOEC (10). A fraction of the CO2 present in the fuel gas stream is electrochemically converted into CO. The resulting CO enriched product gas stream (102) stream is collected from the fuel side of the SOEC. The product gas stream (102) can optionally be fed to a gas purification unit (30), where the product gas stream (102) is divided into a first, CO enriched product gas stream (202) and a second, CO 2 enriched product gas stream (203). The CO2 enriched product gas stream (203) can optionally be recycled back to the fuel side of the SOEC, as described above. A flush gas stream (104) is fed to the oxy-side (13) of the SOEC (10). As a result of the electrochemical reaction on the oxy side, the flush gas stream (104) becomes enriched in oxygen. The oxygen enriched flush gas stream (105) is collected from the oxy-side of the SOEC. Fig 3 is a schematic view of an SOEC stack repeating unit. More specifically, it is shown how an interconnect (40) is located between adjacent SOECs (10). In the figure, the oxy-side of the SOEC is facing upwards, while the fuel-side of the SOEC is facing downwards. The width of the SOEC, W, and the length of the SOEC, L, are schematically shown. Two different, arbitrary interconnect geometries are shown. In Fig. 3a, the average height of the fuel-side gas channel H fuel,av and the average height of the oxy-side gas channel Hoxygen,avare lower than in Fig. 3b due to the geometrical differences between the interconnect designs in the two figures. Figs 4a, 4b, 4c, 4d and 4e depict the relation between coking potential (CP) and each of the various critical process parameters (T, SV flush , SV fuel , %CO, and i), demonstrating the effect of each parameter under otherwise fixed conditions. Figure 4 is explained in more detail in Examples 4-8. The method is illustrated in more detail in the non- limiting examples which follow. EXAMPLES Example 1 An SOEC stack was operated in dry CO2 electrolysis under conditions where coking was not expected based on thermodynamic considerations, but where the coking potential was positive. More specifically, a fuel gas (food-grade CO 2 ) was heated using electric heaters, thereby increasing the inlet temperature (T) to 725°C. The fuel gas composition was ≥ 99.9% CO 2 and the CO-content was on ppm-level (i.e. x CO = 0). The SOEC stack comprised 75 cells connected in series, each with an active area of 108 cm 2 . The total volume of the fuel-side compartment (Vfuel) was 243 cm 3 , while the total volume of the oxy-side compartment (V oxygen ) was 405 cm 3 . Fuel gas was fed to the stack at a volumetric flow rate of 1.1 Nm 3 /h, corresponding to a space velocity of fuel gas (SV fuel ) of 1.26 s -1 . Air was used as flush gas on the oxy-side of the stack and was fed to the stack at a volumetric flow rate of 1.5 Nm 3 /h, corresponding to a space velocity of the flush gas (SV flush ) of 1.03 s -1 . Stack current was fixed at -40 A, corresponding to an electrolysis current density (i) of -0.37 A/cm 2 . Under these conditions, 60% of the CO2 that was fed to the stack was converted into CO, corresponding to a CO/CO 2 ratio of0 60/40 = 1.5 near stack outlet. In a dry CO/CO 2 mixture at 725°C, coking is thermodynamically favored whenever the CO/CO 2 ratio is above 2.47, corresponding to a CO 2 conversion of 71.2%. In other words, based on thermodynamic considerations, no carbon should have formed inside the stack. However, the stack suffered from substantial coking, failing after only 12.5 hours of operation. The coking potential (CP) under the above conditions is 72.3, i.e. coking is in fact strongly favored in the stack, thereby explaining why the stack failed after just a few hours of testing. Carbon formation in the stack was also confirmed in a post-test analysis using Raman spectroscopy. Example 2 An SOEC stack was operated in dry CO 2 electrolysis under conditions where coking was not expected based on thermodynamic considerations, and where the coking potential was negative, i.e. according to the method of the invention. More specifically, a fuel gas (food-grade CO 2 ) was heated using electric heaters, thereby increasing the inlet temperature (T) to 750°C. The fuel gas was a mixture of food-grade CO2 and CO. The CO-content in the fuel gas was on 3.6% (i.e. x CO = 0.036). The SOEC stack comprised 75 cells connected in series, each with an active area of 108 cm 2 . The total volume of the fuel-side compartment (V fuel ) was 243 cm 3 , while the total volume of the oxy-side compartment (Voxygen) was 405 cm 3 . Fuel gas was fed to the stack at a volumetric flow rate of 8 Nm 3 /h, corresponding to a space velocity of fuel gas (SV fuel ) of 9.14 s -1 . A mixture of air and CO 2 was used as flush gas on the oxy- side of the stack and was fed to the stack at a volumetric flow rate of 14.3 Nm 3 /h, corresponding to a space velocity of the flush gas (SV flush ) of 9.81 s -1 . Stack current was fixed at -50 A, corresponding to an electrolysis current density (i) of -0.46 A/cm 2 . Under these conditions, 19.6% of the CO2 that was fed to the stack was converted into CO, corresponding to a CO/CO 2 ratio of (19.6+3.6)/(100-19.6- 3.6) = 0.30 near stack outlet. In a dry CO/CO2 mixture at 750°C, coking is thermodynamically favored whenever the CO/CO 2 ratio is above 3.6, corresponding to a CO 2 conversion of 78.4%. In other words, based on thermodynamic considerations, no carbon should form inside the stack under operation. The coking potential (CP) under the above conditions is -59.9, i.e. coking does not occur. Example 3 An SOEC stack was operated in dry CO 2 electrolysis under conditions where coking was not expected based on thermodynamic considerations, and where the coking potential was negative, i.e. according to the method of the invention. More specifically, a fuel gas (food-grade CO 2 ) was heated using electric heaters, thereby increasing the inlet temperature (T) to 745°C. The fuel gas was a mixture of food-grade CO 2 and CO. The CO-content in the fuel gas was on 3.6% (i.e. x CO = 0.036). The SOEC stack comprised 75 cells connected in series, each with an active area of 108 cm 2 . The total volume of the fuel-side compartment (Vfuel) was 243 cm 3 , while the total volume of the oxy-side compartment (V oxygen ) was 405 cm 3 . Fuel gas was fed to the stack at a volumetric flow rate of 8 Nm 3 /h, corresponding to a space velocity of fuel gas (SV fuel ) of 9.14 s -1 . A mixture of air and CO 2 was used as flush gas on the oxy- side of the stack and was fed to the stack at a volumetric flow rate of 14.3 Nm 3 /h, corresponding to a space velocity of the flush gas (SV flush ) of 9.81 s -1 . Stack current was fixed at -70 A, corresponding to an electrolysis current density (i) of -0.65 A/cm 2 . Under these conditions, 27.4% of the CO 2 that was fed to the stack was converted into CO, corresponding to a CO/CO2 ratio of (27.4+3.6)/(100-27.4- 3.6) = 0.45 near stack outlet. In a dry CO/CO 2 mixture at 745°C, coking is thermodynamically favored whenever the CO/CO 2 ratio is above 3.37, corresponding to a CO 2 conversion of 77.1%. In other words, based on thermodynamic considerations, no carbon should form inside the stack under operation. The coking potential (CP) under the above conditions is -30.5, i.e. coking does not occur. Two stacks were operated under the above conditions for more than a year without coking. From an economic perspective, operation under conditions listed in Example 3 are more lucrative than operation under conditions listed in Example 2, since more CO gas can be produced per stack per hour. Example 4 The coking potential (CP) is estimated for a set of realistic operating conditions. The space velocity of the flush gas is fixed at SV flush = 9 s -1 , the space velocity of the fuel gas is fixed at SV fuel = 7 s -1 , the molar fraction of CO in the fuel gas was xCO = 0.05, and the electrolysis current density was fixed at i = -0.5 A/cm 2 . The effect of varying the inlet temperature (T) was investigated and is plotted in Fig. 4a. Under the chosen set of operating conditions, CP = 7.9 at 675°C, CP = 0 at 703°C, and CP = - 17.9 at 750°C. Generally, the higher the inlet temperature, the lower the CP. Therefore, in order to avoid carbon formation, it desirable to operate the stack at high temperature, provided this does not compromise stack lifetime via other mechanisms (e.g. interconnect corrosion). Example 5 CP is estimated for a set of realistic operating conditions: The inlet temperature is fixed at T = 700°C, the space velocity of the fuel gas is fixed at SV fuel = 7 s- 1 , the molar fraction of CO in the fuel gas was x CO = 0.05, and the electrolysis current density was fixed at i = -0.5 A/cm 2 . The effect of varying the space velocity of the flush gas (SV flush ) was investigated and is plotted in Fig. 4b. Under the chosen set of operating conditions, CP = 6.9 at 1 s -1 , CP = 0.8 at 9 s -1 , and CP = -14.2 at 29 s -1 . Generally, the higher the space velocity of the flush gas, the lower the CP. Therefore, in order to avoid carbon formation, it desirable to operate the stack at high flush gas space velocities, provided this is not prohibitively expensive. Example 6 CP is estimated for a set of realistic operating conditions: The inlet temperature is fixed at T = 700°C, the space velocity of the flush gas is fixed at SV flush = 9 s -1 , the molar fraction of CO in the fuel gas was x CO = 0.05, and the electrolysis current density was fixed at i = -0.5 A/cm 2 . The effect of varying the space velocity of the fuel gas (SV fuel ) was investigated and is plotted in Fig. 4c. Under the chosen set of operating conditions, CP = 134.9 at 1 s -1 , CP = 0.8 at 7 s -1 , and CP = -43.8 at 13 s -1 . Generally, the higher the space velocity of the fuel gas, the lower the CP. Therefore, in order to avoid carbon formation, it desirable to operate the stack at high fuel gas space velocities, provided this is not prohibitively expensive. Example 7 CP is estimated for a set of realistic operating conditions: The inlet temperature is fixed at T = 700°C, the space velocity of the flush gas is fixed at SV flush = 9 s -1 , the space velocity of the flush gas is fixed at SV flush = 9 s -1 , and the electrolysis current density was fixed at i = -0.5 A/cm 2 . The effect of varying the molar fraction of CO in the fuel gas (x CO ) was investigated and is plotted in Fig. 4d. Under the chosen set of operating conditions, CP = -24.6 at x CO = 0.01, CP = 0.8 at x CO = 0.05, and CP = 2.6 at x CO = 0.10. Generally, the higher the molar fraction of CO in the fuel gas, the higher the CP. Therefore, in order to avoid carbon formation, it desirable to operate the stack at low CO molar fractions, provided Ni in the fuel-side inlets of the stack remains in metallic state. Example 8 CP is estimated for a set of realistic operating conditions: The inlet temperature is fixed at T = 700°C, the space velocity of the flush gas is fixed at SV flush = 9 s -1 , the space velocity of the flush gas is fixed at SV flush = 9 s -1 , and the molar fraction of CO in the fuel gas was x CO = 0.05. The effect of varying the electrolysis current density (i) was investigated and is plotted in Fig. 4e. Under the chosen set of operating conditions, CP = -69.8 at -0.1 A/cm 2 , CP = 0.8 at -0.5 A/cm 2 , and CP = 81.8 at -1.5 A/cm 2 . Generally, the more negative the electrolysis current density, the higher the CP. Therefore, in order to avoid carbon formation, it desirable to operate the stack at low electrolysis current densities (i.e. at currents close to zero). However, the production rate of the stack is directly proportional to the absolute value of the electrolysis current, and therefore high current densities (i.e. more negative currents) are required to ensure commercial relevance. Example 9 An SOEC stack consisting of 75 cells is operated at an average temperature of 700°C with pure CO 2 fed to the cathode at a flow rate of 100 Nl/min, while applying an electrolysis current of 50 A and providing a conversion of CO 2 into CO corresponding to 26% CO and 74% CO 2 in the gas exiting the cathode side of the stack. This corresponds to the disclosure in Example 1 of WO 2018/206235. The above example describes an operating point of an SOEC stack in dry CO2 electrolysis. The operating temperature (T) is 700°C and the molar fraction of CO in the fuel gas stream (xCO) is 0. However, D1 does not disclose geometric information about the stack in order to make the estimation of SV fuel , SV flush and i possible. For example, although a value for the volumetric flow rate of the fuel gas is provided (100 Nl/min), it is necessary to know the total volume of the fuel-side compartment (V fuel ) in order to estimate the value for SV fuel . Similarly, although a value for the stack current is provided (50 A), it is necessary to know the active area per cell (and whether the cells are connected in series or parallel) in order to estimate the value for i. Finally, no mention of the flush gas flow rate or space velocity, nor whether a flush gas is used at all, is mentioned in Example 1 of WO 2018/206235. In figure 5, coking potentials have thus been calculated for a number of possible SV fuel , SV flush and i combinations, based on assumptions regarding Vfuel, Voxygen, and cell active area. In Case #1, V fuel , V oxygen and cell active area (A) values have been taken from Example 1 of the current application. For the avoidance of doubt it should be emphasized that these do not represent a preferred embodiment nor are the SV, cell areas mentioned in Example 1 of WO 2018/206235). Cases #2-#4 represent variations in V fuel , which result in changes in SV fuel . By increasing SV fuel , coking can be avoided. At low SVfuel, coking occurs. Cases #5-#6 represent variations in cell active area compared to #1. By increasing cell active area, coking can be avoided. By decreasing cell active area, coking will occur. Cases #7-#8 represent variations in flush gas flow rate. Increasing flush gas flow rate has a small positive effect, making coking slightly less likely. Cases #9-#10 represent variations in flush gas flow rate at a higher SV fuel . Increasing flush gas flow rate has a small positive effect, making coking slightly less likely. However, coking still occurs. In summary these data clearly show that not enough information is disclosed in Example 1 of WO 2018/206235 to accidentally anticipate the subject-matter of the present patent application. Nor are there any hints or suggestions in that direction. Embodiments: Embodiment 1. A method for converting carbon dioxide into carbon monoxide in high-temperature, dry, solid oxide electrolysis, the method comprising the following steps: 1) providing a fuel gas stream comprising 70-100 vol% CO 2 and 0-30 vol% CO, wherein the molar fraction of CO (x CO )is in the range of from 0 to 0.3; 2) providing a flush gas stream; 3)providing a solid oxide electrolysis cell stack (SOEC stack) comprising a plurality of solid oxide electrolysis cells (SOECs), each cell having a fuel side and an oxy side in ionic contact through a solid electrolyte, and the plurality of SOECs being electrically connected in series and fluidly connected in parallel and separated by interconnectors; 4) heating the fuel gas stream to a fuel gas inlet temperature, T, in the range of from 600-1000 °C, such as from 700°C to 850°C; 5) supplying the fuel gas stream to the fuel sides of the SOECs at a space velocity, SV fuel , in the range of from 1-30 s -1 ; 6) supplying the flush gas stream to the oxy sides of the SOECs at a space velocity, SVflush, in the range of from 0.1-20 s -1 ; 7) applying an electrolysis current with a current density, i, in the range of from -0.2 A/cm 2 to -1 A/cm 2 across the solid electrolyte to electrolytically convert a fraction of the CO 2 into CO on the fuel side of the electrode side and to produce an O 2 enriched flush gas on the oxy electrode side of the SOECs. Claims 2-14 may equally be combined with Embodiment 1. Embodiment 2. A method for converting carbon dioxide into carbon monoxide in high-temperature, dry, solid oxide electrolysis, the method comprising the following steps: 1) providing a fuel gas stream comprising 70-100 vol% CO 2 and 0-30 vol% CO, wherein the molar fraction of CO (x CO ) is in the range of from 0 to 0.3; 2) providing a flush gas stream; 3)providing a plurality of solid oxide electrolysis cell stacks (SOEC stacks) comprising a plurality of solid oxide electrolysis cells (SOECs), each cell having a fuel side and an oxy side in ionic contact through a solid electrolyte, and the plurality of SOECs being arranged in SOEC stacks, the SOECs being electrically connected in series and fluidly connected in parallel and separated by interconnects; and each stack being mounted on a manifold for simultaneously feeding the fuel gas stream to each stack and for simultaneously receiving the product gas stream from each stack; 4) heating the fuel gas stream to a fuel gas inlet temperature, T, in the range of from 600-1000 °C, such as from 700°C to 850°C; 5) supplying the fuel gas stream to the fuel side of the SOECs at a space velocity, SV fuel , in the range of from 1-30 s -1 ; 6) supplying the flush gas stream to the oxy side of the SOECs at a space velocity, SV flush , in the range of from 0.1-20 s -1 ; 7) applying an electrolysis current with a current density, i, in the range of from -0.2 A/cm 2 to -1 A/cm 2 across the solid electrolyte to electrolytically convert a fraction of the CO 2 into CO on the fuel side of the electrode side and to produce an O 2 enriched flush gas on the oxy electrode side of the SOECs. Claims 2-14 may equally be combined with Embodiment 2.
REFERENCE SIGNS LIST 1: SOEC 2: SOEC 10: SOEC 11: fuel side 12: oxygen-ion conducting electrolyte 13: oxy side 20: power supply unit 30: gas purification unit 40: interconnect 101: fuel gas/fuel gas stream 102: product gas stream 103: electrolyte 104: flush gas/flush gas stream 105: oxygen enriched flush gas stream 201: gas stream 202: CO enriched product gas stream 203: CO2 enriched gas stream
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