SOFC SYSTEM AND METHOD OF OPERATING A SOFC SYSTEM
20170331132 · 2017-11-16
Assignee
Inventors
Cpc classification
H01M8/04328
ELECTRICITY
H01M8/04291
ELECTRICITY
C01B3/48
CHEMISTRY; METALLURGY
C01B2203/0233
CHEMISTRY; METALLURGY
C01B2203/0827
CHEMISTRY; METALLURGY
H01M8/04776
ELECTRICITY
H01M8/04201
ELECTRICITY
H01M8/04268
ELECTRICITY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P20/129
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C01B2203/0283
CHEMISTRY; METALLURGY
C01B2203/1294
CHEMISTRY; METALLURGY
H01M8/0618
ELECTRICITY
H01M8/04373
ELECTRICITY
International classification
H01M8/04014
ELECTRICITY
Abstract
A SOFC system having a fuel reformer for reforming a gaseous hydrocarbon stream and steam into a hydrogen rich gas, a solid oxide fuel cell stack including an anode and a cathode for electrochemically reacting the hydrogen rich gas and a cathode air stream to produce electricity, an anode exhaust stream and a cathode depleted air stream. The anode exhaust stream and the cathode depleted air stream are kept separate, a burner for combusting a mixture of the anode exhaust stream and a fresh air stream to complete combustion and produce heat for the reformer control unit and a blower are also provided. The control unit controlling the blower for controlling the mass flow rate of the fresh air stream to provide heat to the reformer to reform the gaseous hydrocarbon stream and to produce a burner exhaust stream.
Claims
1.-16. (canceled)
17. A SOFC system comprising: a fuel reformer for reforming a gaseous hydrocarbon stream and steam into a hydrogen rich gas, a solid oxide fuel cell stack including an anode and a cathode for electrochemically reacting the hydrogen rich gas and a cathode air stream to produce electricity, an anode exhaust stream and a cathode depleted air stream, wherein the anode exhaust stream and the cathode depleted air stream are kept separate, a burner for combusting a mixture of the anode exhaust stream and a fresh air stream to complete combustion and produce heat for the reformer, wherein the fresh air stream is fed to the burner, wherein the fuel reformer receiving only the gaseous hydrocarbon stream and steam, the fuel reformer and the burner being integrated in the same unit for compactness, better heat integration and less heat losses, to generate heat in the burner, which is transferred to the reformer, to control the pre-reforming rate in the reformer, a control unit and a blower is provided, the control unit being configured to control the mass flow rate of the fresh air stream by blower such that the reformer is provided with heat to reform the gaseous hydrocarbon stream and steam, and such that a burner exhaust stream provides sufficient heat for generating steam, at least one heat exchanger, which is an evaporator, is arranged after the burner to cool down the burner exhaust stream and to heat condensed water to generate steam, the steam from the heat exchanger is fed to the fuel reformer, the burner exhaust stream is cooled down to produce condensed water, so that there is no need for an external water line, wherein a temperature sensor is arranged for sensing the temperature of the hydrogen rich gas, wherein the control unit is responsive to the temperature sensor to control the blower to maintain the oxygen content of the burner exhaust stream within a preselected range in order to provide sufficient heat to the reformer.
18. The SOFC system according to claim 17, wherein the burner exhaust stream, after passing the evaporator, is fed to at least one additional heat exchanger to cool down and condense the burner exhaust stream to produce a cooled burner exhaust stream comprising condensed water, and wherein the cooled burner exhaust stream is fed to a separator to separate the cooled burner exhaust stream into the condensed water and a residual exhaust gas.
19. The SOFC system according to claim 17, further comprising a second gaseous hydrocarbon stream being connected with the burner to provide additional heat during heat up phase of the system.
20. The SOFC system according to claim 17, wherein after the blower a valve is arranged, wherein the valve is controlled by the control unit, and wherein the valve splits an air stream into the cathode air stream and the fresh air stream.
21. The SOFC system according to claim 17, wherein a filter is arranged to filter the condensed water.
22. A method for operating a SOFC system comprising: reforming a gaseous hydrocarbon stream and steam into a hydrogen rich gas, electrochemically reacting the hydrogen rich gas and a cathode air stream in a solid oxide fuel cell stack to produce electricity, an anode exhaust stream and a cathode depleted air stream, keeping the anode exhaust stream and the cathode depleted air stream in separate streams, supplying the anode exhaust stream to a burner, supplying a fresh air stream to the burner, and burning a combustion mixture of the anode exhaust stream and the fresh air stream to provide heat to the reformer wherein in providing two streams only, a gaseous hydrocarbon stream and steam to the fuel reformer to pre-reform the gaseous hydrocarbon stream and steam, controlling a blower by a control unit to control the mass flow rate of the fresh air stream to provide enough air for a complete combustion in the burner and such that the reformer is provided with sufficient heat to reform the gaseous hydrocarbon stream and steam and sufficient heat to produce a burner exhaust stream having sufficient heat for generating steam, cooling down the burner exhaust stream to produce condensed water, and heating the condensed water by the burner exhaust stream to generate the steam, so that there is no need for an external water line, wherein the hydrogen rich gas exiting the reformer having a temperature (Th), sensing the temperature (Th) of the hydrogen rich gas, determining a pre-reforming rate of the reformer based on the temperature (Th) and a standard table, based on information regarding the fuel utilization in the solid oxide fuel cell stack, calculating the amount of fuel leaving the stack, calculating the amount of air needed for a complete combustion in the burner, and controlling a blower for controlling the mass flow rate of the fresh air stream to maintain at least one of the flame temperature and the oxygen content of the burner exhaust stream within a preselected range.
23. The method of claim 22, wherein the burner exhaust stream having an oxygen content, sensing the oxygen content of the burner exhaust stream, providing a signal indicative of the oxygen content of the burner exhaust stream, and controlling a blower for controlling the mass flow rate of the fresh air stream to maintain at least one of the flame temperature and the oxygen content of the burner exhaust stream within a preselected range.
24. The method of claim 22, wherein the burner exhaust stream passes the evaporator so that steam is generated from the condensed water, wherein after passing the evaporator the burner exhaust stream is cooled down to produce a cooled burner exhaust stream and condensed water, and separating the cooled burner exhaust stream into the condensed water and a residual exhaust gas.
25. The method of claim 22, wherein the oxygen content of the combined streams feeding into the burner is maintained within an air-fuel equivalence ratio λ (lambda) of between 1.1 and 1.4.
26. The method of claim 22, wherein the burner exhaust stream preheats the cathode air stream to cool down the burner exhaust stream.
27. The method of claim 22, wherein the steam is fed into the fuel reformer.
28. The method of claim 22, wherein an air stream is split by a modulating valve into the cathode air stream and the fresh air.
29. The method of claim 22, wherein the condensed water is filtered from impurities before entering the evaporator.
30. The method of claim 22, wherein the oxygen content of the combined streams feeding into the burner is maintained within an air-fuel equivalence ratio λ (lambda) of 1.2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031]
[0032]
[0033]
[0034]
[0035]
DESCRIPTION OF PREFERRED EMBODIMENTS
[0036]
[0037] The operation of the SOFC system according to the first embodiment comprises the following steps: [0038] reforming a gaseous hydrocarbon stream 100 and steam 404 into a hydrogen rich gas 103, [0039] electrochemically reacting the hydrogen rich gas 103 and a cathode air stream 204 in a solid oxide fuel cell stack 2 to produce electricity, an anode exhaust stream 104 and a cathode depleted air stream 205, [0040] keeping the anode exhaust stream 104 and the cathode depleted air stream 205 in separate streams, [0041] supplying the anode exhaust stream 104 or the water depleted anode exhaust stream 104 to a burner 105, [0042] supplying a fresh air stream 300 to the burner 105 to provide enough air for a complete combustion in the burner 105, [0043] and burning a combustion mixture of the anode exhaust stream 104 and the fresh air stream 300 to provide heat to the reformer 102 to pre-reform the gaseous hydrocarbon stream 100 and to produce a burner exhaust stream 106, [0044] cooling down the anode exhaust stream 104 or the burner exhaust stream 106 to condense water 403, and [0045] evaporating the condensed water 403 using the burner exhaust stream 106 to produce steam 404.
[0046] The temperatures in the SOFC system 1 may for example be as follows: The burner exhaust stream 106 may have a temperature in the range of 900° C. to 1000° C. The condensed water 403 may have a temperature in the range of 50° C. to 60° C. The steam 404 may have a temperature in the range of 300° C. to 500° C.
[0047] In the embodiment disclosed in
[0048] In a preferred embodiment the temperature in the reformer 102 may also be controlled. An important parameter that plays a vital role in operation of a SOFC system 1 such as the one depicted in
[0049] The pre-reforming rate in a SOFC system 1 may vary and it depends mainly on the system layout, stack design and developer's expectation and most important on the temperature in the reformer 102. For instance, in the embodiment discussed in
[0050] To provide an optimal operating condition for the reformer 102 it is vital to control properly the flame temperature of the burner 105 and to control the composition of the burner exhaust stream 106.
[0051] A complete combustion in the burner 105 can be achieved by directly or indirectly measuring the flame temperature in the burner 105 and by controlling the provided amount of oxidant. A too low temperature of the flame temperature would cause an incomplete combustion, hence, traces of some poisonous gases, especially CO, may remain in the burner exhaust stream 106 and also not enough heat would be provided for the reformer 102. On the other hand, a too high temperature of the flame temperature may cause some thermal and mechanical stresses on the burner liner materials, in particular metal and the catalyst.
[0052] It is therefore preferred to maintain the temperature of the flame and the temperature of the liner materials, in particular metal, of the burner 105 within a desired range of preferably 1100° C. to 1400° C. However, several factors affect the temperature and controllability of the burner, especially the temperature of the flame.
[0053] Furthermore, the amount of heat that is generated in the burner 105 and transferred to the reformer 102 dictates the pre-reforming rate in the reformer 102, hence the temperature of the reformer outlet, the hydrogen rich gas 103.
[0054] The amount of heat generated in the burner 105 and transferred to the reformer 102 depends on the amount of fuel that is burnt in the burner 105. In the embodiment according to
[0055] The fuel cell systems are usually designed to be thermally self-sustaining and to eliminate the need for any fuel externally. However, if there is a need for additional fuel for example during start of the fuel cell system, the make-up line 500 can be used. Otherwise, the temperature of the burner 105 and the reformer 102 would decrease if not enough fuel and heat was provided, which in its turn would reduce the predefined pre-reforming rate. The fuel cell systems disclosed in
[0056] To have a complete controllability over the system, in the embodiment according to
[0057] To maintain the flame temperature within a desired range a first method using the embodiment disclosed in
[0058] The sensor 600 for sensing the oxygen content of the burner exhaust stream 106 is sensing the oxygen concentration. A control unit 601 is connected to the sensor 600 via a control cable 603. An actuator 602 is connected to the control unit 601 via a control cable 604. The blower 302 is driven by the actuator 602. The control unit 601 is responsive to the sensor 600 and controls the blower 302 for controlling the mass flow rate of the fresh air stream 300 to maintain the oxygen content of the burner exhaust stream 106 within a preselected range. The blower 302 is driven by an actuator 602. Air 303 passes through the blower 302 so that the fresh air stream 300 is fed at a fresh air stream inlet 301 into the burner 105.
[0059] The flame temperature in the burner 105 can be evaluated theoretically by a modelling tool. The embodiment according to
[0060] The embodiment disclosed in
[0061] The anode exhaust stream 104 comprise of steam, carbon dioxide and rest of the hydrogen that is not consumed inside the stack 2. Fuel utilization of the stack 2 is varied between 70-80%, which influences the heat generated in the burner and the amount of air required in the burner 105 for oxidation.
[0062] Due to reasons explained earlier it is important to have a certain amount of air in the burner exhaust stream 106. This is generally related to the amount of air of the fresh air stream 300 that is fed into the burner 105. Whilst doing theoretical calculations it is a good practice to keep a stoichiometric value for the air, which is usually between λ=1.2˜1.4. This means the amount of air fed 300 into the burner 105 is typically more than the theoretical calculation; hence, some oxygen will remain unused at the outlet in the burner exhaust stream 106. For this operating condition, it has been found that the flame temperature can vary between 1100-1400° C. However, by taking a stoichiometry value of exactly λ=1, no more oxygen will remain at the outlet of the burner 105 and this may lead to an incomplete combustion and temperature of the burner may exceed the temperature resistance of the burner liner.
[0063] With the use of an oxygen sensor 600 the amount of oxygen at the burner outlet in the burner exhaust stream 106 is preferably kept between certain values. Experimentally and also theoretically is has been found that with a value in the range between 1.1˜2.2% mole a complete combustion can be guaranteed. Having an oxygen content of more than the upper limit of 2.2% in the burner exhaust stream 106 would cause a decrease of temperature in the burner and having oxygen content of less than the lower limit of 1.1% would increase temperature of the burner. In either cases flame temperature can be out of the desired range and a complete combustion cannot be guaranteed.
[0064] Measuring the actual flame temperature in the burner can be a very challenging and tedious task. The thermal inertia of the burner and also positioning of thermocouple inside the burner can easily influence this measurement. In order to make sure the flame temperature falls in the range specified above and also to assure a minimum amount of oxygen at the outlet of the burner the flow rate of the fresh air 300 is regulated directly. That is the content of the oxygen is measured by sensor 600 and the air flow rate is adjusted with the actuator 602.
[0065] Operation of the embodiment disclosed in
TABLE-US-00001 TABLE 1 Fuel Utilization 80% Anode Burner Burner Outlet Outlet Outlet (exhaust (exhaust (exhaust stream stream stream 104) 106) 106) Gas Composition (%) O2 0 1.1 2.1 N2 0 25.5 28.2 H2O 65.3 59.2 56.3 CO2 19.3 14.2 13.4 CO 0.2 0 0 H2 15.4 0 0 CH4 0 0 0 Fresh Air (stream 300) Mass Flow Rate (Kg/s) 4.1 × 10.sup.−4 4.8 × 10.sup.−4 Volume Flow Rate (L/min) 19.1 22.4 Corresponding Theoretical 1.2 1.4 (λ) Calculated Flame 1262 1217 Temperature (° C.) Dew Point (° C.) 85.8 84.5 Mass Flow Rate 6.6 × 10.sup.−4 1.1 × 10.sup.−3 1.2 × 10.sup.−3 (Kg/s)
TABLE-US-00002 TABLE 2 Fuel Utilization 70% Anode Burner Burner Outlet Outlet Outlet (exhaust (exhaust (exhaust stream stream stream 104) 106) 106) Gas Composition (%) O2 0 1.5 2.8 N2 0 33.7 36.7 H2O 57.6 52.3 48.9 CO2 19.4 12.5 11.6 CO 0 0 0 H2 23 0 0 CH4 0 0 0 Fresh Air (stream 300) Mass Flow Rate (Kg/s) 6.2 × 10.sup.−4 7.2 × 10.sup.−4 Volume Flow Rate (L/min) 28.9 33.6 Corresponding 1.2 1.4 Theoretical (λ) Calculated Flame 1410 1338 Temperature (° C.) Dew Point (° C.) 82.6 81 Mass Flow Rate 6.2 × 10.sup.−4 1.2 ×10.sup.−3 1.3 × 10.sup.−3 (Kg/s)
[0066] In both cases the flow rate of the fresh air 300, calculated stoichiometry values and the flame temperature are presented. By regulating the fresh air stream 300 the molar fraction of oxygen is kept between 1.1-2.8% which in turn keeps the flame temperature in the burner 105 at the predefined range of 1217-1410° C. Based on these results the method for controlling the flame temperature is such that the oxygen content of the burner exhaust stream 106 is measured by sensor 600, and the air flow rate of the fresh air stream 300 is adjusted with the actuator 602 such, that the molar fraction of oxygen is kept between 1.2-2.7%. By using this method the flame temperature in the burner 105 is kept within the range of between 1217-1410° C.
[0067] Furthermore, the dew point of the burner outlet exhaust stream 106 is presented for each case. As mentioned previously, one of the main advantages of separating the anode and cathode exhaust streams 104, 205 from each other is that the dew point of the stream at anode outlet is high and the steam in the line can be condensed with smaller condensers. Enhanced condensation and water recovery is an important aspect in SOFC system as the need for an external water source can be eliminated. On the other hand combining the anode and cathode streams would reduce the dew point of the mixture and the amount of water that can be condensed at the burner outlet. The dew point of the gas mixture at the burner outlet is presented for all cases and it is obvious that condensation starts at temperatures around 80° C.
[0068] The next paragraphs explain a second method in details. The embodiment for the second approach is shown in
[0069] Some assumptions need to be considered for such calculations based on the design and experimental data available from the developers; some of them summarized in tables 4 and 5. The steam reforming and water-gas shift reactions are presented as follows:
TABLE-US-00003 TABLE 3 CH.sub.4 + H.sub.2O .fwdarw. 3H.sub.2 + CO (Steam Reforming Reaction) CO + H.sub.2O H.sub.2 + CO.sub.2 (Water Gas Shift Reaction) CH.sub.4 + 2H.sub.2O .fwdarw. 4H.sub.2 + CO.sub.2 (Complete Reaction)
[0070] The double headed arrow represents that the water-gas shift reaction is in equilibrium. It means, at the end of the reaction both the reactants and products remain at the equilibrium point. The composition of the gases at equilibrium depends on the initial composition of the reactants and the final reaction temperature and pressure. There are theoretical methods that can be used to evaluate the equilibrium composition, which is out of scope of this document and will not be discussed here. The values that are presented here for calculation are collected from some experimental results and it may vary for different equipment. For instance, some stacks are limited with the amount of internal reforming, or the water-gas shift reaction is not always in equilibrium in the reformer or the stack; therefore, these values need to be adjusted accordingly based on experimental data.
[0071] In the fuel reformer 102 it is assumed that the pre-reforming and the water-shift reaction ratio is 50% for both. Whereas in the stack 2 it is assumed that there is a complete internal reforming and the water-shift is 75%.
[0072] Composition of the gas at different stages in the system is evaluated in the following tables 4 and 5. That is the gas input into the fuel reformer, i.e. methane and water. The total gas input is around 5 kW. As explained earlier, inside the fuel reformer by implementing the steam reforming and water-gas shift reactions composition of the outlet gas can be evaluated. Since it is assumed there is a complete internal reforming inside the stack an additional step is considered at the inlet of the stack, where remaining of the methane that is not reformed in the reformer 102 is converted completely. Composition of the gas at the outlet of the stacks is evaluated based on the fuel utilization, internal reforming and water-gas shift reaction. Finally, at the outlet the amount of air 300 required to burn the remaining of the fuel is calculated based on a standard lambda burner.
TABLE-US-00004 TABLE 4 Stack fuel utilization 80% Assumptions S/C (mol) = 2 Uf = 80% Pre-Reforming = Internal- 50% Reforming = Water-Shift = 100% Lambda = Lambda = 50% Water-Shift = 1.2 1.4 Gas Reformate 75% Stack Combustion Air [Nl/min] Input Outlet Stack Inlet Outlet [Nl/min] CH4 8.4 4.2 0 0 0 0 H2O 18.5 12.2 4.8 28.7 0 0 H2 0 14.7 30.5 6.6 0 0 CO2 0 2.1 5.3 8.2 0 0 CO 0 2.1 3.2 0.1 0 0 O2 0 0 0 0 4.0 4.7 N2 0 0 0 0 15.2 17.7 Total 19.2 22.4
TABLE-US-00005 TABLE 5 Stack fuel utilization 80% Assumptions S/C (mol) = 2 Uf = 70% Pre-Reforming = Internal- 50% Reforming = Water-Shift = 100% Lambda = Lambda = 50% Water-Shift = 1.2 1.4 Gas Reformate 75% Stack Combustion Air [Nl/min] Input Outlet Stack Inlet Outlet [Nl/min] CH4 8.4 4.2 0 0 0 0 H2O 18.5 12.2 4.8 25.4 0 0 H2 0 14.7 30.5 9.8 0 0 CO2 0 2.1 5.3 8.2 0 0 CO 0 2.1 3.2 0.2 0 0 O2 0 0 0 0 6.1 7.1 N2 0 0 0 0 22.8 26.5 Total 28.8 33.6
[0073] The embodiment according to
[0074] The total fresh air 300 required to complete the combustion are represented for both cases, the embodiment according to
[0075] The amount of fresh air 300 for the burner 105 was evaluated in two different methods, disclosed in
[0076] In a preferred method, the oxygen content of the combined streams feeding into the burner 105 is maintained within an air-fuel equivalence ratio λ (lambda) of between 1,1 and 1,4, and most preferably of about 1,2. The combined streams feeding into the burner 105 comprises at least the anode exhaust stream 140 and preferably also the second air stream 300 and/or the makeup gas 500.
[0077] The
[0078]
[0079]