CACHE Modules on Energy in the Curriculum Fuel Cells Module 3 (Final Draft): Energy Balance in a Solid Oxide Fuel Cell Module Author: Donald J. Chmielewski Module Affiliation: Center for Electrochemical Science and Engineering Department of Chemical and Biological Engineering Illinois Institute of Technology, Chicago, IL 60616 Course: Material and Energy Balances Text Reference: Felder and Rousseau (2000), Section 9.5 Concept Illustrated: Energy balances on a reactive process with complex geometry; Application of shaft work to a reactive process. Background/Introduction Fuel cells are a promising alternative energy conversion technology. One type of fuel cell, the Solid Oxide Fuel Cell (SOFC) uses hydrogen as a fuel. The fuel reacts with oxygen to produce electricity. Fundamental to SOFC design is an understanding of the heat generated by the reaction and its impact on efficiency. The SOFC reactions are: H2 + O-2 H2O + 2 e1/2O2 + 2 e- O-2 H2 + 1/2O2 H2O Electron Flow (Current) e- e- N2 H2 2- O2 N2 H2 H2 O2 O2- H2O H2O H2 H2O O2O 2- Cell Voltage Air In Anode Gas Chamber Cathode Gas Chamber Fuel Cell N2 H2 Electric Load H2 In O2 O H2O Anode: Cathode: Overall: O2 H2 & H2O Out O2 Anode Cathode Electrolyte Figure 1: Reactions within SOFC Air Out Figure 2: Flow Diagram for SOFC For each mole of hydrogen consumed, two moles of electrons are passed through the electric load. To convert electron flow, Faraday’s constant should be used ( F 96,485 coulombs/mole of electrons). The objective of a fuel cell is to deliver power Draft 4 -1- April 14, 2008 to the load: Power = Current · Voltage. ( coulomb volt joule and joule / s watt ). The fuel cell obtains this power from the enthalpy released during the overall reaction H2 + 1/2O2 H2O; however, only a portion of this enthalpy can be converted to electric power, the remainder will appear as heat released by the reaction. This heat must be removed using the flowing gas streams. The performance of a fuel cell is typically communicated in terms of efficiency, defined as energy delivered to the load divided by the energy available from reaction. Problem Information Example Problem Statement: An adiabatic SOFC is operated at atmospheric pressure with an inlet flow of pure hydrogen at 20 g/s and a hydrogen utilization of 75%. The term utilization is synonymous with the percent conversion, as defined in Section 4.6 of Felder and Rousseau (2000). At the cathode chamber inlet, 2.67x105 standard liters per minute (slpm) of air is fed at 500oC, and the gas exiting the cathode chamber is at 625oC. If the exit stream of the anode chamber is 675oC and the cell voltage is 0.7 volts, then determine the following: 1) The electric current and power delivered to the load. 2) The molar flow from the cathode chamber. 3) The temperature of the gas inlet to the anode. 4) The fuel to power efficiency of the fuel cell. Example Problem Solution: 1) To determine power to the load we must first determine current to the load and combine with cell voltage (given to be 0.7 volts). Since current is proportional to the rate of electrons generated by the half reaction (here we will use the anode reaction), we must first determine the conversion rate for the anode reaction. If 75% of the hydrogen is utilized, then the conversion rate, , is found as: = 20 g H 2 fed mole of H 2 0.75 mole H 2 reacted 7.5 mole H 2 reacted s 2 g H2 mole of H 2 fed s This rate along with the anode stoichiometry (2 mole of electrons per mole of H2) indicate that 15 moles/s of electrons must be delivered to the load. If we now use Faraday’s constant as a unit conversion, we find the current to be (15 mole of electrons/s) x (96485C/mole of electrons) = 1.45x106 amps. This current multiplied by the cell voltage (0.7 volts), gives the load power as 1MW. In the notation of chapter 7 of Felder and Rousseau (2000), this power should be considered shaft work being removed from (or being done by) the system. 2) The molar flow out of the cathode is equal to the molar flow into the cathode minus the molar flow of oxygen through the electrolyte and into the anode. We start by Draft 4 -2- April 14, 2008 calculating the molar flow into the cathode. Assuming air is an ideal gas at standard conditions (1 atm and 0oC), we find that the number of moles per standard liter is: 1 atm n P 0.045moles / L V RT 0.08206 L atm mol 1 K 1 273K and thus the molar flow for 2.67x105 slpm is: 2.67 10 5 L 0.045mole min 200.25moles / s min L 60s Using the reaction stoichiometry and our calculation that 7.5 moles/s of H2 are reacted in the anode, we conclude that 3.75 moles/s of O2 are reacted in the cathode. Thus, the exit flow from the cathode must be 200.25 - 3.75 = 196.5 moles/s. 3) Now that we have performed some initial calculations concerning material and energy flows, we turn to the energy balance of the entire system. After identifying the appropriate balance equation, we find the need to calculate the reaction generated enthalpy, which will leave us with one equation (the energy balance) and one unknown (the temperature inlet to the anode). Since the SOFC is a continuous (or open) process, we should apply Equation 7.4-15 of Felder and Rousseau (2000): (7.4-15) H E k E p Q in W shaft,out Neglecting E k , E p and Q in , the last being due to assumption of adiabatic operation, leaves: (E-1) H W shaft,out To determine H we turn to Equation 9.5-1a of Felder and Rousseau (2000): H Hˆ ro n Hˆ n Hˆ i outlet i i (9.5-1a) i inlet From part (1) we have that W shaft,out =1MW. Then using Table B.1 of Felder and Rousseau (2000) for the reaction H2 + 1/2O2 H2O(g), we find the enthalpy of reaction, ( Ĥ ro ), to be -241.8 kJ/mole of H2 converted. Combining this with the conversion rate we find: 7.5 mole H 2 reacted 241800 J -1800kJ/s = -1.8MW s mole H 2 reacted Hˆ ro Applying this to Equation 9.5-1a and combining with Equation E-1 gives: Draft 4 -3- April 14, 2008 1MW 1.8MW n Hˆ n Hˆ i i outlet or 0.8MW n Hˆ n Hˆ i outlet i i i inlet i i inlet n H 2 ,out Hˆ H 2 ,Ta ,out n H 2O ,out Hˆ H 2O , Ta ,out n N 2 ,out Hˆ N 2 ,Tc ,out n O2 ,out Hˆ O2 , Tc ,out n H 2 ,in Hˆ H 2 , Ta ,in n N 2 ,in Hˆ N 2 ,Tc ,in n O2 ,in Hˆ O2 ,Tc ,in (The subscripts of T correspond to ‘a’ for anode ‘c’ for cathode ‘in’ for inlet and ‘out’ for outlet.) Since we know all of the molar flows into and out of the system, each of the ni terms is known. Summarizing from parts (1) and (2), we have n H 2 ,in 20 g H 2 fed mole of H 2 10 mole H 2 fed s 2 g H2 s n N 2 ,in 200.25 mole air fed 0.79 mole of N 2 158.2 mole N 2 fed s mole of air s 200.25 mole air fed 0.21 mole of O2 42.05 mole O2 fed s mole of air s 10 mole H 2 fed 7.5 mole H 2 reacted 2.5 mole H 2 exiting n H 2 ,out s s s 0 mole H 2 O fed 7.5 mole H 2 O produced 7.5 mole H 2 O exiting n H 2O ,out s s s 158.2 mole N 2 fed 0 mole N 2 reacted 158.2 mole N 2 exiting n N 2 ,out s s s 42.05 mole H 2 fed 3.75 mole O2 reacted 38.3 mole O2 exiting n O2 ,out s s s n O2 ,in Additionally, we can utilize Table B.8 of Felder and Rousseau (2000) to determine Ĥ i for all of the streams except for the inlet to the anode, since temperature of this stream is not known. (Linear interpolation used whenever needed.) Draft 4 -4- April 14, 2008 Hˆ H 2 , Ta ,o u t Hˆ H o 2 , 675 C 19.0 kJ / mole H 2 Hˆ H 2O , Ta ,o u t Hˆ H O , 675o C 23.9 kJ / mole H 2 O 2 Hˆ N 2 , Tc ,o u t Hˆ N 18.2 kJ / mole N 2 o 2 , 625 C Hˆ O2 , Tc , o u t Hˆ O , 625o C 19.3 kJ / mole O2 2 Hˆ H 2 , Ta ,in to be found kJ / mole H 2 Hˆ N 2 , Tc ,in Hˆ N 14.2 kJ / mole N 2 o 2 , 500 C Hˆ O2 , Tc ,in Hˆ O o 2 , 500 C 15.0 kJ / mole O2 This gives: 800 kJ / s n Hˆ n Hˆ i outlet i i i inlet n H 2 ,out Hˆ H 2 , Ta ,out n H 2O ,out Hˆ H 2O , Ta ,out n N 2 ,out Hˆ N 2 , Tc ,out n O2 ,out Hˆ O2 , Tc ,out n H 2 ,in Hˆ H 2 ,Ta ,in n N 2 ,in Hˆ N 2 , Tc ,in n O2 ,in Hˆ O2 , Tc ,in 2.5 19.0 7.5 23.9 158.2 18.2 38.3 19.3 10 Hˆ , 158.2 14.2 42.05 15.0 H 2 Ta , in Solving this equation for Hˆ H 2 ,Ta ,in , yields 16.8 kJ/mole H2. From Table B.8 of Felder and Rousseau (2000), this enthalpy is achieved at 600oC, which would need to be the inlet temperature to the anode. (It should also be noted that implicit in our application of Equation 9.5-1a, we have used 1 atm and 25oC as the reference state, which was dictated by the data received from Tables B.1 and B.8 of Felder and Rousseau (2000).) 4) If we define cell efficiency as the ratio of useful power to chemical energy input, we find Power to the Load W shaft,out 1 MW 0.56 o Enthalpy Re leased Hˆ 1.8 MW r This assumes the un-utilized hydrogen can be recycled. If not, and we are assuming the un-utilized hydrogen is lost, then a more appropriate efficiency value would be based on total conversion of the hydrogen, = 10 mole of hydrogen converted / s. The result of this assumption is be to calculate Ĥ o as (10 mole/s of H2) x (-241.8 kJ/mole H2), r which gives the new efficiency as: W shaft,out Power to the Load 1 MW 0.42 o ˆ Combustion Enthalpy in the H 2 Feed H r 2.4 MW Draft 4 -5- April 14, 2008 Home Problem Statement: An atmospheric pressure, adiabatic SOFC is operated with the following inlet and exit conditions: Anode In: Anode Out: Cathode In: Cathode Out: 200 slpm of pure H2 at 800oC 200 slpm of H2 and H2O at 900oC 2700 slpm of air at 750oC 2633 slpm at 850oC Determine the cell voltage. Draft 4 -6- April 14, 2008