A Compact Fuel Processor Integrated with 75kw PEM Fuel Cells

Du Liming Zhang Jun Sun Liping

Province Key lab of Vehicle Engineering advanced technology Dalian Jiaotong University Dalian, 116028, China e-mail: dlm@djtu.edu.cn AbstractDue to difficulties and inconveniences in storing and transporting of high-pressure pure hydrogen, hydrogen source becomes one of the technical bottlenecks of the commercialization of fuel cell. In this thesis, a compact autothermal reformer suitable for liquid fuel was developed. The fuel processor consists of a fuel evaporating step, two-stage reformer and a two-stage reactor of water gas shift (WGS, one for high temperature water gas shift and the other for low temperature water gas shifter) and a four-stage preferential oxidation (PROX) reactor and some internal heat exchanger in order to achieve optimized heat integration. It is designed to provide enough hydrogen for 75kWel fuel cells. The fuel reformer was combined with polymer electrolyte membrane fuel cells (PEM FC) and a system test of the process chain was successfully performed. During three hours coupling experiment, the fuel processing system and the fuel cells all has been running smoothly. The volume concentration of H2 and CO in product gas (dry basis) was kept in 53% and 20ppm respectively, completely meeting the requirements of PEM fuel cells. The conversion efficiency of the hydrogen producing system based on LHV of fuel and hydrogen can exceed 95.85%. The fuel cells stacks put up strong resistance to CO and its maximum electronic load to the fuel cells reaches 75.5kW. According to the experimental results, the hydrogen source system can produce hydrogen 70.5 m3/hr and its specific gravity power and specific volume power reach 255W/kg and 450W/L respectively. It indicates that it is feasible technically for supplying hydrogen for Proton Exchange Membrane Fuel Cells by catalytic reforming of hydrogen-rich liquid fuel on-board or on-site. (Abstract)
Hydrogen source; 75kW fuel cell; coupling experiment; methanol; autothermal reforming(key words)

Yuan Zhongshan Li Deyi

Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian, 116023, China

clearly has distinct advantages as a fuel for fuel cell vehicle applications: methanol is liquid at atmospheric conditions and has a high hydrogen-to-carbon ratio relative to gasoline, and it can be reformed to hydrogen at much lower temperatures (250-300 ), and is more efficient as compared to gasoline (800-900 ). In addition, methanol is an environmentally friendly fuel, as it is readily biodegradable in air, soil and water. When methanol is used in a fuel cell vehicle, emissions are extremely low. Based on lots of researches, scholars(Brown, 2001, Lffler, 2003) have the view that the mode of hydrogen producing, that is, fuel reforming and water gas shift and preferential oxidation, is one of the most feasible way for hydrogen producing on-board or on-site. GM published successfully the first gasoline with low sulfur reforming fuel cell for pick-up vehicle Cheverlet S-10 in 2001. Toyota Motor Corporation also released desulfurizated gasoline reforming fuel cell vehicles FCHV-5 in the same year. The structure and layout of the hydrogen production system developed by the two corporations are similar and their maximum power outputs are 70kW. The University of DuisburgEssen Germany has developed a compact 2.5kW steam reformer suitable for natural gas, propane and butane. The steam reformer was combined with a 1kW polymer electrolyte membrane fuel cell (PEM FC) and a system test of the process chain was performed (Mathiak et al., 2004). In the present thesis, a compact power supply system is developed for smallscale users, which can eliminate the possible safety concerns regarding in-house storage of the compressed hydrogen. It consists of a methanol fuel processor based on autothermal reforming and fuel cells stacks, and some peripheral components (pumps, blowers and valves) and controls. The target output of the fuel cells stacks is about 75kWel to be suitable for a car or some families. The current focus of the project is set on the characterization of the main components autothermal reformer including water gas shift and preferential oxidation step as CO purification (PROX) and fuel cell stack as well as the combining of these components to a process chain. Laboratory testing has been performed in order to investigate steady state behavior at rated power and at different part load operating points. Performance of the fuel processor such as gas composition, energy efficiency and

I.

INTRODUCTION

Fuel cell vehicles are the promising alternative option for the transportation because of high efficiency and low emissions. While currently all fuel cells being developed for vehicles require hydrogen as a fuel. It is difficult to store and handle hydrogen directly as a kind of on-board fuel. Liquid fuels such as primary alcohols, gasoline and diesel are presently favored by the automotive industry as the most suitable hydrogen carriers for fuel cell vehicles(Lindstrm et al., 2003, Cubeiro & Fierro, 1998). The two top fuel contenders for the fuel cell market today are methanol and gasoline. From the technological point of view, methanol

978-1-4244-8039-5/11/$26.00 2011 IEEE

reaction stability will be presented. The fuel cell stacks behavior like electrical power output will also be introduced. II. HYDROGEN PRODUCTION SYSTEM AND FUEL CELLS STACKS A. Compact fuel processing system The hydrogen producing system consists of control unit, reactors unit and the exhaust unit. The control unit includes real-time operation auto-control and abnormal alarms system. The reactors unit includes an integrated reforming hydrogen producing reactor, combusting-evaporator with plate-fin structure, some heat exchangers and stock pump and storage tank. The integrated reforming hydrogen producing reactor is the most important part in the whole fuel-processing system, which consists of a two-stage reformer and a two-stage reactor of water gas shift (WGS, one for high temperature water gas shift and the other for low temperature water gas shifter) and a four-stage preferential oxidation (PROX) reactor and some internal heat exchanger in order to achieve an optimal heat integration. Tail gas exhausting unit refers to the exhausting system of the burned gases and CO2 etc. Regarding to the combusting-evaporator, a highly favorable and innovational design for efficient coupling of an endothermic water and methanol evaporating reaction with catalytic combustion reaction has been proposed. One of distinguishing features of the evaporator is to adopt the similar structure of plate-fin heat exchanger. The main concept of plate-type evaporator can couple highly endothermic reforming reaction with exothermic reaction together. Its compact configuration minimizes heat transfer resistance. Each chamber of the reactor had a plate-fin configuration, and cross flow was arranged in alternate chambers.

exhausted gas returns to hydrogen sourcing system from the fuel cell system, the pressure is 0.14MPa and the temperature 65 ~75 . The following table 1 represents the most important design specifications of the fuel cell stacks.
TABLE I. SPECIFICATIONS AND FEATURES OF THE 75 KW PEM FUEL
CELL STACKS

Technical data/feature Electrical power output Number of stacks Number of cells for each stack Operating voltage Gas quality Tolerable CO content Operating temperature Operating pressure Cooling Pressure drop anode side Pressure drop cathode side Humidification anode side Humidification cathode side Air ratio

Figure/description 80 kW 2 250 Reformat gas 50ppm 50-80 0.18 MPa Water cooled 004 MPa 0.04 MPa None Internal =2

Remark With pure hydrogen

Air bleed necessary Tolerable temperature T = 25

Humid reformat gas used

Referred to converted H2

III. A.

RESULTS AND DISCUSSION

Fuel-processing system performance The fuel processor is designed to provide enough hydrogen for 75kWel fuel cells, which is typical and suitable for a family car. In the case of low electrical load for fuel cells, it will cause some fuel to waste if the reactant feed rate is still at full capacity (i.e., methanol feed rate of 750ml/min). Therefore, the fuel processor should be able to run stably in accordance with electrical load. After lots of tests, it shows that the CO concentration of the product gas is below 50ppm in the complete power range for steady state operation. The principal design of the process is explained referring to figure 1. For reformer measurements introduced in the following, methane was used as fuel gas in order to have exactly defined inlet parameters for the evaluation of product gas quality and reformer efficiency. Fist of all, evaporating and preheating of the mixture occur in combusting-evaporator and needed heat come from methanol catalytic combustion after adding liquid water to the methanol. Then gaseous mixture of water and methanol are converted at a Pt monolith catalyst at about 400~600 to form a mixture composed of H2, CO2, CO, residual methanol and water steam. When the reforming reaction was carried on steadily, a part of the reformat was sent to the combustion chambers to ensure the whole system perform autothermally. Subsequently in water gas shift reactors, the CO content can be reduced to less than 1% in two separate temperature steps (HT-shift at 340 and LT-shift at 275). At last, the residual CO is removed in a special fine purification unit, namely the preferential oxidation or PROX

Fig.1 75kWel methanol autothermal reformer including CO purification reactors in the test rig

B. Fuel Cell Stacks The fuel cell system consists of two stacks. The gas temperature of the cell system supplied by hydrogen sourcing system is about 60 and the relative humidity is 60% and the product gas pressure at the cell entrance is 0.18MPa. The consuming ratio of H2 in the cell system is about 65%. When

unit. After passing through a particle filter, the reformat gas can be ducted to the PEM fuel cells, where electrical power and heat are generated. When the fuel processing system entered into stably operating status with self sustaining, the flow rate of methanol was gradually increased to 750ml/min, keeping the molar ratio of H2O/CH3OH in 1.5 and OXYGEN/CH3OH in 0.18. As reactant feed rate and air velocity significantly increased, high temperature point moved to the surface from reformer1 to reformer2. Figure 2 shows the temperature of the inlet and outlet of the reforming reactor. When the feed rate of methanol was increased to 750 ml/min and the reactions were in stable status, the temperature of the inlet and centerline of the refomer1 kept in respectively about 300 and 370, while inlet temperature and outlet temperature of refomer2 were respectively 556.5 and 463 . Generally, the temperature distribution in reformer was smooth and steady. It indicates that autothermal reforming reaction can be self sustained smoothly. Gas chromatographic analysis of samples shows that methanol content was less than 100ppm. It means that methanol was completely conversed.

Fig.3 The temperature of the inlet and outlet in the HTS and LTS reactor

Figure 4 shows the temperature of the inlet and outlet in the four-stage PROX. The average temperatures of inlet and outlet in PROX1 were 192 and 306.5 respectively, and the CO concentration decreased from 1% to 0.3%. While in PROX2, the average temperatures of inlet and outlet were respectively 157.5 and 251 and the CO concentration decreased from 0.3% to about 1000ppm. Preferential oxidation reaction of CO and O2 is an exothermic reaction. Therefore, the outlet temperature will higher than the inlet temperature in every stage of PROX. As shown, the temperature difference between the inlet and outlet of PROX1 and PROX2 was up to 104.5 and 93.5 respectively, while it was only 37 and 13 respectively for PROX3 and PROX4. It indicates that most of CO was preferentially oxygenated in PROX1 and PROX2.

Fig. 2 Temperature of the inlet and outlet in the reforming reactor

The temperature in WGS reactor had some fluctuation, as shown in figure 3. The inlet and outlet temperature of high temperature section(HTS) were 321 and 348 respectively, and the maximum fluctuation was up to 27 . The CO conversion was about 25% in this section. While in low temperature section (LTS), the temperature fluctuation was smaller. The maximum temperature fluctuation did not exceed 15 and CO conversion rate was about 50%. The temperature of the rear section of the WGS reactor tended to be stabilized. It indicates that reaction heat tend to maintain balance in WGS reactor.

Fig.4 Temperature of the inlet and outlet in the first two stage PROX

B. Results of the coupling experiment The autothermal reformer and the fuel cells were coupled to form a process chain from methanol as input and electric power as output, when the two subsystems enter in stable operating status. The feed is controlled by mass flow controllers, the gas composition can be measured downstream the LT-shift as well as downstream the PROX in order to prevent the stack from not tolerable product gas qualities and CO peaks. Electronic load to the fuel cells is added smoothly and gradually from 0 kW to 75.5 kW in 15 minutes, and then the fuel cells had been running for about one hour with the output power of 75.5 kW. In the duration of coupling experiment, the fuel cells was kept in good performance, such as, the average voltage of single cell is 0.83V, and the minimum voltage of single cell 0.78V, as shown in figure 7. The fuel processing system kept supplying steadily hydrogen at 70.5 Nm3/hr, the concentration of CO is kept around at 20ppm. No any degradation of performance is found to the fuel cells.
1000

Fig.5 Temperature of the inlet and outlet in the last two stage PROX

When the reactant feed rate was increased to 750ml/min and all reactions in the fuel processor were in steady operation, 123-125m3/hr reformed gas could be produced. The internal pressure of the fuel processor was also raised to requirement of the fuel cells, or gauge pressure 0.2Mpa. Pressure drop of the whole fuel processor was no more than 20kPa according to the results of online monitoring. Hydrogen concentration was about 53% and CO concentration was kept in 18-22ppm in the product gas. Our previous researches shown that the fuel cells stacks can use hydrogen source as fuel safely which contain 50ppm CO. Therefore, the product gas absolutely was qualified enough for the fuel cells. Figure 5 shows the concentration of the product gases in the dry product stream at the exit of the whole fuel processor system. The maximum flux rate of feedstock in design is 850ml and the maximum net reformed gas is 134-136m3/hr, that is, about 72m3 pure hydrogen can be produced per hour. It indicates that energy conversion efficiency of the fuel processor can reach 95.85% according to the low calorific value of methanol. When reformed gas used as fuel, usually 0.7-0.8m3/hr flow rate of hydrogen can produce 1kW electricity. In accordance with the result, hydrogen produced by the fuel processor can meet 85 kW PEM fuel cell in demand at least.
60 50

800

Cell Voltage/mV

600 average single cell voltage minimum single cell voltage

400

200

40

Time/min

80

120

160

Fig.7 Average voltage and minimum voltage of single cell

H2

Composition/%

40 30 20 10 0

N2 CO2

Fig.8 presents a polarization curve and the electrical power output of the fuel cell stack with reformed gas as a function of the current density. The feed gas temperature was kept constant at about 57 and was moistened to 100% relative humidity. During the measurements a fuel utilization of 70% at the anode side and an air ratio of 2 were adjusted. The diagram shows a maximum power density of 0.115 W/cm2. The voltage efficiency v , which may be defined as average cell voltage referred to the free enthalpy G0=-237 kJ/mol resulting in a reversible cell voltage of 1.23V, is about 0.83/1.23=65% or 65% 75kW power output.

20

40

60

Time/min

80

100

120

140

Fig.6 Product gases in the dry product stream at the exit of the fuel-processor system

0.12

average single cell voltage/V

0.8

0.1

0.08 0.6

0.06 0.4 average single cell voltage electrical power density

0.04 0.2

electrical power density / W/cm2

developed successfully. It is designed to provide enough hydrogen for 75kWel fuel cells. The fuel processing system and PEM fuel cells system are successfully integrated together. During 3 hours coupling experiment, the two subsystems have been running stably and smoothly. The product gas of the fuel processing system is qualified for the fuel cells and the fuel cells can generate electricity steadily. It indicates that it is feasible technically that supplying hydrogen for Proton Exchange Membrane Fuel Cells by catalytic reforming of hydrogen-rich liquid fuel on-board or on-site. The fuel-processing system can produce hydrogen 70.5m3/hour. Its power of specific gravity and power of specific volume can reach 255W/kg and 450W/l respectively. During three hours coupling experiment, the volume factor of H2 and CO in reformed gas (dry basis) was kept in 53% and 20ppm respectively, absolutely meeting the requirements of PEM fuel cells. The fuel cells stacks could put up strong resistance to CO and its maximum electronic load to the fuel cells reached 75.5kW. It indicates that conversion efficiency of the hydrogen producing system based on LHV of fuel and hydrogen can exceed 95.85%. Acknowledgment The authors gratefully acknowledge the financial support of this work by the Key project of National Natural Science Foundation of China (Grants No.20590365) and open subjects of traction power state key laboratory (Grants No. TPL0906) References
[1] B Lindstrm, J Agrell and L J pettersoon. Combined methanol reforming for hydrogen generation over monolithic catalysts [J]. Chemical Engineering Journal, 2003, 93:91101 Cubeiro, J.L.G. Fierro. Partial oxidation of methanol over supported palladium catalysts [J]. Applied Catalysis A: General, 1998, 168: 307322 L F Brown. A comparative study of fuels for on-board hydrogen production for fuel-cell-powered vehicles [J]. International Journal of Hydrogen Energy, 2001, 26(4):381-397. D G Lffler, K Taylor, D. Mason. A light hydrocarbon fuel processor producing high-purity hydrogen [J]. Journal of Power Sources, 2003, 117(1-2): 84-91. http://www.gmfuelcell.com/w_shoop/pdf/Udo Winter. GMs Fuel Cell Vehicle Program. Winter(E).pdf. Udo

0.02

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2

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0 0.16

current / A/cm

Fig.8 Polarization curve and electrical power output as a function of current density at a fuel utilizations of 0.7, air ratio of 2 and an average stack temperature of 60 .

The electrical power output of the fuel cell stacks and the thermal hydrogen power output of the autothermal reformer including PROX step is depicted as a function of time. The load changes were performed manually in order to avoid CO peaks of the fuel processor and to establish a stable fuel cell operation. Hence, a careful and stepwise procedure was chosen to vary the load from 20% part load to rated power. A load change lasts about 40 minutes while keeping the CO content downstream the PROX under 22ppm in order to prevent the fuel cell stack from not tolerable CO peaks. It last for about one hour when electrical load was added to 75.5kW, and then the load was decreased gradually. As shown in Fig.9, CO concentration kept in about 20ppm, far lower than 50ppm, it almost does not result in any performance loss for the fuel cells.

[2]

[3]

[4]

Time/min
Fig. 9 Output power of the fuel cells and CO concentration in the product gas of the fuel processing system during the coupling experiment

[5] [6] [7]

Norihiko Nakamura. Working Towards Market: Introduction of FC Vehicles. In: Future Car Congress, Arlington, VA, 2002 J. Mathiak, A. Heinzel, J. Roes, Th. Kalk et al.. Coupling of a 2.5 kW steam reformer with a 1 kWel PEM fuel cell. Journal of Power Sources 131 (2004) 112119.

IV.

CONCLUSIONS

A compact integrated fuel-processing system suitable for liquid fuel such as methanol, diesel and ethanol, was