DOI: 10.1002/fuce.

201200115

ORIGINAL RESEARCH PAPER

Experimental Study of an SOFC Stack Operated With Autothermally Reformed Diesel Fuel
M. Rautanen1*, M. Halinen1, M. Noponen1,2, K. Koskela1, H. Vesala1, J. Kiviaho1
1 2

VTT Technical Research Centre of Finland, Fuel Cells, P.O. Box 1000, Biologinkuja 5, Espoo, FI-02044 VTT, Finland Current affiliation: Elcogen Oy, c/o VTT Technical Research Centre of Finland P.O. Box 1000, Biologinkuja 5, Espoo, FI-02044 VTT, Finland Received July 02, 2012; accepted October 31, 2012; published online December 07, 2012

Abstract
A 500 W SOFC stack provided by Topsoe Fuel Cells A/S was run with reformed diesel fuel for 1,200 h. Diesel fuel used was Swedish Environmental Class 1 containing <10 ppm of sulfur. The fuel was reformed with an autothermal reformer (ATR). The reformer consisted of a mixing chamber and a reactor chamber containing a noble metal catalyst provided by SdChemie. The reformer used the diesel fuel without any pre-treatment such as sulfur adsorbent. The reformer unit was able to achieve high conversion of reactants with only ppm levels of higher hydrocarbons at the reformer outlet. Particulate emissions of the reformer were measured to be 30 lg m3, a very low value even below daily exposure limits in ambient air set by the European Comission directives. The stack was first run with 3% humidified H2 + N2 fuel to obtain baseline performance and then switched to reformate. Diesel reformate was found not to induce significantly more long-term degradation on the stack compared to hydrogen case. However, an initial degradation of about 20 mV cell1 was observed during the first 150 h on diesel fuel reformate. This could be an indication of a poisoning mechanism taking place, but needs further research to be verified. Keywords: Autothermal, Diesel, Reforming, SOFC

1 Introduction
A major advantage of solid oxide fuel cell (SOFC) technology over conventional energy production technologies is that it facilitates the use of commonly available fossil fuels such as natural gas, liquefied petroleum gas, gasoline, and diesel fuel to develop electrical power more efficiently and with lower emissions [1]. Electric power generation in remote areas is often based primarily on diesel fuel because it can be easily transported and stored in large enough quantities for extended periods of time. Power generation from diesel fuel based on SOFC technology also offers the potential to increase fuel efficiency thus lowering the price of produced electricity [2]. When considering transportation applications, missing infrastructure for pure hydrogen and the nearly exclusive use of liquid fuels like gasoline and diesel demands efficient conversion processes for the on-board generation of hydrogen. For this kind of APU application, the fuel will likely be the same fuel as is used to operate the vehicle [3]. Another need for the diesel-based SOFC comes from the more strict emission regulations and increasing electricity demand in modern transportation applications, causing a need to

develop new solutions [4, 5]. Recently particulate emissions from conventional power sources in urban environment have been shown to produce significant health costs [6]. By using SOFC technology, it is possible to reduce these emissions even using the same fuel. Development of diesel reformers for SOFCs widens the application of the SOFC system by making it more fuel-flexible. While technologies for conversion of these fuels are commercially available, the industrial scale processes and the composition of the reformed gas are not ideally suited to SOFC systems. A key step in fuel processing is reforming of the fuel to a mixture containing hydrogen and methane [7]. The goal of the diesel reforming process is to convert fuel into product gas rich in hydrogen and carbon monoxide which can then be fed to SOFC. The composition of the product gas depends on the reforming route and process parameters [8]. High-temperature fuel cells can use carbon monoxide as fuel in contrast to low-temperature fuel cells for which car-

[*] Corresponding author, markus.rautanen@vtt.fi

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bon monoxide acts as a poison. Therefore, fuel processing for high-temperature fuel cells can be attained in fewer stages [9]. The steam reforming route can yield highest electrical efficiencies for the SOFC stack and system, but partial oxidation and autothermal reforming processes can be made thermally self-sufficient. This may be the optimal choice if a fast heat-up, system simplicity, and effortless start-up are needed. The properties of autothermal reforming lie between steam reforming and catalytic partial oxidation [1014]. Diesel is more complex to reform compared to lighter molecular weight hydrocarbons. Longer chain alkanes will undergo pyrolysis upon vaporization and Fig. 1 Simplified illustration of the experimental setup. Gray color marks the trace heated lines. thus the rates of carbon formation are much higher. Diesel fuel is a mixture containing approximately 400 evaporation unit (CEM, Bronkhorst) in which water was atodistinct hydrocarbons, additives and around 20 organic commized with air and evaporated with electric heaters. All the pounds. In diesel fuel the distribution of the carbon number reactants were then fed into the mixing chamber via an inof the hydrocarbon molecules peaks in the range of 1525 carhouse developed atomizing nozzle. The steam-air mixture bon atoms per molecule [15]. exits the nozzle at high speed breaking the diesel fluid into Present day low sulfur diesels usually contain less than very small droplets that evaporate in the chamber. The 10 ppm of sulfur typically in the form of alkylated benzothiorequired inlet overpressure for good atomization of the diesel phenes, dibenzothiophene (DBT) or alkylated dibenzothiofuel was around 350 mbar at nominal operating point of the phenes [16, 17]. A few authors have studied sulfur tolerance reformer. Temperature inside the mixing chamber was conof noble metal catalysts exposed to diesel or gasoline model trolled with electric heating elements outside the chamber walls. compounds containing thiophenes under autothermal The reformer reactor houses a commercial noble metal catreforming conditions and the results seem to correspond well alyst (Sd-Chemie) through which the gas mixture is fed. with those obtained with low-sulfur diesel [1820]. In these Reactor temperature was measured at the inlet and outlet of studies, conversion has been affected by adding sulfur comthe catalyst with 1.5 mm K-type thermocouples. All the pipepounds in the feed but the effect has been relatively small lines containing hot gases were trace heated with external and stepwise rather than constant degradation rate when the heating resistors to compensate for heat losses. sulfur amount has been low (<20 ppm). It has also been The normal starting procedure for the reformer was as folnoticed that in diesel ATR conditions, deactivation of the lows: noble metal catalyst is strongly temperature dependent and (1) Heat the reactor to 780 C and the evaporator to 240 C reforming temperatures above 700 C are proposed to be with N2 purge. ideal for the ATR process [20]. However, it must be noted that (2) Start steam feed of 0.63 lN min1. these tests have only been run for some tens of hours. (3) Start diesel feed of 0.39 lN min1. This paper presents results of an autothermal reformer (4) Start air feed of 1.16 lN min1. combined with SOFC stack. A lab prototype of a diesel refor(5) Switch off the N2 purge. mer unit with a nominal power of 1 kWel was designed, man(6) Ramp the flows up to required flow rates while keeping ufactured, and tested at VTT. The diesel reformer was coupled the inlet H2O/C = 1.25 and O2/C = 0.48 ratios constant. to an SOFC stack supplied by Topsoe Fuel Cells A/S to investiPurpose of starting steam feed first is to purge any residual gate the interaction between the reformer and SOFC stack, and air out of the system. Introduction of diesel after the steam the long-term durability of the stack with diesel reformate. starts endothermic steam reforming reactions and after that air feed can be started without risk of heating up the catalyst 2 Experimental too fast by partial oxidation reactions. Particle emission measurement was used to analyze refor2.1 Experimental Setup mer performance. In the past studies performed at VTT, particulate emissions have correlated well with the performance Figure 1 illustrates the experimental setup. Diesel fuel was of the mixer/evaporator and the reformer as a whole. Particupumped from a tank with a pump whose outlet pressure was late emissions from reformer could indicate cracking of controlled by adjusting a relief valve. Mass flow controllers hydrocarbons and therefore low particulate emissions are (Bronkhorst EL-FLOW, CoriFlow, and Liqui-Flow series) desirable. Particulate measurements were conducted using were used to control the flow rates of diesel, air, and water electrical low pressure impactor (ELPI) manufactured by for the reformer and hydrogen, nitrogen, and air for the Dekati Ltd [21]. SOFC. Air and water were fed to the reformer through an

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The SOFC stack was located in a separate furnace (Figure 2) and was fuelled either with 3% humidified H2 + N2 mixture or diesel reformate. The stack was loaded with an electronic load operated in galvanostatic mode. 2.2 Diesel Fuel Swedish Environmental Class 1 diesel [22] was used in the experiment. This diesel type was chosen because according to specification it contains very low amount (<10 ppm) of sulfur compounds and aromatic hydrocarbon compounds (<5%). Due to the low amount of sulfur in the fuel, a sulfur removal unit was excluded from the system layout. The distillation curve of the Swedish environmental class 1 diesel is presented in Figure 3 [23]. It can be noticed that a majority of the diesel compounds vaporize in the temperature range of 200280 C. Since the autoignition temperature of many of these compounds lies in the same range, it is obvious that fast and controlled heat up and mixing of diesel, air, and steam is required before the reactants are fed to the catalyst. 2.3 Operating Conditions A 25 cell stack based on anode supported cell technology provided by Topsoe Fuel Cells A/S was used in the experiment. Each anode supported cell had an active area of 92 cm2. At steady state, the stack was always run on 20 A

(0.22 A cm2 current density) and 40 NLPM of air. In the first, hydrogen fuelled test, the fuel flow to the stack anode was 10.4 NLPM consisting of 57% H2, 40% N2, and 3% H2O. These flows correspond to 60% fuel utilization and 21% air utilization. The furnace temperature was kept constant at 760 C. In the reformate experiment, the inlet flows to the diesel reformer were controlled by keeping the H2O/C = 1.25 and O2/C = 0.48 ratios constant and varying the total flow. At nominal operating conditions the flows were 2.2 mL min1 (liquid) diesel, 3.6 NLPM(gas) steam, and 6.5 NLPM air. Stack current (20 A), fuel utilization (60%), and cathode air flow (40 NLPM) were kept at the same values as in the hydrogen fuelled test run.

3 Results and Discussion

3.1 Reformer Performance Reformer performance was analyzed by online gas sampling, gas chromatography, and particle emission measurements. A gas sample of the reformate gas was taken during the operation at 1,811 h and analyzed with gas chromatograph. The results of the analysis are presented in Table 1 along with the equilibrium composition calculated at 770 C corresponding to the measured reactor outlet temperature. The equilibrium calculation was done with HSC Chemistry 6.1 and the amounts of reactants were defined using mass flow controller measurements for diesel, air, and steam, and the average composition of diesel (C: 84.8 wt-%, H: 13.5 wt.%). It can be noted that the measured concentrations match reasonably well with the equilibrium calculations. The difference between the values can be explained largely by the deviation of watergas shift reaction from expected equilibrium values. Measured amount of C2C7 hydrocarbons was 7 ppm and the amount of CH4 was 770 ppm indicating very good conversion of diesel to hydrogen and carbon monoxide and thus good performance of the reformer. Faradic equivalent current efficiency is used to describe the availability of electrons for electrochemical reactions after reforming has taken place. The faradic equivalent current efficiency of the reformer is defined as gFar 1
_O 2n _C _ H 4 n n

Fig. 2 The SOFC stack installed in the furnace.

300 280 Temperature / C 260 240 220 200 180 0 0.2 0.4 0.6 0.8 Distilled fraction 1

_ H and _ O is the oxygen atom flow rate (mol s1) and n where n _ C are the equivalent hydrogen atom and carbon atom flow n rates of the diesel fuel. From the definition, steam reforming
Table 1 Measured (dry basis) reformate gas composition compared to equilibrium calculation.
Measured H2 N2 CO CO2 CH4 C2C7 30.3% 42.4% 17.0% 8.2% 770 ppm 7 ppm Equilibrium 35.4% 41.8% 13.9% 8.9% 247 ppm

Fig. 3 Distillation curve of the Swedish Environmental Class 1 diesel [23].

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conditions yield faradic equivalent current efficiency of 100%. With experimental conditions used here (O2/C = 0.48) the faradic equivalent current efficiency is 68%. To ascertain that the mixing chamber was working properly and no cracking of hydrocarbons was taking place, a particle concentration measurement was performed at the reformer exhaust just before the stack was switched to reformate fuel. During a 30 h measurement, the particle concentration at the reformer exhaust was measured to be 30 lg m3, assuming average particle density of 1,000 kg m3. Figure 4 presents the average particle size distribution over measurement period. The measured particulate emissions can be considered extremely small since they are even below daily exposure limits (50 lg m3) in ambient air set by the European Commission directives [24, 25].

sensor in the laboratory caused an automated shutdown at 734 h (#3). After this, the stack was cooled down to room temperature to allow coupling of the diesel reformer and the stack test station. At 1,339 h, stack was again heated up and loaded (#4). At 1,477 h, stack was switched to diesel reformate (#5) and hydrogen and nitrogen flows were cut to zero. After switching to reformate, the pressure in the reformers mixing chamber started climbing, indicating carbon formation in the pipeline between the mixing chamber and reactor. Therefore, the stack was taken back to H2 + N2 (#6) and the carbon was removed from the reformer by cutting the fuel flow to zero and purging with air. The carbon formation was assumed to be due to incomplete evaporation of diesel in the mixing chamber or because of cold spot in the pipeline causing condensation. Therefore, trace heating of the pipeline between the two chambers was consequently raised from 240 to 3.2 Stack Performance 300 C which proved successful since the pressure stayed constant during the rest of the experiment. At 2,030 h (#7) the Figure 5 depicts the stack voltage during the entire test system experienced another automatic shutdown mode but run. The stack located in a furnace was heated up to 760 C was quickly brought back to operating conditions manually. and a steady-state loading with 20 A was started at 43 h after At 2,240 h (#8) the fuel batch was changed and an increase of initial IV curves (#1) occurrence in the figure). At 664 h the stack voltage was observed. After 2,677 h (#9) the test was air compressor which supplied air to the stack malfunctioned concluded and the unit shut down. causing an automated shutdown (#2). After the incident, the In the hydrogen fuelled first test run, the stack voltage stack was again loaded with 20 A until a malfunctioning gas degradation was negligibly small and obscured by initial performance improvement often seen in new 60 cells and stacks. Linear fitting between 100 and 50 660 h yields a value of 0.3%/1,000 h. When the stack was switched to diesel reformate, the average 40 cell voltage dropped instantaneously by 30 16 mV cell1 due to lower partial pressure of fuel 20 species in reformate compared to the H + N + H O mixture. The stack voltage 10 2 2 2 decreased 20 mV cell1 during the first 150 h with 0 44 83 137 215 330 516 818 reformate gas, after which the voltage degradation Median particle size / nm stabilized to level of 0.9%/1,000 h until the fuel Fig. 4 Average particle size distribution during a 30 h measurement. batch change (#8). During the first 200 h after the fuel batch change, the voltage recovered by about #1 #2#3 #4 #5#6 #7 #8 #9 21.6 6 mV cell1. According to the fuel supplier, there was a change in the fuel additives but unfortunately 21.4 no more detailed info was received. No significant voltage degradation could be observed after the fuel 21.2 batch change. The degradation during the entire 21 diesel fuelled test run, excluding the initial performance drop, was about 0.2%/1,000 h. Therefore, it 20.8 can be concluded that no evidence indicating 20.6 increased long-term degradation with MK1 diesel fuel was found. Since diesel is quite complex feed20.4 stock compared to pure H2 + N2 + H2O mixture 20.2 and because the test rig contained no cleaning units for sulfur or other compounds an increased degra20 dation rate was expected beforehand which makes 0 500 1000 1500 2000 2500 Time / h the low degradation rate an interesting finding. However, the observed relatively large voltage degraFig. 5 Stack voltage over the test period. Gray color marks the H2 + N2 fuelled period and black color marks the reformate fuelled period. dation during the first 150 h calls for further research.
Stack voltage / V
Particle fraction / %

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4 Conclusion
A diesel reformer unit with a nominal power of 1 kWel was designed, manufactured, and tested at VTT. The reformer showed good conversion of diesel to hydrogen and carbon monoxide with only ppm levels of hydrocarbons in the reformate gas. Particulate emissions of the reformer were measured to be at a very low level. A 500 W SOFC stack was coupled with the reformer unit and operated successfully with diesel reformate for 1,200 h. The reformer concept was proven reasonably reliable with only two shutdowns during the 1,200 h experiment. The stack voltage degradation during the test run with reformate was of the same magnitude as with hydrogen, except for the larger initial voltage degradation. Further research is needed concerning the initial degradation with diesel fuel.

5 Acknowledgements
Funding for this study was obtained from FINSOFC and SofcPower projects. Finnish Funding Agency for Technology and Innovation in Finland (TEKES) as well as the companies that participated in the projects are gratefully acknowledged for their financial support. Dr. Pekka Simell of VTT Technical Research Centre of Finland is acknowledged for useful discussions.

6 References
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