Chemical Engineering Science 64 (2008) 288 -- 293

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Chemical Engineering Science

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Hydrodesulfurization of jet fuel by pre-saturated one-liquid-flow technology for mobile fuel cell applications
J. Latz a , R. Peters a , J. Pasel a, , L. Datsevich b , A. Jess b
a b

Institute for Energy ResearchFuel Cells (IEF-3), Forschungszentrum Julich GmbH, D-52425 Julich, Germany Department of Chemical Engineering, University of Bayreuth, Universitatsstr. 30, D-95447 Bayreuth, Germany

A R T I C L E

I N F O

A B S T R A C T

Article history: Received 17 July 2008 Received in revised form 17 October 2008 Accepted 17 October 2008 Available online 1 November 2008 Keywords: Desulfurization Jet fuel Catalysis Chemical processes Multiphase processes Multiphase reactions

To prevent the catalysts in fuel cell systems from poisoning by sulfur containing substances the fuel to be used must be desulfurized to a maximum of 10 ppm of sulfur. Thereby, damage to the catalysts in the fuel cell and the reformer can be avoided. Diesel fuel for road vehicles within the EU is already desulfurized at the refinery. However, jet fuel is permitted to have up to 3000 ppm of sulfur. Since the hydrodesulfurization process used in refineries is not suitable for mobile applications, the aim of the present work was to develop an alternative desulfurization process for jet fuel and to determine its technical feasibility. To this end, many processes were assessed with respect to their application in fuel cell based auxiliary power units (APUs). Among them, hydrodesulfurization with pre-saturation was selected for detailed investigations. Laboratory tests revealed that also syngas operation is possible without any performance loss in comparison to operation with hydrogen. Pure hydrogen is not available in a fuel cell system based on reforming of jet fuel. The effects of reaction temperature, operating pressure and liquid hourly space velocity (LHSV) were investigated. Different jet fuel qualities with up to 3000 ppm of sulfur were desulfurized to a level of 1522 ppm. Finally, the technical applicability of hydrodesulfurization with pre-saturation was demonstrated in a pilot plant with an electrical power of 5 kW, going beyond the laboratory scale. In a 200-h experiment, a commercial jet fuel with 712 ppm of sulfur was desulfurized to a maximum sulfur content of 10 ppm. Besides this, H2 S separation by stripping with air turned out to be a suitable method for APU applications. The aim of developing a suitable process for the desulfurization of jet fuel in fuel cell APUs has thus been achieved. 2008 Elsevier Ltd. All rights reserved.

1. Introduction Fuel cells are well suited for on-board power supply in aircraft, ships and heavy goods vehicles. The use of fuel cell systems in aircraft offers the possibility to simplify the aircraft layout. Important systems in aircraft, i.e., the gas turbine powered auxiliary power unit (APU) for electricity supply, the fuel tank inerting system and the water tank, can be substituted by one single system, the fuel cell system. The waste heat of the fuel cell system can be used for ice protection. These measures reduce the consumption of jet fuel, increase aircraft efficiency and allow the operation at low emissions. Additionally, the costs for aircraft related investments, for aircraft maintenance and operation can be reduced. APUs driven by conventional gas turbines operate at an efficiency of about 15% on the ground (Daggett et al., 2003), while an APU based on autothermal reforming of diesel or gasoline in combination with a polymer electrolyte fuel cell

(PEFC) can achieve a system efficiency of up to 36%37% (Ersoz et al., 2006; Specchia et al., 2006). To operate the fuel cells with the fuel available on board, this fuel is converted into a hydrogen-rich gas by a process of catalytic reforming. Since both the catalysts in the reformer and also in the fuel cell are deactivated by the sulfur compounds contained in the fuel, the latter must be desulfurized to a level of a maximum content of 10 ppm of sulfur. Whereas diesel fuel for road vehicles is already desulfurized at the refinery within the EU, jet fuel is permitted to have up to 3000 ppm of sulfur all over the world. Consequently, on-board desulfurization is required for the use of fuel cell APUs on aircraft. In industrial applications, conventional hydrodesulfurization without pre-saturation is a well-engineered process for desulfurization of liquid fuels. In refineries, besides hydrodesulfurization only the S-Zorb process, a novel sorption process developed by Conoco Pillips (Gislason, 2001; Johnson et al., 2003), is used commercially. These processes are not suitable for mobile fuel cell applications for the following reasons: In fuel cell APUs based on reforming pure hydrogen is not available. The syngas to be used contains only 42% (vol.) of hydrogen.

Corresponding author. Tel.: +49 2461 615140; fax: +49 2461 616695. E-mail address: j.pasel@fz-juelich.de (J. Pasel).

0009-2509/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.ces.2008.10.016

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As the hydrodesulfurization process needs a surplus of hydrogen in the reactor, hydrogen recycling is necessary. Since the hydrogen content in the syngas is reduced by the hydrofining reaction, the gas stream cannot be recycled directly. Hydrogen depletion would negatively affect the reaction. Consequently, an additional gas cleaning step would be required, which makes the system too complex. Because of vibrations and continuous variation of the position of the reactor in aircraft it is not possible to apply a conventional trickle bed reactor. The products of the gas-phase hydrodesulfurization process cannot be used directly in the autothermal reformer, as the hydrogen surplus in the gaseous fuel would react with air at unacceptably high temperatures. To desulfurize a fuel with up to 3000 ppm of sulfur to a level of a maximum of 10 ppm, a multi-stage hydrodesulfurization process would be needed in the case of conventional hydrodesulfurization. Therefore a newly developed desulfurization process is needed for this application. Various alternative methods such as adsorption, extraction with ionic liquids, selective oxidation, and pervaporation are discussed in the literature. A large number of these processes were evaluated with respect to their application in fuel cell APUs. As a result, three potentially suitable processes were selected (Peters et al., 2008). Besides the two-step concept of fractionation or pervaporation combined with an adsorption process, hydrodesulfurization with pre-saturation is a very promising approach. The investigations to evaluate this process are presented in this paper. 2. Process design The concept of hydrodesulfurization with pre-saturation is based on the conventional hydrodesulfurization technology. The main difference is that the required amount of hydrogen is dissolved in the liquid fuel before the fuel enters the reactor. In contrast to a threephase reaction system as used in conventional trickle bed reactors, hydrodesulfurization with pre-saturation is based on only one liquid phase besides the solid catalyst. As the diffusion of the gas into the liquid is already complete before it enters the reactor, only a marginal hydrogen surplus is needed in the catalyst bed. Consequently, hydrogen recycling is not required. The process flow sheet is shown in Fig. 1. The feed fuel and the syngas are fed into the saturator, where the gas is dissolved in the liquid fuel at a pressure between 20 and 70 bar. Subsequently, the fuel is heated and passed through the catalyst bed, where the aromatic sulfur compounds are converted to hydrogen sulfide. To separate the gases that are dissolved in the liquid fuel, the fuel is cooled down, expanded to ambient pressure and flushed with air or the off-gas of the catalytic burner of a fuel cell system. This off-gas has a low oxygen concentration of less than 1% (vol.). The H2 S containing gas can be burned in the aircraft's turbine to avoid H2 S expulsion. In contrast to conventional hydrofining, the main advantages of this modified process are as follows: As there is only one liquid phase in the reactor, the process is not affected by the vibrations in a mobile system and it is not affected by operating in various positions. There is neither gas nor liquid recirculation. As a result, the process is distinguished by the unsophisticated technical embodiments and low energy demand. Kinetic studies show that the space velocity can be increased because of better kinetics in the liquid phase reactor (Schmitz, 2003). The principle of hydrogenation with pre-saturation was patented by Berlin and McCall (1963). Similar processes for the

Fig. 1. Process flow sheet of hydrodesulfurization with pre-saturation.

desulfurization of crude oil and gas oil were patented in 1959 and 1969, but no experimental results or industrial applications were published. A detailed process description has been patented by Datsevich and Muhkortov (1997). More detailed developments and lab-scale experiments were published by Schmitz (2003), Schmitz et al. (2004) and Wache et al. (2006). The desulfurization of diesel fuel and gas oil with up to 2250 ppm of sulfur on a lab scale is described. The process was only operated with pure hydrogen and the product sulfur level was significantly higher than 10 ppm. Further investigations were needed to apply this process for mobile fuel cell systems operated with jet fuel: The system must be able to desulfurize jet fuel with up to 3000 ppm of sulfur to a level of 10 ppm. The system must be able to work with syngas instead of pure hydrogen, as no pure hydrogen is available in the APU system. The ability to operate in mobile applications in various positions has to be demonstrated. A process upscale is needed to show that the process is technically feasible. In order to verify the technical applicability of fuel cell APUs, the process was first investigated on a laboratory scale and then on a pilot-plant scale. 3. Experimental section A commercial CoMo-Hydrofining catalyst in extrudate form was used for the experiments (Sudchemie C20-6). The average particle size of the catalyst was 1.7 mm. The reformer syngas was used as the hydrogen supply for hydrogenation. The syngas composition is shown in Table 1. For the experiments different jet fuel qualities were used, as shown in Table 2. The first fuel was a commercial Jet A-1, which was Airport provided by Total Deutschland GmbH at Aachen-Merzbruck in Germany. The fuel contained 712 ppm of sulfur, which is a typical value for commercial jet fuel in the EU. The fuel with the highest sulfur content available (called Jet Fuel HS) was a kerosene fraction from the Spergau refinery in Germany, which was diverted from the fuel stream before the desulfurization step. This fuel was produced from crude oil from Russia. As the sulfur content of 1675 ppm is still

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below the maximum sulfur level of 3000 ppm, sulfur compounds were added to achieve experimental fuels with a sulfur content of 2025 ppm (Jet Fuel HS 2000) and 3031 ppm (Jet A-1 3000). The composition of sulfur compounds, the aromatic content and the density of the fuels is shown in Table 2. The first experiments were conducted on a lab scale while a pilot plant was subsequently used to prove that the process was technically feasible. The lab-scale experiments were conducted with a fixed-bed reactor with an inner diameter of 4 mm and a catalyst bed 500 mm in length. For the pilot plant a fixed-bed reactor with an inner diameter of 64 mm and a length of 933 mm was used. In comparison to the lab-scale test stand that does not include H2 S separation, for the pilot plant an additional stripper was used to separate the dissolved gases from the product stream to achieve a product with a maximum sulfur level of 10 ppm. The flow sheet of both test facilities is shown in Fig. 2. 3.1. Experimental procedure At first the fuel and the syngas are going through the saturation system (1) and (2) to dissolve the gas in the fuel. Subsequently, the fuel is preheated (3) and passes the catalyst bed (4) under the particular conditions that are defined by operating pressure (pR ), reaction
Table 1 Syngas composition. Concentration/% (vol.) Hydrogen Nitrogen Carbon dioxide Carbon monoxide 41.0 38.0 20.0 1.0

temperature (TR ) and the liquid hourly space velocity (LHSV). The duration of each experiment, in which a set of reaction parameters (constant p, T and LHSV) was tested was 99.5 h. The sulfur content in the product was measured every 24 h. It was observed during the whole 99.5 h on stream, that the fluctuations in the sulfur content of the desulfurized product were very small (in the range of a few ppm). The quality of the desulfurized product was found to be good enough to be used in the reformer and in the fuel cell. A Mitsubishi TS-100 total sulfur analyzer with a detection limit of 0.5 ppm was used to measure the total sulfur content in the fuel. To determine the content of the individual sulfur compounds an Ssensitive gas chromatograph with a pulsed flame photometric detector (PDPF) was used (GC Varian CP-3800). As in the lab-scale test bench, no hydrogen sulfide separation unit was integrated, and the product samples were vented until the hydrogen sulfide disappeared completely to estimate the content of aromatic sulfur compounds left over in the product. 4. Results and discussion 4.1. Solubility of hydrogen and syngas in jet fuel A sufficient amount of hydrogen must be dissolved in the liquid fuel to convert all the sulfur contained in the fuel to hydrogen sulfide. The amount of hydrogen that can be dissolved in the fuel is proportional to the overall pressure and can be calculated by Henry's law (Frolich et al., 1931). Due to the other gases contained in the syngas, the overall pressure has to be increased in comparison to hydrogen operation to achieve the same hydrogen partial pressure. The solubility of the syngas components in jet fuel was calculated on the basis of literature data (Frolich et al., 1931; Rachner, 1998; Ronze et al., 2002; Tremper and Prausnitz, 1976). The calculated amount

Table 2 Density and composition of the jet fuel samples used for the experimental investigations. Unit Density Total aromatics Sulfur content C2+C3-thiophene Benzothiophene C1-benzothiophene C2-benzothiophene C3-benzothiophene Dibenzothiophene Overall sulfur content kg/m3 % (mass) ppm ppm ppm ppm ppm ppm ppm Jet A-1 800.6 20.2 182 12 150 188 177 3 712 Jet Fuel HS 802.5 20.7 612 36 453 459 115 1675 Jet Fuel HS 2000 799.7 20.0 595 39 527 479 387 2025 Jet A-1 3000 800.6 20.2 363 299 728 723 901 6 3031

Fig. 2. Flow sheet of the hydrodesulfurization process with pre-saturation.

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Fig. 3. (a) Equilibrium solubility of syngas in jet fuel. (b) Maximum sulfur content in jet fuel to be fully converted depending on syngas pressure in the saturator.

of syngas that can be dissolved in jet fuel is plotted in Fig. 3 as a function of temperature. The comparison with the measured value at 80 C (Fig. 3a) shows that the calculated solubility can be used as reliable data for process estimations. For stoichiometric reasons the conversion of one mole of such compounds as thiophene, benzothiophene or dibenzothiophene demands at least two moles of hydrogen. With regard to the successful elimination of these sulfurorganic species, the total pressure of the syngas makes up, for instance, 24 bar for the jet fuel with sulfur of 700 ppm and 70 bar for the sulfur content of 3000 ppm. Fig. 3b represents the dependence between the sulfur concentration and the pressure of syngas and pure hydrogen, which should be taken into account in order to carry out the process without the hydrogen deficit. For two aforementioned fuels of 700 and 3000 ppm, the consumption of syngas for the reaction can be estimated equal to 4.8 and 11.0 Ndm3 /kg fuel, respectively. During autothermal reforming 1 kg fuel is converted into 10.000 N dm3 hydrogen-rich syngas. That means that the syngas stream required for the hydrodesulfurization reaction amounts to approx. 0.1% of the complete syngas volume.
Fig. 4. Desulfurization of jet fuel with a sulfur content of 2000 with hydrogen and syngas at T = 390 C, LHSV = 0.7 h1 .

4.2. Comparison of hydrodesulfurization carried out with syngas and pure hydrogen Two points related to the use of syngas should be taken into account: (i) necessity of higher pressure compared to pure hydrogen (see Fig. 3b); (ii) unpredictable catalyst behavior due to the presence of such by-products of reforming as carbon dioxide and carbon monoxide. As it is well known, carbon oxides can significantly worsen the activity of hydrogenation catalysts due to irreversible processes on the active catalyst sites. In the case of the hydrodesulfurization reaction with pure hydrogen, the catalyst is also subjected to aging caused for example by the deposition of carbon in catalyst pores. Therefore, two series of experiments with hydrogen and syngas have been carried out in order to compare the impact on the long-time reaction performance. In both experiments, the operating conditions, temperature, feed flow rate and catalyst volume were identical, except the pressure. In the syngas experiment, the total pressure is higher so that the concentration of hydrogen dissolved in the reacting mixture is the same as in the case of pure hydrogen. The results of these experiments are shown in Fig. 4. For pure hydrogen the average sulfur content in the product is 14.5 ppm with a 95% confidence interval of 4.4 ppm. In the case of syngas the product is characterized by the average value of sulfur of 16.8 ppm with a 95% confidence interval of 2.0 ppm. Thus, the comparison of two modes indicates that there is no significant impact of syngas on the hydrodesulfurization reaction.

4.3. Effect of sulfur content in jet fuel To determine the effect of different fuel qualities on the product quality, four different jet fuels with different sulfur contents were used for comparison. The experiments were conducted at an overall pressure of 70 bar, which is enough to convert up to 3000 ppm of aromatic sulfur compounds. The experimental results are shown in Fig. 5. Considering the 95%-confidence intervals as shown in Fig. 5 for all jet fuel qualities, the product sulfur content is between 10 and 25 ppm. The fact that the product sulfur content decreases for fuels with higher sulfur contents could be due to the types of sulfur compounds contained in the fuel and the different aromatic contents. The results show that hydrodesulfurization with pre-saturation has the potential to fulfill the target of a 10 ppm sulfur level for high sulfur contents of up to 3000 ppm. Further improvements are necessary to reach a sulfur content below 10 ppm finally. Only one desulfurization step is needed to achieve this target.

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4.4. Effect of reaction temperature and pressure on product sulfur content For process optimization, a two-level factorial plan (Montgomery, 2005) was carried out to investigate the effect of the reaction temperature and the operating pressure on the product sulfur content. In Fig. 6(a) the factorial plan is shown. The temperature and pressure levels were selected on the basis of literature data (Schmitz, 2003; Wache et al., 2006; Montgomery, 2005). To prove that catalyst degradation has no effect on the results, additionally the first experiment was repeated after all the experiments had been finished, and no significant difference in product sulfur content was observed. The experiments were conducted with Jet Fuel HS with 1675 ppm of sulfur at a LHSV of 0.7 h1 . The results show that the reaction temperature is the dominant effect. The product sulfur content decreases significantly with increasing temperature, while it is influenced only marginally by the operating pressure (see Fig. 6(b)). Based on the experiment at 31 bar and 330 C, the main effects and the interaction were calculated as shown by Latz (2008). All three effects are significant with respect to the 95%-confidence interval (see Table 3). With these results, the regression for calculating the product sulfur content cS,Product in the investigated area can

be estimated: cS,Product = 90 2.533(TR 361) + 0.55(pR 51) 0.0117(TR 361)(pR 51) The maximum reaction temperature consequently has to be chosen for a minimum product sulfur content. As the typical critical temperature of jet fuel is 411 C (Rachner, 1998), the maximum temperature is limited. Further experiments showed that at 405 C and an operating pressure of 30 bar the product sulfur content increased from 30 to 80 ppm within 230 h because of catalyst coking. Thus, it can be concluded that 390 C is the optimum temperature for technical applications. To optimize the operating pressure it can be reduced until it is not lower than the vapor pressure to assure liquid phase reaction and until enough hydrogen for the reaction is dissolved in the fuel. 4.5. Effect of space velocity on product sulfur content The effect of space velocity was investigated with Jet Fuel HS. The experimental results are shown in Fig. 7. Fig. 7 represents the sulfur content in the product with the estimated 95% confidence interval for three space velocities. Although there is a slight decrease in the sulfur concentration at LHSV = 0.676 h1 , it is quite expected that sulfur content rises at the growing flow rate of feed. 4.6. Pilot plant testing To prove the technical concept for H2 S separation, to upscale data and to prove that the process is technically feasible, further experiments were conducted with a pilot plant for a fuel cell system with an electric power of 5 kW. The pilot plant was operated for an experimental time of nearly 200 h with Jet A-1 containing 712 ppm of sulfur. In contrast to the roughly 1 l of fuel that was desulfurized in a single lab-scale experiment, 382 l of jet fuel were desulfurized in the pilot-plant experiment. An amount of 50150 Ndm3 /kgFuel nitrogen

Table 3 Main effects and interactions of temperature and pressure of the reaction on the product sulfur content at LHSV = 0.7 h1 . Effect Main effect TR Main effect pR Interaction S-content/ppm 152 22 14

Fig. 5. Dependence of feed sulfur content on product sulfur content at TR = 390 C; pR = 70 bar, LHSV = 0.7 h1 .

Fig. 6. (a) Experimental plan to determine the effect of reaction temperature and operating pressure on the product sulfur content; (b) product sulfur content depending on reaction temperature and operating pressure at LHSV = 0.7 h1 .

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Experiments for process optimization resulted in an optimum reaction temperature of 390 C, and an LHSV of 0.7 h1 . The optimum operating pressure depends on the sulfur content and the vapor pressure of the fuel. It is 30 bar for a jet fuel with up to 985 ppm of sulfur and 70 bar for a jet fuel with 3000 ppm of sulfur. Finally, the technical applicability of hydrodesulfurization with pre-saturation was demonstrated in a pilot plant for a fuel cell APU with a power of 5 kWe, going beyond the laboratory scale. For that power class a hydrodesulfurization reactor running with an LHSV of 0.7 h1 will have a volume of 2.4 l. The volume of a complete hydrodesulfurization system including the reactor and all balance of plant components will amount to 13.2 l. Further calculations showed that the integration of a hydrodesulfurization unit with pre-saturator into a fuel cell system reduces the overall system efficiency by 1% point. The aim of developing a suitable process for the desulfurization of jet fuel in fuel cell APUs has thus been achieved. Acknowledgments
Fig. 7. Effect of space velocity at TR = 390 C and pR = 30 bar with Jet Fuel HS.

Part of the work was funded by the Ministry of Economy and Technology within the National Aerospace Research Programme (ELBASYS project). The authors thank Mr. R. Dahl, Mr. B. Sobotta, Mr. Y. Wang (Forschungszentrum Julich), Mr. Gerchau, Mrs. Brunner (University of Bayreuth), Mr. Grosch and Mr. Wolfrum (MPCP GmbH) for valuable technical assistance. References
Berlin, N.H., McCall, P.P., 1963. Improvements in the Hydrofining of Hydrocarbon Liquids, Patent: GB 934907. Daggett, D., Freeh, J., Balan, C., Birmingham, D., 2003. Fuel Cell APU for Commercial Aircraft. In: Proceedings Fuel Cell Seminar, Miami Beach, USA. Datsevich, L.B., Muhkortov, D.A., 1997. Process for hydrogenation of organic compounds, Patent: RU 2083540. Ersoz, A., Olgun, H., Ozdogan, S., 2006. Reforming options for hydrogen production from fossil fuels for PEM fuel cells. Journal of Power Sources 154, 6773. Frolich, P.K., Tauch, E.J., Hogan, J.J., Peer, A.A., 1931. Solubilities of gases in liquids at high pressure. Industrial and Engineering Chemistry 23, 548550. Gislason, J., 2001. Refiners' sulfur dilemmaPhillips sulfur-removal process nears commercialization. Oil & Gas Journal. Johnson, M.M., Sughrue, E.L., Owen, S.A., 2003. Desulfurization of Middle Destillates, Patent: WO 03/054117 A1. die Anwendung in Latz, J., 2008. Entschwefelung von Mitteldestillaten fur mobilen Brenstoffzellen-Systemen. Ph.D. Thesis, Forschungszentrum Julich, Julich, Germany. Montgomery, D.C., 2005. Design and Analysis of Experiments. Wiley, Hoboken. Peters, R., Latz, J., Pasel, J., Stolten, D., 2008. Desulfurization of Jet A-1 and heating oil: general aspects and experimental results. ECS Transactions 12 (1), 543554. Rachner, M., 1998. Die Stoffeigenschaften von Kerosin Jet A-1, DLR-Mitteilung 98-01, Cologne, Germany. Ronze, D., Fongarland, P., Pitault, I., Forissier, M., 2002. Hydrogen solubility in straight run gasoil. Chemical Engineering Science 57, 547553. Schmitz, C., 2003. Zur Kinetik und zur verbesserten Reaktionsfuhrung der Ph.D. Thesis, University of hydrierenden Tiefentschwefelung von Dieselol. Bayreuth, Bayreuth, Germany. Schmitz, C., Datsevich, L., Jess, A., 2004. Deep desulfurization of diesel oil: kinetic studies and process-improvement by the use of a two-phase reactor with presaturator. Chemical Engineering Science 59, 28212829. Specchia, S., Cutillo, A., Saracco, G., Specchia, V., 2006. Concept study on ATR and SR fuel processors for liquid hydrocarbons. Industrial and Engineering Chemistry Research 45, 52985307. Tremper, K.K., Prausnitz, J.M., 1976. Solubility of inorganic gases in high-boiling hydrocarbon solvents. Journal of Chemical & Engineering Data 21 (3), 295299. Wache, W., Datsevich, L., Jess, A., Neumann, G., 2006. Improved deep desulphurisation of middle distillates by a two-phase reactor with pre-saturator. Fuel 85, 14831493.

Fig. 8. Feed and product sulfur content after separation of hydrogen sulfide.

was flushed through the product fuel to separate the hydrogen sulfide. The results of the pilot-plant experiment are shown in Fig. 8. The average product sulfur content during the 200-h experiment was 8.3 ppm with a 95% confidence interval of 0.8 ppm. The maximum sulfur level was 10.3 ppm. 5. Conclusions The investigation showed that hydrodesulfurization with presaturation is a feasible process for the desulfurization of jet fuel in mobile fuel cell applications. While earlier investigations on hydrodesulfurization with pre-saturation dealt with pure hydrogen operation, the current studies showed that syngas operation is not a problem.