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F. Fuder1*, D. Landwehr2, G.Geipel2, C. Herkt-Bruns2 and J. Weitkamp3 Aral Forschung, D-44789 Bochum, Germany Degussa AG, Creavis Technology & Innovation, D-45764 Marl, Germany 3 Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany * corresponding author; e-mail: franz.fuder@aral.de
1
Abstract
The hydrocarbons which are easy to reform into hydrogen are hydrocarbons with a chain length of less than six carbon atoms. A new catalyst system which was jointly developed by the group at the University of Stuttgart and Veba Oel opens up a novel route for production of mainly a n-paraffin feedstock with a chain length of less than six carbon atoms from a feed with a high aromatic content. The ratio between aromatic and paraffin compounds in the feed, controls the outlet temperature of the reactor. The aromatics are converted by hydrocracking. The enthalpy of this step is only used as the energy source, for the hydrocracking process including the evaporation of the feed. The aromatics which tend to create problems in the usual steam reforming reaction, are the energy source in this process for the evaporation of the liquid fuel. The crack reactor does not need any external heat and the outlet temperature at around 400 C is controlled by the ratio between aromatic and paraffin compounds in the fuel itself. The hydrocrack product can now be easily converted into hydrogen by the use of a membrane reactor concept. The application of high pressure and a high hydrogen partial pressure enables the use of membranes with a Pd layer of less than 10 m thick. This membrane was developed by our partner Creavis. In comparison to conventional membrane process, this new route provides an economical benefit in terms of Pd content and exchange area. The pressure for the process is mainly produced by liquid pumps, this is also a great advantage in comparison to conventional partial oxidation for fuel cell systems.
Introduction
With the advent of the European Auto Oil Programme in 2005, the content of aromatics in gasoline will have to be reduced from 42 vol.-% to less than 35 vol.-%. Comparable or even more stringent legislation exists or will be implemented in other parts of the world, for example in California the aromatics content of gasoline is limited to 22 vol.-%. The problem with aromatics in gasoline is that the exhaust gas of internal combustion engines may contain small amounts of aromatics. On the other hand, the high octane numbers of aromatics are very beneficial. Using other components as octane boosters, e.g., methyl-tert.-butyl ether (MTBE), brings about other problems. A potential way out of all these problems is a switch to diesel engines which, however, inevitably leads into the problem of particulate emission. The ultimate solution for all these environmental problems is often seen in the fuel cell technology. Upon limiting the aromatics content of gasoline and introducing the fuel cell technology, two major challenges will have to be mastered, viz. finding an outlet for the surplus aromatics and producing hydrogen in a straightforward and economic manner from today's fuels.
Most fuel cell systems require hydrogen as an energy source, hence large efforts are currently undertaken to make hydrogen available in cars. Among the routes discussed are steam reforming and
partial oxidation of conventional hydrocarbon fuels or the use of alternative liquid fuels, such as methanol or liquefied hydrogen. The latter solutions would call for a completely new infrastructure for fuel supply and/or a new technology for producing the large amounts of hydrogen. Obviously, the introduction of such non-conventional fuels would require huge investments by the pertinent industry. Hydrogen as an automotive fuel could either be manufactured from conventional hydrocarbon sources in refinery-like stationary plants or on board the cars by direct reforming. Arguments in favor of the second alternative include the availability of a well established distribution network for hydrocarbon fuels, the high energy density of the hydrocarbons to be transported as compared to hydrogen and the low technical risk of hydrocarbon versus hydrogen transportation. We propose here a novel route for the on-board conversion of aromatics-containing hydrocarbon fuels into hydrogen.
Table 1 Results of the cracking of toluene and decane with hydrogen, autotherm. WHSV Temperature Methane Ethane Propane Butane Residual>C4 [1/ h] [C] [vol.%] [vol.%] [vol.%] [vol.%] [vol.%] 0.6 381 1.9 2.8 78.2 11.8 5.2 1.0 370 3.4 5.6 41.6 32.4 17.0 2.0 312 0.2 1.0 79.7 8.7 10.4
The ratio between these two compounds is so that the reaction produces enough energy to heat the gas up to 400 C. The results are shown in table 2. We measured the heating consumption of the reactor system to show this effect. The temperature is independent from the amount of fuel which goes through the reactor system. The systems work autotherm. The line with base load means the energy consumption without reaction. This system evaporates the fuel which is called "Chemical Evaporator" it can also evaporate commercially available liquid fuels. Therefore, if the content of aromatic compounds is too low, the reactor must be heated. The advantage of the aromatics is, that the reactor needs only a small electric heating system and this makes the whole system smaller because the reactor needs no combusting heating system like a gas burner. One of the big tasks is, in the whole system is hydrogen and after the Pre-treatment step won't be aromatic molecule in the stream, so there no cooking effects in the system. Table 2 Energy consumption during the crack reaction WHSV Temperature Toluene/n-Decane Hydrogen Power Base load [1/h] [C] [g/h] [g/h] [W] [W] 0.49 343 157 13.2 82 126 0.24 338 78 6.7 109 133 0.73 345 237 20 88 126 0.49 343 158 13.2 89 126
To find a solution for the aromatic rich pyrolysis gasoline by naphtha steamcracking, we developed a new process together with Linde and Sued Chemie. This commercial process presently available convert pyrolysis gasoline into a high-value synthetic steamcracker feedstock. This process is called ARINO (Aromatics Ring Opening) process. The commercial catalyst therefore was developed by Sued Chemie.
Figure 2 Thermodynamic concentration as function of the pressure (Propane:Water=1:7@750C). For economic reasons, the membrane reactor must be operated at high pressure, the ultimate reason being the high cost of palladium. As shown in Figure 3, the economic requirements can be met at a membrane thickness of about 10 m and a pressure above 40 bar. The data in Figure 3 were calculated on the basis of a palladium price of 14 US $/g, a PEM efficiency of 50 % and experimentally determined permeation rates of hydrogen through the membrane.
Figure 3 - Costs for the palladium per kW of installed electrical power of the PEM. Among the main advantages of a membrane reactor is the possibility to exceed the thermodynamic yield limitations. This allows to operate the steam reformer at a high pressure. As shown in Figure 2, higher pressures result in decreased CO concentrations, i.e., the concentration of CO2 is higher which is important for the separation unit. A very important point is the quality of the hydrogen produced. The hydrogen from the membrane reactor can be directly used in a fuel cell, i.e., no additional steps like sulphur removal or treatment of carbon monoxide are required. Furthermore, a lower surface area of
the fuel cell can be employed, since there is no nitrogen which must normally pass through the fuel cell. The off-gas from the membrane reactor consists of carbon dioxide, methane, carbon monoxide, water vapor and hydrogen, the concentration of the latter depending mainly on the membrane area and the reaction temperature. An open reactor with the membrane inside is shown in Figure 4.
The Ceramic foil production is a continuous process. The production unit coats the woven fabric with the inorganic suspension, the fabric is dried and hardened. A visual detector excludes defective material. After the ceramic coating process a PVD-process is attached for finishing the membrane with a palladium coating. In dependence of the process parameters thickness of the palladium layer is controlled. The structure of the hydrogen separation membrane is shown in Figure 5. The TEM detail displays the surface of the coated membrane.
Microfiltration: Pores 50500 nm Ultrafiltration: Pores 550 nm Nanofiltration: Pores 0.55 nm Catalytic membranes Woven Fabric Support 80 m
Table 4 Example mixture for testing purpose. Composition [mol] 1.00 0.58 1.58 Concentrations [Vol.%] 0.63 0.37 1.0 Enthalpy [kJ/mol] 92.4 -92.4 0.0
Conclusion
The system described in this paper offers the opportunity to produce hydrogen on a small scale. It does not require complex gas treatment systems, and it can be operated with proven state-of-the-art catalysts in a conventional shape, e.g., pellets. The pressure can be generated by means of liquid pumps which is a significant economical advantage. Just the hydrogen needs a gas compressor, but only 10 to 15 % of the total hydrogen produced must be recycled into the system. However, this compressor decouples the system from the fuel cell, thus providing the opportunity to store hydrogen in a pressurized tank. A huge number of small fuel cell applications is fore-casted to come, and they will all need their own hydrogen sources at the customer. Unfortunately, a price has to be payed for all these advantages of the system, namely a relatively large amount of palladium. Palladium is needed both in the membrane and in the catalyst for ring opening. The question as to whether the system is cost-efficient compared to other fuel cell systems can only be answered by a detailed economic analysis. In Table 5, a comparison is made between the novel system and a unit based on partial oxidation. Table 5 Comparison between partial oxidation and the new concept.
References
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