A non-polluting solar chemical process for production of Hydrogen and Carbon Black by solar thermal methane splitting

*Abraham Kogan, Prof. Emeritus, Dept of Aerospace Engineering, Techniion I.I.T., Haifa.
At present, Visiting Scientist, Solar Research Facilities Unit, The Weizmann Institute of Science, Rehovot, Israel, e -mail: terry.debesh@weizmann.ac.il

Meir Kogan, Shmuel Barak Keywords: Solar thermal Methane Splitting; Non-polluting solar process for co-production of Hydrogen and Carbon Black. BACKGROUND The process of co-production of Hydrogen and Carbon Black (CB) by Solar Thermal Methane Splitting (STMS) is an advantageous alternative to the classical method of Hydrogen production by Methane steam reforming. When the CB by-product is not burnt, but rather used as a valuable raw material in the rubber industry, STMS is a non-polluting endothermal process that can be achieved by the use of concentrated solar energy. The two products of reaction can be easily separated by filtering. The estimated potential impact of the introduction of STMS on CO2 emission reduction and energy saving are 14 kg CO2 avoided and 277 MJ saved per kg H2 produced, respectively, as compared to the separate production of H2 and CB by the conventional processes [1]. THE CASE STUDY An intensive STMS R&D program is underway at the Solar Research Facilities Unit, Weizmann Institute of Science (WIS), since 1997. Three specific problems have been identified at the early stages of this work. Screening the solar window from contact with incandescent CB particles generated in the reaction chamber. The confined tornado flow configuration was invented to solve this problem [2,3]. Transfer of radiation energy to the reactant gas Methane is a transparent gas. Radiation propagating into the solar reactor is not absorbed directly by methane. It heats the reactor wall and part of the heat is transferred to the gas by conduction and convection (surface heating) Following a method proposed by Hunt [4], a gas may be heated by concentrated radiation throughout the volume of the reaction chamber by dispersing small particles in the gas, to form an opaque cloud. Radiation is absorbed by the particles in suspension, which in turn exchange heat with the surrounding gas very effectively, in view of the very large surface area per unit mass of particles (volumetric gas heating). It should be noticed that even in the absence of active seeding, solid carbon particles are generated near the hot surface of the reaction chamber by the methane splitting reaction. These particles start a volumetric absorption process that may spread in a chain reaction into the bulk of the reaction chamber. It was not clear a priori whether this effect is strong enough to render active seeding superfluous. The results of our early STMS tests (1999/2000) with an unseeded solar reactor proved that this is not the case. The maximum extent of reaction achieved in that test series was only 28.1%. Methane flowing through the reaction chamber along streamlines remote from the chamber wall did not get obviously heated enough to undergo dissociation. In recent STMS tests the reactor was seeded with CB particles. The extent of reaction jumped up from 28% to 80%. * Corresponding author 1

 Development of a means to counteract Pyrocarbon formation and deposition. The early STMS tests with an unseeded reactor were performed at temperatures up to 1320K. Most of the carbon generated in the process clung to the irradiated reactor wall and it formed a very hard deposit. In most cases, the tests were terminated when the reactor exit port became choked by the accrued Pyrocarbon deposit. At this early stage we understood that formation and deposition of Pyrocarbon on the reactor wall is a basic problem that must be treated and solved. The conditions that promote carbon deposition on the reactor walls were studied during extensive STMS tests at the WIS Solar tower. We were guided by this information in the evolution of the shape of the axial cross section of the reaction chamber. Its profile is smooth and slender and means are provided for cooling certain critical locations along the inside wall of the reaction chamber. The possibility is also provided for introduction of auxiliary streams of gas into the reaction chamber tangentially to the chamber wall, so as to promote the flow of the Carbon Black (CB) suspension towards the chamber exit port.

Fig. 1: Axial cross section of the WIS 10 Kw prototype reactor

Fig. (1) is an axial cross section of the reactor protected from Pyrocarbon deposition, following the method developed at WIS. In this design part of the zirconia insulation underneath the reactor window is replaced by a hollow stainless steel water-cooled flange (1); part of the zirconia structure at the exit end of the reactor is replaced by a water-cooled shaped cylinder made of Copper (2). A thin metal sheet covers the wall of the reaction chamber in the region (3). It is fastened to the upper end of the copper piece (2). The temperatures of the external surfaces of parts (1) and (2) are kept down by out-of-contact water cooling. Part (3) is partly cooled by a tertiary stream of blowing gas and partly by heat conduction to the Copper piece. Sequence of operations when starting a STMS test (fig 1). 1. The two cooling water flows F(CW), the external cooling air flow F(CA) and the two Nitrogen flows F(N2) (for boundary layer blowing and for quenching of products) are started. 2. The secondary flow F2(He) is started. 3. The confined tornado flow configuration is established in the reaction chamber by starting the whirling flow F1 ' (N2) or F2 ' (He). 4. Concentrated solar radiation is admitted to the reactor window. 5. When the reactor wall reaches a local predetermined temperature the whirling flow of Methane F1(CH4) is started. It enters on the periphery of the reaction chamber at four points disposed symmetrically around the reactor below the reactor aperture plane, pointing to the hottest region in the reaction chamber. 6. When a steady state and steady flow is reached, the whirling flow F1 ' ( N2) or F2 ' (He)may be reduced appreciably. CONCLUSION Effective solutions were developed to solve the three intrinsic problems encountered in the STMS system. The poster will describe in more detail the WIS STMS prototype reactor and will present a concise discussion of the potential of the STMS technology to contribute to the solution of global warming by decarbonization of fossil fuel. REFERENCES
Dahl, JK et al (2004), Rapid solar thermal dissociation of natural gas in an aerosol flow reactor, Energy, 29, 715-725. Kogan, A and Kogan, M, US Pat. No. 6,827,082 B1, Dec. 7, (2004). Kogan, A and Kogan M (2002), The tornado flow configuration an effective method for screening of a solar reactor window, J. Solar Energy Engineering, 124, 206-214. Hunt, AJ, (1979), A new solar thermal receiver utilizing a small particle heat exchanger, Proc. 14th Intersociety Energy Conversion Engineering Conference, Boston, MA, USA.

ACKNOWLEDGEMENTS The STMS R&D program at WIS was supported steadfastly by the Heineman Foundation for Research, Education, Charitable and Scientific Purposes and the Rose Family Foundation, Rochester, NY during 1997-2006. In March 2006 WIS became a participant of the SOLHYCARB Consortium, a specific targeted research project financed by the 6th Framework Program of the European Commission. The author wishes to express his deep gratitude to the Heineman and Rose Foundations and the European Commission for their generous support of our project.