A NON-POLLUTING SOLAR CHEMICAL PROCESS FOR CO-PRODUCTION OF H2 AND CARBON BLACK (CB) BY SOLAR THERMAL METHANE SPLITTING A Kogan,

M Kogan, S Barak
Prof. Emeritus, Dept. of Aerospace Eng., Technion I.I.T. Visiting Scientist, the Weizmann Institute of Science
The four tornado conguration tests illustrated in Fig. 2 were performed with an auxiliary smoke-charged gas maintained at a constant owrate of 2 L/min. In the absence of a whirling main gas stream (Fig. 2a), the auxiliary ow separated from the window surface immediately upon its entry into the reaction chamber. When the whirling main stream was introduced into the reactor cavity at successively higher owrates (Fig. 2bd), the auxiliary stream became progressively stabilized as a thin boundary layer. For a main gas owrate of 15 L/min, the auxiliary gas moved at high speed in the thin boundary layer near the window surface. It covered the entire window surface area and it left nally the reaction chamber through a narrow axially oriented funnel
SOLAR ENERGY RESEARCH FACILITY

INTRODUCTION
The The process of co-production of H2 and CB by Solar Thermal Methane Splitting (STMS) is a h f d ti f d b Sola protable alternative to the classical method of H2 production by Methane steam reforming. When the CB by-product is not burnt but used as a valuable raw material in the rubber industry, STMS becomes 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 ltration. The estimated potential impact of the introduction of STMS on reduction of CO2 emission and on energy saving are 13.9 Kg-equivalent CO2 and 277 MJ fossil fuel/Kg H2 produced, as compared to the separate production of H2 and CB by the prevailing conventional processes [1] . An intensive STMS program is underway at the Solar Research Facilities Unit at the Weizmann Institute of Science since 1999. Three intrinsic problems have been identied in the early stages of this work. (a) An effective method had to be found to protect the reactor window from contact with the incandescent CB particles generated in the reaction chamber. (b) An efcient way had to be worked out to enable absorption of the concentrated solar energy by Methane, which is a transparent gas. (c) A way had to be found to prevent deposition of incandescent CB particles on the reactor wall and the formation of Pyrocarbon deposit.

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 prole 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 ow of the Carbon Black (CB) suspension towards the chamber exit port.
Fig. 5 Axial cross section of the WIS 10 Kw prototype reactor

ENVELOPE OF PERFORMANCE OF THE CONFINED TORNADO FLOW

By further increasing the rate of swirling ow up to 20 L/M a transition point was reached. The ow became unstable, ipping alternatively into a diffuse ow pattern, devoid of the characteristic axial funnel of the tornado ow, and back to the regular tornado ow (Fig. 3)Then by raising the owrate beyond the transition value the ow became stable, assuming continuously the diffuse ow pattern (Fig. 4)

SCREENING THE SOLAR REACTOR WINDOW BY THE TORNADO EFFECT [2]

The quartz window through which concentrated solar radiation enters into the reaction chamber must be protected from contact with solid carbon particles generated by the STMS reaction. These irradiated particles are heated to incandescence. If allowed to come in touch with the window surface, they might stick to it leading to window destruction by overheating. The usual method of screening the window by ooding its surface with a curtain of an auxiliary gas stream requires very substantial auxiliary gas owrates and the heat absorbed by the gas represents a major loss of energy. In an effort to reduce the auxiliary gas owrate to a minimum, a certain ow pattern akin to the natural tornado phenomenon has recently been developed in our laboratory which enables effective reactor window screening by an auxiliary gas owrate less than 5% of the main gas owrate. Details of the tornado effect are discussed in [3]. Following is a brief exposition of the physical background and illustrations of this phenomenon (Figs. 1 and 2).

Fig. 3 Smoke ow visualization of an unstable tornado ow

Fig.4 Smoke ow visualization of a degenerated tornado ow conguration

Fig. 5 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 ange (1); part of the zirconia structure at the exit end of the reactor is replaced by a watercooled 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.

The reactor model shown in Fig.1 had a maximum diameter of 12.9 cm and it was equipped with a grooved impeller ring with 18 slanty grooves that guide the Methane stream entering the reaction chamber through a total normal cross section of 1.08 cm2 to swirl around the reactor axis of symmetry. The Ekman number at the ow transition point was
E tr =
(a) Tangential main ow - 0 L/M (c) Tangential main ow - 10 L/M

D maxV sw

= 3.413 105

SEQUENCE OF OPERATIONS WHEN STARTING A STMS TEST (Fig 5).

1. The two cooling water ows F(CW), the external cooling air ow F(CA) and the two Nitrogen ows

where is the kinematic viscosity of Methane at 25C and Vsw is the swirling velocity of gas at its entry into the reaction chamber. We notice that the kinematic viscosity of gases increases considerably with temperature. By changing from room temperature to 2000 K the kinematic viscosity of Methane goes up by a factor of 25 (Table 1)! This is a fortunate natural circumstance. It enables practical scale up of a Solar Thermal Methane Splitting (STMS) pilot plant to an industrial plant size.
(b) Tangential main ow - 5 L/M (d) Tangential main ow - 15 L/M

Fig. 1: Axial cross section of an early reactor conguration

Fig. 2: Consecutive stages in evolution of tornado ow pattern in reaction chamber

The axisymmetric chamber of the STMS reactor is provided with a transparent window located at one end of the chamber, transversally to the longitudinal axis (Fig. 1). A ow of methane is introduced into the chamber in a manner whirling around the axis, while the reaction products are withdrawn at the opposite end of the chamber through a narrow central tube oriented along the longitudinal axis. The gas ow inside the chamber approximates then a free vortex ow, characterized by a drop of pressure from the periphery of the chamber to its axis. An auxiliary ow of protecting gas introduced at the periphery of the window is directed towards the window central area. It is accelerated by the negative pressure gradient generated by the free vortex ow. The auxiliary boundary layer ow at the window surface is thereby stabilized and it remains attached to the surface all the way to the center of the window. There the radially converging 0 streamlines turn abruptly by 90 in the axial direction, forming a typical tornado-like funnel along the reactor axis. Synergy between the free vortex ow of the main gas and the boundary layer ow of the auxiliary gas is here exploited in order to effectively protect the reactor window. The synergy is expressed by the fact that the auxiliary ow which is desired to form a stable, continuous and non-separated protective layer on the window surface is not disturbed by the whirling main stream. Rather it is stabilized by it. Consequently, the auxiliary ow does not need to be injected with high velocity or with a great owrate in order to adhere to the surface to be protected, because it uses the energy of the whirling main stream against which protection is sought. The tornado effect has been demonstrated in a series of simulation tests at room temperature with the reactor model shown in Fig. 1. The main gas stream was own from an annular plenum chamber through a narrow annular gap towards the upper part of the reaction chamber. An impeller-like ring was implanted in the annular gap. The main gas stream acquired an angular momentum during its passage through slanted grooves in the impeller ring and it entered the reactor cavity in a whirling motion. The auxiliary gas stream was own radially from a second annular plenum chamber through a second narrow annular gap towards the periphery of the inner surface of the window. Both streams consisted of nitrogen gas. The auxiliary stream was made visible by charging it with smoke, while the gas in the main stream was left in its natural transparent condition. In order to enable visual inspection of a cross section of the ow inside the reaction chamber, a laser beam directed towards the reactor window was diffracted by passage through a transverse cylindrical glass rod. The monochromatic laser beam emerged from the glass rod as a planar sheet of light that illuminated a cross section of ow inside the reaction chamber.

Table 1. Temperature dependence of maximum Methane owrate through Reactor A for which the tornado effect provides perfect window screening. T(K) F(CH4) max(L/min) (CH4)(m2/sec) / 293K 293 0.143 x 10-4 1.0 20 1000 1.369 x 10-4 8.4 168 1500 2.636 x 10-4 16.2 324 1900 3.834 x 10-4 23.5 470 2000 4.159 x 10-4 25.5 510

F(N2) (for boundary layer blowing and for quenching of products) are started. 2. The secondary ow F2(He) is started. 3. The conned tornado ow conguration is established in the reaction chamber by starting the whirling ow F1(N2). 4. Concentrated solar radiation is admitted to the reactor window. 5. When the reactor wall reaches a local predetermined temperature the whirling ow 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. The directions of these four streams deviate from the radial direction, so as to generate a whirling Methane stream compatible with the whirling Nitrogen stream F1(N2). 6. The CB seeding stream F(N2-CB) is started. 7. When a steady state and steady ow is reached, the whirling N2 ow F1(N2) may be reduced appreciably.

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 superuous. 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 owing through the reaction chamber along streamlines remote from the chamber wall obviously was not 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%.

CONCLUSION
Effective solutions were developed to solve the three intrinsic problems encountered solv in the STMS system. The project is now mature for up-scaling to an industrial size module of a demonstration plant. Besides its potential impact on reduction of CO2 emission and on energy saving, our non-polluting method of co-production of Hydrogen and Carbon Black by STMS is also expected to be economically competitive with the conventional method of Natural gas steam reforming for H2 production and CB production by standard methods. The expected cost of Hydrogen for large scale solar plants depends on the price of CB: 14 /GJ for lowest CB grade sold at 0.66 /kg, and 10 /GJ for CB sold at 0.8 /kg

REFERENCES

DEVELOPMENT OF MEANS TO COUNTERACT PYROCARBON FORMATION AND DEPOSITION.

The early STMS tests with the unseeded reactors were performed at temperatures of 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.

1. Dahl, JK et al (2004), Rapid solar thermal dissociation of natural gas in an aerosol ow reactor, Energy, 29, 715-725. 2. Kogan, A and Kogan, M, US Pat. No. 6,827,082 B1, Dec. 7, (2004). 3. Kogan, A and Kogan M (2002), The tornado ow conguration an effective method for screening of a solar reactor window, J. Solar Energy Engineering, 124, 206-214. 4. 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 Scientic Purposes and the Rose Family Foundation, Rochester, NY during 1997-2006. In March 2006 WIS became a participant of the SOLHYCARB Consortium, a specic targeted research project nanced 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.