Report submitted to the 36-month SOLHYCARB Meeting DLR, Cologne, Germany

17-18 March, 2009 Recent improvements in the starting procedure of STMS tests at WIS and some corresponding test results.
Abraham Kogan The kinematic viscocity of Methane at room temperature is too low for the establishment of a stable confined tornado flow configuration. The correct starting procedure of a STMS test is by maintaining a whirling flow of a neutral gas (N2, He or Ar) inside the reaction chamber for a short warm-up period. The whirling Methane stream can be admitted into the reaction chamber only when the inside surface of the chamber wall has attained a minimum predetermined temperature. Up until recently the WIS SR10 reactor was equipped with a two-way entry valve through which it was possible to introduce in sequence a transient warming-up flow F1(N2) and then the permanent flow F1(CH4) through the same annular entry port, situated just below the quartz window as shown in Fig 1. The zirconia insulation temperature in the vicinity of the reactor aperture was obviously high enough to sustain the high rate of decomposition of Methane passing through the aperture into the lower part of the reaction chamber. By visual observation of the gas flow inside the reaction chamber during high temperature tests with the SR10 kW reactor equipped with the increased window diameter, we became aware of the danger of window destruction due to slight oscillation in the confined Tornado flow pattern, see, e.g., the heavy Pyrocarbon deposit formed on the periphery of the reactor aperture on the side facing the reactor quartz window, illustrated in figure 2. By increasing the diameter of the reactor window and by removing the window plane from the reactor aperture plane, the interior of the reaction chamber became divided into two distinct parts: an upper part, the area between the aperture and window planes and the main body of the reaction chamber, between the aperture plane and the exit port. In order to avoid this danger, we decided to eliminate the two-way entry valve and to use the annular entry port situated above the aperture plane for the introduction of whirling flow F1(N2) and to install an additional annular entry below the aperture for the introduction of whirling flow F1(CH4). The inside contour of the reaction chamber was designed in line with the following CFD simulation results. 1

Fig. 1 An early configuration of the upgraded SR10 WIS Reactor. The reactor quartz window was increased and moved 28mm by translation from the reactor aperture plane towards the 155cm Secondary Concentrator.

Fig. 2 Formation of a heavy deposit of Pyrocarbon on the periphery of the reactor aperture caused by splitting of Methane during its flow along the surrounding heated Zirconia plate. Fig. 3 shows contours of stream function inside the reaction chamber obtained by CFD simulation with an improved reactor axial cross section [1]. The following four gas flows were postulated: F2(He) = 2 L/M F1(N2) = 26.3 L/M; whirling, horizontal deviation from radial direction = 55 F1(CH4) = 20 L/M; whirling, horizontal deviation from radial direction, = 55 F3,2(N2) = 1 L/M; blowing stream The whirling flow F1(N2) splits upon entry into the reaction chamber into two uneven parts. The smaller part joins the Helium stream to form the gas curtain adjacent to the reactor window. The larger part of stream F1 follows line bcd towards the forced separation point d. It continues almost undisturbed towards the axis of symmetry where it joins the tornado funnel stream. The hefty funnel stream generates by friction the large annular vortex stream dijkl. The ascending branch of the annular vortex 2

stream kl collides with the whirling Methane stream entering at point f and entrains it along the wall fed to join the tornado funnel. A slight blowing stream F3,2(N2) = 1 L/M enters the reaction chamber at point g just out of the influence of the annular whirling stream. It flows along the peripheral boundary gh of the chamber performing a slight blowing and cooling action along wall gh.

Fig. 3 Contours of Stream Function 1

Fig. 4 Contours of Stream Function 2 Fig. 4 shows contours of stream function of a similar flow configuration in which the slight stream F3,2 (N2) = 1 L/M was replaced by an enlarged stream of Nitrogen, 20 L/M. 3

We observe that the large increase in the flowrate of the blowing stream F3,2 did not modify most of the characteristics of the previous flow, except for providing enhanced cooling and blowing along peripheral wall gh. Flow separation at point d, formation of the large annular vortex and entrainment of the Methane flow F1(CH4) towards the aperture plane, which coincides with the secondary focal plane, the hottest region in the reactor cavity, were not much perturbed. The updated design of the STMS reactor is illustrated in Fig. 5. In this design part of the zirconia structure at the exit end of the reactor is replaced by a shaped cylinder made of copper (a). The temperature of the external surfaces of shaped cylinder (a) is kept down by out-of-contact water cooling. The inner surface (b) of the zirconia insulation is partly cooled by blowing a tertiary stream of gas F(N2) at room temperature in a direction tangential to surface (b). The blowing stream entrains any solid particles in gas suspension in region (b) and thus prevents the formation of a Pyrocarbon deposit.

Fig. 5: Axial cross section of the WIS 10 kW prototype reactor

Sequence of operations when starting a STMS test (Fig. 5). 1. The cooling water flow 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). 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 the reaction chamber along a horizontal circle, somewhat below the aperture plane. It is intercepted by the ascending branch of the large annular vortex that was generated by flow detachment at point d (see Figs 3,4) which entrains it towards the aperture, i.e., towards the hottest spot in the chamber. 6. When a steady state and steady flow is reached, the whirling N2 flow F1'(N2) may be reduced appreciably. 7. The Carbon BlackNitrogen suspension F(N2-CB) is admitted into the reaction chamber, pointing also towards the hottest region inside the chamber.

First STMS test with the present version of the WIS SR10 reactor A first STMS test with the WIS SR10 version illustrated in Fig. 5 was performed on Jan. 22, 2009. During 11:07 t 12:15 insolation was 913 I 893 w/m2. In order to prevent influence of a Taylor flow instability we used a 50% N2-50% He by volume gas mixture for the neutral gas mixture flows F1 and F2. During the starting warm-up period (t =11:12-11:25) the neutral gas flow F1 + F2 = 30L/M was heated by concentrated radiation submitted to the reactor through the 60cm x 70cm wicket. The maximum temperature inside the reaction chamber reached 977C. At t =11:27 the concentrated radiation was admitted to the reactor through the 100% open North window. At t = 11:33 the maximum reactor temperature reached near the aperture plane was 1748C. At this time we started seeding the reaction chamber with CB. At 11:40 a flow F1(CH4) = 2 L/M was started into the reaction chamber. During t =11:50 12:09 the Methane flow into the reaction chamber was increased to F1(CH4) = 4 L/M. The GC analysis indicated a 100% extent of reaction.

TIME PARAMETER UNIT Shadow of Solar Tower reaches Heliostat H204 Test discontinued Radiation admitted through 100% open North window TC-B1 near aperture, N TC-B1 Below aperture,N TC-B2 TC-B3 Tpyrometer I (Insolation) F1(N2+He) 50/50% by vol F2(N2+He) 50/50% by vol F1(CH4) Ffluidizer (N2) Freject (N2) F3,2 C Radiation admitted through 60cm x 70cm wicket C C C C W/m2 SLM SLM SLM SLM SLM SLM 906 25 5 0 0 0 20 831 946 242 835 346 934 480 122 913 24 5 0 0 0 20 911 24 5 0 0 0 20 977 325 960 544 126 912 24 5 0 0 0 20 1748 618 1450 841 264 904 24 5 0 8 8 20 1735 756 1446 859 265 911 24 5 2 9 8 4.2 9 9.3 1680 840 1470 943 330 906 1677 860 1430 939 322 885 25 5 4 9 9 20 1675 875 1500 966 330 884 25 5 4 9 8.8 20 1677 886 1454 970 322 893 25 5 4 9 8.8 20
11:07 11:12 11.15 11:20 11:25 11:27 11:33 11:40 11:50 11:57 12:05 12:09 12:15

Table 2. Temperatures during experiment

Fig. 6. A Gas Chromatogram obtained during STMS test of Jan. 22, 2009, at 11:58 (Instrument time: Summertime +1) The second STMS test with the WIS SR10 reactor version illustrated in Fig.5 was performed on Feb. 16, 2009. The original aperture diameter of 65mm was increased to 75mm. The test started at insolation I = 951w/m2. In order to operate at high reactor temperature, a mixture of N2 and He 50%-50% by volume was used again as secondary gas, to alleviate any Taylor flow instability.

TIME PARAMETER UNIT TC-C1N near aperture, N TC-C1N Below aperture,N TC-B2 TC-B3 TCdeflector1 TCdeflector2 Tpyr.housing Tpyrometer Tproduct1 Tproduct2 TCfilter I (Insolation) F1(CH4) F2 F2(CH4) Ffluidizer (N2) Freject (N2) F3,2 (N2) F1(N2+He) 50/50% by vol C C C C C C C C C C C W/m2 SLM SLM SLM SLM SLM SLM SLM 20 0 0 1.2 0 0.1 15 18 Radiation admitted through 60cm x 70cm wicket 16 15 16 15 101 16 15 936 892 774 895 803 16 18 17 123 209 25 25 951 Radiation admitted through 100% open North window 1650 1302 1345 1007 16 20 19 18 253 1790 1418 1410 1030 16.5 23 18.5 310 323 30 30 959 1800 1430 1400 1025 18.5 24 19 310 334 31 29 934 1700 1390 1420 1030 16.7 28 20 310 385 32 28 930 1630 1370 1350 1080 17 30 20 F1 (N2) stopped 308 430 35 25 940 19 2 6 5 8.6 20 24 2 6 8.2 8.7 20 24 2 14 8.5 9.2 20 24 2 19 8.8 9.5 24 20 1700 1340 Close aperture window Tornado disappears; 1330 1173 18 24 20 305 448 40 25 950 19 2 19 Close Methane; 0 0 20 24
11:04 11:15 11:23 11:25 11:26 11:29 11:31 11:35 11:45 12:00 12:05 12:11 12:24

12:25 To 12:35

down to 570

-The Feb. 16, 2009 test endured almost an hour. During 20 minutes after start of CB seeding, the flow of Methane to the reactor was increased gradually up to F1=20 L/M. Then it was kept constant at 19 L/M for half an hour, up to the end of the test. -The tornado whirling flow was observed visually through a small plane reflecting mirror during the whole test duration. It appeared steady. -The Tornado initial driving force, the F1(N2+He)=24 L/M flow was maintained constant throughout the test duration. -The GC recordings indicate approximately 100% extent of reaction. -Seventeen minutes before the end of the test the CB seeding was discontinued. The tornado effect continued unaffected. -The maximum temperature of 1600-1800C was recorded by a C-type thermocouple just below the aperture plane. About 2cm below that location the reactor inner wall temperature was about 1400C, while near the exit port the wall temperature was below 1200C.

Figures 6,7 and 8 are various SEM magnifications of parts of a CB cluster collected from the product filter after the test of Feb. 16, 2009.

Fig. 6

Fig. 7

Fig. 8

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The additional 11 pictures are TEM magnifications of two additional CB samples collected from the product filter after the same test. Figure 9 is a slight magnification TEM picture of four adjacent clusters of CB particles. The object at the extreme left at the base of the uppermost cluster is a Fulerene surrounded by four small Fulerenes in different stages of their evolution. Details of this group are shown in Figures 10-14. The big central unit serves apparently as catalyst in the formation of the smaller four units.

Fig. 9 TEM of four clusters of CB particles

Fig. 10

Fig. 11 11

Fig. 12

Fig. 13

Fig. 14 Figure 15 is apparently a spot of formation of nano-tubes that could be building blocks in the formation of nearby Fulerenes, as suggested by the Figures 16-19 following.

Fig. 15 12

Fig. 16

Fig. 17

Fig.18

Fig. 19

REFERENCE [1] A. Kogan, et al A non-polluting solar chemical process for production of Hydrogen and Carbon Black by solar thermal Methane splitting. 49th Israel Annual Conference on Aerospace Sciences, Israel, March 4-5, 2009.

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