chemical physics of discharges - Argonne National Laboratory

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367 used as blnders, with different producers and consumers using entirely different standards, so the electrode quality tests were used to help evaluate the effective- ness of thermal cracking of the lignite pitch. EQUIPMENT The thermal cracking system is shown in figures 1 and 2. The feed tank (figure 2, A) is made from a 13-in. length of 10-in. diameter schedule 40 pipe, to which a cone has been added for the bottom. The tank is heated by commercial electric heaters. The feed pump (B) is a small gear pump with a variable speed drive. The thermocracker (D) is a 4-1/2 ft-length of 2-1/2-in. diameter schedule 40, type 304, stainless-steel pipe, heated by external electric heaters. The heaters are controlled by outside surface thermocouples welded to the reactor. The receiver (E) is a 20-in. length of 4-in. diameter schedule 40 pipe. The receiver is flanged so that it can be bolted to the bottom of the reactor. The condenser (F') is a 30-in. length of 6-in. diameter pipe, swaged at the bottom end to I-in. diameter and flanged at the top. The top flange supports a water-cooled tube which inserts into the condenser body in the manner of a cold finger. The knockout (G) is a 34-in. length of a 2-in. diameter pipe having a tangential gas inlet about 8-in. from the bottom. The scrubber (H) is a 30-in. length of a 4-in. diameter pipe having a water-spray nozzle near the top. The water from the scrubber drains into a standpipe water-seal tank (I). The water-seal tank is a piece of 6-in. dlameter pipe. The gas meter (J) is a laboratory-type wet-test meter capable of metering 1,000 cu ft of gas at standard conditions. PR OC E DURE Lignite pitch at 200" C was pumped from the feed tank through electrically heated lines into the top of the thermocracker. The temperature of the thermocracker was maintained at approximately 790" C as indicated by the outside surface thermocouples. At the end of a run, the flow of pitch was stopped and the pump was' flushed with a low-boiling tar fraction to keep the impeller of the pump from freezing. Reactions within the cracker produced coke, cracked pitch, oil, and gas. Both the top and bottom of the cracker were removed, and coke was removed from the sides and weighed. Cracked pitch caught in the receiver was weighed and analyzed. The oil removed by the condenser and knockout chamber was weighed and then distilled to 400" C, leaving a pitch residue. This pitch residue was analyzed and, if found to have the desired carbon-to-hydrogen atomic ratio (1. 20 to 1.80), was used as a binder for electrodes. Distillate from the oil may be oxidized to phthalic and maleic anhydrides or separated into acids, bases, and neutral oils. Gas from the cracker was cooled and scrubbed, then metered, sampled, and analyzed by gas chromatography. RESULTS AND DISCUSSION Results of the thermal cracking tests are given in tables 1 to 4. Of the four major products obtained from the pitch--coke, cracked pitch, oil, and gas--the coke averaged about 15 to 25 percent of the feed to the cracker, the cracked pitch amounted to about 20 to 40 percent, the oil was about 20 to 30 percent, while the balance of the feed to the cracker consisted of gas.
Distribution and yield rates of products (figures 3 to 6) are as expected considering the reaction within the cracker at different crude,pitch.feed rates. As the pitch is heated it begins to vaporize, and the turbulenc'e of the vapors splashes some of the iluid onto the hot wall where it sticks and is coked. If enough heat is available, the rest of the pitch is vaporized and cracked. ' As the cracked materiais leave the hot zone, heavy high-b
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)i 1 reesonably complete and accura
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3 inquire about the component of ve
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4 I I 5 To find (t2)av, we assume t
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\ vnich, it is noted can be negativ
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I 7 than or smaller than the second
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i I i I I I ) ) i L , I I . INT1:OD
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13 field per electron is and per co
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. 11. 5. CharRe-Transfer and Ion-Mo
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17 In the followin:: sections much
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above. With that EIN, an estimate o
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21 region in w!iich large, nighlv l
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i ’ understanding: 23 (a) Electro
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Obviously, the secondary ion must h
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27 (22) Franklin, J. L., Munson, M.
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Tables 1-6 present examples of rela
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Table 8 Some Ions Formed by Process
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33 velocity of the reacting partn r
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35 must be added to the Langevin cr
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37 In our laboratory a microwave di
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+ . 4 . r 39 as well as N in a cor0
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ION-MOIECULE REACTION RATES MEASUFI
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43 excitntion 2onditions so that th
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45 In 2 like manner Fig. 3, showing
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47 Absorption Spectra of Transient
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50 maximum fiela. In this manner, a
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52 3 % %- %- 5- a- 7 h W P H 0 L v)
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References I I . A.B.Callear, J.A.G
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._ . _-.. - , , . . ,. . The Pyrex
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58 0 0 0 VI J > I cv . u H a
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.... . 0 2 e I / m 0 H F4 : 1
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\ 0.9 0.8 0.7 06 0.5 0.4 0.3 0.2 01
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65 ' cause of the reduction in the
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INTRODUCTION I' Attachment of polar
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I 69 EXPERIMENTAL The mass spectrom
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+ Figure 1 Mixed water and methanol
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73 ' , radius might be expected bec
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75 Negative Ion Mass Spectra of Som
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A b 1 1 I H I I I FILAMEN T CONTINU
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79 for positive and negative ions,
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51 out to answer some of the questi
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93 INTERACTIONS OF EXCITED SPECIES
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L 4 I*C z 0'2 = a, a U x I m 4 m 0
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I L I, ; > > E Fig. 3 I50 200 150 1
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I 300 r 1 - 200 i io ;' a cn I I. 0
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where DISCUSSION OF XESULTS PERTAIN
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93 where the bar indicates values c
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'I i 'I 0 2. 4 6 8 2 [ N]* x' I 0-2
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Fig. 14 IO 8 6 4F [NO] x IO-" (mole
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for chemiluminescent excitation in
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101 Chemiluminescent Reactions of E
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103 All gases were taken directly f
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10; He: + N2 -. 2He + h': (8) whi!?
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description for both diffusion and
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B. Ions and Electrons I Consider a
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' 112 axial diffusion through the d
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the tube walls occurs continuously
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E2R M ' $6"
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1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. -
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120 . Dlschorge zone Reactor zone 1
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122 In radiation chemistry the cust
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124 4. chemistry seem limited essen
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126 Conversion of Mixtures into Mor
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Hydrazine Synthesis in A Silent dle
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{;I . - . .. . - .., . . .. _- .. .
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1 \ \ \ , \ , \ \ Pmer hnrity K.W.
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. I operating fact that the sloGe i
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_- of ' . 8. - 7 6, Residence Time
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135 Ionic Reactions in Corona Disch
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GAS OUT GAS IN i.ho QUADRUPOLE MASS
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- + ( ~ ~ + 0 H ) ~ O ~ ( H~o)~H+ +
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144 i I , , , , . + 1- u 3c w Inu c
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146 SYNTHESIS OF ORGANIC COIGhTDS B
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mi5 a- dz CI n I a I n +4 - 0 -I- k
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0 z cu I I I
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I- I - t d m a .rl Y x c, t-' d k
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, 155 This result is significant in
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Compound Bond he rgy Li I 82 UBr 10
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, ”..’ 3or 25 - 5 20 - s 3 w Y
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I 161 THE GLOW DISCHARGE DEPOSITION
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Fig. 1 Process Apparatus -__l.ll__
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v) t- at- InIo Io0 t-Q) loo lcua O
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This study is only an approximation
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Mole Reaction Material ratio time e
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\ i (4) Effect of System Pressure T
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173 Pressure. Since pressure is a c
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175 Table VI X-RAY DATA OF DEPOSIT
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177 Another source of weakness is t
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179 PLATING IN A CORONA DISCHARGE R
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\ 3 , ,\ 110 v 60 CPS MANOMETER . F
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I i , \ I i & a - P Fig. 3 Reaction
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\ \' C 0 .d * d .- C U d 0) c( 1) L
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I i I . Q) I, s w 0 v) Y 0 a w W a
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I (b) Polarized Light Fig. 6 Cross
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i m v) Y C i! u o) 23 a a- + 191 m
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i, d C .d c c W Q ) 0 0 L1Y 0 000 0
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i e 4 0 wcr -4 4 al 0 0 0 c) cr 13:
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\ E ‘ 1 TIME FOR RUN 13-1 14-1 -
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199 a red heat in this cell using d
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\ , t j \ I, v) 2 Y . C 0 u m .I C
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203 VAPOR PHASE FORMATION OF NONCRY
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BELL JAR STANC TO VACUUM SYSTEM U T
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207 of the boron oxide film, the fi
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i I, 4 I.( Y I- * 0 i f i 3 0.t I I
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211 The Reacticn 3f Oxygen with Car
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2 E, W t- a Z 9 I- a 2 X 0 I50 too
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'i' 100 50 IC 21 5 2.0 2.5 SURFACE
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I- z W 0 w a a 100 80 60 40 20 215
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s., Literature Cited Berkley, C. ,
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7 h \ F 221 600°C and 1 atmosphere
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223 e I'
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R L ' -1 9mm O.D. 5mm I.D. 45mm 0.D
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Figure 5.- Paschen's law curves. 2-
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\ '? I The water-free product gases
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N I + 0" ON i I + 0 u / 0 0 I 0 cu
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- 233 SOME PROBLEMS OF THE KINETICS
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.. . :. ,. .I , . i ? .. . , ... .
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237 Table 2 Experimental Variables
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239 Zhbie I Eerccnt Consumption of
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241 Discussion The systematic varia
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I \ 1 243 FORMATION OF HYDROCARBONS
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h z - a o m a 20 T IME, minutes . F
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I 1 I I I I 0 I 2 3 4 5 TIME, minut
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The next five coluws in table 1 sho
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\ .\ t 251 Given the existence of t
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I L 253 Epple, R. P. and C. M. Apt.
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1 ' Fig. 1 Schematic of flow discha
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5' . ' I 1 257 co, with excess H2,
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1 1 1 moo 1400 1300 c V' I IPOO I I
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i 25i The Dlssocfatior of ToIuere V
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L ! , c PRODUCTS FROM A 28 MC. DISC
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'\ J ?. , .. . : PRODUCT FORMATION
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'9 / I '\ "1 BENZYL CATION AND RADI
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a
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271 tube serve? as the high voltare
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273 ion (1L.). Zxcitei-ion by colli
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Apparatus and Procedure 275 EXPERIM
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. 277 6. A freshly prepared sam le
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observed. The polystyrene (10% solu
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i i (12) c (11) (14) I 281 LITERATU
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FLOW- METER I ADDITIVE SUPPLY * ,28
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285 TABLE 2 Effect of Haloqenated A
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ANALYTICAL RESULTS Some evidence wa
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DISCUSSION 289 The salient features
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? ~ MENBERSHIP IN THE DIVISION OF F
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292 flow of the reactant gas stream
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294 have suitable residence times i
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0 E < h( E l! d K c 0 .- Y 0 t u t
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298 yields of many chemical product
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- ;i Y . 15. Pressure lOmm 5 > 10-
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302 the best and in many practical
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GENERATION AND MEASUREMENT OF AUDIO
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. The transformer secondary and the
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Vaccum-Tube Amplifier The mobile co
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310 f = Power supply frequency in c
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FUFARCI! INSTITUTE OF TFYDLC UNIVER
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J # I / 4) I . . '8 r4 0 r( P
Page 318 and 319: 317 i Cuencb svsten w.nnar;itus use
Page 320 and 321: epcrte? the noss~kil.itv of nroduct
Page 322 and 323: 1' b t +
Page 324 and 325: 323 ....... - . . . . . . . . . . .
Page 326 and 327: 1 \ i I i , / / / 8 3 1 325 To205 +
Page 328 and 329: - .- - - . - - . . . - . 327 n + c
Page 330 and 331: ' POWER PLASMA GAS l e , ' I ! I I
Page 332 and 333: 331 f'ENI?AL PF'FCLCCFC Dernis, P.R
Page 334 and 335: i J 333 ; mosphere (as opposed to a
Page 336 and 337: ; it raised the question, still &?z
Page 338 and 339: p .I V I .= - - HCN/C(CALC. WITH C
Page 340 and 341: 1 1 339 atmospheric ressure and ach
Page 342 and 343: RESULTS 341 Composition Dependence
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Page 348 and 349: i 4 2 HYDROCARBON-NITROGEN REACTION
Page 350 and 351: I 1 349 c M m ; a e, k M x
Page 352 and 353: 1.0 I - a. I n TEMPERATURE - OK Fig
Page 354 and 355: 353 the experimental results in the
Page 356 and 357: ,) 355 The ceaswed conversion cf ni
Page 358 and 359: 1 6 357 Freezing. 3jpotnesise thzf
Page 360 and 361: 359 \ Frozen Compositior: Calcillat
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Page 364 and 365: \ 36 3 ' h, I 26. H. Purnell, Gas C
Page 366 and 367: In experiments on the direct conver
Page 370 and 371: 369 ' i 1. REFERENCES Berber, John
Page 372 and 373: Distribution and yield rates of pro
Page 374 and 375: . . I . I 370 . . . . ., . . .. . .
Page 376 and 377: 4 372 090- > E w - m c N O - 0 z :
Page 378 and 379: A-Feed tank 6-Thermocracker GReceiv
Page 380 and 381: 80 \ 0 70 60 e 40 a U VI 9 30 20 10
Page 382 and 383: COAL DEASH& AND HIGH-PURITY COKE Wa
Page 384 and 385: 3Pn _. -. - L -J:,J.-;~~~L, ):as se
Page 386 and 387: S ~ l ~ o n~pg:ading r is the resul
Page 388 and 389: The range ~f temperatures and gener
Page 390 and 391: . .. 386 9 * - r. Y 2 .' d a f' r.
Page 392 and 393: .) .L m 388 I
Page 394 and 395: TABLE 4 390 DELAYED COKING OF DEASH
Page 396 and 397: , ! I- on '---
Page 398 and 399: 394 The present method is to keep t
Page 400 and 401: 396 ‘c erperature, while the pres
Page 402 and 403: 2, '! ! Proximate Analysis, wt $ Mo
Page 404 and 405: 0 IS 0 14 LL 9 013 e \ 3 b- m *- 01
Page 406 and 407: 402 HYDROGEN CYANIDE PRODUCED FROM
Page 408 and 409: 404 Before startup, the system is p
Page 410 and 411: 4 OL. ' , I. . TesCs. With.Coals .o
Page 412 and 413: Table 3.- Product Gas Analyses and
Page 414 and 415: 410 BIBLIOGRAPHY 1. American Public
Page 416 and 417: Figure 2. Enclosure surrounding hyd
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0 0 f v) C 0 u m I z 2 c 2 r d J w
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0. E c .4 7 .. .c . I ( - Low tempe
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418 cual. A mjor aa\;antage or' the
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420 Ir ?Y ? ? 9 9 9 pc rod n o c o
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422 Table 3. Room-texperature M'dss
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424 state, depending on the strengt
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Table 4. Room-?;ergerature isomer s
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I' 1.3 . /o 9 IO 9 6 a 425 F F 33 I
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Brooks J.D. and Sternhell S. (1957)
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(52) Gib3 T.C. and Greenwood N.N. (
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434 transducer vas then introduced
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436 yield is quite similar. The con
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?-!??? 0 mv, Uh\OhIe . . . . eirlrl
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4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 4
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442 CHEMICAL REACTIONS IN A CORONA
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helium 444 CORONA REACTOR SYSTEM Fi
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446 The ultraviolet spectrum. for t
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Biphenyl Fraction 448 The low molec
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LUd The actual structural definitio
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I I I I I In m 9 In 2 , I: r- In m
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’. 454 Mechanism I The available
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456 , , . The relatively low yield
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458 h/lethylacetylene, allene and b
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Introduction VAPOR PHASE DECOMPOSIT
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462 more efficient hydrogenation. T
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464 place in parallel with fragment
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466 P rl 0, k 7 rnI rn al k a I hl
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458 TABLE I. COMPOSI'IION OF GASEOU
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REFERENCES 1. C. Hirayama and D. A.
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i 472 Reciprocal Arc Enthalpy ,-> F
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474 be pumped down without altering
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476 Instead a hydrogen deficient fi
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i 478
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480 FATTY ACIDS AND n-ALKANES IN GR
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482 TA5L,E 2. - Carbon number distr
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6. 7. a. 9. 484 Lawlor, D. L., and
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' I ' Sample No. 6 ' 12 IO 8 6 z 4
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. 488 uiolecular weight of which ca
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Xississippi (Sample GS). Stock solu
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492 found at 5.7 and 4.9& for the W
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494 mechanisms. However, the voltad
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For pure polynuclcar arom.i;ic hydr
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- '-'. . ' . . values are listed in
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500 (1;) Ten, T. 17.: a;1d,Dic;
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- ~ Resistivity Czlculation 2: 1 j:
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504 o ' C 0s 2 0 v x i 8 2 0 ! P -
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506 i
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d 601 L P LL
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I I I I I I I I m W N W N 0 (D ? 0
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514 was heated under nitrogen in a
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The line broadening at 79OK of the
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13. 14. 15. 16. 17. 18. 19. 20. 21.
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W L, Z 6 m (1: 0 6 d j o 2 ' 1 0.0
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Coals 522 Studies of the 1600 cm-l
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L in ole i c a c id - 0' Two sample
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526 Table 1.- Ultimate analyses of
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528 6. Friedel, R. A., and H. Retco
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egeneration. The system can be seen
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532 and can be expressed in terms o
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534 in the vapor increases with inc
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NH3 NH3 NH3 NH3 Pyridine Pyridine P
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Mole Ratio of Test No. Quinoline to
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IXPROFJCTION D; M. Mason Institute
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-4:c~rciiny to recent studies o ;i4
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544 Table 1. LIGHT EMISSION OF Y"TR
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emission in a few cases may be by d
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LITERATUR2 CITED i. C. -. .' * il.
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co, CH,,OR 1 - OTHER ADDITIVE FRITT
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FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
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340 350 300 400 4 50 500 600 700 80
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0 554 WITH COOLING (PLATE AT 40°C)
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5 56 then t = to when e = 0 2) the
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5 58 The surface heat transfer coef
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Discussion and Results 560 Three br
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__- ._ 562 Table I THERMAL AND PHYS
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ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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