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THE HEAT OF REACTION?% HYDROGEN AND COAL A. L. Lee, E. L. Feldkirchner, F. C. Schora,and J. J. Henry* Institute of Gas Technology Chicago, Illinois This investigation is a part of the study conducted at the Institute of Gas Technology (1,2,4,5,6,7,9,10,11) to obtain the necessary infor- mation for designing an efficient coal hydrogasification plant. A thor- mgh literature search reveals that there is no reported data on the heat 3f reaction of hydrogen and coal. Therefore, two calorimeters were desisned, constructed, and operated, one to measure the heat of reaction md the other to meesure heat capacity by the drop method. The heat-of- reaction calorimeter can be operated at temperatures up to 1500'F and pressures up to 1500 psia; the drop calorimeter operates at atmospheric pressure and temperatures up to 1500°F. This paper reports the results of the following investigations : APPARATUS 1. The heat of reaction of hydrogen with coals and coal chars after various degrees of gasi- fication. 2. The heat of reaction of coa1,pretreatment. 3. The heat capacity of coals and coal chars. The heat-of-reaction calorimeter built by Dynatech Corporation is shown in Figure 1. The sample is placed in the upper portion of the neck which is cold. The calorimeter body is filled with hydrogen and heated. The temperature of the calorimeter body is measured by foi2 thermocouples and two platinum resistance thermometers. The sample is lowered into the body after the temperature has remained steady for 2 hours. The change in temperature due to a reaction is then measured as a function of time. The drop calorimeter, which was also built by Dynatech, is shown in Figure 2 . The sample is placed in the top f'urnace until it reaches the desired temperature. It is then dropped into the copper receiver,and the heat capacity of the sample is determined from the temperature rise and heat capacity of the copper receiver. EXPERIIQCNTAL FESULTS 'J I' The major problem encountered in determining the heat of coal reactisns at high temperature and high pressure is prereaction, since coals 1 Ceconpose when heated. Meaningful results can be obtained only if the A' czal and hydro&en react at conditions at which the desired temperature I and pressure are stabilized. Therefore, the method of introducing the sayple t2 the reaction conditions is critical. The coal must not react I befsre the conditions are set, and the pressure must not be disturbed when the coal is introduced. !: 1 ' * Dynatech Corp. , Cambridge, Massachusetts. ( > \ c f
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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
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317 i Cuencb svsten w.nnar;itus use
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epcrte? the noss~kil.itv of nroduct
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1' b t +
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323 ....... - . . . . . . . . . . .
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1 \ i I i , / / / 8 3 1 325 To205 +
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- .- - - . - - . . . - . 327 n + c
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' POWER PLASMA GAS l e , ' I ! I I
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331 f'ENI?AL PF'FCLCCFC Dernis, P.R
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i J 333 ; mosphere (as opposed to a
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; it raised the question, still &?z
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p .I V I .= - - HCN/C(CALC. WITH C
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1 1 339 atmospheric ressure and ach
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RESULTS 341 Composition Dependence
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0.09 0.08 0.07 9 0.06 2 U - .$ 0.05
Page 346 and 347: II \ to the Slot So that less of th
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
Page 362 and 363: I 1 \ 361 -. ne reaction proceecis
Page 364 and 365: \ 36 3 ' h, I 26. H. Purnell, Gas C
Page 366 and 367: In experiments on the direct conver
Page 368 and 369: 367 used as blnders, with different
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 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
Page 418 and 419: 0 0 f v) C 0 u m I z 2 c 2 r d J w
Page 420 and 421: 0. E c .4 7 .. .c . I ( - Low tempe
Page 422 and 423: 418 cual. A mjor aa\;antage or' the
Page 424 and 425: 420 Ir ?Y ? ? 9 9 9 pc rod n o c o
Page 426 and 427: 422 Table 3. Room-texperature M'dss
Page 428 and 429: 424 state, depending on the strengt
Page 430 and 431: Table 4. Room-?;ergerature isomer s
Page 432 and 433: I' 1.3 . /o 9 IO 9 6 a 425 F F 33 I
Page 434 and 435: Brooks J.D. and Sternhell S. (1957)
Page 436 and 437: (52) Gib3 T.C. and Greenwood N.N. (
Page 438 and 439: 434 transducer vas then introduced
Page 440 and 441: 436 yield is quite similar. The con
Page 442 and 443: ?-!??? 0 mv, Uh\OhIe . . . . eirlrl
Page 444 and 445: 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
Page 544 and 545:
IXPROFJCTION D; M. Mason Institute
Page 546 and 547:
-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
Page 570:
ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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