Mathematical models of the thermal decomposition of coal 2. Specific heats and heats of reaction David Merrick ‘National Coal Board, Coal Research Establishment, Stoke Orchard, Cheltenham, Glos., GL52 4AZ, UK (Received 20 November 1981; revised 1 July 1982) Published data on the specific heat of coal and coke have been anelysed and have been used to define a model which predicts the specific heat of coal during thermal decomposition. The Einstein model is used ‘to describe the variation of specific heat with tempereture and the effect of composition is determined by assuming that the vibrational energy at any temperatureis the samefor egch atom. A new explanation for the endothermic reactions below 650°C reported by previous workers is proposed as a consaquence of the unexpectedly high specific heats predicted in this region using the ve model. The exothermic reactions occutring at high temperatures appear to be attributable 10 the evolution of methane, (Keywords: coal: mod Design calculations for many coal combustion and conversion processes require the specific heat and heats of reaction o be known to construct an energy balance. The present models were developed as part of a study of coke oven carbonization, but are thought 10 be generally applicable. Specific heats and heats of reaction are particularly mportantincarbonization asthey can havea significant effect on the coking time. The models relate the specific heats and heats of reaction of eoal during thermal decomposition to the changes in the yields and compositions of the char and volatile matter, Since these parameters can be predicted by the model of volatile matter evolution previously described’, the two seis of models may be linked. This fenables estimates of the thermal properties during carbonization to be made from the ultimate and proximate analyses of the coal and the heating rate Published experimental measurements of the specific heats and heats of reuction of coal are based on the total heat required for carbonization to various temperatures. For coal bslow the decomposition temperature, and for coke for the full range of temperatures, heats of reaction can be assumed to be negligible, The specific beats under these conditions ean therefore be caleulated directly from the total heat requirements. For coal during decomposition, however, no independent data on specific heats and heats of reaction are available. For this reason, the approach adopted in the present study is to develop independent theoretical models of the specific heat and hea of reaction Reviews of correlations for the specific heats of coals and cokes have been curried out by Clendenin et al2, Agroskin’, Budzioch* and Kirov’, For coals, the correlations are generally only valid for temperatures up 0016-23613 /080540.078300 G 1963 Butterworth & Co, (Publishers) Ltd ‘thermal decomposition: heat) to ©200°C. There is agreement that the specific heat inoreases with temperature and the volatile matter of the coal. Typical values for the specific heat ofthe "standard 15, 25 and 35 wi% volatile matter coals (defined previously") are illustrated in Figure’ I, based on the correlation of Gladkov and Lebdedev®. The values in the Figure refer to instantaneous specific heats of the daf material. As noted above, specific heat measurements for coke are available over a wider range of temperatures than forcoal. At ambient temperatures, the specific heat of coke is less than that of coal and increases monotonically With temperature, the rate of increase being lower at higher temperatures. Figure J gives typical values for the instuntancous spovific heat of daf coke and graphite based on the correlations of Kirov and Perry and Chilton’ respectively. “Models of the specific heat of eoal have been proposed by Kirov’ and van Krevelen*.In the Kirov model, and the similar model of Eisermann er al”, coal is regarded a & simple mixture of coke, primary volatile matter and secondary volatile matter. Correlations for the variation inthe pectic heats of these components with temperature are proposed and, by assuming additivity, a method of estimating the specific heat of coal during decomposition is oblained. An interesting feature of the model is thi there is some indication of a manimum specific heat at about 400 C which will be discussed later. One of the weaknesses of the Kirov model is that the predicted specific heat ofcoke decreases above about 800 C. casting dob onthe validity of applying the model ubove about 350°C. A further disadvantage les in the use of the broad categories ‘primary volatile matte:* and “secondaty volatile matter'as the model cannot account forthe effets of variations in the compositions of these mixtures.E g ‘_ae a Figure 1 Typical values of ho specie est f col coke sna sgaphite (calculates tom the proximate alysis sig he fEttelatons in veterencee 6,7). Cake) apie ‘The van Krevelen model" is confined to the effect of coal rank on the specific heat at ambient temperature Van Krovelen proposed that, at ambient temperatures, each atom in the coal(C, H,O, Nand S)is able to oscillate ‘monly one dimension (normal tothe layer planes where the binding forces are weak). The instantaneous specific heat is, therefore, R, J kgatom”" K°', ie, 33% of the ‘maximum theoretical value for solids. This is in good agreement with experimental data for coals. The van Krevelen formula for the specific heat of daf coal, c, at ambient temperature can_be expressed in terms of the mean atomic weight, a, of the coal by the equation: e=Rla (kg Ko ao ‘The mean atomic weight. a, can be defined in terms of the timate analysis by ue Pa @ Shere: yi, Sethe mass fractions of carbon, hydrogen, oxygen, nitrogen and sulphur on & dal basis and fi, §= 1.0.5 the respective atomic weights of the ements (13, 1,'16, 14 and 32) ‘The existence of heats of reaction during carbonization «an be inferred from the observation thatthe centre of a sake oven charge becomes hotter thin the walls towards the end of carbonization, This is only possible if an Stothermic reaction is taking place. ‘Qualitative assessments of the absorption or evolution of heat during reactions can be made using differential thermal analysis. Applications of this technigue to ‘atbonization have been reviewed by Nelson" and Howard!" The published studies do not agree on the Pattern of heat evolution and the vale ofthis technique in ‘ssessing the heats of carbonization reactions is therefore Teeurded as uncertain, ‘Quantitative estimates of the beats of reaction during usbonization have been published by Kasperczyk and Sinionis'* and Agroskin etal. Im both investigations. it Wes assumed that the instantaneous specific heat ‘Models of thermal decomposition of coal. 2: D. Merrick increases monotonically from the value for coat at ambient temperature to that for coke at a high perature. The conclusions of the studies are in agreement that, below about 650 C, the reactions are endothermic (144.206 kS kg”), becoming exothermic at higher temperatures (266-441 kJ kp) SPECIFIC HEAT MODEL Structure of the model The approach adopted to model the specific heat of coal and coke isto apply the Einstein form of the quantum theory specific heal description for solids!*. This assumes that all of the atoms in 2 solid oscillate independently in three dimensions, with a common characteristic frequency. The theory leads to the following expression for the enthalpy, k he 3R 0 gef0/T)—(kg-atom™') Br where aole}=1enp(e)—D) 4 ‘and R =the gas constant, mol” K~'; T=the tempers- ture (K); and 0a constant, the characteristic Einstein temperature (K). The specific heat, cis ven by: c=3R g(@/T (I kg-atom™? K where (2) = expled(exp(2)— Dia)? 6 Although a more accurate specific heat model was subsequently developed by Debye, this has not been used in the present study because the small improvement in accuracy forthe teniperatures of interest is not considered to justily the extra computational complexity. The empirical law of Dulong and Petit states that the specific heat of a substance may be calculated as 3R.J ke- atom" K-!, This law is approximately tcue for many Substances at ambient temperature although, in some ceases (including coal and coke). the specific heat at ambient temperature is considerably less than 3R. ta the Einstein specific heat theory, the value 3R represents the theoretical maximum for solids, and is approached at “hight temperatures where all of the vibrational modes become fully excited ‘In a preliminary study, the Einstein model was applied tocoal and coke by assuming that each atom (C,H. O,N and S) oscillates with the same characteristic frequency (ie. has the same characteristic temperature) and in all three dimensions. With a value of 1200K fet the characteristic temperature, the equations become: 600(RValge(1200/7) UF ke) a MR/aye,(1200/7) (I kg" K-49) (8) where asthe mean atomic weight defined in equation (2) A characteristic temperature of 1200 K as selected for this model because, with this value equation (8) recuces to the relationship proposed by van Krevelen equation (1) al ambient temperatures The Finsiein characteristic temperature of 120K. provides a hasis for estimating’ the frequency actor of 13x 10''s"! used im the model of volatile. matter evolution, assuming a typical reaction temperature of TK ‘The form of equation (8) suggests that ca/3R is a FUEL, 1983, Vol 62, May 541‘Models of thermal decomposition of coal. 2: D. Merrick Figure 2_Veseton of cr/38 wih temperature. — Enetin model inssin model with two chaeceisic temperatures" Graphite. ©. coker CL. 38 wee UM 28 WO Via 18 woe VM function of temperature lone. Thisis tested by eplotting the literature data for coals, cokes and graphite given in Figure | as ca/SR against temperature in Figure 2. The ‘mean atomic weights of the eoke und the standard 15,25, and 351, volatile matter coals ure taken 0 be 11.7.82, 79 and 7.7 respectively. As shown in the Figure, the sigrosment belwecn the curves for thecoke and the various ‘cals is reasonable, supporting the use of equation 8 (and algo van Krevelen’s hypothesis, equation (I}}asa means of Predicting the effect of composition on specific heat. ‘Also shown in Figure is the effect of temperature on specific heat predicted by assuming an Einstein characteristic temperature of 1200K. Although the ‘agreement is reasonable, it was found that a more accurate fit to the experimental data could be obtained by ‘assuming to Finsicin characteristic emperatures, one applying within the layer planes where the binding forces fre strong, and the other applying normal to the layer planes where the binding forces are weak. The values Seleted are 1800 and 380K respectively. This allows the ‘rational modes normal tothe layer planes to approach boing flly excited at ambient temperatures. as suggested by van Krovelen, whereas vibrational modes within the layer planes require higher temperatures before ‘approaching the maximum specific heat. The equations become rm (Rol 3809 380/7) + 3600g4(1800/0)] kg) , ) (Raia (380/0 + 244(1800/7] gw! KX") 1b) The agreement between equation (19) and the experimental data is also shown in Figure 2 ‘842, FUEL, 1983, Vol 62, May Limitations of the eodel ‘The upplication of the classical quantum theory descriptions of specific hea io an amorphous and varisble Substance suc ds wou is subject to some limitations. Jn particular, the characteristic temperatures obtained from ‘he analysis reflect the average proptties of the bonds present. In principle, therefore, these may be expected 10 ‘vary withthe chemical structure of the coal and therefore with coal rank. The use of constant values in the present work is supported by the good agresment between van Krrevelen’s Iocel and experimental data at ambient temperature However, there is clearly a need for improved experimental data for a range of coals and temperatures, ‘The availability of such measurements would permit the relationship between the parameters of the model and coal rank (or structure) to be explored in greater detail, “The complex chemical structure of coal suggests that better specific heat model may be provided, at least in principle, by a distribution of characteristic temperatures Corresponding toa distribution of binding forees. Such a ‘model wus derived by assuming alog-normal distribution of characteristic temperatures and fitting the resulting expression for the specific heat to the experimental data. It was found that yood agreement could be obtained with a ‘ean characteristic emperature of 1120 K anda standard, deviation of 1.7. However, the predictions of the model differ Irom those of equation (10) by < 10%, within the temperature range of interes In the absence of moze accurate experimental data, no advantage is seen for the cexira computational complexity of the continuous distribution model and equation (10) has been uscd throughout the remainder ofthe present studies Ejfeet of ash ‘The values predicted by equation (10) refer 10 the instantaneous specific heat of daf material. In. making predictions for ‘as-received’ coal, and the resulting char fand coke, it is necessary to correct for the presence of ‘moisture (at temperatures below 100°C) and ash which can be done by assuming additivity caSng Oke) “ where: C,¢,.¢5,¢4=theinstantaneous specific a5 received coal, daf coal, ash and moisture respectively, ‘and sy =the mass fractions in the'as-received’ coal of the daf coal, ash and moisture, respectively. ‘The value ofc, can be caloutated by equations (8) 0: (10) and ¢ can be taken to be 4187 J kg! KoA ‘comprehensive review of data on the specific heat of coal ‘ash and related minerals was carried out by Kirov’, from which the following equation for the instantaneous specific heat can be derived: 7S440586T (kg! K~') 42) where: Temperature (0. Implementation ‘The model of volatile matter evolution’ can be used to prediet the changes in the composition of the seri-coke Guring carbonization and these, together with equations {2}. 16) 110) 11) and 112), permit the specific heats of coal uring. thermal decomposition to be estimated, The esl for the standard 15,25 and 35 w1, volatile matter80a} 3 SPECIFIC HEAT (2tkg K) & 00] 7 G00 TEMPERATURE (°C) Foue 9 Precis variation of specie heat with tmpertie beating rat 3 Km aco coals! at a heating rate of 3K min“! are ilustrated in Figure 3 (instantaneous specific heats. def coal) Figure J shows that there is comparatively lithe dilrence between the coal ranks, although all exhibit a ‘maximum value ofthe specific heal at about SO0°C. This is ‘consistent with the carlier mode! predictions of Kirov", although more pronounced. More recently, Melchior and Luther'® have reported specific heat measurements of up 102200 kg! K fon coal at 300°C. As this value higher than the Dulong and Petit theoretical maximum for coke, ‘tmay be taken as dircet experimental confirmation ofthe ‘existence of a maximum in the specific heat curve for coal ‘during thermal decomposition, Discussion An analysis of the predictions of the proposed model Drovides a possible explanation for the existence of a ‘maximum specific heat. In Figure 4, the initial increase in the specific heat of eval is attriutable to the effect of temperature alone. For the standard 25 wt”, volatile ‘matter coal, the maximum thearetieal specific heat (3R/a) 4s 3160.1 kg~! K~" (da, Until decomposition begins, the ‘specific heat increases asymptotically towards this value, aching 2213 J ke~! K~! at 400°C. Ascarbonization proceeds, the loss of hydrogen results ‘nan increase in the mean atomic weight of the semi-coke {owards that of carbon. The theoretica| maximum specifi heat therefore falls, taking the value 2110 Ske? K- for ‘aturedaf coke. This fall leads toa reduction inthe actus! Models of thermal decomposition of coal. 2: D. Merrick specific heat of the semi-coke and results in the existence ‘ofa maximum value. fn the final stages of carbonation, the specific heat ofthe semi-coke increases asymptotically to the maximum value of 2110 kg" K~' for mature dat coke, ‘As an increase in hydrogen content reduces the mean atomic weight, the theoretical maximum specif heat enerally increases with the volatile matter of the coal ‘This explains the predicted increase in the actual specific hheat with volatile matter (Figure 3} and also the comparatively low specific heat of coke (Figure 4, ENDOTHERMIC REACTIONS As discussed catlier, the heats of reaction reported by Kasperezyk and Simonis!? and Agroskin et al? are ‘based on measurements ofthe total heat of carbonization and estimated values of the specifie heat during the thermal decomposition of coal. The specific heats were assumed (0 increase smoothly and monotonically froin the measured values for da coal at ambient temperatures to a value for mature daf coke at high temperatures, a shown in Figure 5. Figure 5 also shows the variation of the specific heat with temperature predicted by the present ‘model for the standard daf 25 wt”, volatile matter coal ‘Comparison of the eurves in Figure 5 shows that the present model predits significantly higher specific heats particularly betwcen 490 and 600 C, than assumed in the 0 Fro] howe i305 Figae 4 Analysis of specific het predcvons. Hestng rata, 3 K mi, ‘at con! 25 wee VM FUEL, 1983, Vol 62, May 543‘Models of thermal decomposition of coal. 2: D. Merrick sea woven 20g \ a Nesoons sous femora SPECIE HEAT Ug KD ‘wo ta 00 woo too Figue 5 Comparison of epee heats. Heating rate, 3K mi" Gat col, 25 wae VM, previousanalyses. These high specific eats areequivalent {Gendothsrmic eactionsia their contribution tthe total heat of carbonization “This soggsss that the endothermic reactions below 1650 C reported in previous studies may not, n fact, exist but were thought to oecur as result of assuming specie heals which ate too low. The total heats required for carbonization rom 100°C to 650°C have bean estimated From the dats of Kasperezyk and Simonis!™ and Agroskin'® to be 1136 and LOSSMIKg * (Gal) ‘epectively tinluding the endothermic’ reactions) These valtes compare with a value of LILSMI kg (da) Tor Sibi heat requirements alone peeicted by the present model Using the present specific heat model, the apparent endothermic reactions observed previously can therefore be secounted for by the unexpectaly high specific heals predicted in the temporatue range A00-600-C the in the ‘euion ofthe maninium specie heat). EXOTHERMIC REACTIONS Seructure of the model To confirm and supplement the above analysis of the "apparent endothermic reactions energy bulanes for ihe volatile matter evolution reactions! hase been carticd out. The model can be summarized by the following equation for the rate of release of heat dyjét under isothermal conditions at temperature TC; wie where: @ ym a" the heat release 1 ke-?, daf coal basis; eats of formation at temperature T.1kg™! 0 Wee) 03) 844 FUEL 1983, Vol 62, May and my J=0,...,9=mass fractions of carbonization products daf cos! basis. The ind: 9 refers respectively to the chat and the nine volatile matter species considered in the model of volatile matter evolution® fs, CH,, C,Hg,CO, COs, tar, H,, HO, NHy and HS). “Thelheatsofformation at temperature T*C for the nine volatile malter species ean be expressed approximately as ‘quadratic funetions of temperature: we DPA ‘The coelivients of Pa were derived from standard tables!” of physical and chemical properties. The values are given below: (xs) 03) Species Constant. Coefficient of Coefcient of cH, — -4719000 156 GH, —2866 000, 146 co" 3971000 out CO, 8964000 022 Tar =1936000, 183 a 0 033 {0 —13.468000 033 Ni, 2760000, 084 HS ~630000 024 For the char, the heat of formation can becaleulated from the standard heat of combustion using Hess's and Kirchoffs laws H-Soy,+ah kg) us where: H=the heat of combustion at 25°C: ,, i=1,...,S=constants representing the heals of, combustion of the above elements, C, H, O, N and S, respectively (at 25°C) Jieg!; and AM is the change in enthalpy from 25 to TC, Jkg™ ‘The valuss of the coefficients in Jkg™* aretaken'* ro bbe 32.76 10, 141.77 x 10°, 0, 0,936» 10% respectively. ‘A number of correlations exist in the literature for the heats of combustion of coal and coke in terms of thir ultimate analysis (eg. the reviews by Selvig and Gibson ‘and Mason and Gandhi?" In the present study, he correlation of Mott and Spooner has boen used. ‘This can be expressed in the form: Lay, Oke) 413) where; dy i= 15-045 ane constants ‘The alues’ of the coefficients 4, im Sky"! are 3262410", [41.93% 10%, — 14.53% 108, 0, 9.42510" Tespectivly Although the Mott and Spooner eorrelation was developed for coals, it is found that the predictions agree Well with the heats of combustion for coke reported by ‘Thibaut?. I is therefore assumed in the present study tat the corrclation applies both to coals and coke and, forthermore, that it ean also be used to predict the heutsof ‘combustion of the char residues formed during thermal ‘decomposition ‘The enthalpy change from 25 10 T°C for the cou, char for coke can be obtained direcily from equations (2) and 6Lovant okey 16) (380g (380)/) + 360094(1800/) 156) imo") a7) Equations (12) to (16) give, after substitution and simplification: a3 4 Tet LA OHIO + Whe) (18) ‘The heat release can be expressed in terms ofthe release rates of the nine volatile matter species alone by substituting from equation (10) of the previous paper! 9) 2 Ady +87 Var Y PaT™ . ke) 20, Fee we 5 a 5 8 2 rewenane (°0 ‘our 6 Precio vation of heat eease rte with omperatie, Models of thermal decomposition of oat. 2: D. Merrick The terms A4/m represent the contributions to the heat release of the individual volatile matter species. The heats of combustion referred to above are’all expressed in terms ofthe mass of daf coal, If required in terms ofthe “as-received” coal, the heat release da/d¢ may be calculated from: dQ_ da ar Whe“) @ RESULTS AND DISCUSSION ‘The model of volatile matte release described previously? hhas been used to predict the release rates, dm J=1....,9,of the nine volatile matter species as basis for calculating the rates of heat release during carbonization using equation (19). The results forthe standard daf 5,25 and 35wi% volatile matter coals at 3Kmin~! are illustrated in Figure 6 ‘As shown in the Figure, the reactions are entirely exothermic, providing support for the explanation of the apparent endothermic reactions proposed in the previous section, Equation (19) can be integrated to provide the ‘cumilative eat release, Furthermore, the form of equation (19) enables the heat release to be divided between the various volatile matter species. The breakdown, in MIke” daf coal, of the final cumulative heat release fic. ata high temperature) is given in Table 1 Table J indicates that the exothermic reaction heats may be attributed mainly to the release of methane, the Contribution of the other species being relatively minor. Comparison of the predicted exothermic. reactions (Figure 6) withthe estimates of Kasperezyk and Simonis!? and Agroskin etal! reveals two ateas of disagreement: The magnitude of the heat release. The total heats of reaction for the standard 15, 25 and 3Swt% volatile matter coals are predicted exothermic reactions of 0.465, 0.616 and 0653 Mikg~" (dal coal, respectively. These values are higher than the exothermic reactions estimated by Kasperezyk and Simonis'* and Agroskin etal? to be 0.424 and 0.299 MIke! daf coal, respectively, The temperature ofthe heat release. Figure 6 shows that most of the exothermic heat of reaction is predicted as ‘occurring below about 804°C. in conflict with the observations of Kasperczyk and Simons? and Agroskin etal! who found that most ofthe heat is released above this temperature. The reactions responsible for the centre ‘of 2 coke oven charge becoming hotter than the walls towards the end of carbonization must also occur at high temperatures ‘These discrepancies may aise in pars from thedfculties in obtaining accurate experimental determinations of the Hesoeg rate'3 Kine" dl coal heat release by the methods currently available. The main Tole 1 Fit euraative eat een (MU kg!) inate nt Om cae co co THO HS Toh is o3s7 00s 000 “oa 0052 00s opti 0008 000) oso 2% 207 onea “na? 8 00 016s | Ooaa oni tote ocos Beat as Oae1 cos 008) On 0206 0023 0037 0021 ono O68 FUEL, 1983, Vol 62, May 545‘Models of thermal decomposition of cosh 2: D. Merrick uncertainties in the theoretical method proposed are in the valuss for the heals of combustion (or, equivalently. of formation) of the coal char and tar In particular, theapplivation of equation (15)tocharimplictly assumes thal the molecular rearrangement following the release of the volatile matter is complete. In practice, these changes may occur only slowly, resulting in the heat release being deferred 10 a higher temperature than that of the corresponding volatile matter release. Tn spite of the differences between the experimental data and the predictions of the model, the later does illustrate a method of approach and confirms the existence and order of magnitude of the exothermic eactions associated with coal carbonization Furthermore, analysis of the predictions points to the evolution of methane and tar being indirectly responsible for the exothermic reactions, CONCLUSIONS ‘A new mathematical model of the changes in the spoxiic heat of coal during carbonization is proposed. based on the Einstcin specific heat theory for solids. The model satisfies the Dulong and Peiit theoretical limiting value of 3R J kgatom” K~? at high temperatures and, at ‘ambien! temperatures, reduces to the van Krevelea* equation, "An interesting eaturs of the modelis the prediction ofa ‘maximum specie heat at about 500 C. The enstence of maximum specific beat is supported by recent experimental data!?, and ean be explained in terms ofthe relative rates of inerease in specific heat with temperature ‘and decrease in the maximum attainable specific heat with Tos of hydrogen. ‘The existence of unexpectedly high specific heuts berween 400 and 600°C suggests that the apparent endothermic reactions noted by previous workers!?"? ‘may nol infact, exist and may be explained solely in terms of sensible heat requirements ‘An energy balance model to predict the heats of reaction during the thermal decomposition of eoal was, also developed. The model predicts that the reactions are generally exothermic, An analysis of the predictions Shows thut the evolution of methane und, 10 a lesser textent, tar appears to be indirectly responsible for the heat release ACKNOWLEDGEMENTS ‘The author would like to thank B. Atkinson for carrying ‘oul the computer simulations for this paper and the NCB. for permission to publish. However, any views expressed are those of the author and not necessarily those of the ‘National Coal Board. The work reported in this paper formed part of a PRD thesis submitted by the author 10 the University of London. REFERENCES 1 Merc, D. Fue 1985, 62.534 2 Chenin 1D, Hoa. KM Donal H.2, Gilmore D.W. fund Wight lineal adaxre and Experian Station ‘Tesh Pape Hol i981 3) Agoda A A Ther! sa clos properties of oa, The Steet estas pubbing hover erie 546 FUEL, 1983, Vol 62, May 4 Balen $ BCURA Muh Bll. 1960, 24.498 $RISCN S.Bctet Mn dat 43, 2939 6 Gladhon Ltand Leber A Ne fae Soe Tepe Tre 8 wR Ht ard Chiko. C H,-Chomisal i Hil Now York 1973 pp 119 8 San Kyouka, DW. Coal Typteay Const seve, Amster 1961 p48 6 EatmunaW. Johnson, Pana Conger, WL. Fue Proc. Tech 133.39 10 Nokon 1 B Ful 1955, 4,189 M1 Howard, H. Chin ‘Chemisty of Coal Utiisasio’ (Ed. HL ok Sup Vso Wy sn omy, New Yn, 198, ince Randbook’ 12 Ksspercyh J and Simoni, GhtayForichayefe 197, ah 13 Afonin A. A Goncharov, E.1 and Gryaraoy, N.S, Kaks 14 nun MA "Elmantry Soi State Phy’, Adzon-Weey, Reading, MA, 1918 p87 15 Prox A Aad Peto, KG Kins ae Mchanis Jha Wile a Sone New ork, 1h, p79 16 Melchior, Evan’ Lather, Erdal and KoWe, Erdgas, Pooch 1975, 28.379 17 KageG.WC and Lab,T H. Tablsof Physaland Chemical (Coasts, Longman, Candoa, 1978 1a Rassgve, Ky Handbook of "Theimaynamic Tables and (Ghar MGs Bi New York 1978 19 Romy Wand Coopey, JR. Tacha! Data on Fu, The Bich Navnal Commits The Wonk Foeigy Conference London 1977 120 Say WA! and Gituon FH. in Chomisry of Coal Utilisation’ (HH. Lowry) Joh Wiley and Sons, New Yor, 19859138 21 Mawon,D Aland Gandhi Chem Sy bts Ful Chm Props 1980, 280) 235 22 Mon RA. and Spoone, C.F Fuel 1940.19, 226 3 Thibat, Ch in'Chemie of Coa Uren’ (EMH. Lowe) Supp Vl. Jobn Wiey and Son, New Work, 1963, Ey NOMENCLATURE mean atomic weight © specie heat ) kg? K-") specie heat of af coal (I kg"! K=") specif heat of oal ash (EB K~) f} specie heat of moisture U kp? K~) C_Spevfe heat of aseresived coal (J kg”? K~*) A) Shihalpy fanevon for char Op” *) f Esmssia ently function 2, Einstein specifi heat fanetion enthalpy Oka") Heat of combustion of char at 25°C Ske) mm, mass factions of char and volatiles 7 matria of coeicients 4” heat release for daf coal (ke) heat reas for as-received coal Ske!) R gas constam (8314.4) U kmol-! K!) 7 r time (3) temperature (C) temperature (K) 1, heals of formation of char and volatiles kg") Wes mss fraction of moisture H)ultimate anabyss Summy variable ‘enthalpy of ehar at 7°C (relative to 25°C) 0g) © Einssin characteristic temperature (K) 4, Nestor f constants Oks) 4K alomic weights of elements present 4, heats of combustion of elements present (Jkg ")