JFUE 7314 No.

of Pages 8, Model 5G
5 August 2013

Fuel xxx (2013) xxx–xxx

1

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

5
6

3 Heat capacity measurements of various biomass types and pyrolysis

4 residues
7 Q1 Capucine Dupont a,⇑, Rodica Chiriac b, Guillaume Gauthier a, François Toche b
8 a
CEA, LITEN, Laboratory of Technologies of Biomass, France
9 b
Université Lyon 1, Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, Villeurbanne, France

10
11

1 3
h i g h l i g h t s
14
15  Heat capacity was measured on 21 biomass types and on fast pyrolysis chars.
16  The influence of biomass type was moderated with relative differences below 20%.
17  Linear increase was observed for biomass under the range of temperatures tested.
18  Linear increase was observed for chars except in the range 353–513 K.
19  Exothermal phenomenon of char recombination seemed to occur in the range 353–513 K.

20
a r t i c l e i n f o a b s t r a c t
2
3 2
4
23 Article history: This study aims at measuring heat capacity on a large range of biomass types and on pyrolysis chars 35
24 Received 24 June 2013 obtained under conditions representative of industrial reactors for further use of these data in thermal 36
25 Received in revised form 22 July 2013 conversion models. As expected, linear increase could be observed with temperature for the 21 biomasses 37
26 Accepted 23 July 2013
tested between 313 K and 353 K. The relative difference of heat capacity between the different biomasses 38
27 Available online xxxx
was significant but lower than 20%, with values ranging from 1300 to 2000 J kg1 K1. The sample form, 39
either in block or powder, did not seem to have any influence. Values of about 1000 J kg1 K1 were mea- 40
28 Keywords:
sured on chars, whatever the pyrolysis temperature. These values are in the same order of magnitude as 41
29 Heat capacity
30 Biomass
those extrapolated from literature correlations. As expected, linear increase could be observed with tem- 42
31 Char perature, except in the range 353–513 K, in which an exothermal phenomenon of recombination seems 43
32 Pyrolysis to occur inside the char. 44
33 Ó 2013 Published by Elsevier Ltd. 45

46
47

48 1. Introduction description requires the knowledge of the thermal properties of 63

biomass as well as their evolution with conversion [4]. One of these 64
49 Biomass-to-energy processes have recently gained growing properties is heat capacity. 65
50 interest due to the energy crisis. Indeed, there is a high potential Experimental studies on heat capacity can be found in literature 66
51 of available lignocellulosic biomass, i.e. wood, energy crops and on biomass species of interest for current industrial applications: 67
52 agricultural by-products [1]. Thermal processes, i.e. combustion, woody species [5,6], together with cellulose, which is the main 68
53 gasification and pyrolysis, appear as particularly suitable to con- constituent of biomass and the main product used for pulp appli- 69
54 vert this kind of biomass [2]. All these processes consist in a first cations [7–11] or agricultural biomass for food applications, such 70
55 step of pyrolysis, during which biomass is converted under the ef- as peanut [12], cassava, yam, plantain [13] or cumin seed [14]. 71
56 fect of heat only into gas and a solid carbonaceous residue called To our knowledge, agricultural by-products were considered only 72
57 char. by Mothée and De Miranda [15] with measurements on coconut fi- 73
58 Developing models of biomass thermal conversion is of great bre and bagasse and there are no available heat capacity data on 74
59 importance for reactor design. In such models, one crucial issue energy crops or wood from Short Rotation Forestry (SRF) and Short 75
60 is the description of heat transfers inside biomass particles during Rotation Coppice (SRC). 76
61 pyrolysis, as these phenomena can limit the transformation under There is very little information about the evolution of biomass 77
62 typical reactors conditions, for instance in gasifiers [3]. This heat capacity with conversion. Only Gupta measured thermal 78
properties of softwood and softwood bark chars obtained after 79
Q2 ⇑ Corresponding author. Tel.: +33 687494300. pyrolysis under high heat fluxes conditions at 553 K [16]. 80
E-mail address: capucine_dupont@hotmail.fr (C. Dupont).

0016-2361/$ - see front matter Ó 2013 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.fuel.2013.07.086

Please cite this article in press as: Dupont C et al. Heat capacity measurements of various biomass types and pyrolysis residues. Fuel (2013), http://
dx.doi.org/10.1016/j.fuel.2013.07.086
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2 C. Dupont et al. / Fuel xxx (2013) xxx–xxx

81 These heat capacity measurements were generally performed the available data are scarce, one unique value or average correla- 125
82 either with adiabatic calorimeter such as in [10] or with Differen- tion is chosen for all chars, whatever the pyrolysis conditions, 126
83 tial Scanning Calorimetry (DSC) such as in [13,16]. Many studies on although it is well-known that chars produced under different con- 127
84 food biomass were carried out by the method of calorimetry by ditions may have different properties, both in terms of composition 128
85 mixtures but this technique is not accurate [14]. DSC seems to be and morphology [24]. Ragland et al. [25] assumes that the heat 129
86 a very accurate tool. However, it uses small volumes of solid, and capacity of char is roughly equal to the heat capacity of pure graph- 130
87 therefore small masses of biomass, typically of a few milligrams, ite, but with no experimental data to support this affirmation. 131
88 as biomass density is very low. The resulting heat flow is very Other authors use measurements obtained on charcoal [26], as this 132
89 low and one may doubt about the measurement significance. solid has similarities with char and as it has been much better 133
90 Moreover, as biomass and a fortiori char are heterogeneous, the is- characterised for the last fifty years, for instance in [18,22,27,28]. 134
91 sue of representativeness may also be raised when such small sam- Based on this background, this study aims to contribute to the 135
92 ples are used. Hence the calorimeter, which requires higher masses completion of the existing data by measuring heat capacity versus 136
93 of solid, typically of a few grams, seems to be the reference tool for temperature on: 137
94 biomass heat capacity measurement.
95 Biomass heat capacity is known to be influenced by both tem-  A large range of biomass types considered as potential feedstock 138
96 perature and biomass moisture. There is a general agreement on for gasification process. This panel includes various woods 139
97 the linear increase of biomass heat capacity with temperature, that among which Short Rotation Forestry and Short Rotation Cop- 140
98 goes from 5 K to 423 K depending on the studies. Note that bio- pice, in the form of blocks and powder, as well as agricultural 141
99 mass heat capacity can be measured only up to temperatures of by-products and energy crops. 142
100 about 423 K, as biomass begins to decompose when temperature  Pyrolysis chars obtained under conditions representative of 143
101 is higher than 423 K [17]. Regarding char, Gupta found that the those encountered in industrial reactors, i.e. high heating rate 144
102 heat capacity followed a linear increase from 313 K to 413 K and at the particle surface and temperatures up to 1073 K. 145
103 then a smoother increase characterised by a second-order polyno- 146
104 mial between 413 K and 713 K [16]. This is in agreement with the
2. Materials and methods 147
105 findings of Raznjevik on charcoal [18].
106 The influence of moisture has been studied in a systematic way
2.1. Feedstock preparation 148
107 for several food biomass species. As for temperature, the increase
108 of biomass moisture is generally found to lead to a linear increase
Biomass samples were selected to be representative of species 149
109 of heat capacity [12,19–21]. According to the purpose of Njie et al.
potentially useable as feedstock in thermal processes. They were 150
110 [13], measurement on dry biomass is sufficient to predict the heat
classified as follows: 151
111 capacity of moist biomass. Indeed, the heat capacity of moist bio-
112 mass seems to be satisfactorily predicted by the summative contri-
 Wood: beech, angelim, faveira, maçaranduba, hazelwood, black 152
113 butions of dry biomass and water content except for very moist
pine, mixture Scot pine + spruce, poplar. 153
114 biomass (>60%).
 Short Rotation Forestry/Coppice: SRF of poplar and eucalyptus, 154
115 The influence of the form of the sample-powder, bulk or pellets
two SRC of poplar (numbered 1 and 2). 155
116 – has been studied only in a few papers. According to Vargha-But-
 Perennial crops: miscanthus, switchgrass. 156
117 ler, the smaller the particle size, the lower the heat capacity for the
 Agricultural by-products: wheat straw, rice husk, olive pomace, 157
118 four coals tested [22]. In contrary, no influence has been observed
corn stover. 158
119 between minor millet grains and flours [23]. Wood pellets heat
 Energy crops: triticale, tall fescue. 159
120 capacity was measured by Guo, but not compared with other forms
 One sample of cellulose Avicel was also selected for comparison 160
121 of the same wood [21].
with literature data. 161
122 Based on these experimental data, pyrolysis models generally
162
123 use one unique value or one correlation versus temperature ob-
All samples were ground below 200 lm in order to reduce sam- 163
124 tained for wood whatever the biomass type. Regarding chars, as
ples heterogeneity and to make comparison possible. For this latter 164

Fig. 1. Heat capacity of biomass samples versus temperature.

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 JFUE 7314 No. of Pages 8, Model 5G
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C. Dupont et al. / Fuel xxx (2013) xxx–xxx 3

Fig. 2. Comparison between heat capacity of various woods in powder and block forms.

Fig. 3. Continuous line: experimental values of heat capacity of char produced at 773 K versus temperature; dotted lines: linear correlation from the present study and
correlations from literature.

Fig. 5. Heat capacity versus temperature of chars after different post-treatments.

Fig. 4. Heat capacity of chars produced at 773 K and 1073 K.

165 reason, they were also dried before experiments during 2 h at Char samples were prepared from cylindrical beech wood parti- 170
166 383 K and then weighed when still slightly warm to avoid any cles of 2.0 cm in diameter and 3.0 cm in height. Pyrolysis was car- 171
167 rehydration. Tests were also carried out with four wood samples ried out in an induction furnace, under N2 flow, up to temperatures 172
168 in block form, i.e. small pieces of wood cut in the trunk, in order of 773 K and 1073 K with residence time of 20 min. The heating 173
169 to quantify the influence of the sample form on results. rate was of 773 K s1 at the particle surface. The sample heating 174

Please cite this article in press as: Dupont C et al. Heat capacity measurements of various biomass types and pyrolysis residues. Fuel (2013), http://
dx.doi.org/10.1016/j.fuel.2013.07.086
 4
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Please cite this article in press as: Dupont C et al. Heat capacity measurements of various biomass types and pyrolysis residues. Fuel (2013), http://

5 August 2013
JFUE 7314
Table 1
Heat capacity of biomass samples between 313 K and 353 K.

Heat capacity (J kg1 K1)

Temperature Angelim Beech Black Cellulose Corn Faveira Hazelwood Maçaranduba Miscanthus Mixture scot Olive Poplar Rice SRC SRF SRF SRF Switchgrass Tall Triticale Wheat
(K) pine avicel stover pine + spruce pomace husk Poplar eucalyptus poplar_1 poplar_2 fescue straw
313 1359 1305 1341 1302 1395 1348 1325 1362 1448 1324 1345 1318 1377 1361 1339 1488 1370 1340 1308 1332 1336
314 1362 1308 1347 1303 1398 1348 1325 1359 1457 1330 1350 1321 1378 1365 1337 1489 1374 1344 1315 1338 1334
315 1361 1308 1354 1308 1402 1357 1331 1362 1465 1330 1352 1326 1385 1367 1344 1497 1376 1347 1321 1338 1337
316 1369 1310 1355 1314 1408 1368 1336 1372 1472 1341 1358 1329 1392 1374 1351 1503 1381 1353 1327 1345 1343
317 1377 1314 1357 1319 1419 1369 1344 1379 1479 1346 1366 1332 1403 1384 1367 1512 1396 1359 1334 1351 1349
318 1381 1316 1367 1324 1421 1374 1345 1388 1490 1353 1370 1336 1410 1389 1375 1520 1404 1369 1342 1359 1353
319 1383 1321 1373 1331 1431 1381 1350 1395 1506 1358 1373 1341 1413 1395 1379 1528 1407 1375 1347 1366 1358
320 1391 1321 1379 1331 1430 1382 1353 1402 1515 1363 1377 1347 1413 1394 1382 1536 1406 1376 1352 1368 1361
321 1391 1325 1384 1339 1435 1385 1357 1413 1521 1367 1381 1351 1421 1397 1387 1542 1412 1380 1364 1374 1364
322 1396 1328 1390 1343 1443 1383 1367 1417 1528 1367 1386 1359 1430 1397 1392 1556 1413 1384 1366 1377 1370
323 1403 1332 1396 1348 1450 1402 1370 1424 1538 1378 1392 1360 1443 1404 1400 1565 1424 1394 1378 1384 1378
324 1412 1334 1399 1355 1459 1410 1374 1430 1550 1390 1403 1365 1452 1413 1415 1580 1437 1402 1388 1394 1390

C. Dupont et al. / Fuel xxx (2013) xxx–xxx

325 1412 1336 1408 1359 1462 1412 1379 1434 1563 1395 1408 1370 1456 1410 1418 1589 1431 1406 1388 1394 1391
326 1419 1340 1410 1365 1468 1419 1383 1442 1576 1398 1413 1370 1461 1414 1426 1598 1436 1409 1395 1402 1393
327 1420 1343 1414 1369 1469 1418 1386 1441 1584 1397 1415 1375 1466 1411 1430 1607 1438 1414 1408 1404 1398
328 1425 1348 1419 1371 1475 1422 1390 1447 1594 1406 1416 1380 1477 1416 1435 1616 1440 1417 1407 1408 1404
329 1433 1350 1424 1375 1483 1425 1395 1454 1606 1409 1425 1385 1484 1419 1438 1623 1442 1424 1415 1413 1404
330 1440 1357 1429 1382 1487 1427 1398 1454 1615 1419 1427 1388 1490 1423 1442 1638 1448 1429 1416 1416 1414
331 1442 1356 1433 1386 1490 1431 1400 1463 1626 1423 1438 1391 1500 1428 1449 1647 1453 1435 1420 1423 1420
332 1450 1363 1437 1391 1499 1445 1405 1476 1637 1433 1445 1394 1508 1438 1459 1657 1464 1443 1434 1430 1432
333 1459 1367 1442 1395 1505 1460 1409 1485 1649 1451 1454 1398 1520 1450 1471 1669 1476 1450 1443 1435 1433
334 1463 1369 1447 1401 1510 1455 1415 1483 1663 1442 1456 1402 1521 1451 1469 1677 1473 1450 1446 1437 1439
335 1464 1373 1452 1404 1513 1450 1419 1490 1671 1446 1461 1406 1532 1453 1469 1677 1475 1459 1448 1439 1439
336 1467 1377 1456 1406 1515 1457 1422 1489 1679 1450 1470 1406 1539 1456 1471 1683 1475 1461 1447 1442 1443
337 1471 1381 1461 1413 1523 1461 1426 1495 1688 1452 1472 1409 1545 1462 1472 1693 1477 1464 1451 1446 1445
338 1478 1384 1465 1416 1527 1470 1428 1503 1694 1458 1476 1414 1549 1467 1476 1699 1481 1466 1458 1448 1443
339 1483 1389 1468 1416 1532 1474 1434 1506 1707 1468 1479 1419 1552 1475 1478 1706 1485 1471 1464 1457 1452
340 1489 1395 1474 1425 1537 1481 1437 1506 1713 1472 1487 1420 1565 1478 1482 1709 1489 1479 1467 1461 1454
341 1494 1397 1480 1428 1542 1484 1441 1515 1725 1476 1491 1422 1576 1486 1488 1724 1490 1482 1473 1465 1460
342 1499 1403 1483 1434 1546 1488 1446 1527 1733 1483 1495 1427 1586 1489 1493 1730 1492 1490 1479 1472 1467
343 1507 1407 1489 1435 1555 1492 1449 1528 1741 1490 1503 1431 1595 1496 1497 1734 1498 1492 1484 1475 1475
344 1510 1410 1492 1440 1561 1499 1452 1534 1749 1498 1508 1433 1603 1505 1503 1749 1500 1497 1489 1480 1477
345 1517 1415 1496 1446 1567 1505 1455 1541 1757 1497 1514 1439 1609 1514 1507 1755 1504 1501 1493 1483 1483
346 1521 1421 1503 1448 1572 1509 1463 1544 1768 1507 1517 1439 1613 1518 1512 1762 1508 1506 1492 1489 1487
347 1527 1426 1505 1454 1576 1518 1467 1553 1772 1512 1525 1442 1619 1525 1512 1774 1511 1512 1508 1497 1491
348 1532 1430 1510 1458 1580 1523 1470 1560 1778 1522 1529 1448 1624 1529 1521 1780 1515 1515 1498 1504 1497
349 1540 1436 1516 1464 1590 1530 1473 1564 1786 1525 1534 1450 1623 1541 1526 1788 1523 1521 1507 1513 1500

No. of Pages 8, Model 5G

350 1545 1439 1521 1468 1596 1536 1477 1565 1790 1534 1538 1457 1635 1548 1530 1795 1529 1524 1509 1518 1509
351 1551 1445 1525 1472 1601 1542 1482 1576 1799 1539 1545 1459 1641 1554 1534 1805 1534 1529 1515 1528 1513
352 1554 1452 1528 1477 1605 1548 1486 1579 1804 1543 1554 1462 1649 1556 1539 1813 1537 1532 1520 1532 1516
353 1560 1455 1534 1479 1610 1554 1488 1583 1815 1543 1553 1467 1653 1567 1539 1822 1541 1536 1526 1541 1522
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C. Dupont et al. / Fuel xxx (2013) xxx–xxx 5

175 and the furnace are fully described in [29]. As biomass samples, Table 2
176 char samples were ground below 200 lm before measurement. Heat capacity of wood samples in block form.

Heat capacity (J kg1 K1)

177 2.2. Experimental facility and procedure Temperature (K) Beech Black pine Hazelwood Poplar
313 1311 1323 1303 1281
178 Heat capacity measurements were performed through a C80 314 1315 1324 1305 1289
179 Calvet calorimeter. Stainless steel standard vessels with a volume 315 1318 1329 1308 1290
316 1326 1333 1311 1299
180 of 9 cm3 and intermediary bottom have been used. Sample mass 317 1330 1340 1315 1296
181 loads were in the range between 1 and about 2 g. The program 318 1333 1343 1317 1296
182 temperature was as follows: 319 1337 1347 1324 1303
320 1341 1351 1326 1300
321 1345 1357 1332 1311
183  Stabilisation of the heat flow signal during 90 min.
322 1349 1360 1334 1314
184  Isothermal step of 90 min at 298 K. 323 1354 1365 1340 1315
185  Heating from 298 K to 383 K at 0.2 K min1. 324 1359 1368 1343 1322
186  Isothermal step of 90 min at 383 K. 325 1365 1374 1349 1323
187 326 1370 1379 1350 1328
327 1372 1383 1355 1335
188 Two or more runs were carried out on each sample. The rela-
328 1377 1388 1360 1338
189 tive difference between replicates in the range 313–353 K was 329 1379 1389 1362 1340
190 found to be between 1% and 6%. This difference is higher than 330 1386 1397 1368 1350
191 the measurement uncertainty of the apparatus, which was deter- 331 1390 1401 1370 1346
332 1396 1406 1374 1348
192 mined on sapphire and was found to lie between 0.2% and 1% in
333 1403 1411 1381 1356
193 the range 313–353 K. This difference must be due to the unavoid- 334 1406 1416 1384 1361
194 able sample heterogeneity and to the possible slight adsorption of 335 1408 1417 1390 1359
195 water coming from the air captured in the vessel during sample 336 1411 1424 1391 1367
196 preparation. 337 1412 1429 1396 1370
338 1421 1434 1403 1376
339 1425 1436 1406 1386
340 1430 1440 1412 1383
197 3. Results and discussion
341 1431 1444 1418 1389
342 1437 1450 1420 1391
198 Results are proposed in the form of graphs to give the paper a 343 1442 1458 1430 1402
199 visual aspect. However, the reader can also find the full set of data 344 1446 1457 1429 1402
200 in the form of tables in appendix. 345 1450 1462 1437 1406
346 1456 1466 1439 1412
347 1460 1472 1442 1415
201 3.1. Heat capacity measurement on biomasses 348 1465 1476 1446 1423
349 1470 1481 1456 1428
350 1474 1485 1458 1436
202 As can be seen in Fig. 1, the heat capacity of the different bio- 351 1475 1490 1463 1431
203 masses varies from 1300 to 2000 J kg1 K1 in the temperature 352 1483 1492 1470 1435
204 range 313–353 K. These values are in the range of values com- 353 1487 1498 1473 1446
205 monly found on biomass in literature. Very good agreement was
206 found with previous measurements on cellulose [10].
207 As expected, linear increase can be observed with temperature
Finally, as shown in Fig. 2, the influence of the sample form ap- 235
208 for all biomasses in the range studied with coefficients of determi-
pears as very limited under the conditions studied. Indeed, for the 236
209 nation R2 higher than 0.99. The slope of heat capacity versus tem-
four wood species tested, the relative difference of heat capacity 237
210 perature varies according to samples. As a consequence, the
between samples in block and in powder is of about 2%, which is 238
211 relative difference between samples does not remain constant with
close to the experimental uncertainty. 239
212 temperature. It tends to increase from about 10% at 313 K to 20% at
213 353 K. This relative difference between samples is significant as it
214 is higher than the difference between replicates. Whatever the bio- 3.2. Heat capacity measurement on chars 240

215 mass type, the evolution of heat capacity with temperature is sig-
216 nificant, with an increase up to 20% between 313 K and 353 K. The study on chars was carried out only on chars from one bio- 241

217 Hence, this evolution should be taken into account in gasification mass, namely beech, in order to limit the number of tests. How- 242

218 models to describe heat transfers in an accurate way. The heat ever, as all biomasses tend to exhibit similar trends regarding 243

219 capacity of all samples tested lies between the SRF poplar heat heat capacity, one can reasonably think that it must be possible 244

220 capacity and the beech heat capacity, which are described respec- to extrapolate, at least qualitatively, the results obtained on chars 245

221 tively by Eqs. (1) and (2) between 313 and 353 K. In average, bio- from one specific biomass to chars from other biomass types. 246

222 mass heat capacity follows the Eq. (3). Values of about 1000 J kg1 K1 were measured, that are in the 247
223 same order of magnitude as typical values found in literature 248
225 Cp ¼ 8:558T  1197 ð1Þ [16,26,30]. 249

226
As can be seen in Fig. 3, the heat capacity undergoes a signifi- 250
228 Cp ¼ 3:783T þ 111 ð2Þ cant linear increase from 313 to 353 K using the following 251
equation: 252
229 253
231 Cp ¼ 5:340T  299 ð3Þ Cp ¼ 1:400T þ 688 ð4Þ 255

232 It can be noted that there is no visible link between heat capac- An unexpected decrease can be seen from 353 K in Fig. 3. Such a 256
233 ity and species, as shown for example by the different behaviours decrease is in agreement with the unexplained decrease observed 257
234 of the two samples of SRC of poplar. from 353 K on dry coal by Vargha-Butler et al. [22]. In the present 258

Please cite this article in press as: Dupont C et al. Heat capacity measurements of various biomass types and pyrolysis residues. Fuel (2013), http://
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6 C. Dupont et al. / Fuel xxx (2013) xxx–xxx

Table 3
Heat capacity of char obtained at 773 K.

Temperature T (K) Heat capacity Cp (J kg1 K1) T Cp T Cp T Cp T Cp T Cp T Cp

313 1127 353 1190 393 315 433 2431 473 801 513 1326 553 1497
314 1129 354 1188 394 260 434 2455 474 732 514 1338 554 1492
315 1131 355 1186 395 203 435 2463 475 656 515 1348 555 1497
316 1134 356 1181 396 143 436 2477 476 580 516 1349 556 1478
317 1134 357 1177 397 83 437 2477 477 506 517 1359 557 1481
318 1139 358 1169 398 19 438 2487 478 428 518 1366 558 1482
319 1143 359 1166 399 47 439 2479 479 351 519 1376 559 1477
320 1144 360 1161 400 115 440 2475 480 272 520 1378 560 1477
321 1148 361 1152 401 185 441 2464 481 200 521 1383 561 1480
322 1151 362 1145 402 257 442 2452 482 129 522 1397 562 1481
323 1156 363 1136 403 331 443 2433 483 54 523 1396 563 1480
324 1158 364 1128 404 406 444 2405 484 20 524 1405 564 1483
325 1159 365 1116 405 485 445 2381 485 91 525 1413 565 1485
326 1165 366 1108 406 561 446 2349 486 164 526 1421 566 1478
327 1165 367 1096 407 642 447 2321 487 236 527 1425 567 1482
328 1168 368 1082 408 724 448 2284 488 311 528 1434
329 1172 369 1069 409 807 449 2247 489 383 529 1437
330 1174 370 1055 410 891 450 2212 490 455 530 1438
331 1179 371 1039 411 975 451 2163 491 524 531 1445
332 1178 372 1023 412 1061 452 2115 492 594 532 1453
333 1184 373 1004 413 1145 453 2059 493 663 533 1457
334 1184 374 984 414 1228 454 1993 494 732 534 1461
335 1185 375 965 415 1310 455 1941 495 799 535 1466
336 1189 376 942 416 1397 456 1904 496 858 536 1471
337 1190 377 919 417 1484 457 1851 497 915 537 1473
338 1193 378 896 418 1567 458 1797 498 964 538 1474
339 1191 379 868 419 1645 459 1732 499 1008 539 1477
340 1195 380 840 420 1726 460 1675 500 1050 540 1486
341 1196 381 812 421 1804 461 1614 501 1089 541 1490
342 1195 382 781 422 1874 462 1551 502 1128 542 1491
343 1198 383 748 423 1942 463 1484 503 1154 543 1493
344 1198 384 713 424 2016 464 1420 504 1187 544 1498
345 1198 385 678 425 2077 465 1353 505 1214 545 1498
346 1197 386 639 426 2138 466 1284 506 1236 546 1500
347 1198 387 598 427 2191 467 1221 507 1254 547 1502
348 1197 388 556 428 2240 468 1150 508 1271 548 1500
349 1195 389 515 429 2285 469 1083 509 1284 549 1503
350 1193 390 467 430 2333 470 1014 510 1299 550 1505
351 1194 391 418 431 2365 471 943 511 1307 551 1503
352 1193 392 368 432 2405 472 873 512 1318 552 1500

259 study this decrease tends to become sharper until 443 K. Then a predict char heat capacity whatever the pyrolysis temperature. 286
260 symmetrical increase can be seen until 513 K. From this tempera- However, the decrease of heat capacity observed from 353 K with 287
261 ture, the heat capacity seems to increase linearly again and to come chars produced at 1073 K occurs at lower temperature and seems 288
262 back to the linear correlation valid up to 353 K. From this observa- to be more marked for chars formed at 773 K. The onset of the exo- 289
263 tion it may be assumed that an exothermal chemical phenomenon thermal reaction may be displaced to lower temperatures due to 290
264 occurs in char between 353 K and 513 K. The heat reaction was the different chemical composition of the solid. It contains more 291
265 found to be of 279 J kg1. O and H [29] and might be more subject to recombination. 292
266 To better understand the origin of this phenomenon, thermo- As shown in Fig. 3, literature correlations used in thermal con- 293
267 gravimetric analysis was carried out on char under the same ther- version models and obtained by Gupta are in the same order of 294
268 mal program. No mass loss could be observed. Hence, this reaction magnitude as the linear correlation of the present study. There is 295
269 does not seem to be linked with the release of volatiles from the a very good agreement between 313 K and 353 K with those men- 296
270 solid. As a confirmation, char leaching was also performed through tioned by Razjnevic [18] and by Koufopanos et al. [31] with average 297
271 two methods in order to remove tars potentially condensed in char relative differences of 2% and 4% respectively. The agreement is not 298
272 during pyrolysis experiment. In the first method char was pro- so satisfactory with the correlation proposed by Gupta et al. [16] 299
273 duced with a residence time longer than usual of 40 min. The sec- on biomass chars, with a difference of 34%. Such difference is not 300
274 ond method consisted in washing the char with isopropanol after very surprising as the conditions of char production and the bio- 301
275 grinding. As can be seen in Fig. 5, where reference char is reported mass type were different from those of the present study. Note also 302
276 for comparison, there was no clear influence of leaching on the re- that the heat capacity measured in the present study seems to be 303
277 sults. This tends to confirm that the phenomenon is not linked with slightly less impacted by temperature than what was predicted 304
278 tars condensed in char. The reaction might then be attributed to by the other correlations. 305
279 recombination of carbon, hydrogen and oxygen inside the solid it-
280 self. This result shows that char is not a stable material under the 4. Conclusion 306
281 conditions studied. Thus, this highlights the difficulty of character-
282 ising this material and then modelling its behaviour. Heat capacity was measured versus temperature on various 307
283 As shown in Fig. 4, the temperature at which chars were pyrol- biomass types and pyrolysis chars produced under conditions rep- 308
284 ysed does not seem to have any clear influence up to 333 K. Hence, resentative of industrial reactors in order to complete the limited 309
285 up to this temperature, one correlation appears to be sufficient to set of data available for biomass thermal conversion modelling. 310

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Table 4 not major but significant with relative difference up to 20%. Hence, 314
Heat capacity of char produced at 1073 K and of chars post-treate. as a rough approximation, one average linear correlation may be 315
Heat capacity (J kg1 K1) sufficient for describing heat capacities of all biomasses in thermal 316

Temperature Char Char washed with Char produced after long conversion models. However, for a more accurate description of 317
(K) 1073 K isopropanol residence time heat transfers, one dedicated linear correlation might be used for 318

313 1130 1106 1086

each biomass. Regarding chars, linear increase could be observed 319
314 1134 1111 1090 up to around 353 K and from 513 K. Between these two values, 320
315 1142 1118 1096 an exothermal phenomenon of recombination seemed to occur in- 321
316 1152 1126 1103 side the solid, showing the chemical instability of the chars pro- 322
317 1162 1138 1114
duced. The pyrolysis temperature did not seem to have any 323
318 1170 1144 1122
319 1179 1151 1128 strong influence, except on the onset of the exothermal phenome- 324
320 1186 1158 1133 non. Hence, as a rough approximation in thermal conversion mod- 325
321 1193 1164 1139 els, one linear correlation may be sufficient to predict heat capacity 326
322 1196 1170 1142
up to 570 K whatever the pyrolysis temperature. 327
323 1210 1179 1154
324 1224 1187 1165
325 1226 1194 1167 Acknowledgements 328
326 1234 1203 1172
327 1240 1205 1176
328 1247 1213 1179 The authors would like to thank gratefully FCBA, GIE-Arvalis 329
329 1251 1217 1189 ONIDOL, RAGT and SFB for the supply of biomass samples. 330
330 1258 1225 1192
331 1266 1232 1200
332 1276 1241 1207 Appendix A. Data tables 331
333 1288 1247 1217
334 1286 1253 1218
See Tables 1–4. 332
335 1291 1257 1221
336 1293 1260 1222
337 1299 1265 1226 References 333
338 1300 1269 1230
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