Product Distribution fromPyrolysis of Wood and Agricultural

Residues
Colomba Di Blasi,* Gabriella Signorelli, Carlo Di Russo, and Gennaro Rea
Dipartimento di I ngegneria Chimica, Universita degli Studi di Napoli Federico I I , P.leV. Tecchio,
80125 Napoli, I taly
The pyrol ysi s characteri sti cs of agri cul tural resi dues (wheat straw, ol i ve husks, grape resi dues,
and ri ce husks) and wood chi ps have been i nvesti gated on a bench scal e. The experi mental system
establ i shes the condi ti ons encountered by a thi n (4 10
-2
m di ameter) packed bed of bi omass
parti cl es suddenl y exposed i n a hi gh-temperature envi ronment, si mul ated by a radi ant furnace.
Product yi el ds (gases, l i qui ds, and char) and gas composi ti on, measured for surface bed
temperatures i n the range 650-1000 K, reproduce trends al ready observed for wood. However,
di fferences are quanti tati vel y l arge. Pyrol ysi s of agri cul tural resi dues i s al ways associ ated wi th
much hi gher sol i d yi el ds (up to a factor of 2) and l ower l i qui d yi el ds. Di fferences are l ower for
the total gas, and approxi mate rel ati onshi ps exi st among the rati os of the mai n gas speci es
yi el ds, i ndi cati ng comparabl e acti vati on energi es for the correspondi ng apparent ki neti cs of
formati on. However, whi l e the rati os are about the same for wood chi ps, ri ce husks, and straw,
much l ower val ues are shown by ol i ve and grape resi dues. Large di fferences have al so been
found i n the average val ues of the speci fi c devol ati l i zati on rates. The fastest (up to factors of
about 1.5 wi th respect to wood) have been observed for wheat straw and the sl owest (up to
factors of 2) for grape resi dues.
Introduction
Pyrol ysi s and gasi fi cati on are thermochemi cal conver-
si on routes to recover energy from bi omass and waste
fuel s. Pyrol ysi s i s not onl y an i ndependent conversi on
technol ogy but al so part of the gasi fi cati on process,
whi ch can be broadl y separated i nto two mai n stages,
sol i d devol ati l i zati on (pyrol ysi s) and char conversi on
(combusti on and gasi fi cati on). Gi ven a certai n bi omass,
the rati o between the yi el ds of sol i d char and vol ati l e
pyrol ysi s products depends on temperature, pressure,
and heati ng rate. Char reacti vi ty i n the second stage i s
dependent upon the formati on condi ti ons (essenti al l y
temperature and heati ng rate) and the amount and
composi ti on of the i norgani c content. I n addi ti on, the
type of bi omass (chemi cal composi ti on and physi cal
properti es) al so l argel y affects both bi omass devol ati l -
i zati on and char conversi on.
Gi ven the key rol e pl ayed by the devol ati l i zati on stage
i n the conversi on processes, numerous studi es have been
carri ed out i n order to determi ne product di stri buti on
and gas, and someti mes l i qui d, composi ti on. Extensi ve
i nformati on i s avai l abl e on product di stri buti on from
wood (popl ar, beech, oak, mapl e, etc.) for fl ash pyrol ysi s
carri ed out through fl ui d-bed reactors
1-5
or other de-
vi ces
6
and conventi onal pyrol ysi s i n rel ati on to si ngl e
(l arge) parti cl es/sampl es
7-9
and packed beds.
10
The
pyrol ysi s of some agri cul tural resi dues has al so been
exami ned under di fferent experi mental condi ti ons.
11-14
However, apart from the l i mi ted vari ety of resi dues
exami ned, for the i nvesti gati ons carri ed through packed
beds,
12,14
the temperature range i s very narrow or the
thermal condi ti ons are not exactl y known. Furthermore,
the di fferent experi mental condi ti ons do not al l ow the
resul ts to be compared i n rel ati on to both di fferent
agri cul tural resi dues and wood. Therefore, basi c i nfor-
mati on i s not currentl y avai l abl e for the understandi ng
of the compl ex i nteracti on between chemi stry and
transport phenomena i n chemi cal reactors and thus for
the sel ecti on of the most appropri ate fuel s and the
opti mal condi ti ons for pyrol ysi s/gasi fi cati on. Devol ati l -
i zati on characteri sti cs are al so needed for the formul a-
ti on of rel i abl e computer model s of the gasi fi cati on
process. I ndeed, both the temperature dependence of
pyrol ysi s product cl asses (char, gases, and l i qui ds), due
to reacti on sel ecti vi ty,
15,16
and the gas composi ti on
shoul d be taken i nto account. The use of consi stent data,
val i d over wi de temperature ranges and for di fferent
fuel s, i s parti cul arl y i mportant because, contrary to coal
gasi fi cati on where the devol ati l i zati on stage contri butes
onl y for 20-40% of the total vol ati l es rel eased, i n
bi omass gasi fi cati on thi s contri buti on i ncreases up to
60-80%. On the other hand, the pyrol ysi s characteri s-
ti cs i nfl uence the predi cti ons of both the producer gas
qual i ty and acti vi ty of gasi fi cati on reacti ons, through
hydrogen, carbon di oxi de, and steam concentrati ons.
I n thi s study, the devol ati l i zati on behavi or of several
agri cul tural resi dues typi cal of Medi terranean countri es,
such as ol i ve husks, grape resi dues, wheat straw, and
ri ce husks,
17
i s i nvesti gated and compari sons are made
wi th (fi r) wood chi ps. The external heati ng condi ti ons
are the same for al l bi omasses and correspond to those
of a rel ati vel y thi n packed bed of parti cl es suddenl y
exposed i n a hi gh-temperature envi ronment, wi th the
purpose of reproduci ng the devol ati l i zati on stage of
fi xed-bed countercurrent and concurrent reactors (py-
rol yzers and gasi fi ers). The heati ng rates are those of
conventi onal pyrol ysi s because of the coarse parti cl es
usual l y requi red and/or the i ndi rect heati ng modal i ti es
appl i ed. For gasi fi ers, the heati ng rates are sl ower for
the countercurrent confi gurati on, where, gi ven the
strati fi cati on of the di fferent processes al ong the reactor
* Correspondi ng author. Tel : 39-081-7682232. Fax: 39-081-
2391800. E-mai l : di bl asi @uni na.i t.
2216 I nd. Eng. Chem. Res. 1999, 38, 2216-2224
10.1021/i e980711u CCC: $18.00 1999 Ameri can Chemi cal Soci ety
Publ i shed on Web 05/13/1999
axi s, the secti ons of combusti on (hi gh temperatures) and
dryi ng/devol ati l i zati on are l ocated at the two extremes.
On the contrary, i n concurrent gasi fi ers, devol ati l i zati on
and combusti on occur roughl y at the same l ocati on;
therefore, temperatures and heati ng rates are hi gher.
The focus of the work i s mai nl y on the temperature
dependence of the product yi el ds and gas composi ti on.
The characteri zati on of l i qui d products, whi ch i s i m-
portant for thei r successi ve uti l i zati on (pyrol ysi s) or for
the desi gn of effecti ve gas cl eani ng procedures (gasi fi ca-
ti on), i s currentl y underway.
Experimental Section
Pyrol ysi s of packed bi omass beds has been carri ed out
through a bench-scal e pl ant (Fi gure 1). Bi omass par-
ti cl es are packed i n a stai nl ess steel mesh, cyl i ndri cal -
shaped hol der, so that the desi red bed densi ty can be
achi eved. The bed i s verti cal l y posi ti oned i n the uni -
forml y heated zone of a radi ant furnace. Thi s, manu-
factured by Research I nc., presents four tubul ar quartz
i nfrared l amps wi th a tungsten wi re fi l ament that emi ts
radi ant energy i n proporti on to the appl i ed vol tage.
El l i pti cal , pol i shed-al umi num, water-cool ed refl ectors
focus the hi gh-densi ty i nfrared energy, emi tted by
l amps, onto a cyl i ndri cal -shaped target area (di ameter
6.5 x 10
-2
m). To avoi d i nteracti on between the vol ati l e
pyrol ysi s products and the l amps, a quartz tube (I D 6 x
10
-2
m and l ength 22 x 10
-2
m), transparent to i nfrared
radi ati on, i s l ocated i nsi de the furnace and used as a
reacti on chamber. A ni trogen fl ow i s appl i ed at the top
of the quartz tube i n order to reduce the extra-bed
resi dence ti me of vol ati l e pyrol ysi s products and to
establ i sh the proper reacti on envi ronment.
For each chosen radi ati on i ntensi ty, steady temper-
atures of the radi ant heater are achi eved wi thi n a coupl e
of mi nutes, but, gi ven the bed depth, pyrol ysi s takes
pl ace under heat-transfer control . For each test, a fi xed
amount of bi omass parti cl es i s uni forml y di stri buted
i nsi de the sampl e hol der and posi ti oned i n the constant
radi ati on zone of the reactor (bed l ength 5 10
-2
m). A
ni trogen fl ow i s establ i shed and mai ntai ned for 30
mi n i n order to remove the ai r from the reacti on
chamber, and then the test begi ns. Temperatures al ong
the bed radi us at the medi an secti on are conti nuousl y
moni tored (0.5 mm bead chromel -al umel thermo-
coupl es), whi l e the composi ti on of the gas i s anal yzed,
at sel ected ti mes. Thi s i s carri ed out through a gas chro-
matograph (Perki n-El mer Auto-System XL), equi pped
wi th a thermal conducti vi ty detector (TCD) and a
packed col umn (Supel co 60-80 Carboxen 1000, 15 ft)
wi th hel i um as the carri er gas. The oven program i s as
fol l ows: an i sothermal stage of 403 K for 3.2 mi n
fol l owed by a rate of 25 K/mi n up to 513 K (i njector
temperature 423 K). An external standard method i s
appl i ed wi th two-poi nt cal i brati on of a mi xture of seven
gaseous pyrol ysi s products.
Steady gl obal mass bal ances over the system al l ow
the exi t vol umetri c fl ow rate and mass of each gaseous
speci es to be determi ned, gi ven the i nl et condi ti ons
(ni trogen fl ow rate, temperature, and pressure) and the
measurement of speci es mol ar fracti ons at the exi t
(assumed to be at ambi ent pressure and temperature).
More preci sel y, the mass bal ance on ni trogen i s used to
eval uate the vol umetri c fl ow rate at the exi t, whereas
the other mass bal ances (upon i ntegrati on) gi ve the gas
speci es mass as a functi on of ti me (i n parti cul ar, al so
the fi nal total mass i ndi cated as gas). After compl ete
conversi on, the power i s turned off and the sol i d resi dual
i s l eft under a ni trogen fl ow unti l i ts temperature l owers
to ambi ent val ues. Thi s resi dual i s i ndi cated as char.
The l i qui ds are col l ected through a condenser trai n,
consi sti ng of water-cool ed traps, cotton wool demi sters,
and a si l i ca gel bed. Al l of the condensabl e products
col l ected and wei ghed from the traps (organi c com-
pounds and product water formed) are i ndi cated as
l i qui ds.
Results
Pyrol ysi s tests, through the experi mental system
previ ousl y descri bed, have been carri ed out for (fi r) wood
chi ps, ol i ve husks, grape resi dues, ri ce husks, and wheat
straw. The el emental and chemi cal anal yses of the
feedstocks are reported i n Tabl e 1. For the determi na-
ti on of C, H, and N (CHNO-Rapi d, Heraeus-Foss El -
ementar GmbH anal yzer) the sampl e i s burned i n pure
oxygen at 1223 K. The carri er gas (hel i um) and the
combusti on products, after compl ete oxi dati on, are
passed over heated copper to remove excess oxygen and
to reduce NO
2
to N
2
. Gases are then passed through a
heated chromatographi c col umn to separate and el ute
N
2
, CO
2
, and H
2
O. Concentrati on of each el uted gas i s
measured by TCD. The same anal yzer i s used for O. The
sampl e i s pyrol yzed i n the presence of pure carbon at
1423 K and hel i um. Al l of the oxygen i s then present i n
the form of CO. The gaseous pyrol ysi s products are
passed over heated copper and copper oxi de to remove
sul fur contai ni ng gas and to oxi di ze CO to CO
2
, whi ch
i s then measured by TCD. For sul fur determi nati on
(Sul mhomat-Wosthoff anal yzer) the sampl e i s burned
i n an oxygen stream at 1573 K. The reacti on gases are
Figure1. Schemati c representati on of the bench-scal e pyrol ysi s
system: (1) radi ant heater, (2) quartz reactor, (3) sampl e hol der,
(4) fl owmeter, (5) data acqui si ti on, (6) condensers, (7) fi l ters.
Table 1. Elemental Analysis and Chemical Composition of Wood Chips and Agricultural Residues
bi omass C H N S extracti ves (%) hemi cel l ul ose (%) cel l ul ose (%) l i gni n (%) ash (%)
wood chi ps 46.4 5.9 0.085 0 4.6 31.8 31.8 19.0 0.45
wheat straw 43.6 6.2 0.30 0.08 7.4 27.3 27.3 16.4 5.5
ol i ve husks 50.9 6.3 1.37 0.03 8.7 18.5 18.5 28.0 2.8
grape resi dues 47.9 6.2 2.11 0.09 15.6 17.2 17.2 30.4 5.1
ri ce husks 40.3 5.7 0.30 0.03 8.0 24.3 24.3 14.3 15.3
I nd. Eng. Chem. Res., Vol . 38, No. 6, 1999 2217
puri fi ed, and the sul fur di oxi de i s absorbed i n an
el ectri cal conducti vi ty cel l , whi ch contai ns di l uted sul -
furi c aci d and hydrogen peroxi de. The SO
2
reacts to form
sul furi c aci d and causes changes i n the thermal con-
ducti vi ty (a l i near functi on of the absorbed sul fur
di oxi de).
Extracti ves and hol ocel l ul ose are determi ned by
means of the extractor Soxhtec HT2. Acetone (60 mL)
i s used as the sol vent for extracti ves (1 g of bi omass)
wi th resi dence ti mes for the boi l i ng and ri si ng stages
equal to 90 and 20 mi n, respecti vel y (temperature equal
to 363 K). Hol ocel l ul ose (extracti ve-free basi s) i s deter-
mi ned accordi ng to the Kurschener-Hoffer method. A
sol uti on of 40 mL of ethyl al cohol and 10 mL of ni tri c
aci d i s used as the sol vent for 1 g of bi omass wi th
resi dence ti mes of 3 h for the boi l i ng stage and 20 mi n
for the ri si ng stage (sol vent temperature equal to 363
K). Hemi cel l ul ose i s extracted from hol ocel l ul ose by
means of a sodi um i drate sol uti on (1% mol ) wi th a
temperature of 353 K and the same resi dence ti mes as
those for hol ocel l ul ose extracti on. Fi l trati on, washi ng
(hot water, a sol uti on of aceti c aci d of 10% mol , and
agai n water), and dryi ng of the resi due (cel l ul ose) al l ow
the hemi cel l ul ose fracti on to be determi ned by di ffer-
ence. Li gni n i s determi ned accordi ng to the Kl ason
method.
Tabl e 2 reports the mai n physi cal characteri sti cs of
the bi omasses, that i s, densi ty of the bed, parti cl e si ze,
i ni ti al moi sture content (dry basi s), and i ni ti al sampl e
mass. The woody bi omass (fi r) i s a forestry resi due,
whi ch al so retai ns i ts bark and has been cut i n more or
l ess uni form pi eces of typi cal si ze (thi ckness) of 1-3 mm.
No pretreatment i s appl i ed before pyrol ysi s of agri cul -
tural resi dues, so that si gni fi cant di fferences are seen
i n the bed characteri sti cs.
Tests have been carri ed out by varyi ng the i ntensi ty
of the appl i ed radi ati ve heat fl ux. As pyrol ysi s takes
pl ace i n the presence of spati al (radi us) gradi ents, the
steady temperature attai ned by the char bed, about 2
mm bel ow the heat exposed surface, T
b
, i s taken as the
characteri sti c process temperature. For the range of
condi ti ons i nvesti gated, thi s vari es from about 650 to
1000 K. Though the external heati ng condi ti ons are the
same for al l bi omasses, the di fferent chemi cal and
physi cal properti es of the bed gi ve ri se to di fferent
heati ng rates, as expected i n practi cal appl i cati ons.
Therefore, the pyrol ysi s characteri sti cs (conversi on
ti mes, product yi el ds, and gas composi ti on) determi ned
here refl ect both the di fferences i n the bi omass i ntri nsi c
reacti vi ti es and the di fferent thermal condi ti ons under-
gone duri ng pyrol ysi s.
Prel i mi nary tests have al so been made to eval uate
the i nfl uence of the ni trogen fl ow rate, bed depth, and
parti cl e si ze on the process characteri sti cs. These effects
have been i nvesti gated for wood chi ps and hi gh tem-
perature (T
b
) 800 K), when both pri mary and second-
ary pyrol ysi s reacti ons take pl ace (mass cl osure com-
pri sed betwen 95 and 99%). For a bed di ameter of 4
10
-2
m, the ni trogen fl ow rate has been vari ed from 1
10
-3
to 6 10
-3
m
3
/mi n, correspondi ng to a nomi nal
gas vel oci ty (ambi ent condi ti ons and cross secti on of the
quartz tube) i n the range 0.0042-0.025 m/s. Char yi el ds
are i ndependent of thi s parameter, whereas vari ati ons
i n the vol ati l e yi el ds are al so smal l for ni trogen fl ow
rates of 1.5 10
-3
m
3
/mi n and above. At l ower val ues,
the l i qui d yi el ds sl i ghtl y i ncrease (correspondi ngl y gas
yi el ds decrease), as a consequence of the acti vi ty of
secondary tar cracki ng reacti ons. Maxi mum vari ati ons
are, however, smal l and correspond to about 5%(l i qui ds)
for the l owest ni trogen fl ow rate. Ni trogen fl ow rates
bel ow 1 10
-3
m
3
/mi n have not been consi dered
because, at these l ow gas fl ow rates, the l i qui d col l ecti on
trai n i ntroduces a si gni fi cant del ay i n the gas col l ecti on
and anal ysi s, so that temperature and speci es evol uti on
become two separate processes. Al l of the tests have
been made for a ni trogen fl ow rate equal to 6 10
-3
m
3
/mi n (nomi nal gas vel oci ty of 0.025 m/s and nomi nal
resi dence ti mes of vol ati l es al ong the heated secti on of
about 3 s). I t shoul d be noted that the true resi dence
ti mes are much shorter, gi ven the gas expansi on at the
pyrol ysi s temperatures and the presence of the sampl e,
whi ch reduces the voi d secti on of the quartz tube.
A bed di ameter of 4 10
-2
m i s chosen for al l of the
tests, but the resul ts are not trul y i ndependent of thi s
parameter. Char yi el ds i ncrease by about 6% when the
bed di ameter i s vari ed from 2 to 4 10
-2
m, whi l e the
gas yi el ds decrease by about 15% (wi th an i ncrease i n
the l i qui ds), as a consequence of pri mary reacti ons
taki ng pl ace at l ower temperatures and, probabl y, of the
shorter vol ati l e resi dence ti mes and reduced acti vi ty of
secondary reacti ons. Fi nal l y, i n agreement wi th previ -
ous studi es (for i nstance, ref 10), i t has been found that,
for a chosen bed densi ty, parti cl e si zes do not i nfl uence
the pyrol ysi s characteri sti cs for the range of val ues used
i n thi s study (0.5-3 mm), i ndi cati ng that the heat-
transfer resi stance across the bed predomi nates over
that across the parti cl es. I ndeed, the bed radi us i s from
1 to 2 orders of magni tude l arger than the parti cl e si zes.
Comparison with Literature Data. I n order to
compare the experi mental system and procedure chosen
i n thi s study wi th condi ti ons previ ousl y empl oyed i n the
l i terature, product yi el ds (percent of the i ni ti al moi sture-
free (mf) sol i d mass) measured for wood chi ps have been
reported i n Fi gure 2A,B as functi ons of temperature
together wi th other data obtai ned wi th fl ui d-bed
3
(mapl e
wood parti cl e 0.6 mm thi ck, vol ati l e resi dence ti mes of
about 0.5 s) and packed-bed
10
(8 g of hol m-oak parti cl es
0.4-2 mm thi ck) reactors. I n pri nci pl e, di fferences can
be due to reactor confi gurati ons (external heat-transfer
rates), operati ng condi ti ons (vol ati l e resi dence ti mes and
parti cl e characteri sti cs), and wood type. However, i t i s
bel i eved that the fi rst two factors are predomi nant, as
vari ati ons i n the wood chemi cal composi ti on cannot
account for di fferences as l arge as those shown i n Fi gure
2A,B.
As the temperature i ncreases, the fi nal sol i d resi dual
i ni ti al l y decreases, as a resul t of the competi ti on be-
tween charri ng and devol ati l i zati on reacti ons, whi ch
become successi vel y more favored. Then, at hi gh tem-
peratures, the char yi el d tends to become constant,
because the vari ati on i n the actual wood degradati on
temperature (i n rel ati on to the external heati ng tem-
perature) becomes very l ow, because of the narrow range
Table 2. Characteristics of the Packed Beds for Wood
Chips and Agricultural Residues (Moisture Content on a
Dry Basis)
bi omass
bul k
densi ty
(kg/m
3
)
%
moi sture
(kg/kg)
parti cl e
si ze
(mm)
parti cl e
si ze
(mm)
mi
(kg)
wood chi ps 270 8 1-3 1-3 0.017
wheat straw 160 7 0.5-1 0.5-1 0.010
ol i ve husks 515 8.5 0.5-3 0.5-3 0.032
grape resi dues 325 9 1-3 1-3 0.020
ri ce husks 150 7 0.2-1 0.2-1 0.009
2218 I nd. Eng. Chem. Res., Vol . 38, No. 6, 1999
of temperatures characteri sti c of bi omass pyrol ysi s and
heat-transfer resi stance through the packed bed (thi s
study and ref 10) or the parti cl e.
3
The char yi el ds are
about the same for both the two packed-bed confi gura-
ti ons (sl i ghtl y l arger i n thi s study, presumabl y as a
resul t of a thi cker bed and/or the presence of bark)
11
whi l e, for temperatures above 700 K, they are much
l ower for the thi n parti cl es (600 m) pyrol yzed i n a fl ui d-
bed reactor. Al so, i t i s worth noti ng that, at l ow
temperatures, when chemi cal reacti on i s control l i ng, the
char yi el ds tend to become i ndependent of the conver-
si on uni t.
As expected, l i qui d yi el ds are maxi mi zed under fl ash
pyrol ysi s condi ti ons
3
and, i n al l cases, they present a
maxi mum as a functi on of temperature. Thi s resul ts
from both pri mary vol ati l e formati on and secondary
degradati on of tar vapors becomi ng successi vel y more
favored by hi gher temperatures.
15
However, the rates
of i ncrease (l ow temperature) and decrease (hi gh tem-
perature) are much l arger for fl ui d-bed conversi on,
because the di stri buti on of vol ati l e products i s mai nl y
di ctated by extraparti cl e secondary reacti ons, whi ch
occur i n a nearl y i sothermal envi ronment. On the
contrary, for (l aboratory) packed-bed reactors, secondary
reacti ons take pl ace both across the bed (i ntraparti cl e
acti vi ty may al so be si gni fi cant for l arge parti cl e si zes)
and i n the heated extra-bed envi ronment. However,
gi ven the l arger vol ume and the hi gher temperature,
the extra-bed zone i s the mai n reason for tar cracki ng,
unl ess the resi dence ti mes of vol ati l es are made short
through forced (i nert) convecti on and a rel ati vel y smal l
heated zone. I t i s pl ausi bl e that the extra-bed resi dence
ti mes accompl i shed i n the packed-bed system of thi s
study are much shorter than those of ref 10. Conse-
quentl y, the correspondi ng l i qui d yi el ds are hi gher (and
gas yi el ds l ower). Moreover, at very hi gh temperatures
(above 950 K) they are al so hi gher than those of fl ui d-
bed conversi on. I ndeed, apart from the short extra-bed
vapor resi dence ti mes, the exi stence of radi al gradi ents
across the bed gi ves ri se to temperatures on the average
l ower; hence, secondary reacti ons occur at a l ess extent.
ProcessDynamics. The macroscopi c behavi or of the
di fferent bi omasses whi l e degradi ng i s qual i tati vel y
si mi l ar, wi th quanti tati ve di fferences i n the heati ng
ti mes caused by the di fferent bed properti es (i n par-
ti cul ar, densi ty). Fi gure 3 shows the radi al temperature
profi l es at several ti mes, for a radi ati on i ntensi ty
correspondi ng to T
b
) 900 K, as measured for wheat
straw. For al l radi ati on i ntensi ti es, si gni fi cant spati al
gradi ents are observed, so that the temperature i n-
creases more sl owl y as the di stance from the heated
surface i ncreases, but they become successi vel y hi gher
as more severe heati ng condi ti ons are establ i shed.
Moi sture evaporati on i s responsi bl e for the fl at profi l es
observed cl ose to the sampl e centerl i ne for temperatures
bel ow the normal boi l i ng poi nt of water, whi l e gas
rel ease curves i ndi cate that devol ati l i zati on begi ns for
temperatures above 550-575 K. The temperature pro-
fi l es show that i ni ti al l y onl y a thi n l ayer beyond the
surface i s heated and undergoes a degradati on process.
Successi vel y, the thermal (and reacti ve) front propa-
gates al ong the bed radi us, wi th an i ncreasi ng thi ckness,
unti l degradati on i s compl ete.
For T
b
> 750 K, the temperature conti nuousl y i n-
creases, attai ni ng a maxi mum at the compl eti on of the
process, as a consequence of i nert char heati ng. For
l ower T
b
, temperatures sl i ghtl y hi gher than the fi nal
steady val ue are detected i n the l ast part of the
degradati on process. Maxi mum temperature di fferences
are about 15-50 K for the di fferent bi omasses and are
probabl y associ ated wi th exothermi c l i gni n degrada-
ti on.
18-20
Fi nal l y, temperature profi l es show maxi mum
val ues si gni fi cantl y dependent on the external heati ng
condi ti ons. However, they are attai ned onl y after sol i d
devol ati l i zati on, whi ch takes pl ace for comparabl e ther-
mal condi ti ons al ong the whol e bed radi us, as the
temperatures typi cal of bi omass degradati on are rather
l ow. Thus, for hi gh furnace temperatures, pri mary
degradati on i s onl y weakl y affected by the vari ati on i n
the spati al temperature profi l es.
The dynami cs of gas-phase speci es are shown through
the ti me profi l es correspondi ng to T
b
) 900 K (Fi gure
4), as measured for wheat straw. From the qual i tati ve
poi nt of vi ew, al l gas-phase speci es profi l es are si mi l ar,
that i s, they present a maxi mum as a functi on of the
rel ease ti me, whi ch becomes successi vel y shorter, as the
reacti on temperature i ncreases. The posi ti on of the
maxi mum i s, however, dependent on both the temper-
ature and the component. The speci es CO
2
and CO are
Figure 2. (A) Char yi el ds as functi ons of temperature for wood
chi ps. (B) Li qui d and gas yi el ds as functi ons of temperature for
wood chi ps. Li terature data are al so encl osed for compari son
purposes.
Figure 3. Radi al profi l es of temperature for wheat straw at
several ti mes for Tb ) 900 K.
I nd. Eng. Chem. Res., Vol . 38, No. 6, 1999 2219
rel eased at shorter ti mes, as compared wi th the other
components (H
2
, CH
4
, C
2
H
4
, and C
2
H
6
). At l ow temper-
atures, the evol uti on of CO (and CO
2
and water vapor)
i s due mai nl y to the degradati on of hemi cel l ul ose and
the acti vi ty of the fi rst path i n cel l ul ose degradati on,
l eadi ng to gas and char formati on.
21
As the temperature
i ncreases, the formati on of tar vapor from cel l ul ose
becomes predomi nant, whi l e al so l i gni n degradati on
begi ns. Thi s process i s l argel y responsi bl e for char
formati on and al so for the evol uti on of CO
2
, CO, CH
4
,
and H
2
(the l ast two speci es at hi gh temperatures). On
the other hand, secondary tar degradati on reacti ons
become acti ve for temperatures above 700 K (wood
22
),
wi th CO as the mai n product, fol l owed by C
2
H
4
and
CH
4
.
23
Pyrolysis of Agricultural Residues. For a chosen
radi ati on i ntensi ty (temperature) and bed depth, the two
mai n parameters whi ch determi ne product di stri buti ons
and conversi on ti mes are the densi ty of the bed, l argel y
responsi bl e for the heati ng characteri sti cs, and the
i ntri nsi c reacti vi ty of the bi omass. Conversi on ti mes (not
shown), defi ned as the ti mes when 95% of the total gas
mass has been rel eased, show a fi rst regi on, where the
temperature dependence i s very strong, fol l owed by a
tendency toward constant val ues. Thi s can be expl ai ned
by the rel ati vel y narrow temperature range where
bi omass undergoes pyrol ysi s. Thus, despi te the i ncrease
i n the temperature of the heati ng system and the
average bed temperature, pri mary degradati on charac-
teri sti cs (i n parti cul ar, gas rel ease ti me and char yi el ds)
tend to become constant. Conversi on ti mes are about
the same for ol i ve husks and grape resi dues (vari ati ons
from about 23 to 7.5 mi n, for the range of temperatures
consi dered) and are l onger than those for wood (up to
factors of about 2). On the other hand, they are shorter
for ri ce husks and mai nl y for wheat straw (factors of
1.5 wi th respect to wood). Thi s behavi or can be, i n part,
expl ai ned by the al most l i near i ncrease of the conversi on
ti me wi th densi ty, gi ven the successi vel y sl ower parti cl e
heati ng rates,
24-25
whereas the surpri si ngl y l ong ti mes
for grape resi dues, whose bed densi ti es are comparabl e
to those of wood chi ps, coul d be due to a l ower reacti vi ty.
Thi s seems to be confi rmed by Fi gure 5, where the
temperature dependence i s shown of the average devol -
ati l i zati on rates, for the di fferent bi omasses.
The average devol ati l i zati on rate i s defi ned as the
rati o between the total mass fracti on of vol ati l es (i n-
cl udi ng the moi sture content) and the conversi on ti me.
The l owest val ues, measured for grape resi dues, i ndi cate
that both the amount of vol ati l es rel eased i s l ow and
thei r rel ease ti me i s l ong. Wood chi ps show i ntermedi ate
val ues (al most coi nci dent wi th ri ce husks) compri sed
between those of wheat straw (hi gher up to factors of
1.4-1.2) and ol i ve and grape waste (l ower by factors of
1.2-2). Al so, Fi gure 5 shows that bi omasses under study
can be roughl y cl assi fi ed i nto two categori es. The fi rst
(ri ce husks, wheat straw, and wood) presents average
degradati on rates hi ghl y i ncreasi ng wi th temperature
(wi th val ues up to 5 ti mes hi gher), whi l e the dependence
i s weaker for the second category (rates for ol i ve and
grape waste rates onl y i ncrease by factors of 3-3.5).
For al l of the bi omasses, fi nal product yi el ds (ex-
pressed on a moi sture-free basi s) as functi ons of tem-
perature (Fi gure 6A-C) show the same trends as those
al ready di scussed for wood, but di fferences are quanti -
tati vel y l arge. The mass cl osure i s very good for wood
(95.5-99%) and ol i ve husks (95-100%), whi l e errors i n
the l i qui d col l ecti on are l arger for straw (92.5-98%),
grape resi dues (92-97%), and ri ce husks (90-96%).
Therefore, for a better presentati on of the data, dashed
l i nes have al so been i ncl uded i n Fi gure 6B correspond-
i ng to l i qui d yi el ds computed by di fference.
Al l of the char yi el ds show the same qual i tati ve
dependence on temperature, but di fferences are quan-
ti tati vel y l arge. I n compari son wi th wood, agri cul tural
resi dues al ways gi ve ri se to l arger char yi el ds. These
fi ndi ngs are i n qual i tati ve agreement wi th previ ous
studi es, where the hi gher char yi el ds observed for
agri cul tural resi dues were attri buted to the hi gher
l i gni n (and carbon) contents
13
or to the presence of l arge
amounts of i norgani cs whi ch favor charri ng reacti ons.
11
Another di fference (Fi gure 6A) i s that the char yi el d
curves of agri cul tural resi dues show a tendency toward
a constant val ue at temperatures sl i ghtl y l ower than
those of wood (800-850 K agai nst 900 K), probabl y as
a consequence of hi gher degradati on rates at l ower
temperatures, often associ ated wi th the presence of
extracti ves and ashes.
The chemi cal composi ti on of the chars (Tabl e 3),
obtai ned for i ntermedi ate val ues of the radi ati on i nten-
si ty (T
b
) 850 K), shows that the carbon content
i ncreases i n the order of bi omasses wi th a successi vel y
l ower ash content. As a consequence, the cal ori fi c val ue
of the sol i d resi dual al so i ncreases, gi ven a smal l er
contri buti on of i norgani cs i n i ts composi ti on. Therefore,
i n vi ew of char uti l i zati on as fuel , what i s real l y needed
i s a compari son of the di fferent yi el ds on a moi sture-
and ash-free (maf) basi s, as shown i n Fi gure 7. Thi s pl ot
confi rms that the pyrol ysi s of agri cul tural resi dues i s
associ ated wi th sol i d yi el ds much hi gher than those
from wood, but grape resi dues gi ve the hi ghest val ues,
i nstead of ri ce husks. Apart from l ow temperatures, they
are fol l owed by ol i ve and ri ce husks and straw.
Figure 4. Ti me-speci es profi l es for wheat straw and Tb )
900 K.
Figure 5. Average devol ati l i zati on rates (rati o of vol ati l e mass
fracti on and conversi on ti me) as functi ons of temperature for wood
chi ps, ri ce husks, wheat straw, grape resi dues, and ol i ve husks.
2220 I nd. Eng. Chem. Res., Vol . 38, No. 6, 1999
As a consequence of the l arge char yi el ds, the l owest
l i qui d and gas yi el ds (Fi gure 6B,C) are observed for ri ce
husks fol l owed by grape resi dues. Wood gi ves the
hi ghest l i qui d yi el ds, wi th a maxi mum of about 51%,
but i t i s straw whi ch i s associ ated wi th the hi ghest gas
yi el ds (up to 31%), whereas ol i ve husks present i nter-
medi ate val ues of the l i qui d yi el ds. I t i s worth noti ng
that the l i qui d yi el ds, measured by di fference, though
they sti l l retai n the characteri sti cs previ ousl y i l l us-
trated, i ndi cate that ri ce husks and grape resi due yi el ds
on the one si de and straw and ol i ve husks on the other
gi ve comparabl e val ues, so that di fferences between
resi dues are reduced. A compari son on a maf basi s (not
shown) i ndi cates that the di fferences i n the gas yi el ds
are smal l and maxi mum l i qui d yi el ds are associ ated
wi th mi ni mum char yi el ds (wood) (conversel y mi ni mum
l i qui d val ues are associ ated wi th maxi mum char val ues
i n the case of grape resi dues). Thi s fi ndi ng confi rms that
the mai n route for char formati on i s the conversi on of
monomers and ol i gomers i nto char and l i ght vol ati l es.
26
The pyrol ysi s gas consi sts (mf basi s) mai nl y of CO
2
(the l argest contri buti on), CO, CH
4
, and l ower amounts
of H
2
and C
2
hydrocarbons. For T
b
) 850 K, CO
2
contri butes to the total gas yi el d for about 59% (wood),
60% (ri ce husks), 62% (straw), 67% (ol i ve husks), and
76% (grape resi dues). Contri buti ons are l ower for CO
and are about 14% (grape resi dues), 23% (ol i ve husks),
28% (straw), 32% (ri ce husks), and 34% (wood). The
contri buti on of CH
4
vari es from about 4%(straw) to 6%
(ol i ve husks) and that of C
2
hydrocarbons from 1.6%
(ri ce husks) to 3% (grape resi dues), whereas hydrogen
i s al ways very l ow (from 0.1%for straw to 0.5%for grape
resi dues). On the whol e, the yi el ds of al l of the gas
components i ncrease wi th the reacti on temperature, as
shown by Fi gure 8A-E, though some di fferences exi st
between the speci es CO
2
and the others. I ndeed, these
show a conti nuous i ncrease wi th temperature, whereas,
for temperatures bel ow 850 K, the yi el ds of CO
2
onl y
sl i ghtl y i ncrease or remai n al most constant and then,
apart from wood chi ps, start to i ncrease wi th a rather
hi gh rate. The exi stence of two di fferent regi ons i n the
CO
2
yi el ds i s i n qual i tati ve agreement wi th previ ous
l i terature (for i nstance, see ref 3). Thi s was attri buted
to the fact that CO
2
i s a product of the pri mary pyrol ysi s
of cel l ul ose and hemi cel l ul ose by a pathway that be-
comes l ess favored as the temperature i ncreases, resul t-
i ng i n a pl ateau for val ues of about 723 K (fl ui d-bed
reactor). Then, the successi ve i ncrease i s attri buted to
secondary reacti ons. The measurements carri ed out i n
thi s study i ndi cate that CO
2
yi el ds from wood remai n
roughl y constant (val ues of about 13%) whi l e the other
gas speci es i ncrease. I t can be argued that thi s i s
essenti al l y due to pri mary reacti ons and to a competi -
ti on between gas and char formati on i n the degradati on
of the l i gni n fracti on, wi th gas becomi ng successi vel y
more favored wi th hi gh temperatures. Thi s expl anati on
i s al so consi stent wi th the conti nuous char reducti on
even at rel ati vel y hi gh temperatures, whi l e the vari a-
ti ons i n the l i qui d yi el d are smal l . Agri cul tural resi dues
present a si gni fi cant di fference wi th wood i n that the
second regi on of si gni fi cant i ncrease i n the CO
2
yi el ds
i s cl earl y vi si bl e for temperatures above 850 K (ol i ve
husks, straw, grape resi dues) or 950 K (ri ce husks).
Because the thermal condi ti ons of the bed are roughl y
the same for both wood and agri cul tural resi dues, i t can
Figure 6. (A) Char yi el ds from pyrol ysi s of wood chi ps and
agri cul tural resi dues as functi ons of temperature. (B) Li qui d yi el ds
from pyrol ysi s of wood chi ps and agri cul tural resi dues as functi ons
of temperature. (C) Gas yi el ds from pyrol ysi s of wood chi ps and
agri cul tural resi dues as functi ons of temperature.
Table 3. Elemental Analysis of Chars fromWood Chips
and Agricultural Residues (Tb ) 850 K)
bi omass
char C H N O S
HHV
(MJ/kg)
wood chi ps 83.3 3.1 0.21 11.38 0.015 30.53
wheat straw 64.27 2.39 0.48 14.31 0.30 22.66
ol i ve husks 78.68 2.83 0.98 12.88 0.032 28.26
grape resi dues 68.48 2.62 2.05 16.53 0.11 23.83
ri ce husks 51.52 2.14 0.46 9.77 0.021 18.73
Figure 7. Char yi el ds (maf basi s) from pyrol ysi s of wood chi ps
and agri cul tural resi dues as functi ons of temperature.
I nd. Eng. Chem. Res., Vol . 38, No. 6, 1999 2221
be argued that vapors produced i n the l atter case are
more reacti ve than those of wood and thus are more
prone to undergo cracki ng. Thi s behavi or al so appears
to be consi stent wi th the char yi el d whi ch tends to
become constant at l ower temperatures compared to
wood (that i s, the rati o between pri mary vol ati l es and
char becomes constant).
A compari son between the gas composi ti on measured
for wood and that for agri cul tural resi dues al so i ndi cates
that the l atter, apart from ri ce husks, are characteri zed
by a hi gher CO
2
producti on (yi el ds up to 17.5-18.7%).
Few tests carri ed out wi th wood chi ps, after bark
el i mi nati on, gi ve ri se to a reducti on i n the gas yi el ds
and i n parti cul ar i n the CO
2
yi el ds (for i nstance, for T
b
) 735 K, they decrease from 12% to 8.6%), whi ch
become l ower than those measured for ri ce husks.
Agai n, these fi ndi ngs, i n rel ati on to both CO
2
yi el ds and
bark i nfl uence, are i n qual i tati ve agreement wi th pre-
vi ous studi es carri ed out under fl ui di zed-bed condi -
ti ons.
11-13
Wood, straw, and ri ce husks present compa-
rabl e yi el ds of CO at l ow temperature (5-6%), but the
i ncrease wi th temperature i s si gni fi cantl y hi gher for
wood (val ues up to about 13%). The CO yi el ds are l ower
for ol i ve husks and especi al l y for grape resi dues (val ues
from 2 to 6.5%).
At l ow temperatures (bel ow 800 K) the producti on of
hydrogen i s negl i gi bl e for al l bi omasses. A rapi d i ncrease
i s then observed for temperatures above 850-900 K.
Ol i ve and mai nl y grape resi dues, presumabl y as a
consequence of thei r hi gher l i gni n content, are charac-
teri zed by the hi ghest C
2
yi el ds, fol l owed by the com-
parabl e val ues for wood and straw and the l ow val ues
of ri ce husks. Fi nal l y, though the CH
4
yi el ds are
comparabl e for al l of the bi omasses, on the average, the
hi ghest val ues are observed for ol i ve husks.
Fl ash pyrol ysi s studi es report very general approxi -
mate rel ati onshi ps among the rati os of the major gas-
phase products, CO, CH
4
, CO
2
, and C
2
hydrocarbons,
over wi de ranges of experi mental condi ti ons (tempera-
tures). These are expl ai ned to be due to comparabl e
val ues of the acti vati on energi es for the formati on of
di fferent speci es,
3,11,20
wi th model s usual l y representa-
ti ve of apparent ki neti cs, whi ch i ncl ude both pri mary
and secondary reacti ons. Because one of the moti vati ons
for thi s study was to provi de data on the gas charac-
teri sti cs to be used for reactor model i ng, i t i s i mportant
to understand i f the gas yi el ds, previ ousl y presented,
obey the same apparent ki neti cs i n rel ati on to di fferent
speci es and bi omasses. Thus, a pl ot i s constructed of the
l ogari thm of the rati o of yi el ds of major gas-phase
Figure 8. (A) CO, (B) CO2, (C) H2, (D) CH4, (E) C2 (C2H4 and C2H6) yi el ds for wood chi ps and agri cul tural resi dues as functi ons of
temperature.
2222 I nd. Eng. Chem. Res., Vol . 38, No. 6, 1999
speci es on the l ogari thm of temperature. An exampl e
for CO/CO
2
and CO/C
2
, i s shown i n Fi gure 9. I n qual -
i tati ve agreement wi th previ ous studi es carri ed out for
fl ash pyrol ysi s,
3,11
i t can be seen that a l i near depen-
dence i s roughl y establ i shed, confi rmi ng that major gas
speci es present comparabl e ki neti c constants (i n par-
ti cul ar, acti vati on energi es) al so for conventi onal py-
rol ysi s. As expected, there are some di fferences between
the rati o of val ues eval uated i n thi s study and those
reported for fl ash pyrol ysi s, because of the di fferent
rates of gas formati on. I ndeed, i n the fi rst pl ace, the
actual degradati on temperature i s l ower than the
surface temperature (here used as the characteri sti c
temperature), especi al l y at hi gh thermal severi ty. More-
over, the i ncrease i n the gas yi el ds at hi gh temperatures
i s due mai nl y to secondary reacti ons whi ch, as al ready
observed, occur at a l arger extent i n fl ash pyrol ysi s
uni ts. Fi gure 9 al so i ndi cates two di fferent cl asses of
bi omass fuel s wi th reference to gas rel ease behavi or,
that i s, wood, straw, and ri ce husks on the one si de and
grape and ol i ve resi dues on the other (though wi th
di fferences between the l ast two). More preci sel y, the
l atter speci es present al ways l ower val ues of the l oga-
ri thms, because of the l ower yi el ds of CO and the hi gher
yi el ds of CH
4
, C
2
, and CO
2
speci es, probabl y as a resul t
of the hi gher l i gni n content. On the basi s of these
resul ts, i t can be concl uded that the gas rel ease char-
acteri sti cs are si gni fi cantl y dependent on the type of
bi omass and, probabl y, a correl ati on can be suggested
wi th the chemi cal composi ti on (that i s, l i gni n and
hol ocel l ul ose).
Conclusions
A bench-scal e system has been appl i ed to i nvesti gate
the pyrol ysi s characteri sti cs of wood chi ps and some
agri cul tural resi dues, through packed beds (conven-
ti onal pyrol ysi s). Contrary to previ ous studi es conducted
for very sl ow external (furnace) heati ng rates, the
pyrol ysi s condi ti ons establ i shed i n thi s study are es-
senti al l y those determi ned by the physi cochemi cal
properti es of the packed bed. The mechani sm of external
heati ng i s radi ati on, and di fferent i ntensi ti es have been
appl i ed, whi ch correspond to maxi mum bed tempera-
tures i n the range 650-1000 K. Al so, extra-bed second-
ary reacti ons are mi ni mi zed through a reduced l ength
of the heated zone and short resi dence ti mes of vol ati l e
products. Product yi el ds and gas composi ti on have been
determi ned over the above temperature range.
From the qual i tati ve poi nt of vi ew, the dependence
of the product yi el ds on temperature, for al l fuel s, i s the
same as that observed i n fl ash pyrol ysi s, wi th quanti ta-
ti ve di fferences resul ti ng from the characteri sti c process
l ength (bed depth) bei ng about 1 order of magni tude
hi gher and the reduced acti vi ty of secondary reacti ons.
For conventi onal pyrol ysi s, wood chi ps show i nter-
medi ate val ues of the average devol ati l i zati on rate
(al most coi nci dent wi th ri ce husks), compri sed between
those of wheat straw (hi gher up to factors of 1.4-1.2)
and ol i ve and grape waste (l ower by factors of 1.2-2).
I n compari son wi th wood, char yi el ds from agri cul tural
resi dues are hi gher up to factors of 2, wi th correspond-
i ng l ower l i qui d yi el ds. I n parti cul ar, on a maf basi s,
grape waste gi ves ri se to the hi ghest char yi el d. The
total gas yi el ds present smal l di fferences, wi th compa-
rabl e acti vati on energi es of the apparent ki neti cs of the
mai n speci es rel ease rates. However, the di fferences i n
the composi ti on are agai n si gni fi cant. Thus, whi l e the
behavi or of gases from straw and ri ce husks can roughl y
be assi mi l ated to wood, ol i ve and grape resi dues trends
are hi ghl y affected by the l ower carbon monoxi de yi el ds
and the hi gher carbon di oxi de, methane, and C
2
hydro-
carbon yi el ds.
Acknowledgment
The research was funded i n part by the European
Commi ssi on i n the framework of the Non Nucl ear
Energy Programme (JOULE I I I ; Contract JOR3-CT95-
0021).
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Received for review November 10, 1998
Revised manuscript received February 24, 1999
Accepted March 23, 1999
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