Kinetic Severity Function as a Test for Kinetic Analysis.

Application to Polyethylene Pyrolysis

Juan A. Conesa* and Rafael Font
Department of Chemical Engineering, University of Alicante,
Apartado 99, E-03080 Alicante, Spain
Received October 5, 1998
I n thi s paper a method i s descri bed for the val i dati on of ki neti c model s i n compl ex pyrol ysi s
processes where n-pentane i s formed. The method requi res the cal cul ati on of the ki neti c severi ty
functi on (KSF) and the measure of the yi el ds of di fferent compounds i n di fferent condi ti ons. The
fi rst condi ti on that the cal cul ati on must ful fi l l i s that the sl ope of the l n(pentane yi el d) vs KSF
graph must be l ogi cal , consi deri ng the decomposi ti on ki neti c l aw of the n-pentane. The method
i s appl i ed to pol yethyl ene pyrol ysi s i n order to test the model i ng previ ousl y carri ed out and to
anal yze the vari ati ons of the di fferent yi el ds of each compound vs KSF when the waxes are
cracked.
Introduction
I n the 1960s
1
a new functi on cal l ed the ki neti c
severi ty functi on (KSF) was i ntroduced i n the context
of the pyrol yti c cracki ng of di fferent products, such as
ethyl ene, naphtha fracti ons, oi l , etc. The KSF was
rel ated to equi val ent n-pentane conversi on.
The use of thi s functi on began due to the fact that, i n
consi deri ng the heavi er hydrocarbons, i t i s conveni ent
to rel ate thei r vel oci ty constants to that of n-pentane
at the same temperature. I f any normal paraffi n i s
desi gnated by the subscri pt i (i ts number of carbons)
and uses the subscri pt 5 to desi gnate n-pentane, then
the exponenti al form of the Arrheni us equati on can be
expressed as
The yi el ds of the products obtai ned from a pyrol ysi s
process are due to the raw materi al decomposi ti on
(pri mary reacti ons) and to the reacti ons suffered by the
pri mary vol ati l es (secondary reacti ons). Study of the
avai l abl e data i ndi cates that a fi rst-order reacti on can
be consi dered
2
and that the acti vati on energi es for the
cracki ng of the major part of the normal paraffi ns can
be assumed to be equal wi thout seri ous error.
1,3
Such
an assumpti on causes the exponenti al term of the l ast
equati on to become uni ty, so that
The KSF was then defi ned by the fol l owi ng equati on
where i s the total ti me. I n thi s functi on, the i ntegra-
ti on of the ki neti c constant k
5
i s done over the ti me and
temperature condi ti ons of the reactor. Thus, i f one were
to say that certai n naphtha was bei ng cracked at a KSF
of 2.3, thi s woul d be equi val ent to sayi ng that the ti me-
temperature condi ti ons i n the reactor were such that
n-pentane woul d be converted to the extent of 90%. Thi s
means that the KSF i s a magni tude rel ated to the
i ntensi ty of the thermal effect, consi deri ng both ti me
and temperature.
I f the temperature i s constant, k
5
i s al so constant and
then
The KSF i s very useful both for correl ati ng yi el d data
and for desi gni ng and eval uati ng the performance of
cracki ng coi l s. The most obvi ous advantage i s that i t
recogni zes and i ncorporates both ti me and temperature
i n such a way that i t i s consi stent wi th ki neti cs. The
most seri ous di sadvantage i s that i n i ts determi nati on
a detai l ed knowl edge of the temperature profi l e for the
process stream fl owi ng through the reacti on coi l i s
requi red. Thi s di sadvantage coul d be regarded as an
advantage, consi deri ng that, as used i n the present
paper, i t coul d be a useful tool to check whether the
profi l es cal cul ated usi ng heat transfer coeffi ci ents i n
si mul ati on programs are correct.
Consi deri ng that the rate of di sappearance of the
reactant, i n the pyrol ysi s of i ndi vi dual hydrocarbons,
i s general l y i ndependent of the surface-to-vol ume rati o
of the reactor and pressure, the di sappearance can be
consi dered to be uni mol ecul ar and fol l ows a fi rst-order
mechani sm.
3
The i ntegrated form of the fi rst-order
reacti on i s
* To whom correspondence shoul d be addressed. E-mai l : ja.conesa@
va.es.
(1) Zdoni k, S. B.; Green, E. J.; Hal l ee, L. P. Oil Gas J . 1967, 10,
192.
(2) Grantom, R. L., Royer, D. J., Ethyl ene I n Ullmans Encyclopedia
of I ndustrial Chemistry; 1005; Vol . A.10.
(3) Narayanan, S. Specialists Workshopon Fast Pyrolysisof Biomass
Proceedings, October 20-22, 1980, Cooper Mountai n, CO.
k
i
) A
i
exp
(
-
E
i
RT
)
; k
5
) A
5
exp
(
-
E
5
RT
)
k
i
/k
5
) (A
i
/A
5
) exp
(
- E
i
+ E
5
RT
)
(1)
k
i
/k
5
) A
i
/A
5
(2)
KSF )

k
5
dt (3)
KSF ) k
5
(4)
678 Energy & Fuels 1999, 13, 678-685
10.1021/ef980209m CCC: $18.00 1999 Ameri can Chemi cal Soci ety
Publ i shed on Web 03/02/1999
where R i s the fracti onal di sappearance of the reactant
and C
50
and C
5
are the i ni ti al concentrati on of pentane
and the concentrati on at the correspondi ng val ue of
KSF, respecti vel y. Consi deri ng eqs 2 and 5, the KSF,
eval uated usi ng the pentane fracti onal di sappearance,
i s a measure of the extent of the reacti on for any
compound wi th a si mi l ar apparent acti vati on energy to
that of pentane.
I n the mi d-1970s,
4,5
the KSF was eval uated usi ng
octane as the reference compound. The use of the
functi on was restri cted to i sothermal condi ti ons, due to
the compl exi ty of the i ntegrati on at that ti me. These
papers show that the pl ot of the yi el ds of di fferent
compounds vs the KSF i s a very good approach for the
i nterpretati on and study of the di stri buti on of the major
products.
Later, i n the 1980s vari ous authors used the KSF to
test the performance of the equi pment. Narayanan
3
showed that, i n a typi cal naphtha cracki ng, the severi ty
di agram can be di vi ded i nto three zones. I n zone 1 (KSF
< 1), the pri nci pal reacti ons i n progress are those
i nvol ved i n the pri mary di sappearance of saturates i n
the feedstocks. I n zone 2 (up to KSF ) 2.4), the pri mary
reacti ons conti nue but the secondary reacti ons become
domi nant. I n zone 3 (KSF > 2.4), pri mary reacti ons
vi rtual l y cease and al l further changes i n the consti tu-
ti on of the mi xture are attri buted to secondary reacti ons.
I n thi s way, cracki ng severi ti es desi gnated as mi l d
were equi val ent to a KSF of about 0.6-0.8, moderate
severi ty covered the range of KSF ) 0.8-1.5, and the
severi ty functi on correspondi ng to severe cracki ng was
approxi matel y 1.5-2.0.
Antal
6
showed that the total yi el ds of permanent
gases evol ved by the gas-phase pyrol ysi s of cel l ul ose-
and l i gni n-deri ved vol ati l e matter cannot be correl ated
mathemati cal l y wi th the commonl y used KSF. The
dependence of gas yi el ds on temperature was then
expl ai ned by a gl obal mechani sm composed of two
competi ng reacti ons, the fi rst creati ng permanent gases
and the second creati ng refractory condensabl e materi -
al s. Neverthel ess, some arrangement of the experi men-
tal resul ts can be observed usi ng the KSF val ues. I n
the paper by Antal , the condi ti ons were sel ected to
mi ni mi ze the onset of the secondary reacti on duri ng the
pri mary pyrol ysi s.
Contrary to Szepesy et al .
4
(who cal cul ate the KSF
usi ng the conversi on), Antal
6
uses the val ues of the
preexponenti al factor and acti vati on energy of the
pentane cracki ng, together wi th the experi mental tem-
perature profi l es, to cal cul ate the KSF
Many other papers tal k about the severi ty of the
cracki ng i n a pyrol ysi s process, but do not quanti fy (i .e.,
measure) the severi ty usi ng the cal cul ati on of the KSF
(see, for exampl e, refs 7-9). These papers show si mi l ar
effects to the papers menti oned previ ousl y and coi nci de
i n the i dea that a consi derabl e gai n i n sel ecti vi ty can
be achi eved by the proper combi nati on of the process
gas temperature profi l e and resi dence ti me i n the
cracki ng coi l . A l i near process gas temperature profi l e,
wi th whi ch temperature ri ses l i nearl y wi th the reactor
coordi nate, l eads to hi gher sel ecti vi ti es than the com-
mon, convex temperature profi l e, whi ch achi eves the
major part of the temperature ri se i n the fi rst secti on
of the reactor.
I n the present paper, the pyrol ysi s i n a fl ui di zed-bed
reactor of two types of pol yethyl ene i s studi ed usi ng the
severi ty functi on and consi deri ng the pri mary and the
secondary yi el ds. Two previ ous papers
10,11
showed the
ki neti c model s used i n the model i ng of the batch and
conti nuous pyrol ysi s of the pol yethyl ene. The cal cul ati on
of the KSF has been carri ed out by adapti ng the
programs for the model i ng, usi ng the opti mum val ues
of the parameters.
I n the model for batch pyrol ysi s, two heat transfer
coeffi ci ents were used: one for the heat transfer between
the sand bed and the sampl e and the other for the heat
transfer between the vol ati l es and the reactor wal l .
Actual l y, the second parameter i n the batch case i s not
a heat transfer coeffi ci ent. I t was i ntroduced i n order
to correct the temperature measured wi th the thermo-
coupl e when onl y the i nert gas fl owed through the
reactor. I n addi ti on, the model i ncl udes the ki neti c
parameters for the cracki ng of wax (secondary product
formed from the pri mary decomposi ti on of pol yethyl ene)
i n the gaseous phase.
The extensi on to the conti nuous case consi dered i n
fi rst the el i mi nati on of thi s correcti on factor (assumi ng
that i n the stati onary regi me, the temperature of the
vol ati l es and that measured wi th the thermocoupl e were
the same, si nce the temperature i n these experi ments
i s measured duri ng the pyrol ysi s process). However, on
the contrary, i t was necessary to keep a heat transfer
coeffi ci ent i f i t was i ntended to reproduce the compl exi ty
of the experi mental data. Thi s coeffi ci ent accounts for
the fact that the vol ati l es are not heated i nstanta-
neousl y.
11
The mai n objecti ve of the paper i s then to anal yze the
ki neti c model s proposed i n the previ ous papers,
10,11
usi ng the KSF concept, and consequentl y i n order to see
i f the vari ati on of the pentane yi el d i s l ogi cal i n
accordance wi th the operati ng condi ti ons. I n thi s way,
ki neti c model s can be tested usi ng the ki neti c severi ty
functi on. Other objecti ves are the study of the evol uti on
of the di stri buti on of products produced i n a thermal
cracker when varyi ng the KSF and the compari son wi th
other authors concl usi ons.
(4) Szepesy, L.; Wel ther, K.; Szal ai , O. Hung. J . I nd. Chem. 1977,
5, 233-244.
(5) Szepesy, L.; Whel ther, K.; Szal ai , O. Hung. J . I nd. Chem. 1977,
5, 161-174.
(6) Antal , M. J., Jr. I nd. Eng. Chem. Prod. Res. Dev. 1983, 22, 368.
(7) Pl ehi ers, P. M.; Froment, G. F. I nd. Eng. Chem. Res. 1991, 30,
1081.
(8) Landau, M. V.; Herskowi tz, M., Gi voni , D.; Lai chter, S.; Yi tzhaki ,
D. Fuel 1998, 77, 3.
(9) Frei haut, J. D.; Prosci a, W. M.; Seery, D. J. Energy Fuels 1989,
3, 692-703.
(10) Conesa, J. A.; Marci l l a, A.; Font, R. J . Anal. Appl. Pyrol. 1994,
30, 101.
(11) Conesa, J. A.; Font, R.; Marci l l a, A.; Cabal l ero, J. A. J . Anal.
Appl. Pyrol. 1997, 40-41, 419.
KSF )

k
5
d ) l n
(
1
1 - R
)
) l n
(
C
50
C
5
)
) l n C
50
-
l n C
5
(5)
KSF )

k
5
dt )

(1.77 10
12
) exp
(
-
27 989
T(t)
)
dt
(6)
Kinetic Severity Function Energy & Fuels, Vol. 13, No. 3, 1999 679
The use of the KSF wi th the n-pentane i s very useful
for studyi ng decomposi ti ons si mi l ar to those shown i n
thi s paper, because n-pentane i s moderatel y cracked.
Experimental Section
The properti es of the pol yethyl enes used are presented i n
Tabl e 1. The mel ti ng heat of type A pol yethyl ene i s l ess than
that of type B, i ndi cati ng that type A has a greater branchi ng
degree (i .e., l ower crystal l i ni ty) than type B.
12
The experi mental equi pment consi sted of two fl ui di zed-bed
reactors, descri bed el sewhere.
13,14
Yi el ds of 13 products were
determi ned as functi ons of the operati ng condi ti ons. Tabl e 2
presents, as an exampl e, the yi el ds obtai ned at two di fferent
condi ti ons.
I n the experi ments carri ed out i n batch mode, the sampl es
were di scharged from a hopper l ocated at the upper part of
the reactor, wi th the si ze i ndi cated i n Tabl e 1, whereas i n the
conti nuous reactor, the sampl es were cryogeni cal l y crushed
and si eved to a si ze of 0.105-0.210 mm. Neverthel ess, i t i s
conveni ent to bear i n mi nd that pol yethyl ene mel ts before i ts
decomposi ti on.
Mathematical Procedures
I n the model i ng of the batch pyrol ysi s of pol yethyl ene
i n a fl ui di zed-bed reactor, i t was assumed
10
that as a
consequence of the pri mary reacti on undergone by the
pol yethyl ene sampl e di scharged onto the hot bed, a
smal l amount of vol ati l es (V
1
) i s generated i n a smal l
i nterval (t
1
). The V
1
formed i s pushed by the hel i um
(i nert gas used) fl ux through the hot zone above the
fl ui di zed sand bed. I n thi s zone, the vol ati l es are cracked
as a consequence of the secondary reacti ons and the
mi xture expands. Over the next ti me i nterval (t
2
),
another amount of vol ati l es (V
2
) i s generated. Thi s i s
al so pushed by the hel i um fl ux to the top of the reactor.
Pushed by the hel i um fl ux, V
1
conti nues ri si ng and
the new vol ati l es i ncrement V
2
. The process conti nues
unti l the total sampl e decomposi ti on and 99.9% of
vol ati l es evol ved have l eft the reactor.
I t i s assumed that the secondary reacti on i s produced
i n the freeboard, the zone above the hot sand bed.
Al though some cracki ng woul d occur i n the sand bed,
two facts must be borne i n mi nd: (a) The vel oci ty of
the fl ui di zi ng gas (u 3u
mf
) i s not hi gh enough to
si gni fi cantl y produce the descent and mi xi ng of the
emul si on zone of the fl ui di zed bed, i n such a manner
that the pri mary vol ati l es are formed i n the top of the
sand bed and pass al most i nstantaneousl y through the
freeboard. (b) The experi mental val ues of the yi el ds of
several compounds obtai ned i n the fl ui di zed-bed reactor
approach that obtai ned usi ng the Pyroprobe 1000
anal yti cal apparatus, where the secondary reacti ons are
assumed to be suppressed. Thi s behavi or i s fol l owed not
onl y by the pol yethyl ene, but for a great vari ety of feed
materi al (l i gni n, muni ci pal sol i d wastes, al mond shel l s,
scrap ti res, etc.), as tested.
14-16
I n the conti nuous pyrol ysi s, the fundamental s are
si mi l ar, but i n thi s case al l the materi al di scharged i s
decomposed under steady state. The di fferenti al equa-
ti ons used i n the model can be resumed i n the fol l owi ng
fi ve poi nts.
10
(i ) The formati on of pri mary vol ati l es
(gases + tars + waxes) has a ki neti c l aw that coul d be
expressed by
where V
Vp
i s the total vol ati l e vol ume (pri mary gases +
pri mary tars and waxes), V
Vp
i s i ts maxi mum val ue,
and PE refers to the pol yethyl ene. The pri mary pol y-
ethyl ene decomposi ti on (dPE/dt) fol l ows a three-reacti on
model as presented i n previ ous papers.
10
(i i ) The sec-
ondary reacti on of cracki ng of the tars and waxes, as a
functi on of the extent of the reacti on (X
s
), fol l ows fi rst-
order reacti on ki neti cs. (i i i ) The expansi on of the total
vol ati l es (pri mary and secondary) as a consequence of
the cracki ng of tars and waxes i n the secondary reacti on
i s cal cul ated usi ng
V
V2
i s the total vol ume of gases (pri mary + secondary)
that are wi thi n a vol ume V
R
consi dered, V
Vp0
i s the
vol ume of vol ati l es (gases + tars + waxes) generated
when ti me equal s zero, and R i s an expansi on factor that
can be cal cul ated for each i nterval . (i v) The heat transfer
between the fl ui di zed bed and the pol yethyl ene parti cl e
i s model ed usi ng the equati on
(12) Whi tel ey, K. S.; Heggs, T. G.; Koch, H.; Mawer, R.; I mmel , W.
Pol i ol efi ns I n Ullmans Encyclopedia of I ndustrial Chemistry; 1992;
Vol . A21, p 487.
(13) Conesa, J. A.; Marci l l a, A.; Font, R. EnergyFuels 1997, 11, 126.
(14) Conesa, J. A.; Font, R.; Marci l l a, A.; Garci a, A. N. EnergyFuels
1994, 8, 1238.
(15) Font, R.; Marci l l a, A.; Verdu, E.; Devesa, J. I nd. Eng. Chem.
Process Res. Dev. 1986, 25 (3), 491-496.
(16) Garc a, A. N., Font, R., Marci l l a, A. Energy Fuels 1995, 9 (4),
648-658.
Table 1. Properties of Polyethylenes Used
pol yethyl ene
type A type B
manufacturer Repsol S. A. Dowl ex Europe S. A.
grade PE-021 NG 2431 E
pol ymeri zati on process hi gh-pressure
process
copol ymeri zati on
ethyl ene-octene
densi ty (kg/m
3
) 920 935
average di ameter (mm) 0.50 0.252
mel t i ndex (g/mi n) 2.0 0.7
degree of crystal l i zati on (%) 33.3 45.8
mel ti ng heat (J/g) 37.94 64.39
mel ti ng poi nt (C) 119 130
Table 2. Pyrolysis of Polyethylene in a Fluidized-Bed
Reactor at 800 C
a
pol yethyl ene type A pol yethyl ene type B
batch conti nuous batch conti nuous
methane 14.7 6.11 12.7 7.37
ethane 3.71 3.79 4.59 4.54
ethyl ene 31.1 33.6 30.4 35.7
propane 0.28 1.51 0.51 1.58
propyl ene 10.1 15.3 15.1 25.7
acetyl ene 0.04 0.05 0.09 0.02
butyl ene 3.46 6.61 2.40 8.90
butane 0.31 1.10 0.15 0.45
pentane 3.63 5.28 4.50 9.17
benzene 15.2 15.2 3.40 3.36
tol uene 2.16 1.47 0.32 0.65
xyl enes + styrene 0.04 1.70 0.06 0.10
total gas 84.7 91.8 74.3 97.6
a
Yi el ds i n wt %. Mass di scharged i n batch experi ments 3g.
Feed rate i n conti nuous experi ments 1 g/mi n.
dV
Vp
dt
) - V
Vp,
dPE
dt
V
V2
) V
Vp,0
(1 + RX
s
)
680 Energy & Fuels, Vol. 13, No. 3, 1999 Conesa and Font
where T
b
i s the temperature of the fl ui di zed bed, T
p
i s
the actual temperature of the sampl e at ti me t, and S
i s the external surface of the pol yethyl ene. U
1
i s the heat
transfer coeffi ci ent and C
p
the speci fi c heat.
The parameter S i s the surface exposed to the
surroundi ng atmosphere. I n the si mul ati on of the
pri mary pyrol ysi s, i ndependent of the temperature of
the sand bed, the pol yethyl ene parti cl e i s heated con-
ti nuousl y unti l the fi nal temperature whi l e i t i s decom-
posed. The val ue of S i s an esti mati on of the average
surface exposed to the atmosphere duri ng thi s pri mary
pyrol ysi s, consi deri ng that the pol yethyl ene mel ts before
i ts decomposi ti on on the top of the sand bed.
(v) The heat transfer between the reactor wal l s and
the vol ati l es i s represented by
where T
i
i s the real temperature of the vol ume consi d-
ered, T
R
i s the reactor temperature accordi ng to the
temperature profi l e measured at the posi ti on of the
vol ume, and H
s
i s a fi tti ng parameter. Thi s parameter
was i ntroduced because the temperature of the gas
mi xture (hel i um +pyrol yti c products) i s di fferent to that
measured by the thermocoupl e pri or to the di scharge
of the materi al . I t i s al so di fferent than the temperature
measured under steady-state condi ti ons i n the conti nu-
ous pyrol ysi s, due to radi ati on and correcti on effects as
expl ai ned el sewhere.
11
I n the previ ous papers,
10,11
the best ki neti c param-
eters were presented, but i t must emphasi zed that al l
these parameters are very i nterrel ated. Thi s means that
an acceptabl e correl ati on can al so be obtai ned wi th
another set of parameters.
The average KSF, consi deri ng thermal treatment i n
gas phase, has been cal cul ated for each di fferenti al
vol ume el ement (KSF
i
, subscri pt i represents each
i ncrement), usi ng eq 6 and the temperature profi l e
cal cul ated. The average ki neti c severi ty functi on has
been cal cul ated usi ng the fol l owi ng rel ati onshi p
I n thi s equati on, m
i
i s the wei ght l oss of the
pol yethyl ene sampl e i n the pri mary decomposi ti on i n
the ti me i nterval t
i
. The reason for usi ng eq 7 i s based
on the fact that the mean nonreacted pentane i s the
wei ghted nonreacted pentane i n each vol ume el ement.
I n the model i ng of the conti nuous experi ments under
the stati onary regi me, i t i s assumed that there are
parti cl es decomposi ng at l ow, i ntermedi ate, and hi gh
temperatures. The vol ati l es generated when pyrol yzi ng
a parti cl e of pol yethyl ene pass through the 12 000
i nterval s that form the upper part of the reactor, each
one at the temperature corrected by the heat transfer
coeffi ci ent. I n thi s case, the cal cul ati on of the KSF i s
easy to do, si nce there i s no need to average. The KSF
can be cal cul ated i n the stati onary regi me for any one
of the i nterval s.
Consi deri ng that di fferent set of correcti on param-
eters, i ncl udi ng the correcti on factor H
s
can l ead to
di fferent cal cul ated temperature profi l es (and conse-
quentl y di fferent val ues of KSF); i t woul d be very useful
to study the vari ati on of the yi el ds correspondi ng to the
di fferent pyrol yti c products, especi al l y that of the pen-
tane, to see i f thi s vari ati on i s l ogi cal and admi ssi bl e.
Thi s i s the mai n goal of thi s paper.
Let us fi rst consi der, i n more detai l , the process of
formati on and cracki ng of an i ntermedi ate product such
as pentane from pol yethyl ene waxes
Thi s bri ef l i near model used i s programmed i n the
computer by the use of a model that al so i ncl udes the
way the gas l eaves the reactor and the expansi on of the
vol ati l es produced i n the pri mary reacti on, as expl ai ned
previ ousl y. Logi cal l y, thi s scheme i s a si mpl i fi cati on of
the wi de network of reacti ons that can be present, but
thi s si mpl i fi cati on i s useful for the purpose of thi s paper.
I n addi ti on to the formati on of pentane, there i s an
i ni ti al amount of pentane formed by the pri mary
decomposi ti on of pol yethyl ene (C
50
). k
p
i s the ki neti c
constant of the pol yethyl ene waxes cracki ng, and k
5
i s
the ki neti c constant for the pentane decomposi ti on.
Consi deri ng thi s reacti on as fi rst order, then eq 3 can
be appl i ed and al so
where C
p
i s the concentrati on of the speci es pol yethyl ene
waxes i n the scheme of the reacti on. I f we assume that
k
p
and k
5
have si mi l ar acti vati on energi es
where M equal s the rati o between the preexponenti al
factor of the pol yethyl ene waxes cracki ng to the pentane
decomposi ti on, then
On the other hand
where C
5
i s the pentane concentrati on. The di fferenti al
eq 11 has the fol l owi ng boundary condi ti on
where C
50
i s the concentrati on of pentane formed by the
pri mary decomposi ti on of pol yethyl ene.
Sol vi ng eq 11, then
dT
p
dt
)
U
1
S
C
p
(T
b
- T
p
)
dT
i
dt
) H
s
(T
R
- T
i
)
exp(- KSF) )

i
m
i
exp(- KSF
i
)

i
m
i
(7)
pol yethyl ene waxes 98
k
p
pentane 98
k
5
gases or sol i d resi dues
dC
P
dt
) - k
p
C
p
w l n
(
C
P
C
p0
)
) -

k
p
dt (8)

k
p
dt ) M

k
5
dt ) M(KSF) (9)
C
p
) C
p0
exp(- M(KSF)) (10)
dC
5
dt
) k
p
C
p
- k
5
C
5
w
dC
5
k
5
dt
)
k
p
k
5
C
p
- C
5
dC
5
d(KSF)
)
k
p
k
5
C
p0
exp(- M(KSF)) - C
5
(11)
when KSF ) 0, then C
5
) C
50
(12)
Kinetic Severity Function Energy & Fuels, Vol. 13, No. 3, 1999 681
From eq 13, when M i s l arge, we obtai n
Thi s i s l ogi cal beari ng i n mi nd that C
p0
represents the
maxi mum val ue of the concentrati on of pentane i f al l
the waxes where to produce pentane. For l arge val ues
of M, the decomposi ti on of the pol yethyl ene waxes woul d
produce a l arge amount of pentane i n a very short peri od
of ti me that wi l l not decompose. On the other hand, C
5
woul d equal C
p0
i n the case that k
5
) 0 and no other
compound woul d be formed from the cracki ng of the
pol yethyl ene waxes. I f pentane i s much more rapi dl y
formed than decomposed, the concentrati on of pentane
wi l l be (C
50
+ C
p0
). As thi s i s not true, eq 13 corrects
thi s resul t for the di fferent val ues of KSF.
Fi gure 1 shows the curves obtai ned for di fferent
val ues of M, C
p0
, and C
50
when pl otti ng l n(C
5
) vs KSF.
Thi s fi gure shows that the maxi mum of the curves coul d
vary i ts posi ti on and magni tude dependi ng on the val ues
of the parameters and al so that the sl ope of the curves
at l ow val ues of KSF coul d be di fferent at a gi ven val ue
of KSF. I n thi s fi gure, we can see the effect of a decrease
of the ki neti c constant for the decomposi ti on of pentane
(k
5
) mai ntai ni ng the val ue of k
p
(i .e., a decrease i n the
val ue of M): when compari ng the curves obtai ned wi th
the same val ues of C
50
and C
p0
, the decrease of M
produces a softeni ng of the curve and a decrease i n the
val ue of the sl ope for a gi ven val ue of KSF. I n al l these
graphs, at hi gh val ues of KSF, al l the curves are
converted i nto strai ght l i nes wi th sl opes tendi ng to
approach uni ty.
Results and Discussion
Fi gure 2 shows the natural l ogari thm of the yi el d of
some of the compounds anal yzed vs the KSF cal cul ated
usi ng the program for the batch experi ments and for
pol yethyl ene type A. Fi gure 3 corresponds to pol yeth-
yl ene B and batch runs. The reason for representi ng the
natural l ogari thm of the yi el ds, i nstead of the yi el ds, i s
that i n thi s way a sl ope cl ose to uni ty i s expected at
hi gh val ues of KSF for the pentane, fol l owi ng eqs 5 and
2, when there i s no compound formati on. Note that i n
runs carri ed out at hi gh temperatures, the range of KSF
l ogi cal l y al so extends to hi gh val ues.
The val ues depi cted at KSF ) 0 correspond to the
yi el d of each compound obtai ned at each temperature
i n a Pyroprobe 100 anal yti cal apparatus, where the
secondary reacti ons are suppressed,
10,14
and represent
the pri mary yi el d wi th no cracki ng of the vol ati l es.
Let us anal yze the graph for pentane i n Fi gures 2a
and 3a for both types of pol yethyl ene. For pol yethyl ene
type B (Fi gure 3), the temperature of the process pl ays
an i mportant rol e when anal yzi ng the KSF. For tem-
peratures l ower than 800 C, the yi el d of the pentane
must come from the pri mary and secondary reacti ons,
gi vi ng a curve i n the graph si mi l ar to curves I V of
Fi gure 1. Neverthel ess, anal ysi s of the poi nts of the
graph correspondi ng to 900 C, al so consi deri ng the
pri mary poi nt at KSF ) 0, i s si mi l ar to curves I I of
Fi gure 1, showi ng that at thi s temperature the pentane
yi el d i s due to secondary reacti ons. I n the experi ments
carri ed out at 800 C, the behavi or i s i ntermedi ate
between that of 600-700 C and 900 C, wi th experi -
ments cl ose to both extremes. The vari ati ons of the yi el d
correspondi ng to propane, propyl ene, and butyl ene are
qui te si mi l ar to that of pentane (Fi gures 2a and 3a; the
fi gures correspondi ng to propane and butyl ene are not
shown i n order to si mpl i fy the presentati on). Neverthe-
l ess, the vari ati on of the yi el ds correspondi ng to meth-
ane, ethyl ene, benzene, and ethane fol l ows a general
i ncreasi ng tendency wi th KSF, showi ng a smal l de-
crease at hi gh val ues for ethyl ene and ethane. Fi gures
2d and 3d show thi s behavi or. The behavi or of tol uene
and xyl enes (not shown i n the fi gures) i s si mi l ar to that
of benzene, al though the yi el d of xyl enes i s very smal l
and the vari ati on i s not cl ear.
The temperature al so pl ays an i mportant rol e i n the
pyrol ysi s of pol yethyl ene type A (Fi gure 2). For the runs
at 600-700 C correspondi ng to pentane, propane,
propyl ene, and butyl ene, the vari ati ons are si mi l ar to
curves I of Fi gure 1. For the runs at 900 C and
correspondi ng to pentane, a l i near vari ati on wi th nega-
ti ve sl ope 0.86 can be observed, i ndi cati ng that the
pentane i s not formed by secondary cracki ng and that
the di sappearance of pentane i s i n accordance wi th that
predi cted by the KSF. Thi s val ue of -0.86 has been
obtai ned by correl ati on of al l the poi nts, al so consi deri ng
the pri mary poi nt at KSF ) 0, and excl udi ng the l ast
poi nt obtai ned i n extreme condi ti ons where the assump-
C
5
C
50
)
C
p0
C
50
M
1 - M
[exp(- M(KSF)) + exp(- KSF)] +
exp(- KSF) (13)
l i m
Mf
(
C
5
C
50
)
)
(
C
50
+ C
p0
C
50
)
exp(- KSF)
Figure1. Curves obtai ned for di fferent val ues of M, Cp0, and
C50.
682 Energy & Fuels, Vol. 13, No. 3, 1999 Conesa and Font
ti ons of the ki neti c model are not ful fi l l ed. I f the sl ope
of the pl ot l n(pentane) vs KSF was very di fferent from
uni ty (i .e., 0.1, 10, or 1000), i t woul d be concl uded, wi th
no further cal cul ati ons, that the model i ng i s not correct.
The ki neti c constants for the pentane decomposi ti on
used i n eq 6 have gi ven good resul ts for many research-
ers, so the experi mental yi el d of pentane must be i n
accordance wi th them (i nsi de the l i mi ts that the experi -
mentati on al l ows). The behavi or of the other compounds
i s al so si mi l ar to that presented for pol yethyl ene B.
An i mportant di fference between the behavi or of
pol yethyl enes A and B i s i n the cracki ng rate of the
waxes. Wi th pol yethyl ene A (l ower degree of crystal l i n-
i ty), the wax cracki ng takes pl ace at smal l val ues of KSF
and then at hi gher val ues of KSF the cracki ng of the
unstabl e organi c compounds takes pl ace. On the other
hand, wi th pol yethyl ene B (hi gher degree of crystal i za-
ti on), the wax cracki ng takes pl ace at smal l , i ntermedi -
ate, and hi gh val ues l of KSF, causi ng the unstabl e
organi c compounds to have consi derabl e yi el ds, because
al though they are cracked, they are al so formed from
the wax cracki ng.
Szepesy et al .
4
found more groups of compounds wi th
a si mi l ar behavi or: some compounds have a curve
starti ng wi th a convex zone and passi ng through a
maxi mum (butadi ene, propane, butyl ene) and other
compounds, represented by pentane, present a convex
zone passi ng through a mi ni mum when cal cul ati ng the
KSF usi ng the octane yi el d. The other compounds show
si mi l ar characteri sti cs both i n the present work and i n
the work of Szepesy but wi th di fferent val ues of KSF.
For exampl e, the maxi mum i n the evol uti on of propy-
l ene i s found at KSF ) 0.3 (for pol yethyl ene type A),
and i n the work of Szepesy i t i s at 2.1. The di fference
i n the val ues of KSF may, on one hand, be due to the
di fferent methods used to cal cul ate the functi on and,
Figure 2. Natural l ogari thm of the yi el d of each compound anal yzed vs KSF. Batch experi ments pol yethyl ene type A: (O) 600
C, (9) 700 C, (4) 800 C, (b) 900 C.
Kinetic Severity Function Energy & Fuels, Vol. 13, No. 3, 1999 683
on the other hand, to the di fferent cracki ng rate of the
materi al used.
Narayanan
3
al so reached si mi l ar concl usi ons concern-
i ng the speci fi c yi el ds of vari ous compounds, but at
di fferent KSF (for exampl e KSF ) 1.7 for the maxi mum
i n the propyl ene). Thi s author cal cul ates the KSF usi ng
the pentane yi el d. Note that i n the present work, the
behavi or i s al so si mi l ar for both pol yethyl enes but the
val ues of KSF are di fferent from one another. I t must
be remembered that the KSF here i s cal cul ated usi ng
the ki neti c constants and the temperature profi l es are
cal cul ated usi ng the programs, not the pentane yi el d.
Fi gure 4 shows, as an exampl e, some of the graphs
correspondi ng to the conti nuous pyrol ysi s and si mul a-
ti on. For pol yethyl ene A, runs at 900 C were not carri ed
out due to a probl em i n the experi mental equi pment.
Consequentl y, the KSF i n these experi ments i s l ower
than that of the batch experi ments. The scal e of the KSF
axi s i n the fi gure has been mai ntai ned as i n the batch
case for compari son. For both types of pol yethyl ene, as
can be seen, the coi nci dence between batch and conti nu-
ous experi ments i s al most compl ete. Each compound has
the same behavi or as the batch pyrol ysi s, but due to
the condi ti ons of the experi ments, i n the case of pol y-
ethyl ene A, the curve i s not so compl ete. The pl ots for
the other compounds are al so si mi l ar to the batch mode
and are not shown for si mpl i ci ty.
As can be seen throughout thi s paper, the use of the
KSF i n the ki neti c anal ysi s and model i ng, al l ows the
val i di ty of the model to be checked by representi ng the
yi el ds of the di fferent compounds anal yzed vs the KSF
and anal yzi ng thei r behavi ors. We can concl ude that the
ki neti c opti mi zati on carri ed out i n the previ ous pa-
pers
10,11
was qui te correct, confi rmi ng that the model i ng
Figure 3. Natural l ogari thm of the yi el d of each compound anal yzed vs KSF. Batch experi ments pol yethyl ene type B: (O) 600
C, (9) 700 C, (4) 800 C, (b) 900 C.
684 Energy & Fuels, Vol. 13, No. 3, 1999 Conesa and Font
of the heat transfer and of the decomposi ti on i n general
was correct.
Conclusions
When representi ng the yi el ds of the di fferent com-
pounds anal yzed i n a pyrol ysi s process vs the ki neti c
severi ty functi on, three or four types of curves can be
obtai ned. The sl ope of the graph l n(pentane yi el d) vs
KSF shoul d be cl ose to uni ty when there i s no formati on
of pentane. On the other hand, changes i n the formati on
of di fferent compounds from tars or waxes can be
understood consi deri ng the ki neti c severi ty functi on.
The use of the KSF can al so be val i d to test the
val i di ty of the assumpti ons carri ed out i n the model i ng,
especi al l y when heat transfer coeffi ci ents are consi dered
to cal cul ate the decomposi ti on temperature.
I n the case presented i n thi s paper, thi s process has
al l owed some aspects of the ki neti c process i n the
pyrol ysi s of pol yethyl ene to be cl ari fi ed, both i n batch
and i n conti nuous operati on. When treati ng two types
of pol yethyl ene, the anal ysi s has shown that pol yeth-
yl ene wi th hi gher crystal l i ni ty produces waxes that
decompose sl ower than that wi th l ess crystal l i ni ty.
Acknowledgment. Support for thi s work was pro-
vi ded by CYCI T-Spai n, Research project AMB96-1076.
EF980209M
Figure4. Natural l ogari thm of the yi el d of some compounds anal yzed vs KSF cal cul ated usi ng the program: (a-c) Pol yethyl ene
type A; (d-f) pol yethyl ene type B. Conti nuous experi ments: (O) 600 C, (9) 700 C, (4) 800 C, (b) 900 C.
Kinetic Severity Function Energy & Fuels, Vol. 13, No. 3, 1999 685