V~. 2 N ~ 3, pp. 2 3 3 ~ 5 ~ 1~96
C0pyr19ht • 1996 E~ev~r 5dence Ltd
Pr1nted 1n 6reat 8r1t~n. A11 r19h~ ~ e d
Renewa61e E n e r 9 y ,
~
P~9am0n
P11: 50960-1481(96)00006-7
0960-1481~6$1~00+~00
7HE 1NFLUENCE 0F 7EMPERA7URE AND
HEA71N6 RA7E 0N 7HE 5L0W
PYR0LY515 0F 810MA55
P A U L 7. W1LL1AM5 and 5ERP1L 8 E 5 L E R
Depa~mem 0f Fud and Ener9y, 7he U~v~f1ff 0f Leed~ Leed5 L52 9J7, U.K.
(Reee1ved 20 N0vem6er 1995; accep~d 6 Janua~ 199~
A65tract--7he ~0w pyr0~f15 0f ~0ma55 1n the f0rm 0f ~ n e w00d wa5
~ve5t19a~d ~ a 5tat1c 6a~h react0r at pyr0~f15 ~mperatu~5 fr0m 300 t0
720°C and heat1n9 ra~5 fr0m 5 t0 80 K m1n -~. 7he c0mp0f1f10n5 and
pr0pert1~ 0f the der1ved 9a5e5, pyr0~t1c 0115and 50f1d char w~e de~rm1ned
1n rdat10n t0 pyr0~f15 ~ m p ~ a t u n 5 and heat1n9 rate5.1n ad~t10~ the w00d
and the m~0 r c0mp0nent5 0fthe w00d--ce11u105e, hem1ce11u10~and 119~n-we~ py~01y~d ~ a therm09ra~metr1c ana1y5er ( 7 6 A ) under the 5ame expe~
1ment~ c0n~t10n5 a5 1n the 5tat1c 6atch react0r. 7he 5tat1c 6atch react0r
n 5 ~ 5h0wed t h ~ a5 the pyr0~f15 ~ m p ~ u n
wa5 ~ e a 5 e ~ the p~cen~9e
ma55 0f 50f1d char decrea5ed, w ~ 9a5 and 011 pr0du~51ncrea5ed. 7here wa5
a 5m~1 effe~ 0f heat1n9 r a~ 0n pr0du~ ~ d d . 7he 10wer ~ m p ~ a t u n n ~ m e
0f dec0mp0~t10n 0f w00d 5h0wed that m~n1y H20, C0~ and C 0 w en
ev01ved and at the ~9her ~ m p ~ a t u n n ~ m e , the ma1n dec0mp0f1t10n pr0duct5 were 011, H~0, H2, hydr0car60n 9a5e5 and 10wer c0ncentrat10n5 0f
C 0 and C02. F0ur1er tran5f0rmat10n ~ f ~ n d 5pecW0~0py and e~ment~
an~yf15 0f the ~ 5h0wed they were ~ 9 ~ y 0xy9ena~d. 7he 7 6 A n 5 ~
f0r w00d 5h0wed tw0 m ~ n n ~ m ~ 0f w~9ht 1055, the 10wer ~ m p ~ m u n
~ m e c0 ~d ~e c0~e1a~d w1th ~he dec0mp0f1t10n 0f hem1ce11u10~ and the
1~t1a1 ~a9e5 0 f c e ~ 0 ~ dec0mp0~t10n w~1~ the uprer ~ m p e r ~ u n ~ m e
c0 r r d a~d m~n1y w1th the 1ater 5ta9e5 0f ceHu105e dec0mp0f1t10n. L19~n
~m~
dec0mp0f1t10n 0ccurred thr0u9h0ut the ~ m p ~ u n
ran9e 0f
pyr01y5~. C0pyr19ht • 1996 E~e~er 5~ence Ltd.
1N7R0DUC~0N
7here 15 nnewed 1ntere5t 1n the pr0dUCt10n 0f ener9y fr0m n n e w a ~ e 50urCe5. 0ne 5Uch
50urce 15 ~0ma55 and the therm0Chem1ca1 reC0very 0f ener9y may 6e n ~ 1 ~ d 6y ~rect
C0m6u5t10n, 9af1f1cat10n, 114ue~Ct10n 0r pyr0~f15. Pyr0~f15 0f ~0ma55 ha5 nC~ved much
recent 1ntere5t [1-2 f1nce the pr0ce55 pr0duce5 f14~d pr0du~5 w~ch have a ~9h ener9y
den~ff, and ~50 the p0~nt1~ f0r ad~t10n t0 p ~ r 0 ~ u m nf1nery ~ed5t0ck5, f0r up9ra~n9
t0 ref1ned pnm1um-9rade fUd5 0r f0r the nc0very 0f ~9h-va~e chem1Ca15.7he p r 0 d u ~ n
0f a f14~d pr0duct ~crea5~ the ea5e 0f handf1n9, 5t0ra9e and ~an5p0~ and hence the
pV0duct d0e5 n0t have t0 6e u5ed at 0r near the ~0ma55 pyr01yf15 phnt. W h e n e~Ctr1~ty
233
234
P. 7. W~MAM5 ~ d 5.8E5LER
9enerat10n fr0m the f14u1d 15 the m ~ n ut11~at10n 0pt10n, then the dec0upf1n9 0f the
tran5f0rmat10n 0f the ~0ma55 t0 a f14~d fun a110w5 the 9enerat10n 0f 1he e~ctr1dty t0 6e
c0ncentrated 1n per10d5 0f ~9her demand when the pr1ce 0f Ne~r~1ff 15 m0re pr0f1ta61e.
1n add1t10n t0 the f14~d pr0du~, p y r 0 ~ 5 ~50 pr0duce5 a char w~ch may 6e u5ed a5 a
fu~ 0r up9raded t0 act1vated car60n. Add1t~na11y, the 6 ~ p r 0 d u ~ 9a5 15 0f ~9h ca10r1f1c
v~ue and may 6e u5ed t0 pr0~de the fun f0r the pyr01yt~ pr0ce55.
7he 1nf1uence 0f pyr01y515 react10n paramem~ 5uch a5 mmperatu~ and heat1n9 rate have
6een 5h0wn t0 d~erm1ne the ~ d and c0mp0~t10n 0f the der1ved pr0du~5 [6]. Fa~
pyr~y5~ w1th ~9h heat1n9 ram5 0f up t0 1000°C 5-~ at ~mper~u~5 6N0w 650°C and
w1th ra~d 4uench1n9 cau5e the f14~d 1ntermed1ate pr0du~5 0f pyr~y~5 t0 c0nden5e 6ef0re
fu~her ~act10n 6~ak5 d0wn ~ 9 h e ~ m 0 ~ c ~ a ~ w ~ 9 h t 5ped~ ~t0 9a~0u5 pr0duct5. Char
f0rmat10n 15 m1~m1~d 6y the ~9h react10n rate5. H19h heat1n9 rate5 t0 ~9h ma~mum
mmperatu~5 ~v0ur the f0rmat10n 0f 9a5e0u5 pr0du~5. 510w heat1n9 r ~ c0up1ed w1th a
10w f1na1 ma~mum mmperatu~ 0e55 than 500°C) and 10n9 9a5 and 50f1d re~dence t1me5
ma~m~e the f1Nd 0f char ~ a ~c0ndary c0~n9 and mp0~mer15at10n ~act10n5. H0wever,
1f the heat1n9 rate 15 1ncrea5ed t0 6~ween a60ut 20 and 100°C m1n-~ w1th ma~mum
mmperatu~5 0f 600°C, then f14~d and 9a5 ~Nd5 are marke~y 1ncrea5ed [~. 8r1d9wamr
and 8r1d9e [9] have ~ e w e d the ran9e 0f p y r 0 ~ 5 react0r5 u~n9 ~0w and ~ p y r 0 ~ 5
and the pr0pert1~ 0f the pr0du~5 af1~n9 fr0m the ~ffe~nt type5 0f ~chn~09y. F0r
examp~, fa5t p y r 0 ~ 5 ha5 6een carr1ed 0ut u~n9 f1u1~2ed 6ed, c y d 0 ~ e n ~ n e d f10w,
v0~ex and a6~f1ve react0~. 510w p y r 0 ~ 5 ha5 6een unde~aken 1n f1xed 6ed5, m~t1~e
hearth5 and r0tary ~ 5 .
C0nvent10n~1y, fa~ p y r 0 ~ 5 ha5 6een u5ed where the de~red end pr0du~ 15 the f14~d
hydr0car60n 0r ~0-~1 and 510w p y r 0 ~ 5 ha5 6een u5ed f0r the pr0duct10n 0f char.
H0wev~, the pr0ce55 c0n~t10n5 f0r ~0w p y r 0 ~ 5 can 6e ~ m ~ d t0 pr0duce ~9n1f1cant
4uant1t1e5 0f 610-0~ and 9a5 1n ad~f10n t0 the char. 7he m~0r 1nf1uence5 0n the ~0w
pyr01y~5 pr0ce55 affect1n9 pr0duct ~ e ~ are mmperatu~ and heat1n9 rate, h0weve~ there
are ~wer data 0n the ~f1uence 0n the deta11ed c0mp0~f10n 0f the char, 011 and 9a5 when
~mr1n9 the~ paramem~.
1n t~5 pape~ the c0mp0~t10n 0f the pr0du~5 ff0m the ~0w pyr0~f15 0f 6~ma55 1n the
f0rm 0f ~ne w00d wa5 1 n v e ~ a m d 1n ~hf10n t0 pyr0~f15 mmperatu~ and heat1n9 ram
~ a ~at1c 6a~h react0r at pyr~yf15 mmperatu~5 ran~n9 ff0m 300 t0 720°C and heat1n9
ram5 fr0m 5 t0 80 K m1n- ~. 1n ad~t10m the w00d and the m~0r c0mp0nent5 0fthe w00d-c e ~ 0 ~ , hem1ce11u10~ and f19n1n--were p y r 0 ~ d ~ a therm09ra~m~f1c an~y5er (76A)
under the 5ame c0n~t10n5 0f mmperatu~ and heat1n9 rate. 7he ~ 5 ~ ff0m the tw0
react0r5 were c0mpared.
EXPER1MEN7AL
7he Nne w00d wa5 cut 1nt0 1 cm 3cu6e5 and 5t0~d 1n the ~60r~0ry under dry c0nd1t~n5.
7a6~ 1 5h0w5 the Mt1m~e and pr0x1mam anMy~5 0f the 5amp~. W00d and the m~0r
c0mp0nenU 0f w00d---ce11u10~, hem~e~M05e and 119n1n--were pyr~y5ed u~n9 therm09ra~m~r1c anMy~5. CN1~0~ ~ m1cr0cry5ta111ne f0rm and hem~e11~05e 1n the f0rm 0f
x~an were 06tNned c0mmerNa11y. L19Nn wa5 ex~a~ed ~0m the w00d u51n9 the ~andard
m~ m~h0d f0r aNd-1n5MuNe 119Nn u51n9 5u1phur1c add [1~.
7he N0w pyrMy515 5tat1c 6atch react0r wa5 c0n~ructed 0f ~Nn1~5 5teN and had a
7he ~0w p~0~f15 0f ~ 0 m ~ 5
235
7 a ~ e 1. U ~ m ~ e and pr0~m~e ana1yf15 0f p1ne w00d
(wt%)
~ement~
an~yf15*
W00d
an~yf15
W00d
C
H
N
0
5
48.2
5.9
0.1
45.7
<0.1
M015ture
V01at11e5
A5h
7.0
92.2
0.8
Pm~ma~
* Dry a5h free.
n0m1na1 200 cm ~ capadty. 1t wa5 heated 6y an de~f1c r1n9 furnace. 7he react0r wa5
c0nt1nu0u5~ pur9ed w1th n1~09en at a f1xed metered f10w rate t0 5weep the ev01ved 9a5e5
~ 0 m the react10n 20ne, there6y reduNn9 the extent 0f 5ec0ndary react10n5 5uch a5 t h e r m E
crack1n9, rep01ymer15at10n and rec0nden5at10n. 51mf1ar 9a5-pur9ed 5tat1c 6atch react0r5
have 6een u5ed 6y 8 e a u m 0 n t and 5chw06 [11] f0r the 510w p y r 0 ~ 5 0f w00d, and 6y
ME1ya and H d t [1~ f0r the ~0w pyr0~f15 0f mun1NpE 50f1d wa~e. A 25 9 5amp1e wa5
p1aced 0n a 5upp0~ 1n the centre 0f the h0t 20ne 0f the react0r and heated at a c0n~0Hed
rate 0f 5, 20, 40 0r 80 K m1n-1 t0 a f1nE ~ m p e r a t u r e 0f 300, 420, 600 0r 720°C and he1d
at that ~ m p e r a t u r e f0r 2 h 0r unt11 there wa5 n0 fu~her ~9n1f1cant rdea5e 0f 9 a 5 . 7 h e 011
wa5 c0nden5ed 1n a Na55 f1ner 1n~de a c01d ~ a p and c0nf1~ed 0f an a4ue0u5 pha5e and an
011 pha5e. 7he 011 wa5 5epara~d ~ 0 m the a4ue0u5 pha5e 6y centr1fuNn~ decant1n9 and
r e m 0 v E 0f the a4ue0u5 pha5e 6y p1pe~e and the 5amp~5 were 5t0red under n1~09en 1n
refr19erated c0nd1t10n5 6ef0~e anEy~5. F19ure 1 5h0w5 a 5chemat~ d1a9ram 0f the 510w
pyr01y~5 5tat1c 6atch react0r.
7he ev01ved pyr01yt1c 9a5e5 ~ 0 m the ~0w p y r 0 ~ 5 5tat1c 6atch react0r were 5amp1ed at
1n~rvM5 6y mean5 0f a 9a5 5yr1n9e and were ana1y5ed 0ff-f1ne 6y packed c01umn 9a5
chr0mat09raphy. 7he 9a5e5 were anEy5ed f0r C 0 , H2 and CH4 u~n9 a m0~cu1ar ~eve 5A
60-80 c01umn w1th ar90n a5 the cart1er 9a5 and a t h e r m E c0nduct1•ty detect0~ Car60n
d10~de wa5 de~rm1ned uf1n9 a 511~a c01umn and ar90n a5 the carr1er 9a5 w1th a t h e r m E
c0nduct1~ty detect0~ 6a5e0u5 hydr0car60n5 up t0 C~ were determ1ned 0n a P0r0511 C 80100 c01umn w1th n1~09en a5 the cart1er 9a5, uf1n9 a f1ame 10n12at10n detect0r.
Funct10nM 9r0uN c0mp0~t10nE anEy~5 0fthe der1ved 01N wa5 perf0rmed u51n9 F0ur1er
tran5f0rm 1n~a-red 5pec~0metry (F7-10. 7he 5y~em u5ed wa5 a Perk1n E1mer 1750 F 7 4 r
5 p e c ~ 0 m e ~ r w1th a data pr0ce5Nn9 and 5pectre f16rary 5earch faN~ty. A th1n un1f0rm
~ y e r 0f the 011 wa5 p1aced 0n a 5amp1e ce11 and peak hN9h~ were n0rma112ed t0 the
m ~ 0 r C - H peak. CM0r1f1c vEue5 and 5u1phur c0ntent5 0f the der1ved 0115 and char5 were
de~rm1ned 6y 60m6 ca10f1m~ry and e1ementE anEy515 6y 5tandard pr0cedu~e5.
7herm09ra~metr1c anNy515 ( 7 6 A ) 0f1he w00d, ce11u105~ hem1ce11u105e and w0cd f19n1n
wa5 carr1ed 0ut u~n9 a 5tant0n Redcr0~ 280 5er1e5 7 6 anMy5e~ 1n th15 w0rk the 5amp1e,
a p p r 0 ~ m a t e ~ 20 m9 1n wN9hL wa5 heated t0 720°C at 5, 20, 40 and 80 K m1n-1 heat1n9
rate5 uf1n9 n1~09en a5 the pur9e 9a5.7he apparatu5 pr0~de5 f0r the c0nt1nu0u5 mea5urement 0f 5amp1e wN9ht a5 a funct10n 0f ~ m p e r a t u r e and pr0~f10n 15 made f0r an dec~0n1c
d1fferent1at10n 0f the wN9ht f19nE t0 Nve the rate 0f w~9ht 1055.
P.7. W1LL1AM5and5.8E5LER
N1tr09~n
236
Preheater ~
~ ]
5amp1e~
Pyr0~515React0r
Hea~r
~
C0n~
~
0~ ~1y515
~1 ~ 1ce/Ace~neC0n~5
~9. 1.5chema~c~a~am0fthe~0wp ~ 5ta~c6atchreact0~
RE5UL75AND D15CU5510N
Pr0duct y~1d
7a61e 2 5h0w5 the t0tM ma55 ~ d d re5u1~ f0r the w00d 5amp1e5 pyr0~5ed at heat1n9
rate5 0f 5, 20, 40 and 80 K m1n -1 t0 f1nM ~mperature5 0f 300, 420, 600 and 720°C f0r each
c0nd1t10n the ~e1d5 are cumu1at1ve. A5 the ~mperature wa51ncrea5ed f0r each heat1n9 rate,
there wa5 a decrea5e 1n the ~e1d 0f char and a c0rre5p0nd1n9 1ncrea5e 1n the ~ d d 0f 0~
and 9a5. 7he a4ue0u5 ~e1d at 420°C and a60ve remNned ~ u a 1 1 y c0n5tant at a60ut 37
wt%. 7he char ha5 6een 5h0wn t0 c0n~5t 0f car60n and pa~1M~ pyr0~5ed matef1N 5uch
a5 hydr0car60n5 0f h19h m0~cu1ar wd9ht [1N. 7heref0re, a5 the ~mperature wa51ncrea5ed,
the 1ncrea5ed ~ d d 0f h4u1d wa5 m 0~ pr06a61y der1ved ~0m the v01at11~af10n and thermM
de9radat10n 0f the h19h-m0~cu1a~w~9ht hydr0car60n5 w1th1n the char. 7he ma~mum
c0nverf10n 0f wa5te t0 f14u1d 0ccurred a60ve 420°C, where there wa5 m0re than 50%
c0nver~0n. 5haf12adeh [13, 1~ ha5 M50 5h0wn a decrea5e 1n the y1dd 0f char w1th 1ncrea~n9
~mperature 0f p y r 0 ~ 5 . 7 h e 1nf1uence 0f heat1n9 rate 0ver the ran9e ~ud1ed wa5 5ma11,
h19her heat1n9 rate5 ~ad1n9 t0 the f0rmat10n 0f 10wer ~dd5 0f char and h19her ~dd5 0f
9a5 and 0~, wh115t the a4ue0u5 pha5e remNned c0n~ant at 37 wt% and wa5 1ndependent
0f heat1n9 rate. 7he 1nf1uence 0f heat1n9 rate 5u99e~5 that the h19her heat1n9 rate5, wh115t
n0t appr0ach1n9 th05e 0f fa5t pyr0~515, f19n1f1can~y1nf1uence the char, 0~ and 9a5 pr0du~
~ d 5 . 1 n add1t10n, ~nce the N0w pyr01yf15 react0r wa5 c0nt1nu0u51y pur9ed w1th n1~09en,
the 5ec0ndary react10n5 0f the pyr01y~5 vap0ur5 t0 pr0duce char were m1n1m15ed. 7he very
h19h char ~ d d at 300°C 5u99e5t5 that the w00d had n0t under90ne c 0 m p ~ tranNt10n t0
char.
7he ~0w p ~ y ~ 5 0f ~ 0 m ~ 5
237
7a6~ 2. Pr0du~ f1~d fr0m the 510w pyr01y515 0f w00d
Char f1e~
(wt%)
011 f1~d
(wt%)
A4ue0u5 f1dd
(wt%)
6 ~ f1~d
(wt%)
5K ~ n ~
300°C
420°C
600°C
720°C
53.8
29.7
24.4
23.2
10.6
12.4
12.4
13.0
21.0
35.9
36.6
37.0
14.6
21.5
26.4
26.8
20K m 1 n 300°C
420°C
600°C
720°C
~
55.6
27.2
22.6
19.6
10.1
12.2
12.8
14.1
20.5
37.4
37.6
37.5
14.0
23.0
27.0
28.8
40K m 1 n 300°C
420°C
600°C
720°C
~
58.0
26.4
20.4
18.4
6.7
11.8
13.2
14.3
21.7
34.2
37.6
37.7
13.6
27.6
28.8
29.6
8£K m1n
300°C
420°C
600°C
720°C
~
60.8
25.2
18.7
16.2
6.4
11.9
•4.6
15.9
21.6
36.9
37.8
37.7
11.2
26.0
29.1
30.2
7 h e c~0r1f1c v~ue5 0f the 0t15 and char were demrm1ned and f0und t0 6e 0n avera9e 23
and 32 MJ k9 ~, re5pect1ve1y, and were e55ent1a11y ~ d e p e n d e n t 0f heat1n9 ram.
6a5 c0mp051t10n
7he 9a5 c0mp0f1t10n ~ rdat10n t0 m m p e r ~ u ~ 15 5h0wn 1n F19. 2 and ~pre5ent5 c0mp0f1f10n~ data taken dur1n9 the pyr01y515 0f ~0ma55 heamd at 5 K m1n -~ t0 a f1n~
m m p e r a t u ~ 0f 720°C. 7he 9a5 an~yf15 data deaf1y 5h0wed tw0 ~5t1n~ area5 0f 9a5
ev01ut10n, c0nf15t1n9 0f C 0 and C02 at 10wer m m p e r a t u ~ 5 m~n1y 6~ween 200 and 400°C
and H2, w1th ~ w e r c0ncentrat10n5 0f C 0 and C02, CH4 and 0ther hydr0car60n5 at ~ 9 h e r
m m p e r ~ u m 5 . 7he peak5 0f 9a5 ev01ut10n f0r the ~ 9 h e r heat1n9 rate5 0f 20, 40 and 80 K
m1n ~mnded t0 mer9e a5 the heat1n9 ram wa51ncrea~d. F19ure 3 5h0w5 the c0mp0f1f10n~
and t 0 t ~ 9a5 ~ d d 0f the 9a5e5 ev~ved w1th 1ncreaf1n9 heat1n9 rate. A5 the heat1n9 rate wa5
1ncrea5ed, the ~e1d5 0f C 0 , C02, H2, CH4 and C2H6 1ncrea5ed, and there were ~50 10wer
c0ncentrat10n5 0f pr0pane, pr0pene, 6utane and 6utene w h ~ h ~50 5h0wed an ~crea5e 1n
~ d d w1th heat1n9 rate. 7he 9a5e5 have a ~9~f1cant c~0r1f1c v ~ u e : the t0ta1 ca10r1f1c v~ue5
c a ~ a t e d ff0m the 9a5 an~yf15 d a m f0r the w00d 5 a m ~ heamd t0 720°C at heat1n9 r a t ~
0f5, 20, 40 and 80 K m1n -~ wem 13.6, 15.7, 15.7 and 15.8 MJ m 3, m5pect1ve~. Water wa5
rdea5ed 1n the eaf1y 5ta9e5 0f p y r ~ y ~ 5 ff0m a60ut 200°C w~15t 011 wa5 re1ea5ed fr0m
a60ut 300°C, then 60th wamr and 011 were ev0Ned thr0u9h0ut the ~ 9 h e r m m p e r a t u ~ 5 0f
the pyr0~f15 react10n up t0 the f1n~ m m p e r ~ u r e 0f 720°C. 7he ~ d 0f f14md5 and 9a5e5
5h0wed a h m r ~ 5 ~ t0 ~ 9 h e r ~ m p e r a t u m 5 f0r the 1~t1at10n 0f pyr0~f15 and ~50 peak
238
P. 7. W1LL1AM5and 5.8E5LER
200
...... C0
6
t~
t:~:
~:
~
~
160
M01e5
m1n-1
(x10-5~20
~
~
~
1~
.---
•
~
C02
, H 2
--.-- CH 4
1:
1:
~
1:
~
..... C2H 6
~
~
•
•
1
•
1:
~
1
•
1~
80
~
•
•
200
~.
~
400
"0
600
720 (H01d)
7emperature (=C)
~9.2. C0mp051t10n 0fthe p ~ y ~ 5 9a5 ~r w00d p y r 0 ~ d at5 K ~n-~ t0 a f1n~ ~mperam~ 0f
720°C.
f14u1d and 9a5 ~e1d a5the heat1n9 ra~ wa51ncrea5ed, 7h15 phen0men0n wa5 n0ted f0r 60th
the a4ue0u5 and 0~ pha5e5 0fthe f14u1d ~acf10n and M50 f0r 1nd1~duN 9a5e5.
0 ~ charac~r~at~n
Funct10na1 9r0up c0mp0f1t10nM anNy515 0f the pyr01yt1c 0115 5eparated ~0m the c0nden5ed ~4u1d pr0duct wa5 acc0mp115hed 6y F0ur1er tran5f0rm 1n~a~ed 5pectr05c0py (F71~. F19ure 4 5h0w5 typ1cM F7-1r 5pectra f0r the pyr0~f15 0f w00d, 5h0w1n9 the 1nf1uence
0f mmperature. 7he F74r 5pectra 5h0w the pre5ence 0f 0 - H ~6rat10n5 6~ween 3050 and
3600 cm -~ wh~h t09~her w1th the pre5ence 0fC~---0 5tretch1n9 ~6rat10n5 6etween 1650
and 1850 cm-~ 1nd1cate the pre5ence 0f ear60~y~ add5 and th~r def1vaf1ve5.A num6er 0f
car60xyf1c aNd5, f0r examp~ f0rm~ and acet1c and5, have 6een detected 1n 0115 ~0m the
pyr0~f15 0fw00d [1 ~. 7he pre5ence 0fC~--0 ~retch1n9 v16rat10n5 w~h a650r6ance 6etween
1650 and 1850 cm-~ may M501nd~ate the pre5ence 0f ket0ne5 and Ndehyde5 f1nce a1dehyde5
have 6een 1dent1f1ed 1n the pyr01y~5 011 ~0m w00d [1~. 7he pre5ence 0 f C - H ~r~ch1n9
7he ~0w pyr01y5150f 610ma55
250
239
C0
• C02
•
/
• CH 4
200
• H2
M01e5
~
~ C2H 6
(x10-3)
150
100
--~
50
0
-
~--
-•7
20
~
*
40
60
~*
80
Heat1n9 Rate (=K m•n-1)
F19. 3. 70t~ 9a5 ~ d d ~0m w00d pyr~y5ed t0 a f1n~ ~rnper~ure 0f 720°C 1n re~f10n t0 heat1n9
rate.
•6raf10n5 6~ween 2800 and 3000 C m - 1 and C - H def0rmat10n ~6rat10n5 6~ween 1350
and 1475 cm-11nd1cate the pre5ence 0f Mkane5 wh1ch have 6een detected 1n w00d p y r 0 ~ 5
0115 [1~. M0n0cyc11~ p01ycyc11c and 5u65t1tuted ar0mat1c 9r0up5 are 1nd1cated 6y the
a650rpt10n peak5 6etween 675 and 900 cm -~ and 1575 and 1625 cm-1.51nN~r1n9 ar0mat1c
c0mp0und5 and p01ycycf1c ar0mat1c c0mp0und5 have 6een detected 1n 610ma55 pyr01yf15
0115 [17-1~. 7he a650r6ance peak 6etween 1625 and 1675 cm -~ repre5ent5 C 2 C ~retch1n9
~6rat10n5 1nd1cat1ve 0f a1kene5 wh1ch have 6een detected 1n p y r 0 ~ 5 0115 der1ved ~ 0 m
w00d [1~. 7he peak5 6~ween 850 and 950 cm ~1nd1cate the pre5ence 0 f e t h e r 5 . 7 h e 9r0up
0f 0ve~app1n9 peak5 6etween 950 and 1325 cm-~ m05t pr06a61y repre5ent5 the pre5ence 0f
pr1mary, 5ec0ndary and ~rt1ary a~0h015 and N50 phen015 due t0 the C - 0 5~e~h1n9 and
0 - H 1n-p~ne def0rmat10n5 0f the5e funcf10nM 9r0up5. A1c0h0N and phen015 have 6een
1dent1f1ed 1n w00d-der1ved pyr01yt1c 0115 [1~.
7he 1nf1uence 0f ~mperature 0n the pyr01yt1c 0115 15 5h0wn 1n F19.4 f0r the 0115 5amp1ed
240
P. 7. W ~ M A M 5 and 5.8E5LER
~
1
1
3000
1
1
2000
1
1600
Wavenum6er
1200
1 .
1000
1
600
(cm-1)
F19. 4. F7-k 5pectra f0r w00d der1ved pyr01y515011f0r w00d pyr01y5ed at 5 K m1n- ~t0 300,420, 600
and 720°C.
at 300, 420, 600 and 720°C, dur1n9 a 9n91e pyr01y95 exper1ment where the w00d wa5
pyr01y5ed at 5 K m1n -1 t0 a f1na1 temperature 0f 720°C. 7here are deaf1y 50me chan9e5 1n
peak 1nten9t1e5 and theref0re c0mp0~t10n 0f the 0~5 a5 the temperature wa5 1ncrea5ed.
7he 9r0up 0f peak5 6etween 675 and 900 cm-~ and 1575 and 1625 cm -1, repre5ent1n9
m0n0ar0mat1~ p0~ar0mat1c and 5u65t1tuted ar0mat1c c0mp0und5 5h0w5 an 1ncrea5e 1n
1nten~ty a5 the ~mperature 0f pyr01y~5 wa5 1ncrea5ed ~ 0 m 300 t0 720°C. 7he f0rmat10n
0f m0n0cyc11c and p01ycyc11c ar0mat1c 5pec1e5 6y a D1e15-A1de~type react10n N we~ kn0wn
~ 0 - 2 ~ , and ha5 6een 5u99e~ed a5 a mechan15m f0r the f0rmat10n 0f ar0mat~ c0mp0und5
1n 610ma55 pyr01y~5 0115 5u6jected t0 5ec0ndary 0r te~1ary crack1n9 react10n5 ~3, 2 4 . 7he
react10n5 1nv01ve the pyr01y~5 0f Nkane5 t0 pr0duce a1kene5 wh1ch are 5u65e4uent1y
ar0mat15ed 6y a D1e15-A1de~type react10n t0 f0rm Nn91e-r1n9 ar0mat1c c0mp0und5 wh1ch
may then fu~her react t0 91ve p01ycyd~ ar0mat1c h y d r 0 c a r 6 0 n 5 . 7 h e react10n ha5 6een
5h0wn t0 6e 1nf1uenced 6y h19h temperature5 0r 10n9 re~dence t1me5 ~ 0 - 2 ~ .
E~menta1 ana1y~5 0f the 01N de~ved ~ 0 m w00d pyr01y5ed at heat1n9 rate5 0f 5, 20, 40
and 80 K m1n-~ t0 a f1na1 temperature 0f 720°C are 5h0wn 1n 7 a 6 ~ 3. 7he 0~5 are
~eaf1y h19h1y 0xy9enated, a5 ref1ected 1n the 0xy9enated c0mp0und5 1nd1cated 6y the F7~ ana1y~5.7he c0ncentrat10n5 0f n1~09en and 5u1phur are 10w when c0mpared t0 a med1um
7he ~0w pyr~y~5 0f ~0ma55
241
7a~e 3. E1emen~1 an~y~5 0f the ~1 der1ved fr0m the
p y r 0 ~ 5 0f w00d ~ rdaf10n t0 heat1n9 ra~
Heat1n9 r~e (K m1n-~)
7emp~u~
720°C
~em~t
C
H
N
5
0
5
~
40
59.50 61.30 60.90
9.04 9.10 9.57
0.87 0.85 0.82
0.82 0.80
0.75
29.77 27.95 27.96
80
61.65
9.60
0.95
0.70
27.10
0r heavy f u d 011 and c0n5e4uent1y th15 011 ha5 advanta9e5 0ver th05e fu~5 ff0m a c0m6u5t10n
em15510n5 per5pect1ve. 7here appear5 t0 6e an 1ncrea5e 1n the car60n and hydr09en and a
decrea5e 1n 5u1phur and 0xy9en c0ntent5 0f the 0t15 a5 the heat1n9 rate wa5 1ncrea5ed fr0m
5 t0 80 K m1n -~.
7herm0#rav1me~ ana~515
7he m ~ 0 r c0mp0nent5 0f 610ma55 have 6een 5h0wn t0 6e 0f ce11d05e, hem1ce11~05e
and 119~n ~ .
7herm09rav1metr~ ana1yf15 ( 7 6 A ) wa5 u5ed t0 de~rm1ne the t h e r m ~
de9radat10n 0f the w00d and 5am~e5 0f ce11~0~, hem1ce11~05e and f19~n at pr0ce55
c0n~t10n5 the 5ame a5 1n the 510w pyr0~f15 6atch react0r. F19ur~ 5-8 5h0w the 7 6 A
therm09ram5 and ~ f f e ~ n f 1 ~ c a ~ a t 1 0 n 5 0f the we~ht 1055 t0 ~ v e the rate 0f w~9ht 1055
( D 7 6 ) f0r the w00d, ce11~05~ hem~d1u10~ and f19n1n at heat1n9 ra~5 0f 5, 20, 40 and 80
K m1n-~ t0 720°C, ~5pect1ve~.
Fr0m the 7 6 A dam, 1t can 6e 5een that f0r the w00d there 15 an 1~f1~ 1055 0f v0ht1~
m a t e r fr0m the 5am~e. 7he t h e r m ~ dec0mp0f1t10n 0f the w00d 5ta~5 at a p p r 0 ~ m a ~
280°C, and there f01~w5 a m ~ 0 r 1055 0f w~9ht w h e n the m ~ n dev~at1f12at10n 0ccur5 and
15 e 5 ~ n t 1 ~ c 0 m p ~ 6y appr0~mate1y 450°C. 7 ~ 5 15 f0H0wed 6y a 510w fu~her 1055 0f
w~9ht unt11 720°C, af1er w ~ c h there 15 e5~nf1a11y n0 fu~her 1055 0f w~9ht. 7he r e 5 ~ u ~
char am0unted t0 a p p r 0 ~ m a t d y 20% and wa5 e55ent1a11y unaffe~ed 6y the heat1n9 ra~.
7here wa5 a h ~ r ~ 5~f1 1n the 7 6 A curve5 t0 ~ 9 h e r ~ m p e r ~ u r e 5 a5 the heat1n9 rate wa5
1ncrea5ed.
D1fferent1a1 c~c~at10n 0f the w~9ht ~ wa5 carr1ed 0ut a u t 0 m a f 1 c ~ t0 ~ve the rate
0f w~9ht ~ 5h0wn a5 the D 7 6 curve5 1n F~5 5 - 8 . 7 h e r e are c ~ a ~ y tw0 area5 0f w~9ht
1055 pr0du~n9 tw0 peak5 0n the D 7 6 curve5 and a5 the heat1n9 rate wa5 1ncrea5ed, the
tw0 peak5 6ec0me pr09~5f1vdy mer9ed. 7he c0mp0~t10n 0f 1he ~0ma55 wa5 ceH~0~,
hem1ce11u105~ f19~n and ex~ane0u5 c0mp0nent5 and the t h e r m ~ de9radat10n 0f the 1nd1~ d u ~ c0mp0nent5 ha5 6een 5h0wn t0 extrap~ate t0 the 0vera11 de9radat10n 0f1he 0f1~n~
~0ma55 ~6, 2~. W00d ~ 0 m a 5 ~ 5 ha~e 6een 5h0wn t0 6e m ~ y c 0 m p 0 ~ d 0f c e H d 0 ~
and hem~e11~0~ ~ and 1n t~5 w0rk the f19~n wa5 de~rm1ned t0 6e 27.5 wt%, c0n5e4uenf1y the three m ~ 0 r c0mp0nent5 0f ~0ma55 were ~ p r ~ e n t e d a5 m ~ 0 r pr0p0rt10n5 0f
the w00d. 1n t~5 w0rk h e m ~ d ~
rep~n~d
6y x~an, ce11~05e 1n m1cr0cry5ta111ne
f0rm and f19~n der1ved ff0m the w00d were a n ~ y ~ d 6y 7 6 A ~ the 5ame heat1n9 r a t ~ a5
f0r the w00d 5amp~5. 7he ~5uR5 are 5h0wn 1n F195 5-8. Hem1ce11u105~ a~er 50me 1055 0f
v0hf1~ m ~
6e~n5 t0 t h e r m ~ d e c 0 m p 0 ~ ~ a60ut 250°C, and the m ~ n w~9ht 1055
242
P. 7. W1LL1AM5 and 5 . 8 E 5 L E R
(a)
100
1
80
60
Wt%
~1~
40
"~
~~ ~ ~ ~ ~
%
20
~
0
•
1
~
1
~
•
~
1
~
•
(6)
-5
1
11
11
-10
•
dw/dt
1~
~
•
11 • 1~
-15
1
1
1
-2£
...... W00d
---- Ce11u105e
~
--•-- H e m 1 c e 1 1 u 1 0 5 e
-2
L19n1n
1
100
1
200
1
1
1
300
400
500
7emperature
1
600
•
700
(*C)
~9.5. (a) 7 0 A and (6) D 7 0 ~erm0~am5 ~r w00d p ~ e d
~ 5 K m1n- ~t0 720°C
7he ~0w pyr01y~5 0f 610ma55
100
(a)
111
11
1
,
•
80
243
%1
60
Wt%
40-
~k
• "~.~.: ~ , . ~ , ~
20
%
~
0
(6)
1
1,
1
~
~
~
~
~
1
•
~
~
~
•
~
°
~ 1~...~11
1 ~•• ~,.0
•
-10
~ ~
dw/dt
~ 111, 00~
~1,~,°
-20
~
11 11
. . . . . . W00d
11
~
--"-- Ce11U105e
111•
--•-- Hem1ce11u105e
••
1~
~
-30
100•
200
•
300"
4~0
--
L19n1n
500•
600"
700•
7emperature (°C)
~9. 6. (a) 7 6 A and (6) D 7 6 ~erm09ram5 ~ r w00d pyr~y~d ~ 20 K m1n-1 t0 720°C.
2~
P. 7. W ~ A M 5 and 5.8E5LER
100
80
60
Wt%
•
1 •
~ :
1 1 :.
40
20
~
~ : ~ ~ ~
~
~
~
w
~
1
~
.
-20
1
dw/dt
.
1
11
-40
1
~ 0
1.
,•
~ 1•
1 1
,
...... W00d
1•11•1,• ----.~
-60
"
~
•
100
•
200 •
L~9n~n
•
•
300
400
7emperature
•
500
•
600
L
700
(°C)
F19. 7. (a) 7 6 A and (6) D 7 6 therm09ram5 f0r w00d pyr0~5ed at 40 K m1n-~ t0 720°C.
7he ~0w pyr01y~5 0f 610ma55
245
100
80
60
wt%
~
40
•
t~
1:
-~,1~
~°~::~~"~°~
°" ~a.
20
%
~
~
~
"~~
•
(6)"
,.•
-40
11
dw/dt
-80
........
W00d
1~
1;
------Ce11u105e
•1
-- •-- Hem1ce11u105e
-120
~
L19n1n
•
•
1
•
•
100
200
300
400
500
7emperature
1
600
•
700
(°C)
F19. 8. (a) 7 6 A and (6) D 7 6 thenn09ram5 f0r w00d pyr~y5ed at 80 K m1n -~ t0 720°C.
P. 7. W ~ A M 5
246
~ d 5.8E5LER
0ccur5 6~ween 250 and 350°C, a~er w ~ c h there 15 a ~0wer w d 9 h t ~55 t0 the f1na1
~ m p e r a t u ~ 0f 720°C. 7 h e char w ~ 9 h t at the f1n~ ~ m p e r a t u ~ 0f 720°C ~ p ~ n ~
appr0x1m a t d y 20% 6y w d 9 h t 0f the 0 f 1 ~ n ~ hem1ce11u105e. Ce11u105~ a~er a 5ma111055 0f v~at1~
m a t ~ L 6e~n5 t0 d e c 0 m p 0 ~ at a60ut 325°C, and the m ~ n wd9ht 1055 0ccur5 6etween
a60ut 325 and 400°C, a~er w ~ c h the w d 9 h t 1055 dec11ne5 t0 a60ut 8% char 6y the f1n~
~ m p e r ~ u ~ 0f 720°C. L19~n 5h0w5 a 9 r a d u ~ 1055 0f w d 9 h t ~ 0 m a60ut 200°C t0 the f1n~
~ m p e r a t u ~ 0f 720°C. 7he f1n~ char at 720°C repre5ent5 a60ut 55% 6y w e ~ h t 0f the
0 f 1 ~ n ~ f19n1n. C 0 n ~ 4 u e n t 1 ~ the c e 1 1 u ~ and hem1ce11u10~ c0mp0nent5 0f the w00d are
m~y
~5p0nf1~e f0r the v0ht11e p0rt10n 0f the p r 0 d u ~ , w ~ t f19~n 15 the m ~ n c0ntd6ut0r t0 the char, a5 wa5 ~50 5h0wn 6y 5haf12adeh and M c 6 1 n ~ 5 ~ .
7 a ~ e 4 5h0w5 the ~ m p ~ u ~ 5
f0r the 5tart and f1~5h 0f the m ~ n w d 9 h t ~ 5 ~ 5 , and
the ~ m p e r ~ u ~ 0f the m a ~ m u m rate 0f w e ~ h t 1055 f0r the tw0 m ~ n peak5 0f the D 7 6
curve5 and ~50 the 1 n ~ r m e ~ a t e ~ m p e r a t u ~ f0r w00d, c e H ~ 0 ~ , h e m ~ d 1 u ~ and f19~n
f0r the heat1n9 rate5 u5ed. 7he p01nt5 at w ~ c h the ~ m p e r ~ u ~ 5 were a5f19ned are def1ned
1n F19. 9 . 7 h e a5f19nment 0f the 7~ ~ m p e r a t u ~ pr0ved ~ff1c~t t0 de~rm1ne a c c u r a ~
due t0 ~ff1c~t1~ ~ dedd1n9 where the m ~ 0 r part 0f the we19ht 1055 6 e ~ n ~ whe~a5 the
m a ~ m u m m m p e r a t u ~ 5 0 f w d 9 h t 1055, 7m~x, and 7~ax: were much eaf1er t0 a5f19n. 7 a 6 ~ 4
5h0w5 t h ~ t h e ~ wa5 a 1 a ~ r ~ 5h1~ t0 ~ 9 h e r ~ m p e r ~ u ~ 5 f0r 7m~ and 7max~f0r the w00d,
ce1~,
h e m 1 c e 1 1 u ~ and f19~n a5 the heat1n9 r ~ e wa5 ~ e a 5 e d . 7he h t e r ~ 5 ~ 15 M50
f11u5trated 1n F195 5-8 f0r the 7 6 A and D 7 6 curve5. 7he h t e r ~ 5 ~ ha5 6een rep0rted
f0r ~ f f e ~ n t type5 0f 6~ma55 ~8-31] and ha5 6een a5f19ned a5 6~n9 due t0 the c 0 m ~ n e d
effe~5 0fthe heat ~ a n 5 ~ r at the ~ f f e ~ n t heat1n9 ra~5 and the ~ n e f 1 ~ 0fthe dec0mp051t10n
re5u1t~9 1n d d a y e d dec0mp051t10n ~ 9 - 3 ~ . Heat ~ a n 5 ~ r ~ 0 m the furnace t0 the 5amp1e
7 a ~ e 4 . 7 e m p ~ a t u ~ ran9e5 and ~mp~atu~5 0f ma~mum wd9ht 1055
~ r the pyr~y~5 0f w00d, ce11~05e, hem~eH~0~ and ~9~n 6y 7 6 A
(n0menc~tu~ def1ned 1n F19. ~
Heat1n9 r~e
(K m1n-1)
~
(°C)
7m~
CC)
72
CC)
7m~x,2 73
CC)
(°C)
W00d
5
20
40
80
260
260
270
280
325
340
375
400
340
360
380
410
385
400
410
450
405
420
440
480
CeH~0~
5
20
40
80
-----
-----
310
325
300
310
350
370
385
390
380
405
425
430
Hem~10~
5
20
40
80
250
270
280
290
285
310
320
325
320
330
360
400
~9~n
5
20
40
80
300
300
300
300
1
1
380
390
420
460
430
460
500
530
7he ~0w p~NyN5 0f N0m~5
247
dv
~t
(m9 5 - 1 [
1
1
1
$
•
•
71
7~
1~~
1 72
7~
~
2
73
•
1
7emperature (~C)
N9. 9. D 7 6 n0mend~ure ~ r 7a6~ 4.
ha5 6een 5h0wn t0 6e a pr061em 1n determ1n1n9 k1net1c paramem~ [3N and the d05e
c0upf1n9 0f the mea5ur1n9 ~mperature therm0c0up1e t0 the 5amp~ 15 de~ra6~; 1n th15
w0rk the therm0c0up1e mea5ured the ~mperature 0f the 5amp1e 60at.
7he tw0 d1fferent reN0n5 0f wN9ht 1055 repre5en~d 6y w00d pyr01y~5 at the d1fferent
heat1n9 rate5 are ref1ected 1n the D 7 6 curve5 f0r hem1ce11u105e and cd1u105e at each
heat1n9 rate. 7he 10wer temperature D 7 6 peak 0f w00d wa5 mNn1y repre5ented 6y the
dec0mp0f1t10n 0f hem1ce11u105e, and the h19her ~mperature D 7 6 peak wa5 mNn1y repre5ented 6y ce11u105e. L19n1n dec0mp0~f10n 0ccu~ thr0u9h0ut the temperature ran9e u5ed,
6ut the mNn area 0f w~9ht 1055 0ccur5 at the h19her temperature5. Wh115t there 15 d05e
a9reement 1n the D 7 6 peak5 f0r cd1u105e and hem~d1u105e 1n rdat10n t0 the tw0 D 7 6
peak5 f0r w00d, there 15 n0t an exact c0rre1at10n. 7he pure ce11u105e and hem~e11u105e
a1way5 dec0mp05e at 10wer temperature5 than f0r the w00d. 7h15 15 m05t pr06a61y due t0
the 1nh161t1n9 effect 0n the dec0mp0f1t10n react10n5 w1th the w00d due t0 the pre5ence 0f
the 0ther m~0 r c0mp0nent51n the c0mp~x matr1x 0f the w00d. 1n add1t10n, 1n th15 w0rk
pure m1cr0cry5ta1f1ne ceHu105e wa5 u5ed thr0u9h0ut and 5haf12adeh ~4] ha5 5h0wn that
the pur1ty and phy~ca1 pr0pert1e5 0f ce11u105ehave a ~9n1f1cant effect 0n 1~ dec0mp0~t10n.
A1~rat10n 0f the phy5~M 5tructure and pack1n9 den~ty 0f ceHu105e ha5 6een 5h0wn t0
have a pr0n0unced ef1~ct 0n the nature 0f the pyr01yN5 react10n5 and the pre5ence 0f even
very 10w c0ncentrat10n5 0f 1mpur1ty have 6een 5h0wn t0 Nther cata1y5e 0r 1nh16~ the
de9radat10n 0fcd1u105e ~4].
C0mpar150n 0f the data ~0m the 7 6 A and 510w pyr01y~5 5tat1c 6atch react0r 5h0w5 a
f1m11ar tw0-~a9e thermM dec0mp0~f10n 0f w00d ~0m the 7 6 A data and a tw0-5ta9e
ev01ut10n 0f pr0duct5 ~0m the N0w pyr01y~5 react0r. 5haf12adeh [13] ha5 5h0wn f0r
248
P. 7. W1LL1AM5and 5.8E5LER
ce11u105e t h ~ at ~ w ~ ~ m p ~ u ~ 5 , 6d0w 300°C, 1he d0m~ant ~acf10n mecha~5m
pr0duce5 wa~L C0, C02 and ~har. At ~9~er ~ m p ~ u ~ 5 , c e ~ 0 ~ 15 dec0mp0~d 6y an
aRernat1ve p~hway, and the m~0r ev0Ned pr0du~ ~ tar, w~ch c0nt~n5 ~v0~uc05an a5
the m~0r c0mp0nent w1th ~dehyd~, ket0ne5 and 0r9a~c add5 1n add1t10n t0 C0, C0~,
H~ and char [33]. 5haf12adeh [3~ ha5 5h0wn that pyr0~f15 0f hem1ce11~05e 1n the f0rm 0f
x~an at 500°C pr0duced m05f1y ~ r t09~her w1th C0~, wa~r, char and 0ther hydr0car60n5.
5haf12adeh [13] ha5 a150 5h0wn that at ~9her ~ m p ~ u ~ 5 , the ~ f 0 r m 1 n 9 react10n5
acce1erate r a ~ y and 0ve~had0w the pr0duct10n 0f char and 9a5e5. L19~n dec0mp051t10n
~v0N~ a ~w~-~mp~u~
rdea5e 0f C0, C0~, wa~L m ~ h a n ~ and tar and at ~9her
~ m p ~ u m 5 a60ve 500°C, the r d e a ~ 0f H2 and C0 [3~. 7he data p m ~ n ~ d here are
c0nf1~ent w1th the mecha~5m f0r the pyr~y~5 0f ce11~0f1c m~ef1~ pr0p05ed 6y 5haft2adeh [13, 3~, ~ t h ~ the ~wer ~mperature ev01ut~n 0f C02, C 0 and w ~ ~ m ~ y due
t0 the dec0mp0f1t10n 0f hem1ce11~05e and 1he f1r~ 5~9e dec0mp05~0n 0f c e ~ 0 ~ and
the ~ 9 h ~ - ~ m p ~ a t u ~ ev0~f10n 0f 011 and 0ther hydr0car60n5 15 due t0 the 5ec0nd5ta9e dec0mp051t10n 0f ceHu105e and ~50 the ~f1du~ hem~e11~05e. L19~n dec0mp0~5
thr0u9h0ut the ~ m p ~ u ~ re~me pr0dudn9 m ~ y char, 6ut ~50 C02, C0, wa~r and
~ r ~ 10wer ~ m p ~ u ~ 5 , and the ~ 9 ~ e ~ m p ~ u r e
r d e a ~ 0f H2 and C0.
C0NCLU510N5
7he 5~w pyr0~f15 0fw00d ha5 6een unde~aken 1n a ~af1c 6a~h react0r and the pr0du~
c0mp0f1t10n c0mpared t0 the therm~ de9radat10n 0f w00d and the m~0r c0mp0nent5 0f
w00d ~ a therm09ra~m~f1c a n ~ y ~
1. F0r the 5tat1c 6atch react0r, the ~ w e ~ m p e r a t u ~ ~ m e 0f dec0mp051t10n 0f w00d
5h0wed that m~n1y wa~L C 0 and C0~ were ev0Ned, and under the ~9her-~mperature ~ m ~ the m ~ n dec0mp051t10n pr0duct5 were 0f1, wa~L H~, hydr0car60n
9a5e5 and 10wer c0ncen~at10n5 0f C 0 and C0~.
2. 7he 7 6 A ~5u1~ f0r w00d 5h0wed tw0 m ~ n ~ m e 5 0f we~ht 1055, the 10we~
~mperature ~ m e c0~d 6e c 0 ~ a ~ d w1th 1he dec0mp0f1t10n 0f hem1ceH~05e and
the 1n1t1~ ~a9e5 0f ce11u10~ dec0mp0f1f10~ wh11~ the u p p e ~ m p e r ~ u ~ ~ m e
c0rre1ated m~n1y w1th the 1ater 5ta9e5 0f ceH~0~ dec0mp0f1f10n. L19n1n therm~
dec0mp051t10n 0ccurred thr0u9h0ut the ~ m p e r ~ u ~ ran9e 0f pyr0~f15.
3. A5 the heat1n9 rate wa5 1ncrea5ed ~0m 5 t0 80 K m1n-1 there wa5 a 5~f1 t0 ~9her
~mperatu~ v ~ e 5 f0r the ma~mum ra~ cf w~9ht 1055 f0r the 7 6 A and a150 the
ev0~f10n 0f 9a5e5 and 0f1 ~0m the f10w pyr0~f15 ~af1c 6atch react0r.
Ac~n0w~dyement~--7h15 w0rk wa5 5upp0~ed 6y the U.K. 5~ence and En~neef1n9
Re5earch C0un~1 under 9rant num6er5 6R/F/06074, 6R/F/87837 and 6 R / H / 8 3 3 ~
wh05e 5upp0~ we 9r~efu1~ ackn0w1ed9e. We w0u~ ~50 f1ke t0 thank Leed5 U~verf1~
~aff P~er 7h0mp50n and J0hn 7a~0r.
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7he ~0w p ~
0f ~0m~5
249
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250
P. 7. W1LMAM5 and 5.8E5LER
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