Analysis of Nitrogen-Containing Species during

Pyrolysis of Coal at Two Different Heating Rates

Koh Ki dena, Yoshi hi sa Hi rose, Toshi hi ro Ai bara, Satoru Murata, and
Masakatsu Nomura*
Department of Applied Chemistry, Faculty of Engineering, Osaka University,
2-1 Yamada-oka, Suita, Osaka 565-0871, J apan
Received J une14, 1999. Revised Manuscript Received September 15, 1999
The effect of heati ng rate on the conversi on of ni trogen i n coal to ni trogen-contai ni ng speci es
duri ng pyrol ysi s of coal was i nvesti gated. Two pyrol ysi s apparatuses were empl oyed i n thi s study.
One was an i nfrared i mage furnace (I I F) whi ch can heat a sampl e up to 1100 C at a heati ng
rate of 10 K/s. The other apparatus was a Curi e-poi nt pyrol yzer (CPP) whose heati ng rate was
around 3000 K/s. Conversi on of ni trogen i n coal to HCN from CPP pyrol ysi s at 1040 C was
hi gher than that i n the case of I I F pyrol ysi s at 1000 C. On the other hand, I I F pyrol ysi s
experi ments at 1000 C produced l arge amounts of N
2
from l ow rank coal s. The resul ts i ndi cate
that heati ng rate can be one of the domi nant factors affecti ng the behavi or of ni trogen rel ease as
a range of heati ng rate appl i ed i n thi s study. The pyrol ysi s of a ni trogen-contai ni ng model pol ymer
showed si mi l ar behavi or to coal pyrol ysi s.
Introduction
Many power pl ants i n Japan and other countri es are
now usi ng a vast amount of coal as a fuel because they
have reasonabl e cost performance and there are i nher-
ent hazardous probl ems to construct and operate a
nucl ear power pl ant. However, coal combusti on technol -
ogy has to overcome the severe regul ati on about NO
x
and SO
x
emi ssi ons si nce coal contai ns a few percentages
of heteroatoms such as ni trogen and sul fur. NO
x
and
SO
x
are, i n general , bel i eved to cause both aci d rai n and
photochemi cal smog. Recentl y, regul ati on of NO
x
from
power pl ants or cars i s becomi ng a seri ous i ssue and a
l ot of attenti on i s pai d to the reducti on of NO
x
.
1-3
There
are three pathways of NO
x
evol uti on duri ng combusti on
of nitrogen-containing fuels in the air: fuel-NO
x
, thermal-
NO
x
, and prompt-NO
x
.
4,5
Fuel -NO
x
ori gi nates from
ni trogen atoms i n the fuel , thermal -NO
x
i s formed by
the reacti on between ni trogen and oxygen i n the ai r at
hi gh temperature, and prompt-NO
x
i s produced by the
reacti on of ni trogen i n the ai r wi th hydrocarbon speci es.
The suppressi on of thermal -NO
x
can be achi eved by the
devel oped combusti on techni que, the so-cal l ed advanced
combusti on technol ogy,
6
and the amount of prompt-NO
x
i s consi dered to be smal l .
7-9
Therefore, to reduce NO
x
emi ssi ons from coal combusti on, fuel -NO
x
shoul d be
suppressed, and the i nvesti gati on of mechani sms of fuel -
NO
x
formati on from coal i s i mportant. The formati on
of fuel -NO
x
i s consi dered to occur i n two steps: the fi rst
step i ncl udes the conversi on of ni trogen speci es i n coal
to NO
x
precursors such as HCN or NH
3
, and the
fol l owi ng step i s thei r oxi dati on under combusti on
condi ti ons to form NO
x
.
7-9
To cl ari fy the phenomena of
ni trogen rel ease from coal , numerous coal pyrol ysi s
exper i ments have been done i n var i ous poi nts of
vi ew,
5,10-20
and several revi ews i ncl udi ng evol uti on of
ni trogen speci es from coal were publ i shed.
21-23
However,
there i s no si mpl e rel ati onshi p between coal ni trogen
content and the amount of NO
x
emi ssi on. Many re-
* Author to whom correspondence shoul d be addressed. Fax: +81-
6-6879-7362. E-mai l : nomura@ap.chem.eng.osaka-u.ac.jp.
(1) Lyngefel t, A.; Leckner, B. Fuel 1993, 72, 1553.
(2) Shi mi zu, T.; Tachi yama, Y.; Fuji ta, D.; Kumazawa, K.-i .; Wakaya-
ma, O.; I shi zu, K.; Kobayashi , S.; Shi kada, S.; I nagaki , M. EnergyFuels
1992, 6, 753.
(3) Shi mi zu, T.; I nagaki , M. Energy Fuels 1993, 7, 648.
(4) Pershi ng, D. W.; Wendt, J. O. L. 16th Symposiumon Combustion,
1976, p 389.
(5) Chen, S. L.; Heap, M. P.; Pershi n, D. W.; Marti n, G. B. Fuel 1982,
61, 1218.
(6) Jensen, A.; Johnsson, J. E.; Andri es, J.; Laughl i n, K.; Read, G.;
Mayer, M.; Baumann, H.; Bonn, B. Fuel 1995, 74, 1555.
(7) Nel son, P. F.; Buckl ey, A. N.; Kel l y, M. D. 24th Symposiumon
Combustion, 1992, p 1259.
(8) Nel son, P. F.; Kel l y, M. D.; Wornat, M. J. Fuel 1991, 70, 403.
(9) Kel l y, M. D.; Buckl ey, A. N.; Nel son, P. F. Proceedings of I CCS
1991, Newcastl e, UK, 1991, p 356.
(10) Kambara, S.; Takarada, T.; Yamamoto, Y.; Kato, K. Energy
Fuels 1993, 7, 1013.
(11) Ohtsuka, Y.; Mori , H.; Watanabe, T.; Asami , K. Fuel 1994, 73,
1093.
(12) Kambara, S.; Takarada, T.; Toyoshi ma, M.; Kato, K. Fuel 1995,
74, 1247.
(13) Leppal ahti , J. Fuel 1995, 74, 1363.
(14) Nel son, P. F.; Li , C.-Z.; Ledesma, E. Energy Fuels 1996, 10,
264.
(15) Hamal ai nen, J. P.; Aho, M. J. Fuel 1996, 75, 1377.
(16) Wu, Z.; Ohtsuka, Y. Energy Fuels 1997, 11, 477.
(17) Li , C.-Z.; Buckl ey, A. N.; Nel son, P. F. Fuel 1998, 77, 157.
(18) Bassi l aki s, R.; Zhao, Y.; Sol omon, P. R.; Seri o, M. A. Energy
Fuels 1993, 7, 710.
(19) Bartl e, K. D.; Tayl or, J. M.; Wi l l i ams, A. Fuel 1992, 71, 714.
(20) Stanczyk, K.; Boudou, J. P. Fuel 1994, 73, 940.
(21) Johnsson, J. E. Fuel 1994, 73, 1398.
(22) Leppal ahti , J.; Kol jonen, T. Fuel Process. Technol. 1995, 43, 1.
(23) Wojtowi cz, M. A.; Pel s, J. R.; Moul i jn, J. A. Fuel Process.
Technol. 1993, 34, 1.
184 Energy & Fuels 2000, 14, 184-189
10.1021/ef9901241 CCC: $19.00 2000 Ameri can Chemi cal Soci ety
Publ i shed on Web 11/20/1999
searchers focused thei r i nterest on the functi onal i ty of
ni trogen i n coal . XPS (X-ray photoel ectron spectroscopy)
i s a common techni que to i nvesti gate ni trogen-contai n-
i ng speci es i n coal .
24-27 15
N NMR (nucl ear magneti c
resonance) spectroscopy
28,29
and XANES (X-ray adsorp-
ti on near-edge structure)
30
have al so been used to
i nvesti gate ni trogen functi onal i ty i n coal . By usi ng these
anal yti cal techni ques, the rel ati onshi p between the
behavi or of ni trogen rel ease from coal and the functi onal
form of ni trogen i n coal was reported. Nel son et al .
7
concl uded that thermal stabi l i ty of ni trogen speci es i n
the tars obeyed the fol l owi ng order: pyrrol i c <pyri di ni c
< cyanoaromati c. Kel emen et al .
25
empl oyed XPS mea-
surement to i denti fy and quanti fy the changes i n
organi cal l y bound ni trogen forms whi ch are present i n
the tars and chars after pyrol ysi s. They found that
pyrrol i c ni trogen decreased and ni trogen i n graphi ti c
type i ncreased i n the char as the temperature i ncreased.
However, there are no l ogi cal vi ewpoi nts to di scuss
ni trogen rel ease from coal .
The di stri buti on of ni trogen-contai ni ng gaseous prod-
ucts was si gni fi cantl y di fferent among experi ments as
summari zed i n the papers,
18,21-23
thi s bei ng partl y due
to the di fferent pyrol ysi s condi ti ons. Ohtsuka et al .
11
reported resul ts from pyrol ysi s i n a fi xed-bed quartz
reactor, showi ng that the major ni trogen-contai ni ng
gaseous product was N
2
. Stanczyk al so detected the
predomi nant formati on of N
2
by mass spectroscopy
duri ng sl ow heati ng of coal .
20
On the other hand,
Takarada et al .
10,12
found that HCN was the mai n
ni trogen-contai ni ng gaseous product i n pyrol ysi s experi -
ments by usi ng a pyroprobe. Nel son et al .
7
observed
HCN and NH
3
as ni trogen-contai ni ng gaseous products
at a hi gh heati ng rate i n a fl ui di zed-bed reactor. I n the
paper above meti oned, the di fferences of experi mental
resul ts may be caused by the vari ati on of coal sampl e
and pyrol ysi s condi ti ons i ncl udi ng di fferent heat-treat-
ment temperature and heati ng rate. Al though the
compari son of data from the pyrol ysi s at di fferent
heati ng rates was done i n several papers and re-
vi ews,
18,21-23
onl y a few coal s were used as objects of
the studi es, or the di fference of heati ng rate was too
l arge to di scuss the effect of heati ng rate on the pyrol ysi s
products. I n the present study, the anal ysi s of ni trogen-
contai ni ng speci es duri ng pyrol ysi s of coal at two
di fferent heati ng rates by usi ng a seri es of the coal
sampl es was performed i n order to i nvesti gate the effect
of pyrol ysi s condi ti ons on the pyrol ysates. The pyrol ysi s
of a model pol ymer was al so exami ned wi th these two
pyrol ysi s techni ques.
Experimental Section
Samples. Seven ki nds of sampl e coal s were empl oyed i n
thi s study. These sampl es were provi ded by Argonne Nati onal
Laboratory, Center for Coal Uti l i zati on, Japan, and Ni ppon
Brown Coal Li quefacti on Co. Ltd., Japan. Thei r anal yti cal data
are shown i n Tabl e 1. The sampl es were pul veri zed under 100
mesh, and dri ed at 60 C i n vacuo pri or to use.
Pyrolysis of Coal with IIF and Analysis of Products.
I n the experi ments usi ng an i nfrared i mage furnace (I I F,
Shi nku-Ri ko Co. Ltd., QHC-P610CP), about 0.5 g of dri ed coal
sampl e was put on the quartz pl ate at the center of the furnace.
The temperautre was moni tored by a thermocoupl e posi ti oned
at the center of the furnace and cl ose to the coal parti cl es. By
moni tori ng temperature, i nfrared output was control l ed to
keep the programmed temperature. Al l runs were carri ed out
under He fl ow (99.99%, 200 mL/mi n) after the i nteri or of the
furnace was purged wi th He for more than 2 h. The ni trogen
l evel after purgi ng was checked by usi ng GC (vi de i nfra)
connected di rectl y to the furnace, and we observed a smal l and
constant amount of ni trogen after purgi ng. Then, the sampl e
was heated to the determi ned temperature at a heati ng rate
of 10 K/s fol l owed by a 10 s hol di ng ti me at that temperature.
The char fracti on that remai ned on the quartz pl ate and
the tar fracti on that deposi ted on the i nner surface of the
furnace were col l ected and wei ghed to cal cul ate the yi el d of
each fracti on. The yi el d of vol ati l e fracti on was obtai ned by
subtracti ng the wei ght of char and tar fracti ons from the
wei ght of i ni ti al sampl e. Ni trogen content of these fracti ons
was determi ned by the el emental anal ysi s of each fracti on. Al l
gaseous products were col l ected i nto an al umi num gas bag
whi ch was pl aced at the exi t of the pyrol ysi s furnace by fl owi ng
hel i um for 2 h from the begi nni ng of the pyrol ysi s. Amounts
of HCN and NH3 col l ected i n the gas bag were quanti fi ed by
a gas detector tube (Gastec Co. Ltd.). Yi el ds of N2 were
esti mated by on-l i ne GC-TCD (Shi madzu GC-8A) equi pped
wi th Mol ecul ar si eve-5A (2 m) stai nl ess steel col umn under
the fol l owi ng condi ti ons: col umn temperature ) 70 C, i njec-
ti on and detector temperature ) 100 C, and TCD current )
180 mA. The ni trogen l evel i n GC anal ysi s i ncreased by a
factor of 100 (i n maxi mum) agai nst the l evel of background
ni trogen. Observed background ni trogen may come from a He
bomb or ai r, but we confi rmed that i t was constant before
pyrol ysi s. The amount of ni trogen from pyrol ysate was esti -
mated by subtracti ng the area of backgound N2 from the
observed N2 area. Furthermore, the ni trogen l evel after
pyrol ysi s decreased exponenti al l y, and i t dropped i nto back-
gound l evel after 2 h. Therefore, the amount of N2 coul d be
cal cul ated by i ntegrati ng the peak area duri ng 2 h of anal ysi s.
Pyrolysisof Coal with CPP andAnalysisof Products.
I n the experi ments usi ng a Curi e-poi nt pyrol yzer (CPP, Japan
Anal yti cal I ndustry Co. Ltd., JHP-3), about 1.0-1.5 mg of dri ed
coal sampl e was used. The detai l ed procedure of the pyrol ysi s
i s descri bed el sewhere.
31
CPP can heat up the sampl e to the
determi ned temperature i n 0.3 s. Therefore, the heati ng rate
i n CPP experi ments was cal cul ated to be 2000-3300 K/s. The
yi el ds of char and tar fracti ons were obtai ned by wei ghi ng
them, the remai nder (wei ght of coal sampl e - wei ghts of char
and tar fracti ons) bei ng the vol ati l e fracti on. Onl y HCN coul d
be anal yzed by GC (Shi madzu GC-14B, wi th fl ame thermoi oni c
detector, FTD) wi th a fused si l i ca capi l l ary col umn, Pora PLOT
Q (0.53 mm 25 m). FTD can detect onl y ni trogen and
(24) Burchi l l , P.; Wel ch, L. S. Fuel 1989, 68, 100.
(25) Kel emen, S. R.; Gorbaty, M. L.; Kwi atek, P. J. Energy Fuels
1994, 8, 896.
(26) Buckl ey, A. N. Fuel Process. Technol. 1994, 38, 165.
(27) Sawada, Y.; Ni nomi ya, Y. Proceedings of 9th I CCS, Essen,
Germany, 1997, p 433.
(28) Kni cker, H.; Hatcher, P. G.; Scaroni , A. W. EnergyFuels 1995,
9, 999.
(29) Sol um, M. S.; Pugmi re, R. J.; Grant, D. M.; Kel emen, S. R.;
Gorbaty, M. L.; Wi nd, R. A. Energy Fuels 1997, 11, 491.
(30) Ki rtl ey, S. M.; Mul l i ns, O. C.; El p, J.; Cramer, A. P. Fuel 1993,
72, 133.
(31) Murata, S.; Mori , T.; Murakami , A.; Nomura, M. Energy Fuels
1995, 9, 119.
Table 1. Properties of the Sample Coals
coal C%(daf) N%(daf) ash%(db)
Pocahontas No.3 PC 91.1 1.33 4.8
Upper Freeport UF 85.5 1.55 13.2
Pi ttsburgh No.8 PT 83.2 1.64 9.3
Mi i ke MK 79.9 1.20 16.0
Tai hei yo TH 78.7 1.17 12.6
South Banko SB 72.3 1.36 2.7
Yal l ourn YL 65.9 0.63 1.6
Analysis of Nitrogen-Containing Species in Pyrolysis Energy & Fuels, Vol. 14, No. 1, 2000 185
phosphorus-contai ni ng organi c compounds i n hi gher sensi ti v-
i ty than the TCD by a factor of 10
6
. Gaseous HCN was
synthesi zed from potassi um cyani de (5 mg) and sul furi c aci d
(0.18 mol /L, 0.2 mL) at 40 C and used as the standard sampl e
i n order to determi ne the concentrati on of HCN from GC
anal ysi s. Hel i um carri er and TCD shoul d be used for the
anal yses of N2 and NH3; however, they were not successful
because of a trace amount of these products and the detectabl e
l i mi tati on. On the other hand, si nce the use of N2 (i nstead of
He) was appropri ate enough to anal yze HCN, we determi ned
to use N2 as a carri er i n the CPP experi ments. The observed
area of HCN i s hi gher than the l i mi t of detecti on by a factor
of 10
5
.
Results and Discussion
Pyrolysisof Coal withIIF. Pyrol ysi s of seven ki nds
of coal s was conducted at 1000 C wi th I I F. The yi el ds
of char, tar, and vol ati l e are shown i n Fi gure 1. We
empl oyed coal sampl es wi th a wi de range of carbon
content, from C 65.9% for YL coal to C 91.1% for PC
coal . Ni trogen content ranged from 0.6% to 1.6%. I n
hi gher rank coal s such as PC and UF, the yi el ds of char
were hi gh, and l ower rank coal s, YL and SB, yi el ded
l arger amounts of vol ati l e. Such tendency was observed
i n the proxi mate anal yses (vol ati l e matter) data of coal .
The resul ti ng char, tar, and gaseous products such as
HCN, NH
3
, and N
2
were found to contai n ni trogen.
Fi gure 2 presents the ni trogen bal ance from pyrol ysi s
of coal wi th I I F. N conversi on to each product was
cal cul ated on the basi s of ni trogen content i n ori gi nal
coal and above products as shown i n eqs 1-5:
For exampl e, coal -N conversi on to char-N was defi ned
as the rati o of the amount of ni trogen i n char to that i n
the ori gi nal coal . Fi gure 2 shows that coal -N conversi on
to char-N was hi gh wi th hi gh rank coal s, whi l e that to
vol ati l e-N was hi gh wi th l ow rank coal s. However, YL
pyrol ysi s resul ted i n hi gher char-N than SB and TH.
Thi s may be caused by the l ow content of ni trogen i n
YL, the rel ati vel y l arge error bei ng i nvol ved i n cal cul a-
ti on of N conversi on to each product. The cumul ati ve
conversi on of ni trogen i n the products, ni trogen recovery
was excel l ent, rangi ng from 92 to 105%. Therefore, the
contri buti on of other ni trogen-contai ni ng vol ati l e prod-
ucts such as ni tri l es, ami nes, ami des, or pyri di ne shoul d
be smal l , even i f they are present as gaseous products.
The pl ots of coal -N conversi on to N-contai ni ng gaseous
products agai nst carbon content of coal are shown i n
Fi gure 3. Thi s fi gure cl earl y i ndi cates that coal -N
conversi on to N
2
for l ow rank coal s, YL, SB, and TH,
was very hi gh. Al though N conversi on to HCN was
sl i ghtl y hi gher than that to NH
3
, i ts rank dependence
was not observed; the coal -N conversi ons to HCN and
NH
3
were 3-10%and 2-6%, respecti vel y. I n the revi ew
papers
18,21-23
compari ng the resul ts from l ow and hi gh
heati ng rates, NH
3
yi el d i s hi gher than HCN yi el d at
l ow heati ng rates. The resul ts i n thi s study were
di fferent from thei r resul ts. Ohtsuka et al .
16
observed
N
2
i n the pyrol ysi s of l ow rank coal s, and the heati ng
rate of thei r experi mental condi ti ons was comparabl e
to our condi ti ons; therefore, we can confi rm that l ow
rank coal s generate N
2
at a certai n heati ng rate.
To i nvesti gate the effect of pyrol ysi s temperature on
the product di stri buti on and coal -N conversi on, I I F
pyrol ysi s experi ments of TH coal at 700-1100 C were
performed. Both fracti on yi el ds and coal -N conversi on
to gaseous ni trogen-contai ni ng products were pl otted
agai nst pyrol ysi s temperature as shown i n Fi gure 4.
Figure 1. The yi el d of I I F pyrol ysi s of the coal s at 1000 C
for 10 s.
Figure2. Ni trogen bal ance of each product after I I F pyrol ysi s
of coal .
Figure 3. Pl ots of coal -ni trogen conversi on to ni trogen-
contai ni ng gaseous products from I I F pyrol ysi s at 1000 C: 4,
N2; ], HCN; 0, NH3.
HCN )
HCN(mol )
[wt of sampl e (g)] %N,raw(db)/100/14
(1)
NH
3
)
NH
3
(mol )
[wt of sampl e (g)] %N,raw(db)/100/14
(2)
N
2
)
N
2
(mol ) 2
[wt of sampl e (g)] %N,raw(db)/100/14
(3)
char-N )
char yi el d (wt%, db) %N,char(db)
%N,raw(db)
(4)
tar-N )
tar yi el d (wt%, daf) %N,tar(daf)
%N,raw(daf)
(5)
186 Energy & Fuels, Vol. 14, No. 1, 2000 Kidena et al.
Ni trogen bal ances for each pyrol ysi s temperature are
not shown here, but they ranged from 93 to 105%, these
bei ng sati sfi ed wi thi n the experi mental error. As the
pyrol ysi s temperature i ncreased from 700 to 1100 C,
the yi el d of the vol ati l e fracti on sl i ghtl y i ncreased, and
coal -N conversi on to N
2
doubl ed. Coal -N conversi on to
HCN al so i ncreased wi th pyrol ysi s temperature. Those
resul ts were not contrary to the reported ones: not onl y
vol ati l e fracti ons but al so ni trogen speci es i n coal can
rel ease more easi l y duri ng pyrol ysi s at hi gher temper-
atures. However, coal -N conversi on to NH
3
di d not
change i n the temperature range exami ned here.
Pyrolysisof Coal with CPP. At fi rst, the pyrol ysi s
of TH coal wi th CPP was conducted at 670, 764, 920,
and 1040 C because we coul d not choose the pyrol ysi s
temperature arbi trari l y due to the l i mi ted number of
pyrofoi l s commerci al l y avai l abl e i n CPP experi ments.
The yi el d of vol ati l e fracti on from pyrol ysi s wi th CPP
i ncreased wi th temperature and the yi el d at 1040 C
was si mi l ar to the vol ati l e yi el d from I I F pyrol ysi s at
1000 C. The pyrol ysi s experi ments wi th CPP were
conducted at 1040 C usi ng seven ki nds of sampl e coal s.
The yi el ds of char, tar, and vol ati l e fracti ons are gi ven
i n Fi gure 5. The yi el d of each fracti on changed depend-
i ng on coal rank i n a fashi on si mi l ar to I I F pyrol ysi s.
Hi gh rank coal s showed hi gher yi el ds of char, whi l e l ow
rank coal s yi el ded l arge amounts of vol ati l es.
We next carri ed out anal ysi s of HCN i n the CPP
experi ments. Coal -N conversi on to HCN i s shown i n
Fi gure 6. I t ranged from 11 to 23%, and decreased wi th
an i ncrease i n coal rank. I t i s noted that coal -N
conversi on to HCN i n CPP pyrol ysi s was hi gher than
that i n I I F pyrol ysi s for al l the coal s studi ed. Thus, the
behavi or of ni trogen rel ease duri ng pyrol ysi s of coal can
be consi dered to be di fferent dependi ng on the heati ng
rate of pyrol ysi s experi ments. Furthermore, the di s-
crepancy observed i n the di stri buti on of ni trogen-
contai ni ng gaseous products among the previ ous reports
by other researchers
5,7,8,10-20
seemed to be rel ated to the
di fference of pyrol ysi s condi ti ons, especi al l y heati ng
rate. Therefore, when we di scuss the ni trogen rel ease
from coal , we shoul d pay attenti on to the pyrol ysi s
condi ti ons, especi al l y to the heati ng rate. The heati ng
rate i n CPP experi ments i s cl ose to that i n pyroprobe
by Kambara et al .
10,12
Al though we coul d not anal yze
ni trogen-contai ni ng gaseous products other than HCN,
the amount of NH
3
and N
2
are consi dered to be smal l
accordi ng to the resul ts usi ng pyroprobe. I n a recent
paper, Takagi et al . found onl y a smal l amount of N
2
i n
CPP experi ments.
32
Influence of the Heating Rate on the Distribu-
tion of Pyrolysis Products. The vol ati l e yi el ds were
di fferent from coal to coal , therefore, i t i s not cl ear
whether the amount of ni trogen-contai ni ng gaseous
products i s proporti onal to the amount of vol ati l e
fracti on or not. To esti mate the di stri buti on of N-
(32) Takagi , H.; I soda, T.; Kusakabe, K.; Morooka, S. Energy Fuels
1999, 13, 934.
Figure4. (a) Pyrol ysi s yi el ds and (b) ni trogen conversi on to gaseous products from I I F pyrol ysi s of TH coal at vari ous temperatures.
Figure 5. The yi el ds of CPP pyrol ysi s of the sampl e coal s.
Figure6. N conversi on to HCN obtai ned from the pyrol ysi s
wi th CPP at 1040 C.
Analysis of Nitrogen-Containing Species in Pyrolysis Energy & Fuels, Vol. 14, No. 1, 2000 187
contai ni ng gaseous products i n the vol ati l e fracti on,
sel ecti vi ty of each N-contai ni ng gaseous product toward
whol e amounts of vol ati l e materi al s was esti mated
accordi ng to the fol l owi ng assumpti on: ni trogen atoms
were di stri buted uni forml y among each pyrol ysi s frac-
ti on. The pl ots of the sel ecti vi ty of ni trogen-contai ni ng
compounds i n gaseous products agai nst carbon content
of coal are shown i n Fi gure 7. Hydrogen cyani de
sel ecti vi ty i n CPP pyrol ysi s reached 50-100%. Thi s
supports that HCN i s the mai n product among ni trogen-
contai ni ng gases. Al though the coal -N conversi on to
HCN decreased wi th an i ncreasi ng carbon content of
coal as shown i n Fi gure 6, HCN sel ecti vi ty was hi gh
for the hi gh rank coal . Therefore, products other than
HCN shoul d be consi dered as the gaseous speci es i n l ow
rank coal s. On the other hand, i n I I F experi ments,
ni trogen i n the vol ati l e fracti on i s di stri buted to N
2
,
HCN, and NH
3
. The sum of the sel ecti vi ty of three gases
di d not reach 1.0 as shown i n Fi gure 7. Thi s i ndi cates
the assumpti on for the determi nati on of the sel ecti vi ty
i s not correct. Char-N/char-yi el d was >1.0 i n al most al l
cases exami ned. Therefore, ni trogen atoms tend to be
concentrated i n char fracti on wi th thi s pyrol ysi s, espe-
ci al l y at l ower heati ng rates. However, we can appl y thi s
assumpti on i n order to di scuss the vol ati l i ty of each
gaseous product i n the pyrol ysi s experi ments. I n hi gh
rank coal s, HCN seems to be vol ati l i zed easi l y i n both
pyrol ysi s systems, and N
2
sel ecti vi ty became hi gh for
three l ow rank coal s at l ow heati ng rate. Al though we
coul d not anal yze N
2
and NH
3
i n CPP experi ments,
there i s si gni fi cant i nfl uence of the heati ng rate on the
di stri buti on of gaseous products. Hi gh sel ecti vi ty of N
2
i n I I F pyrol ysi s of l ow rank coal agrees wel l wi th the
resul ts reported by Ohtsuka et al .
16
Thei r pyrol ysi s
condi ti ons were si mi l ar to our condi ti ons, and they al so
empl oyed l ow rank coal s. The heati ng rate of our I I F
experi ments and Ohtsukas experi ments were rel ati vel y
l ower than that of CPP experi ments. I t may bri ng about
a secondary reacti on of other speci es to N
2
duri ng
pyrol ysi s. Leppal ahti et al .
22
al so di scussed the effect
of heati ng rate on the di stri buti on of pyrol ysate i n the
reacti on system. At l ow heati ng rate, resi dence ti me
becomes rel ati vel y l ong, and the pyrol ysates have
chances to react wi th other fracti ons. I n the present
study, si nce the sel ecti vi ty of HCN was hi gh i n the CPP
experi ment and l ow i n the I I F experi ment, the fol l owi ng
i dea coul d be proposed: HCN was rel eased from coal
as a pri mary gaseous product, and then i t reacted wi th
char-N or tar-N to generate other speci es, N
2
, especi al l y
i n l ow rank coal s.
Pyrolysisof Model Compounds. To i nvesti gate the
decomposi ti on behavi or of pyri di ni c and quaternary
ni trogen wi th the two pyrol yzers, we empl oyed model
compounds such as pol y(4-vi nyl pyri di ne) (PVP) whi ch
represents pyri di ni c type compounds. Pyrol ysi s of PVP
and aci d-treated PVP were conducted. Aci d treatment
of the pol ymer was conducted by sti rri ng the mi xture
of 10% HCl (aq) and pol ymer at room temperature for 2
h. The conversi on of pyri di ni c ni trogen i n PVP to
quaternary (protonated) form was esti mated as 85%on
the basi s of the atomi c rati o of chl ori ne to ni trogen i n
the treated PVP. Tabl e 2 shows the pol ymer-N conver-
si on to ni trogen-contai ni ng gaseous products i n I I F and
CPP pyrol ysi s experi ments. I n both pyrol ysi s experi -
ments, pol ymers pyrol yzed al most compl etel y; char yi el d
was approxi matel y zero, and N conversi on to gaseous
product was l ow. The remai nder shoul d be tar fracti on.
When we anal yzed the tar fracti on col l ected, pyri di ne
and i ts ol i gomer were observed. Therefore, i n the
pyrol ysi s of the model pol ymer, degradati on of the
pol ymer chai n occurred al ong wi th the decomposi ti on
of the heteroaromati c ri ng. I nfl uences of heati ng rate
were al so observed i n the pyrol ysi s of the model
pol ymer. From Tabl e 2, the N conversi on to HCN was
hi gher i n CPP pyrol ysi s than i n I I F pyrol ysi s, thi s bei ng
si mi l ar to the resul ts from coal pyrol ysi s. The resul ts
i ndi cate that the decomposi ti on of the heteroaromati c
ri ng i s easy i n the rapi d heati ng. I n thi s case, I I F
pyrol ysi s degraded the pol ymer to ol i gomer preferabl y.
However, a detectabl e di fference between the pyrol ysi s
of PVP and that of aci d-treated PVP was observed: N
conversi on to HCN i n the I I F pyrol ysi s of PVP was l ess
than the detectabl e range, whi l e aci d-treated PVP
generated a detectabl e amount of HCN i n I I F pyrol ysi s.
Therefore, decomposi ti on of the heteroaromati c ri ng
occurred i n I I F pyrol ysi s. However, aci d-treatment
affected N conversi on to HCN i n di fferent way for the
two pyrol ysi s systems. I n the present study, al though
we can menti on the di screpancy of pyrol yti c behavi or
i n two di fferent pyrol ysi s systems, we coul d not di scuss
the rel ati onshi p between the ni trogen form i n the
pol ymer and the product di stri buti on.
Conclusions
By usi ng two di fferent pyrol ysi s furnaces, an i nfrared
i mage furnace (I I F), and a Curi e-poi nt pyrol yzer (CPP),
the pyrol ysi s experi ments of seven coal sampl es were
performed. I n the I I F pyrol ysi s, we succeeded i n anal yz-
i ng gaseous products such as HCN, NH
3
, and N
2
Figure 7. The pl ots of the sel ecti vi ty of ni trogen i n gaseous
products to whol e ni trogen i n vol ati l e fracti on duri ng the
pyrol ysi s wi th I I F (open symbol s) or CPP (fi l l ed symbol s): 4,
I I F-N2; ], I I F-HCN; 0, I I F-NH3; [, CPP-HCN.
Table 2. N Conversion to N-Containing Gaseous
Products in the Pyrolysis of N-Containing Polymer
N conversi on (%, coal -N basi s)
pyrol ysi s system
(condi ti ons)
N-contai ni ng
gases PVP
a
PVP + HCl
b
I I F HCN -
c
2.7
(1000 C, 10 s) NH3 0.3 -
N2 - -
CPP HCN 5.5 4.0
(1040 C, 3 s)
a
Pol y(4-vi nyl pyri di ne).
b
10%HCl (aq)-treated PVP.
c
Less than
detectabl e l i mi tati on (<0.1%).
188 Energy & Fuels, Vol. 14, No. 1, 2000 Kidena et al.
quanti tati vel y. On the other hand, onl y the amount of
HCN was determi ned by GC i n the CPP pyrol ysi s of
coal . We obtai ned good ni trogen bal ance i n the I I F
pyrol ysi s. Coal -N conversi on to N
2
was hi gh i n the I I F
pyrol ysi s of l ow rank coal s. On the other hand, coal -N
conversi on to HCN i n CPP pyrol ysi s was rel ati vel y
hi gher than that i n I I F pyrol ysi s. To compare the
vol ati l i ty of ni trogen-contai ni ng gaseous products under
two di fferent pyrol ysi s condi ti ons, we cal cul ated the
sel ecti vi ty of each product accordi ng to an assumpti on
i n whi ch ni trogen atoms were di stri buted uni forml y
among each pyrol ysi s fracti on. The sel ecti vi ty of HCN
i s rather hi gh i n CPP pyrol ysi s; on the other hand, i n
the case of I I F pyrol ysi s, sel ecti vi ty of N
2
i s l arge for
l ow rank coal . Therefore, i t i s consi dered that rapi d
pyrol ysi s i nduced the emi ssi on of HCN and the second-
ary reacti on occurred to form N
2
i n the pyrol ysi s at
l ower heati ng rates. Fi nal l y, the pyrol ysi s of the model
pol ymer was performed. I t al so i ndi cated the i nfl uence
of heati ng rate on the behavi or of ni trogen rel ease. Aci d
treatment can affect the N conversi on to HCN i n both
pyrol ysi s systems i n di fferent ways.
Acknowledgment. Thi s work was performed as an
i nternati onal research grant sponsored by the New
Energy and I ndustri al Technol ogy Devel opment Orga-
ni zati on (NEDO), Japan.
EF9901241
Analysis of Nitrogen-Containing Species in Pyrolysis Energy & Fuels, Vol. 14, No. 1, 2000 189