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