Journal of Analyksd and Applied Pyrolysis

ELSEYIER

a-41

(1997) 91- 103

Hydropyrolysis: a versatile technique for solid fuel liquefaction, sulphur speciation and biomarker release

High oil yields (ca. WA both daf and carbon basis) with relatively low hydrocarbon gas yields can he achieved for coals and oil &ales in fixal-bed pyrolysis at high hydrogen pressure (hydropyrolysis, 15 MPa) with relatively fast hwing and a suitable dispmaa catalyst, such as sulphided MO or Fe. This article reviews the application of hydropymlysb to biomass and its adaptation as an analytical technique to spec@ organic sulphur forms and to rekasc covakntiy-bound biomarka hydmcahons for co& and ptroti source
rocks. Results for allulosc,

eucalyptus

wood and sugar cane bagassc demonstrate

the

potential of hydropyrolysis for producing bio-oils with much lower oxygen contents than by traditional pyrolysis proccws. The inhcmt drawbacks with tanpmturc pmgmmmcd redurxioa (TPR) for specifying the organic sUtphur forms in saSmcn_ organic matIer in that (i) thiophenic sulphur has Iargely been undectabk and (ii) sulph.&s interconwt readily into thiophenes have been overcome by the use of the well-swept fixed-hcd h.vdropyrorySis reactor operating at I$ MPa. The application of high prcsurc TPR to pyrite-free bituminous coal and a type-US kcrogen is described. To illustrate the ability of hydropyrolysis to release covaleatly-bound biomarker hydrocarbons from sedimentary or@c matter, tbc yitkls and conformations of the hopanes and steranes released from a type I kerogen act -ted. Q 1997 Elsetier Science 3.V. Keywords. Hydropyrolysis;
Biomass; Coal; tkganic

sulphur; Covahtiy-bound

biomarkers

??

Corresponding author.
rwmd.

016S-2370/97/Sl7,00 0 1997 Elsevicr Scicncc B.V. AlI figh PIISOt65-2370(97)0004l-7

J.D. Ruclta et d. ;-I. Anal. Appl. Pyrolwis 40-41

(1997) 91.-103

1. introduction

The pyrohysis of coals and oil shales under high hydrogen pressures (hydropyrtllysis) has received considerable attention as a means of obtaining much higher oil yields t!ran can be obtained by conventional retorting/pyrolysis processes [l--3]. For coal liquefaction, hydropyrolysis provides a process configuration that avoids rhe use of recycle solvent which constitutes up to two-thirds of the reactor stream for conventional liquefaction processes. Although technolog; for feeding ground solids into high pressure reactors is well-established, coal pyrolysis processes are usually associated with relatively low conversions to liquid products, Further, hydrogen consumptions are high due to large quantities of methane invariably being produced via char fiydrogasification and cracking of the primary volatiles at temperatures above 6WC, normally required to achieve substantial liquid yields [1,2]. Selectivity to liquid products can be improved by operating at relatively low temperatures (ca. SOOC) but long solids residence times are required to maxim& oil yields. Indeed, it has been demcnstrarecl that oil yields of ca. 60% daf coal with relatively low gas yields can be achieved for bituminous coals in fixed-bed reactors using hydrogen pressures (hydropyrolysis) of ca. 15 MPa [3-61. A sulphided molybdenum (Mo) or other suitable dispersed catalyst is required since tar yields without catalyst are typically no more than 35%. For low-rank coal*, catalysts are generally less effective at high pressure, increasing tar yields typically no more than 10% daf coal [3,6]. Biomass has the potential to replace fossil sources of fuels and chemicals. Prehminary work with cellulose [q, Euphorbia rigida wood and sunflower bagasse [8,9] has established that bio.oils can be obtained in higher yield and with lower oxygen contents via hydropyrolysis compared to normal pyrolysis. A major advantage of hydropyrolysis for bio-oils is that they can be upgraded in the vapour phacr by having a two-stage reactor in which a catalyst bed is situated immediately after the hydropyrolysis zone. This avoids the need for liquid phase hydroprocessing which has been studied with a number of catalysts [IO-131. Although rapid heating is invariably needed in process situations [I,31 slow heating is being used in analytical applications of hydropyrolysis or high pressure temperature programmed reduction (TPR) to specify organic sulphur forms [14] and to release covalently-bound biomarkers in coals and other forms of sedimentary organic matter [15,16]. This article reviews the develop ment of these two applications after first of all assessing how pressure, the use of catalyst and heating rate in hydropyrolysis affect oil yield for some coats and biomass %cdstocks, namely cellulose, eucalyptus wood and sugar cane bagasse. For the latter, the effect of these parameters and second-stage vapour phase hydrotreating on the hydrodeoxygenation of the bio-oils are also rcported.

J.0

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2. ExpwImcntai The fixed-bed resistively-heated reactor (0.8 cm i.d.) used for hydropyrolysis has been described previously [3-6,141. For TPR, a quadrupole mass spectrometer is used to monitor the release of hydrogen sulphide (H$) and other volatiles fl4J. Samples (0.1-4 g, dried in vacua at XK) are diluted in sand to help overcome mass transfer restrictions to the releasing of volatiles. Most tests reported here for coals and an oil shale classified as a type I kerogen (G@niik, N.W. Turkey) have been conducted using I5 MPa hydrogen pressure at temperatures of 52ooC and . For the catalytic tests, 6OO*Cwith heating rates of 5, 50 and 300C min- ammonium dioxydithlomolybdate was impregnated onto the sampIes to give a Mo loading of I% (daf basis). A hydrogeu flow of 10 dm3 min - I, measured at ambient
temperature and ntc?ssure,ihrough the WSWMrnsures that overall conversions are

not limited by mass transfer in the SampIe bed [ISj and 50, once formed, the volatiles quickly escztp. Qiis are collected in a tmp cooled with dry-ice and rectivered in dichloromethane @CM) for subsequent fractionation. For the biomass feedstocks investigated, namely ceIlulose (AIdricb, c 200 m), sugar cane bagasse (from a Brazilian ethanol distiIIety) and eucalyptus wood (from a &&tan cultivated forest), normal pyrolysis and hydropyrolysis tests were conducted at 520C using nitrogen and hydrogen pressures of 0.5 and 10 MPa, respectively with heating rates of 5 and 300C min- . A &oidal FeS catalyst was used in some tests (Fe loading of 5%, daf basis). Two-stage tests were also carried out with the biomass feedstocks in the 6xed bed reactor. A commercial Ni-Mo[ P:Al,O, (Criterion 424) hydrotreating catalyst was loaded in the Iower part of the reactor after ex-situ sulphidation at 400C. About I g of catlyst was used in each run with the temperature in second stage being kept constant at 4CKK.
For high pressure TPR [14], ca. 50 mg of 6nely ground kerogen was diluted in a 1:lO w/w mixture with acid-washed sand (250-75 p) to increase the voidag in the fixed-bed reactor. The samples were heated from ambient to 6CHYC at a rate of ST

min- with the hydrogen volumetric flow rate of 5 dm3 min - i measured at ambient conditions corresponding to a superlkiai gas veltity of approximately 0.5 ms- in the reactor. Liquid products were collected in a~ ice/water cooled trap and at the end of each run these were recovered in dichlorometbane. The HJ evolved l rom the reactor was detected using a VG Quadrupcles O-300 a.m.u. mass spectrometer. For the biomarker studies, KM-soluble products from i.nitiaI solvent extractions (DCM and pyridine) and the subsequent catalytic hydrogenation (conducted
in a mlcroreactor at 350C and 7 MPa and hydropyrolysis tests are separated by silica gel adsorption chromatography into aiiphatics, aromatics and polars by

elution with n-hexane, x:-hexane-toluene (I:1 v/v) and JDCM/methanol (I:1 v/v), respectively. Yields are determined after evaporating the solvents in a stream of nitrogen. The aliphatic fractions are then anaIysA! by gas chromatography-mass spectwmetrv @C-MS, Varian .?400GC linked to a Finn&an MAT 15470 tripIe quadrupole MS). The single ions monitored include m/z !91 (triterpanes), 217
(steraaes) and 231 (methylsteranes). The addition of a ster;ine standard (S/?(H)-

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Anal. Appl. Pyrv~sis

40-41 (1997) 9i- IO3

cholane) to the alkane fractions prior to X-MS sterane concentrations to be estimated [ 15.16].

analysis allowed the hopane and

3. Heating rate effects in hydrapyrolysis Table 1 compares the hydropyrolysis product yields obtained at 5 and 300C min ~ I, with and without catalyst, for a UK bituminous coal, Gedling and Wyodak sub-bituminous coal (Argonne Premium Coal Sample. APCS) [17]. In contrast to pyrohysis in nitrogen, both tar yields and overall conversions increased markedly by lo- 15% daf coal as the heating rate was lowered from 300 to 5 C min - I. For both coals, these increases occurred both with and without the catalyst. Further, for the bituminous .:oal, the char yield with catalyst was below loQ/ daf coal which corresponds to a significant fraction of the inertinite being converted. The effects of heating rate and catalyst (Fe) addi ion on the biomass samples investigated (Table 2) are similar to the coal samples. A combination of slow heating and the FE for all the cbtdlyst used at a pressure of 10 MPa gives rise to conversions of 1M)o/o three biomass samples investigated. The improved volatile yields are ascribed to the much longer times available with slow heating at temperatures below approximately 45O C for the hydrogen and catalyst to mediate bond s&ion (hydrocracking and heteroatom removal) reactions. Although higher conversions have also been reported for hydropyrolysis in heated-grid reactors as the heating rate falls [I 81, the effects appear less pronounced than in the fixed-bed reactor used here, probably due to a combination of the much lower gas velocities through the sampte and the slowest rate used being 60C min-I.

Table I Hydropyrolyais yields for Gedling coal and Wyodak APCS al 520C Heating rate rC min- ) Calalyst (MO) Product disrribuGonb (% daf basis) Char Gedling 5 300 5 3M) Wyodak 5 300 5 300 a From ref. [ 17). b Estimated error of + Tar C,-C, gases

No NQ YeS Yes

42 57 8 22

39 34 76 62

II 7 9 7

No No Yes Yes

21 30 8 22

57 52 73 62

9 8 9 7

I-Z%.

J.D. R&a

ct al. , J. Awl. Appl. Pywlysir M-41 (1W7) 91-103

95

Table 2 Hydropyrolysis product yields for ccIIuIuse, eucalyptus wood and sugar me ICI.0 MPa. Heating rate ( C min- ) Catalyst (Fe)

bagaw

at 52o C and --

Product distribution (7.bdaf basis) Char Bi0-d

G-C, gam
4.8 5.2 3.1 5.5 5.4 7.4 7.0 5.9 7.1 7.9 3.4 9.1 -

ccllulosc
5 NO

300 5 3# Eucalyptus wood 5 Ml 5 300 Sugar cmc b+se 5 300 5 300 [Ai ,~xygen in biwil. p cwmatcd error of f l-z%.

NO YC3 YeS No No Yt!S Yf!S No ND YeS Yes

16 13 <l 5 16 20 0 17 I5 21 <I 7

38 37 52 45 40 37 62 44

[MI [ZOI (261 [14] P] PSI [30] [34]

40 [32] 41 [24] 52 p7j 48 121

4. Hydr&fE4ygeIultisa of b&&i Overall conversions, bio-cil and gas yields and the oxygen contents of the biosils from pyrolysis under nitrogen are shown LI Table 3 for the three feedstocks investigated. Cellulose gave very similar hehaviour to eucalyptus wood and sugar cane bagasse with overall conversions and bio-oil yields close to 75 and 40 S, respectively, and hydrocarbon gas yields of ca. 1%. The bio-oils contained about 35% oxygen (Table 3). Clearly, the pyrolysis of biomass kdstc&s at atmospheric
Table 3 Conversion (lOO?khar yield), b&oil and gas (C,-C,) yields for otlIulosc, &UIS wood and sugar cane bagassc pyrolysis a: 52VC. 0.5 MPa N2 pnssurc tirh a heating rate 3OO C mh-

Char Cellulm Eucalyptus wood Sugar cane bagassc 24 25 24

Bio-oil 42 139 38 I35l 38 [N.D,]

C,G 0.9 0.3 L.0

@==

v] oxygenin bio+iI.
N.D. = not determined. a estimated error of f l-Z%.

J.D. Rnch rr d/J. Anal. Appt. Pytdysis 40-Ji (1997) W-103

Char Blo-all

Water
Gm (Cl-C4)

: 2 1

ID

12

Pressure,MPa
Fig. 1. Product yields from cellulose for the iwo-stage
CilliIlySl.

hydropyroiysis

experiments

with a

Ni-Mo/P:A1201

pressure has received considerable attention and the yields and high oxygen contents of the oils suumarised here from the same reactor as used for hydropyrotysis are consistent with those from fludised-bed and entrained flow pyrolysis experiments on wood at similar temperatures [19-211. As well as increasing conversions (Table 2, see above) and hydrocarbon gas yields, hydropyrolysis with and without the dispersed FeS catalyst at IO MPa gave rise to higher bio-oil yields with somewhat lower oxygen contents when compared to normal pyrolysis. However, the reductions in oxygen conteut Jo not hollow any particular trend. They vary from ca. 5-20% with the highest reduction king obtained for cellulose with the catalyst (Table 2). The effect of the iron catalyst was most pronounced with slow heating with increases in total conversions and bio-oil yields of 15 and 12-20%, respectively, with reductions of ca. 5% in the oxygen contents of the bio-oils (Table 2). The effect of a commercial Ni-Mo/P:AIzOOS catalyst in two-stage hydropyrolysis ior cellulose at different hydrogen pressures is presented in Fig. 1. Raising the pressure from 2.5 to 10 MPa conversion does not markedly affect thebio-oil yield, but the oxygen content of the oil decreases by about 20%, from 32 to 10% (Table 4). The H/C ratios are higher and O/C ratios smaller for all the two-stage bio-oils compared to their single stage counterparts. However, for hydrodeoxygenation, the dimerence in the O/C ratios between the single and two-stage bio-oils increases with pressure (Table 4), the oxygen content being ca. 10% for the two-stage oil at 10 MPa. GC analysis has indicated that the average boiling point of the virtually colourless two-stage bio-nil obtained at 10 MPa is no more than ca. 150C. The major hydrocarbon and oxygenated compounds identified by GC-MS include

J.D.

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97

acyclic and cyclic alkanes, alkyl knzenes, alcohols and acetalsjketones. together with ~lkyl Dhennntcin !$P ti$z X Lng material. MicrazzAysis cc ttc used cata?yd detected less than 1% of carbon for the 10 MPa two-stage test, indicating that the extent of coking was very low with hardly any loss of carbon from the oil. In comparison, the same experiments for coals give rise to carbon contents of ca. 5% of carbon for the used catalysts.

5. High Pressure TPR The principal inherent drawbacks with low pressure TPR for spec fying the organic sulpbur forms in solid fuels in that (i) thiophenic sulphur is only partially detectable and (ii) sulphides can interconvert into thiophenes have largely been overcome by the use of the well-swept fixed&d hydropyrolysis reactor operating at 15 MPa [ 141. The technique has been applied to a range of pyrite-f= coals and kerogens [14] and has been calibrated with sulphw compounds immobilised on silica [22] and incorporated into phenolic resins [23]. The H$ reduction temperatures for tne model substrates investigated previously [22.23] are summarized in Table 5. Although high pressure TPR is a thermal technique and may still suffer some interferences from retrogressive chemistry involving the non-thioyhenic sulphur forms, the resolution obtained between thiopherles, aromatic and aliphatic sulphides and dijpolysulphides is vastly superior to that fur X?S and XANES as illustrated by the following examples [14,22]. Fig. 2 and Fig. 3 show the H$ evoIution profiles in high pressure TPR for a typz IL-S kerogen, Monterey and a high-volatile bituminous coal (Beringen, both samples are low in pyrite). For both samples, the H,S observed amounts for 75% of the organic sulphur with the remaining 25% being released as thiophenic compounds in the tars. The profile for Monterey kerogen exhibits two main features, a broad peak from approximately 2OWlOO*C representing predominately monosulphides and a sharper peak giving a T_ at around 480C indicative of
Table 4 Elemental compositions of biwils +XllUlOst. Pressure (Ml%) /Olaf basis c TS 2.5 5.0 7.5 10.0 a By dii krcnce 62.0 70.4 77.9 81.9 ss 64.1 69.1 71.2 74.2 H -TSSSTS 6.3 7.0 7.7 8.3 5.0 5.7 5.8 5.9 31.7 22.4 14.4 9.8 o* Ss 30.9 25.2 23.0 19.9 1.22 1.19 1.18 1.21 0.94 a.99 0.98 0.95 0.3s 0.24 0.14 0.09 0.36 0.X 0.24 0.20

from two-stage (Ts) and sin&e stage (SS) hyd:opyrolysis of

Atomic WC ratio TS ss

komic l-s

OK

ratio SS

Table 5 Summary of reduction temperatures for sulphur containing model substrates in high pressure TPR (compiled from Rcfs. [22] and 1231) Sulphur form r,,, ( C) lmmobilised substrates 480 320 360 270 I50-250 180 Others

Resites Dibenzothiophene Diphrnyl sutphidc Thioanisole Phenyl benzyl sulphide Dilpolywlphides in vulcanised pitch Thiol. cysteine 500 320 300 280

dibenzothiophene-type structures. Assuming that the 20-25% organic sulphur in the TPR oil is predominately thiophenic, then it is estimated that thiophenes account for a maximum of ca. 40% of organically bound sulphur. The H,S evolution profile for the bituminous coal (Beringen, Fig. 3) indicates that complex thiophencs are the major form present with the major peak centred at 470C accounting for ca. 65% of the H,S evolved and corresponding fairly closely to the reduction temperature of dibcnzothiophene (Table 5) [22,23]. From this, it can be deduced that ca. 75% of the organic sulphur is present in complex thiophenes, again taking account of the thiophenic compounds in the tar. The remaining H,S that evolves below 43PC arises from :L mixture of aromatic and

Fig. 2. Hydrogen sulphidc evolution profile in high prcssurc TPR of Monlrrcy k-rogen.

99

Fig. 3. Hydrogen sulphide evolulion profik in high prauux TPR of lkringm coaI.

aliphatic sulyhides and simple thiophenes. liowever, aromatic sulphides and simple thiophenes are thought ?3 +minete since lit?!: HIS evolves below 350C ( < 5%). In common with XPS and XANES and other pyrolysis methods, high pressure TPR indicates that the proportion of thiophenic sulphur increases with rank, as illustrated here for Beringen coal which contains hardly any aliphatic carbon-bound sulphur. Indeed, he proportions of aromatic-bound sulphur derived from high pressure TPR are generally higher than by X-ray t&miques with bituminous coals containing no more than 10% organic sulphur as ahphatic suiphi&s [14,24]. Work to be published on recent sediment samples which contain predominately aliphatic ;.oly/mono-sulphides with little or no thiophenic sulphur, as determined by high pressure TPR [251, prov+s reasoably strong evidence that this d8brence is unlikely to be due to secondary reactions in hydropyrolysis.

6. Reiease of cav&ntly-hotmd

Mamarkers

To illustrate the potential of hydropyrolysis to release covalently-bound biomarker hydrocarlxms from coals and petroleum source rocks, the yields and conformations of the hopanes and steranes released from Gi5yntik oil shale (from NW Turkey, immature type I kerogen lacustrine) are presented [ 16) The results are compared with those for traditional solvent extraction and batchwise hydrogenation at the much lower temperature of 300C. Table 6 lists the total extract and aliphatic fraction yields obtained from the sequential extraction of the shale with DCM and pyridine followed by sequential catalytic hydrogenation and hydropyrolysis of the resultant kerogen. The yields obtained From a pyrolysis exwriment in nitrogen on the hydrogenation residue are also included. The total conversion is ca. 93% w/w. Further, the high yield of aliphatic hydrocarbons released by catalytic

loo

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hydropyrolysis (Table 6, 222 mg- (g TOC)) is consistent with the relatively low aromaticity of the shale (ca. 30%). As expected, the more selective hydrogenation procedure gave much lower total extract and aliphatic yields. Similar trends in aliphatic hydrocarbon yields have also been found for bituminous coal vitrinite concentrates 1151. The yields of selected hopanes and sleranes reIeased by the sequential extraction of the shale with DCM and pyridine followed by hydrogenation and hydropyrolysis of the residual ketogen are listed in Table 7. The fact that the triterpanes are dominated by hopanes up to Cj5 with the biologically-inherited, but thermodynamically unstable 17/I(H), 2lb(H)-configuration, demonstrates the unique ability of hydropyrolysis to maximise the yields of covalently-bound alkane biomarkers without at%cting their stereochemistries. The yields of the C29-C35l?@(H), 21/J(H)hopanes are Z- 10 times greater than those from DCM extraction, mild hydrogenation and normal pyrolysis. Further, the yields of the C33-CJJ l7fl(H), 21/?(H)-hopanes, not found in DCM extracts, were again much higher than for hydrogenation. Although hopane parameters for easily extractable species are sensitive to small changes in vitrinite reflectance, significant variations have been found for coals between easily extractable (DCM), ciathrated (pyridine-extractable) and covalenQybound biomarkers [15]. The hydropyrolysis results thus suggest that the incorporation of biomarkers into kerogen affords steric protection making covalently-bound hopanes and stcranes relatively immature. However, the much higher yields of 17/?(H), &?(H)-hopanes obtained by hydropyrolysis than by the lower temperature hydrogenatiou stage indicates that most of the points of aitachment of hopanes
Table 6 Total extract and aliphatic fraction dichloromethane followed by pyridinc hydropyrolysis (the yields from
purposes of comparison)d

yields from sequential degradation of Giiynbk oil shaleextraction, then catalytic hydrogenation and fmaliy, catalytic nitrogen on the pyridine-extracted shale are included for

pyrolysis in

Stage

Yield, mg of extract Aliphatics

(g TOC

initial shale)-

I
Total DCM-sooluble extracl

Aromatics 9.5 20 50 163 I40

DCM ext. Pyridine ext. Cat. hydrog. Cat. hypy. Pyrolysisb Estimated

2.0 8.1 15 222 76

55 97 168 [229] 749 [882] (93%) 652 [78!) (69%)

plus gas and water. mg (g TiX- . I%) = total % w/w conversion of organic matter to DCM-solubles plus gas and wvater, % dmmf shale. Cat. = catalytic. Hydrog. = hydrogenation, Hypy = hydropyrolysis. From ref. [16]. b The nitrogen pyrolysis yields should strictly be compared with those from catalytic hydrogenation plus hydropyrolysis since the nitrogen pyrolysis experiment was carried out on the pyridine-extracted shale.

[ ] = total cumulative

error for extract yields is f 5% of listed values. conversion at a particular stage to KM-solubles

Table 7 Comparison of the yields kg (s TCK in initial shale)- 1 of selccW immature hopanes and suxuws obtained from scquenrial dichloromcthane and pyridine extraction, catalyric hydrogenation ard hydropyrotysis of Gbyntik oil shattb

Cat. hydrog. Cat. hypy. Pyrolysis

53 <o,t 27 tsg 31 24 co.1 6 62 12 4 ~0.1 I2 32 4 r0.1 .ZO.l 6 14 2

43 CO.1 18 68 18

<O.l <O.l 3 II 0.5

<II,1 CO.1 6 I4 <O.l

7 I.0 1 16 4

19 0.5 17 46 13

Eslimated error for comparative biomarker yields is f 10% of vats for rha aterartes and f 20% for the hopanes. Cal. = cataIy&. Hydrog. = hydromtion. Hypy - hydropyrotyais. Yictds assum equal rtrponac facton for arulyk and SF(H)-chotanc &mot standard. b From ref. [Ml. The nitrogen pyrolysis yield1 tihould aMctly tx compared ti.h those from caiatylic hydrogcnarion pluo hydropyrotysir as the nitrogen pyrolysis CWcrbWnt was cankd out on rhc pyridinc-exrractcd Ihalc.

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of the residual kerogen are fisted in Table 7. The fact that the triterpanes are dominated by hopanes up to Cj5 with the biologically-inherited, but thermodynamicaffy unstable 17@(H), 21p(H)-configuration. demonstrates the unique ability of hydropyrofysis to maximise the yields of covalently-bound afkane biomarkers without affecting tfleir stereochemistries. The yields of the C29-C35f7#?(H), 2fP(H)hopancs are 2-10 times greater than those from DCM extraction, mild hydrogenation and normal pyrufysis. Further, the yields of the C&-C,, 17@(H), 21,9(H)-hopanes, not found in DCM extracts, were again much higher than for hydrogenation. Although hopane parameters for easily extractable species are sensitive to small changes in vitrinite reflectance, significant variations have fz+eenfound for coals between easily extractable (DCM), cfathrated (pyridine-extractable) and covalentfybou41d biomarkers [I 51. The hydropyrofysis results thus suggest that the incorporation of biomarkers into kerogen affords steric protection making covalentfy-bound hopancs and steranes relatively immature. However, the much higher yields of 17/I(H), Ill/?(H)-hopanes obtained by hydrapyrolysis thhn by the lower temprature hydrogenation stage indicates that most of the points of attachment of hopanes are thro,l& more stable covalent bonds than the weak heteroatomic linkages formed from the original biofipids.

Acknowle3gements
Coal & Steel Community, the Engineering The authors thank rhe lmopean Physical S;iences Research Council (EPSRC) and British Gas plc for financial support. J.D. Rocha thanks the Brazilian Federal Agency for Post-Graduate. Education XAPES) for an award to study at the University of Strathclyde.

References
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