International Journal of Coal Geology 66 (2006) 108 – 118

www.elsevier.com/locate/ijcoalgeo

A comparative study of experimental maturation of peat, brown coal

and subbituminous coal: Implications for coalification
Suping Yao a,*, Chunyan Xue a, Wenxuan Hu a, Jian Cao a, Chuanlun Zhang b
a
Department of Earth Science, Nanjing University, Nanjing, 210093, China
b
Savannah River Ecology Laboratory and Marine Sciences Department, University of Georgia, P.O. Box Drawer E, Aiken, SC 29802, USA
Received 16 February 2005; received in revised form 22 June 2005; accepted 13 July 2005
Available online 26 September 2005

Abstract

Laboratory experiments were performed on a peat, a brown coal, and a subbituminous coal using closed-system pyrolysis. The
samples were heated isothermally for 48 h from 150 to 500 8C. All three samples had similar pathways of thermal evolution, which
can be divided into four phases based on vitrinite reflectance (Rm). Phase 1 (b 250 8C or b 0.6% Rm) was characterized by a rapid
increase in CO2, phase 2 (200–350 8C or, 0.6% b Rm b1.1%) by simultaneous generation of oil and gas, and phase 3 (350–400 8C,
1.1% b Rm b 1.3%) and phase 4 (N400 8C, Rm N 1.3%) by production of methane. Phase 3 and phase 4 also caused the
condensation of aromatic rings, which resulted in a rapid increase in Rm in the solid residue and decrease in the potential of
hydrocarbon generation. The yield of gas, however, varied from sample to sample. The amount and composition of bitumen
generated also differed significantly among these samples.
The results indicated that coalification under these experimental conditions appeared to have similar evolutionary pathways
regardless of the original stage; the quantity and the composition of products, however may vary during the coalification process. In
this study, the difference mainly occurred during the process from peat to high volatile bituminous coal, which generated a large
amount of CO2 and bitumen that contained over 95% polar compounds. This study also demonstrated that early-stage coalification
occurred mainly as a loss of oxygen in organic matter. Results of this comparative study enhanced our understanding of the
mechanisms of coalification.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Experimental coalification; Pyrolysis; Peat; Brown coal; Subbituminous coal; Methane; Carbondioxide

1. Introduction ature physical and chemical processes (Stach et al.,

Coalification includes stages from burial of plants
to coal formation. The early stage of coalification
from peat to brown coal is mainly mediated by
low-temperature biogeochemical processes. The later
stage is from brown coal and/or bituminous coal to
anthracite coal, which is mediated by higher temper-
* Corresponding author. Tel.: +86 25 83592921.
E-mail address: spyao@nju.edu.cn (S. Yao).
0166-5162/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2005.07.007
1982).
Prior to coal formation, microorganisms play impor-
tant roles in biogeochemical cycling of organic matter
in peat (Casagrande and Given, 1980; Hu, 1998; Perry
et al., 1979; Ren, 1987). Based on the types and con-
tents of amino acids, Casagrande and Given (1980)
estimated that about 5–10% of organic matter in a
peat deposit in Florida, USA, comes from microbial
biomass. Wang et al. (1997) observes that the content of
the mineral–bitumen matrix is closely related to micro-
 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118
bial activity in Panchiao basin, China. Microorganisms
can even turn humic material to sapropel material,
which contains more hydrogen and is oil-prone during
maturation processes (Hu, 1998; Ren, 1987).
Deposition of organic matter in different environ-
ments can lead to the formation of different coals
(Heijden et al., 1994; Moore, 1995; Peng et al.,
1999; Phillips and Dimichele, 1990; Scott, 1989;
Teichmüller, 1989). Thompson et al. (1985) suggest
that re-worked coastal plain peats could form drift
deposits along coastal margins resulting in enriched
liptinite. Noble et al. (1991) and Mukhopadhyay et al.
(1991) also note that delta plain coals can be oil-
prone. Powell (1987) recognizes that in certain non-
marine environments the oil-potential of Type III
kerogens and coals is enhanced because bacterial deg-
radation of these materials results in the enrichment of
oil-prone components.
Numerous experiments have been performed to ex-
amine the changes in structure and composition of
organic matter during coalification (Bailey and
Cohen, 1993; Cohen and Bailey, 1997; Lucas et al.,
1988; Orem et al., 1996; Rollins et al., 1991; Shearer,
1994; Wu and Zhang, 1993). It is generally accepted
that the maturation process is mainly driven by the rise
of temperature and duration of time. For example,
organic matter exposed to higher temperature for a
shorter period of time has the same maturity as organic
matter exposed to lower temperature for a longer period
of time (Stach et al., 1982). This suggests that temper-
ature and time compensate for each other as effects on
organic matter maturity. Therefore, it seems to be valid
to simulate the natural maturation process in the labo-
ratory by increasing temperature during a short period
of time.
In the past couple of decades, the process of oil and
gas generation has been successfully simulated in the
laboratory (e.g., Han et al., 2001; Huang, 1996; Peters
et al., 1981; Rohrback et al., 1984). These simulations
have used both open and closed systems. In particular,
algae were frequently used to simulate hydrocarbon
generation from such organisms (e.g., Song, 1991;
Wu and Zhang, 1993). Recently, experiments have
also been performed on lipids, lignins, barks, spores,
pollen and bacterial spores for their potential for oil
generation (Li et al., 1999; Yao and Jin, 1996). The
catalytic effects of water and minerals on hydrocarbon
generation have also been examined (e.g., Huang et al.,
1995).
Simulation studies have also been intensely con-
ducted on coals because of their potential to generate
oil and gas (Law and Rice, 1993). Bituminization is a
109
very important process and has two important jumps
during coalification. Thus, this process has implications
for studying the mechanism of hydrocarbon generation
from coal because it is known to often generate large
amounts of oil and gas.
Experimental simulations and naturally matured
samples have been used to determine the coalification
mechanisms for different coals. However, results are
sometimes inconsistent among the different approaches;
there is also considerable overlap in the range of tem-
perature for degradation simulations. Additionally var-
iations in one or several physical or chemical properties
with rank, age, geographical distribution, or environ-
ment of deposition, make it unlikely that any small
selection of coals could be truly representative of all
coals. Thus, data obtained from any suite of coals, and
conclusions drawn from their study, can only be trans-
ferred elsewhere with caution.
In this study, artificial simulation experiments were
performed on peat, brown coal, and low-rank bitumi-
nous coal collected from Tengchong–Lianghe areas of
Yunnan Province in China. These coals were from the
same location and were believed to have found in
similar depositional environments from similar source
materials; however, they had different burial depths
and ranks of coalification. The object was to compare
the thermal simulation processes in each type of ma-
terial and understand the mechanisms of coalification
for different types of organic matter. The results may
enhance our understanding of natural coalification,
especially the transformations from peat to bituminous
coal.
2. Materials and methods
2.1. Field location and sample description
Samples used in this study include a peat, a brown
coal (R m = 0.29%) and a subbituminous coal (R m =
0.52%) from the Tengchong–Lianghe basin (Fig. 1),
Yunnan Province, China. The peat is a near-surface
deposit of Quaternary age, the brown coal is from the
Pliocene Mangbang Formation, and the subbituminous
coal is from the Miocene Nanlin Formation and Mio-
cene in age. These samples are particularly rich in
vitrinite (81–87%) and contain abundant exinite (8–
11%) (Table 1).
The Tengchong-Lianghe basin is located in the su-
ture belt between the India plate and Eurasian plate.
And it is one of a series of inter-mountain basins
formed as the result of Himalayan movement. The
basement rock of the basin is granite formed during
110 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118
Fig. 1. The location of Tengchong-Lianghe basin samples used in the study.
Yanshan movement. And the overburden mainly con-
sists of clastic and volcanic rocks.
The Nanlin Formation, at the bottom of this section
(Fig. 2), consists of grey siltstone, grey-white fine
conglomerate, grey-black carbonaceous mudstone, and
a coal seam. The subbituminous coal is located in the
middle of the Nanlin Formation (Fig. 2). The Man-
gbang Formation is above the Nanlin Formation (Fig.
2) and is made up of granitic sand and conglomerate,
fine sandstone and siltstone, and basalt. The brown coal
is located at the bottom of the Mangbang Formation.
The Quaternary deposits are at the top of the section
and consist of volcanic rock, sand and mud at the
bottom, and peat at the top. The peat is black in color
and low in content of fibers. The macerals in the peat
mainly consist of ulminite, fusinite, and semifusinite;
sporinite and cutinite are also present. The fiber matrix
Table 1
Petrographic data for the unaltered original samples
Samples Vitrinite (%) Inertinite (%) Liptinite (%)
Peat 87 (Ulminite) 5 8
Brown coal 85 5 10
Subbituminous coal 81 8 11
is characterized by maroon fluorescence color. Algae
also occur in the peat.
Although these samples are from different diagenetic
phases, the types and amounts of macerals from the
samples are very similar (Table 1). This may be because
the organic matter was likely deposited continuously in
similar environments in the Tengchong-Lianghe basin
from Early Tertiary to Quaternary.
2.2. Experimental procedure
The artificial experimental system used in this study
is the same as those used in Bailey and Cohen (1993),
Landais and Gérard (1996), and Han et al. (2001). In
brief, the samples were crushed to 60 mesh (0.25 mm).
The crushed peat/coals were placed in a high-pressure
stainless steel reactor (80-mm in internal diameter and
120-mm in length). For each set of experiment, the
reactor held about a 20-g sample. Distilled water was
added in the reactor to generate vapor pressure during
the heating process, which was to simulate high-pres-
sure environments under geologic conditions. After
that, the reactor was sealed and heated in a tempera-
ture-programmed furnace. Eight rounds of experiments
 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118
Fig. 2. Chrono-and lithostratigraphy of the Tengchong-Lianghe basin. Note the similarity in sedimentary environment but different ages and
diagenetic phases of the peat, brown coal and subbituminous coal.
were conducted at difference temperatures between 150
and 500 8C. The furnace temperature increased at 5 8C/
min and was held for 48 h isothermally after reaching
each chosen temperature.
After pyrolysis, the valve of the reactor was opened
and the generated gases and oil were collected and
determined. The reactor was then opened and the reac-
tion residues were weighed and extracted with chloro-
form in an ultrasonic bath for 24 h. The extracts from
the residue and the oil expelled during pyrolysis col-
lectively contributed to the quantity of bitumen.
The solid residues after chloroform extraction were
mounted with epoxy into drilled holes on plastic rods.
The mounted sample-plugs were polished and exam-
ined for maceral composition and vitrinite reflectance
using a Leizt MPVIII microscopic photometer system.
Rock-Eval pyrolysis was conducted according to
Espitalié et al. (1985). The chloroform extracts and
oil were fractionated into saturated, aromatic and
polar compounds by liquid chromatography on micro-
columns. Before fractionation, asphaltenes are precipi-
tated in hot heptane and recovered after filtration.
Chromatographic analyses of saturates were performed
on a Hewlett Packard 6890 gas chromatograph (GC).
111
Analysis of gases was performed using GC according
to Gérard et al. (1994).
3. Results
3.1. Vitrinite reflectance
As temperature increases from 150 to 500 8C, the
vitrinite reflectances (Rm) of all three samples increase
systematically (Table 2). This is consistent with obser-
vation of natural rank series (Taylor et al., 1998) and
numerous maturation simulation experiments (e.g.,
Cohen and Bailey, 1997; Huang, 1996; Murchison,
1978; Peters et al., 1981; Rohrback et al., 1984; Han
et al., 2001). However, the alteration trend of Rm vs.
temperature is nonlinear and different for the three
types of coals (Fig. 3). We define four phases of mat-
uration based on the variation in Rm with temperature.
The first phase occurs below 200 8C for the peat and
the brown coal, and below 250 8C for the subbitumi-
nous coal (Fig. 3). Rm increases very slowly and does
not exceed 0.66% in any samples in this phase.
The second phase is between 200 and 3508C. In this
phase, Rm increases from 0.47% to 1.37% for the peat,
112 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118

Table 2
Summary of artificial maturation experimental results
T (8C) Peat Brown coal Subbituminous coal
Rm Oil Gas Total Rm Oil Gas Total Rm Oil Gas Total
(%) mg/gTOC (%) mg/gTOC (%) mg/gTOC
OS n.d 27.0 n.d 27.0 0.29 20.9 n.d 20.9 0.52 25.3 n.d 25.3
150 0.32 71.7 0.4 72.1 0.35 37.3 0.1 37.4 0.6 25.6 0.5 26.1
200 0.47 106.2 2.1 108.3 0.39 40.6 0.4 41.0 0.6 34.6 0.8 35.4
250 0.72 73.6 13.0 86.6 0.58 38.3 1.6 39.9 0.66 28.4 0.9 29.3
275 0.93 64.2 13.8 78.0 0.66 40.6 3.8 44.4 0.75 33.7 1.6 35.3
300 1.06 68.7 19.9 88.6 0.76 53.3 7.0 60.3 0.82 43.9 3.7 47.6
350 1.37 113.8 81.2 195.0 1.11 128.8 46.1 174.9 1.07 118.7 32.8 151.5
400 2.08 50.5 164.0 214.5 1.81 63.9 131.0 194.8 1.34 62.7 96.7 159.3
500 2.66 45.5 239.7 285.2 2.42 29.2 209.0 238.2 1.87 30.2 164.0 194.0
OS=original samples; Gas=hydrocarbon gas; total=hydrocarbon gas and oil; n.d.=no data.

from 0.39% to 1.11% for the brown coal, and from
0.66% to 1.07% for the subbituminous coal.
The third phase (350 to 400 8C) and fourth phase
(N400 8C) exhibit different variations in Rm among
peat, brown coal, and the subbituminous coal (Fig. 3).
In the third phase, Rm increases with a greater slope
than in Phase II for the peat (1.37% to 2.08%) and
brown coal (1.11% to 1.81%). The increase in Rm is
3 bituminous (1.87%) at 500 8C only corresponds to
Peat
2.5
2 III
Ro (%)
significantly smaller for these samples above 400 8C
(2.08% to 2.66% for the peat and from 1.81% to 2.42%
for the brown coal).
For the subbituminous coal, however, Rm increases
in the same slope in Phase III and Phase IV as in Phase
II (from 1.07% at 350 8C to 1.87% at 500 8C).
To summarize, with increasing temperature Rm
increases fastest for the peat followed by the brown
coal and the subbituminous coal. The Rm of the sub-
IV semianthracite. At the same temperature, however, the
Rm of the peat (2.66%) and brown coal (2.42%) indi-

1.5 cates a maturity at the anthracite stage of coalification.

II
1
3.2. Rock-Eval pyrolysis
0.5 I
0
0 100 200 300 400 500 600 The initial petroleum potential or hydrogen index
Temperature (ºC) (HI) is significantly higher (211 mg/g) for the subbitu-
2.5 minous coal than the peat and brown coal (about 160 mg/
Brown Coal IV
2 g) during the artificial maturation. A non-linear decrease
III in HI is recorded (Fig. 4). This decrease shows three
Ro (%)

1.5
stages. The first stage is from room temperature (24 8C)
1 II
to 200 8C, during which the HI of the three samples
0.5 I shows no or slight change (Fig. 4). The second stage is
0
0 100 200 300 400 500 600
250
Temperature (ºC)
Peat
2.5 200 Brown Coal
HI (mg / g TOC)

Subbituminous Coal Bituminous Coal

2 IV 150
Ro (%)

1.5 I
III 100
II
1
I II
50
0.5
III
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (ºC) Temperature (°C)

Fig. 3. Evolution of the vitrinite reflectance as a function of Fig. 4. Evolution of the residual petroleum potential (Hydrogen Index,
temperature. HI) as a function of temperature.
 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118
from 200 to 350 8C, during which the HI decreases
sharply and reaches a minimum value of 10–16 mg/g at
the end for all three experiments (Fig. 4). The last stage
is from 350 to 500 8C, which only exhibits a slightly
further decrease in HI (b 3 mg/g) at the end (Fig. 4).
These results correspond to changes in Rm (Fig. 3).
The rapid changes in HI and Rm both occur between
200 and 350 8C for all the samples. This stage generates
large amounts of oil and gas and results in a significant
decrease in HI of the remaining solids.
3.3. Generation of gas and oil
One significant consequence of increase in temper-
ature during the artificial maturation of these samples is
the generation of gas and/or oil (Table 2), which is
summarized in Fig. 4. By using temperature as the
vertical scale, each of the plots simulates a simplified
homogenous geological scenario, in which gas and oil
may be generated from a source material as burial depth
(and temperature) gradually increases.
Between the beginning of the experiments and 200
8C, the total yield of gas and oil increases slowly for all
samples. A peak in generation is pronounced for the peat
at 200 8C but is much less for the brown coal and the
subbituminous coal (Fig. 5). The total yield decreases
until 250 8C (275 8C for subbituminous coal) and then
slowly increases between 250 and 300 8C. The yields of
both oil and gas acutely increase between 300 and 350
8C, peaking at about 350 8C (Fig. 5).
Fig. 5. The evolutional pattern of oil and gas generation from peat, brown coal and subbituminous coal as a function of heating temperature,
showing a similar evolutional trend despite different coalification stages in original samples.
113
At 350 8C, the extractable bitumen increases by
three times in both brown coal and subbituminous
coal compared to that generated at 200 8C; the extract-
able bitumen of the peat, on the other hand, is almost
the same as that at 200 8C (Fig. 5). The generation of oil
decreases quickly above 350 8C and becomes lower
than that of the original sample at 500 8C.
The generation of hydrocarbon gas is also similar for
all three samples above 300 8C (Fig. 5). The yield of
hydrocarbon gas increases very slowly at the beginning
of the experiments, and then slightly decreases between
200 and 300 8C. However, it goes up sharply between
300 and 350 8C and continually increases above 350 8C
at a relatively slow rate (Fig. 5). The hydrocarbon gas
yield of the peat is higher than that of both brown and
subbituminous coal below 400 8C. When temperature
continues to rise, the generation of hydrocarbon gas
from the three samples decreases, especially from the
peat.
At the end of the heating process (500 8C), a total of
203.6 mg hydrocarbon gaseous products/gTOC is gen-
erated from the peat, 209 mg from the brown coal, and
164 mg from subbituminous coal. These results show
that the process of peat artificial coalification is consis-
tent with that of brown coal and subbituminous coal.
3.4. Compositions of gases
CO2 and CH4 make up the bulk of the total gas
for all three samples. The variation of total gas differs
114 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118

0.6
considerably from sample to sample (Fig. 6A).
0.5
Below 300 8C, the peat has the fastest production

(S+A) / (N+B)
of total gas (1.1 cm3/gTOC/8C) and the subbitumi- 0.4

nous coal the slowest production (b0.2 cm3/gTOC/ 0.3

8C); the brown coal has an intermediate rate of pro- 0.2

Peat
duction (0.6 cm3/gTOC/8C) (Fig. 6A). Above 300 0.1 Brown Coal
Subbituminous Coal
8C, the rate of total-gas generation is similar for all 0
0 100 200 300 400 500 600
three coals (about 1.6 cm3/gTOC/8C). The final yield Temperature (ºC)
of total gas, however, is not the same; the peat has
the highest yield (654.0 cm3/gTOC), the brown coal Fig. 7. Change in the chloroform-extract composition in terms of
(S + A) / (N + B) with temperature. S = saturates, A= aromatics,
the second (473.7 cm3/gTOC), and the subbitumi-
N = non-hydrocarbons and B = asphaltenes.
nous coal the lowest (328.4 cm3/gTOC) (Fig. 6A).
These results suggest that about 50% yield may be increases above 300 8C (Fig. 6C). As a result, the ratio
lost during coalification from peat to subbituminous of CO2 versus total gas goes up to the maximum at
coal. about 200 8C and the ratio of CH4 versus total gas goes
CH4 and CO2 have different change tracks as the up at all times. The amount of CH4 exceeds that of CO2
temperature increase (Fig. 6B and C). The amount of at 500 8C in all samples (Fig. 6B, C).
CO2 rapidly increases until 350 8C and then almost
stops increasing above 350 8C (Fig. 6B). At 350 8C, the 3.5. Compositions of extractable bitumen
amount of CO2 from peat is slightly higher than that of
brown coal and about 6 times higher than that of the The composition of the chloroform extracts include
subbituminous coal. saturates (S), aromatics (A), non-hydrocarbons (N), and
In contrast to the evolution of CO2, the amount of asphaltenes (B). These extracts are characterized by a
CH4 slowly rises below 300 8C and then rapidly gradual decrease for all three samples of the contribu-
tion of the polar compounds with increasing tempera-
A ture and an increase in the percentage of saturates and
700
aromatics (Fig. 7).
Total Gas cm3 / gTOC

600 Peat
Brown Coal The ratio of (S + A) / (N + B) can reflect the degree of
500
Subbituminous Coal
400 evolution of source rocks when the type of organic
300 matter of the source rocks is similar. This ratio indi-
200 cates that the contents of the saturated and aromatic
100
hydrocarbons is very low and the percentage of the
0
0 100 200 300 400 500 600 polar compounds in chloroform extracts in peat and
B brown coal is greater than 10 times that of subbitumi-
250
nous coal at 300 8C (Fig. 7). But the contents of polar
CO2 (cm3 / g • TOC)

200
compounds rapidly decrease in peat and brown coal
150 between 300 and 350 8C (Fig. 7). So the content of the
100 polar compounds is higher in peat and brown coal at
50 low temperature and relatively lower for subbitumi-
nous coal.
0
0 100 200 300 400 500 600
Temperature (ºC) 3.6. Changes in n-alkanes
C
300
CH4 (cm3 / g • TOC)

250 Gas chromatography allows detailed observation of

200 changes in saturated hydrocarbons during maturation.
150
Samples experiencing low maturity (from original sam-
100
ple to 300 8C) are marked by the predominance of high
50
0
molecular weight n-alkanes of C25–C29 range. With
0 100 200 300 400 500 600 increasing temperature, the maximum of n-alkanes is
Temperature (ºC) progressively shifted from 29 to 23 for peat, and from
Fig. 6. Changes in total gas (A), CO2 (B) and CH4 (C) as a function of 29 to 25 for brown coal and subbituminous coal (Table
temperature. 3). This progressive shift may be attributed to the
 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118 115

Table 3
Summary of GC analysis results
Peat Temperature (8C) OS 150 200 250 275 300 350 400 500
Maximum of n-alkanes nC21 / nC22+ CPI nC29 nC29 nC24 nC27 nC25 nC27 nC25 nC23 nC23
0.3 0.21 0.27 0.1 0.16 0.17 0.45 0.72 0.59
1.51 1.36 0.9 0.96 1.19 1.82 1.7 1.19 1.03
Brown coal Temperature (8C) OS 150 200 250 275 300 350 400 500
Maximum of n-alkanes nC21 / nC22+ CPI nC29 nC29 nC29 nC29 nC29 nC29 nC25 nC25 nC25
0.12 0.07 0.09 0.13 0.1 0.1 0.2 0.43 0.55
2.31 2.34 2.15 1.36 1.16 1.06 1.27 1.34 1.26
Subbituminous coal Temperature (8C) OS 150 200 250 275 300 350 400 500
Maximum of n-alkanes nC21 / nC22+ CPI nC29 nC29 nC29 nC29 nC29 nC27 nC25 nC25 nC25
0.12 0.12 0.13 0.14 0.11 0.13 0.41 0.37 0.23
1.47 1.44 1.48 1.35 1.36 1.37 0.96 1.23 0.76
OS—original sample.

enhanced secondary cracking of high molecular weight
n-alkanes (Behar et al., 1991).
With increasing maturation, the Carbon Preference
Index (CPI) (Bray and Evans, 1961) gradually
decreases from 150 to 500 8C (Fig. 8A), thus revealing
the disappearance of the initial predominance of odd
n-alkanes in the C23–C29 range. However, the CPI
evolution is not linear and shows two inflexion points
(250 and 300 8C for peat sample, 300 and 350 8C for
brown coal, and 350 and 400 8C for subbituminous
coal). Monthioux (1986) interpreted this progressive
decrease as an evidence for absence of recombination
reactions during confined pyrolysis.
Fig. 8B is the plot of \ nC21 / [ nC22 versus tem-
perature. This plot shows that oil generation is marked
by high molecule weight hydrocarbons below 300 8C
A results of the simulation experiments in this study.
2.5
2 in the original samples so that the timing of hydrocar-
1.5
CPI
and an increase above 300 8C in amounts of hydrocar-
bon with molecules weighs lower than C21 during
artificial maturation.
4. Discussions
Results of the artificial coalification experiments
performed in this study demonstrate that the thermal
evolution process from peat to anthracite stage is char-
acterized by three distinct phases, which differ in quan-
tity and compositions of products generated.
When vitrinite reflectance is used to measure matu-
rity of source material, 0.5% Rm is generally accepted
as the oil generation threshold. Moreover, this threshold
may vary from 0.35% to 0.60% Rm depending on the
type of organic matter (Taylor et al., 1998; Tissot and
Welte, 1984). These values are consistent with the
Coalification stage and vitrinite reflectance are different
bon generation of these samples may also be different

1
(Fu et al., 1990; Teichmüller, 1989). However, the
Peat experimental data show that the timing of peak oil
0.5 Brown Coal
Bituminous Coal and gas generation of the three samples during the
0
0 100 200 300 400 500 600 artificial maturation is generally similar (Fig. 4). The
Temperature (ºC) three samples reach maximum generation rates at about
B 200 and 350 8C although original samples have differ-
0.8
0.7 Peat ent coalification stages.
Brown Coal
0.6 Bituminous Coal The vitrinite reflectance shows four stages with three
≤nC21/ ≥nC22

0.5 turning points occurring at 200, 350 and 400 8C. The
0.4 first two turning points are also peaks in oil generation.
0.3
Because of the release of a large amount of liquid, the
0.2
aromaticity of the residual solids increases, which
0.1
0
results in increase in their vitrinite reflectance.
0 100 200 300 400 500 600 The difference in the vitrinite reflectance in the three
Temperature (ºC) samples can be used as a proxy relating to the different
Fig. 8. Change of CPI (A) and \nC21 / [nC22 ratio (B) of peat, coalification stages that the three samples experience. It
brown coal and subbituminous coal with temperature. is generally accepted that organic matter exposed to
116 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118
higher temperature for a shorter period may have the
same maturity as organic matter exposed to lower
temperature for a longer period (Stach et al., 1982).
Subbituminous coal has experienced the processes of
early-stage biogeochemistry and a longer period of
maturation. But buried peat may have just passed the
biogeochemical processes and is a few million years
younger than the subbituminous coal at least. So below
200 8C, the peat needs higher temperature to reach the
same vitrinite reflectance as the subbituminous coal.
Previous studies on coalification mechanisms have
found that organic matter undergoes two types of reac-
tions with increasing thermal stress: decomposition and
condensation (e.g., Derbyshire et al., 1989; Derbyshire,
1991; Taylor et al., 1998). Decomposition results in
generation of gaseous and liquid materials, whereas
condensation enhances aromaticity. The experimental
results of this study are generally consistent with the
previous observations. In addition, the results indicate
that rapid decomposition is accompanied by rapid con-
densation. This explains why the two major hydrocar-
bon generation phases are accompanied by strong
increase in vitrinite reflectance (Table 2). Moreover,
peat decomposes more organic matter and produces
more hydrocarbon than the other samples during the
artificial maturation. As a result, the rate of Rm%
increase in the peat is faster than that of the brown
coal and subbituminous coal.
One marked difference among the three samples is
in the quantity and compositions of products generated
during the first stage of coalification. Peat generates
more CO2 and polar compounds in the chloroform than
brown coal and subbituminous coal. And simultaneous
with oil and gas generation, peat reflectance rapidly
increases, whereas that of subbituminous coal becomes
less reactive to thermal stress. The characteristic of the
brown coal is between peat and subbituminous coal.
There exists both decomposition and condensation
from peat to bituminous coal. Decomposition results
in oxygen removal, which is why peat can generate
abundant CO2 and polar compounds in the first phase,
while subbituminous coal cannot. Condensation results
in smaller molecules being recombined into the net-
work of macro-molecules of the peat. Peat generates
fewer hydrocarbons than subbituminous coal in the
second phases, because peat has not undergone the
condensation process from peat to coal, so that abun-
dant volatile matter is lost in the first phase. The
differences in the quantity and types of products gen-
erated in this phase among the three samples (Figs. 4–8)
show the influence of early-stage coalification on the
outcomes of thermal reaction. This phenomenon is also
proved by previous observation (Stach et al., 1982;
Taylor et al., 1998).
The beginning of the second peak of oil generation
observed in this study generally corresponds to the
second coalification jump (Stach et al., 1982). It is
also consistent with the oil-generation peak of predom-
inantly humic organic matter during the natural matu-
ration process (Huang et al., 1995), where macerals
undergo striking physical and chemical changes includ-
ing rapid generation of liquid products.
Considerable differences also exist in the thermal
evolution among the three samples. First, yields of
CO2 from peat and brown coal are 5–10 times more
than from subbituminous coal before 350 8C. While
CO2 is the main type of gas generated from peat and
brown coal, CH4 is the main component of gas in
subbituminous coal. Secondly, bitumen generation
peaked at vitrinite reflectance of about 0.6% and
1.0% with the first peak generating far more bitumen
from the peat sample than from brown coal and subbi-
tuminous coal. But the amounts of bitumen generation
in the second peak from the brown coal and subbitu-
minous coal are more than that from peat. And polar
compound molecules containing many oxygen-bearing
groups are the main components of the bitumen from
pyrolysis of the peat sample. In brown coal and subbi-
tuminous coal, hydrocarbons increase rapidly during
the second peak of bitumen generation. Finally, the
vitrinite reflectance of the peat and brown coal sample,
which is originally lower than that of subbituminous
coal, increase faster in the second phase and exceeds
that of the subbituminous coal at about 0.7% (250 8C)
and 1.3% (350 8C) vitrinite reflectance, respectively.
Although the original samples have different matu-
ration stages, they do not affect the nature of the
products for late-stages of coalification. Actually,
when temperature rises above 350 8C, gases are con-
tinuously generated and shorter chain alkanes start to be
produced (Fig. 7), as previously formed bitumen or oil
is cracked. Thus, CH4 becomes the end product above
500 8C for all the samples (Han et al., 2001).
5. Conclusions
The study reveals that the peat, brown coal, and
subbituminous coal have similar thermal evolution
pathways during artificial maturation experiments. All
three samples have low maturity with Rm vitrinite
reflectance at 0.29% for the brown coal, and 0.52%
for the subbituminous coal. With increasing tempera-
ture, the maturity of the samples goes up systematically,
with the peat and the brown coal achieving anthracite
 S. Yao et al. / International Journal of Coal Geology 66 (2006) 108–118
stage (2.66% Rm and 2.42% RM, respectively) and the
subbituminous coal achieving semi-anthracite stage
(1.87 % Rm).
Three phases of maturation/coalification are ob-
served. Phase 1 (b250 8C or b0.6% Rm) is character-
ized by a rapid increase in CO2, and by high oil
generation and very low hydrocarbon gas generation.
Phase 2 (200–350 8C, 0.6 b Rm b 1.3) is characterized
by generation of both oil and hydrocarbon gas, which
peak at 350 8C. Phase 3 (350 8C, N1.0–1.5% Rm)
corresponds to the production of methane and the con-
densation of aromatic rings, which results in a rapid
increase in vitrinite reflectance in the solid residue and
decrease in the potential of hydrocarbon generation.
Considerable differences exist in the thermal pro-
ducts among the three samples. For example, yields of
CO2 from the peat and brown coal are 5–10 times more
than from the subbituminous coal before 350 8C. While
CO2 is the main type of gas generated from peat and
brown coal, CH4 is the main type of gas generated from
the subbituminous coal. Also, the oxygen-bearing polar
compounds are the main component of the bitumen
from pyrolysis of the peat; whereas, in the brown coal
and subbituminous coal, hydrocarbons are predomi-
nant. Differences in the yield and composition among
the three samples indicate that the early-stage coalifi-
cation can significantly impact product generation.
Acknowledgements
This work was supported by the National Natural
Science Foundation of China (Grant No. 40073017)
and by The National Basic Research Program of
China (973 Program) (Grant No. 2003CB214608).
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