92

2007
2007

. ,
, ,
. , .
. .

,
Institute of Geology and Geochemistry of Petroleum and Coal, RWTHAachen Institute of Chemistry and Dynamics of the Geosphere, ICG V: Sedimentary
Systems, Juelich Research Centre ,
,
(FU-SAV,
Bratislava, Slovakia).
: :
25% 75%
()-K -.
.

, .

:
Ralf Littke Dr. Bernhard Krooss, Institute of Geology and

Geochemistry of Petroleum and Coal, RWTH-Aachen ,

,
Dr. Andreas Lcke Dr. Anne Richter, Institute of Chemistry and

Dynamics of the Geosphere, ICG V: Sedimentary Systems, Juelich Research Centre
Dr. Peter Svec, Department of Metal Physics, Institute of Physics, Slovac

Academy of Sciences ,
. . , . , . , . , .
, . .
.
, .
, .
, ,

, , .
- ,
. .
- .
,

.
, 2007

ii

.
(, , , )
,
.
67% ,
.
, 62-63%
.

. ,

, CO, CO2, H2, CH4 2
,
.
,
(FTIR), Rock Eval II
(TG/DTA),
.
,
. matrix ,
, matrix ,

.
, ,
, .
( ),
.
. 31,0% 64,5%,
iii
8,7% 45,5%, 37,2% 58,5%

3.851-6.735 kcal/kg.
38,9% 67,3%,
28,4% 48,5%.
33,7% 46,8%
2.473-4.897 kcal/kg.

, , , .
.
32,3-59,3%, 2,5-5,9%, 0,5-2,2%, 0,4-3,9% 13,0-34,3% .
17,2-42,4%, 2,0-3,8%, 0,91,5%, 2,6-5,6% 10,2-28,8% .
. ,
/.

-
(maceral).
E- . 0,24-0,42%,
(0,19-0,37%).
maceral (75-97%),
(22-90%), T (5-70%).
(3-18%),
(<7%). TPI, GI GWI, VI .
,
/
.
,
/
.
(Al, Ca, Fe, Mg, Si, Ti),
(Ni, Mn, Cr, B, Be, Co, Cu, Mo, V, Y, Zn)
.

. Ni Cr,
iv
, V Mo
.
max,
, RockEval II, 405C 430C. max
(358-406C),
, .
() 74-218 mg HC/Corg ()
50-150 mg C2/Corg,
.
,
.

, , ,
,
.
.
,

.
,

.
(15)
2,92 3,80. 15 4% 26%
, 15
. 15

.

CH4, CO, CO2, H2 N2.
250oC 800oC.
CH4
v
460oC,
10 30C .
CH4 8,12 mg/g 11,74 mg/g .
, (5,45 6,60 mg/g)
.

, .
100C
670C. CO2 .
310-330C 91,62 mg/g 121,41 mg/g,
CO2
305C 310C 63,10 mg/g 109,49 mg/g.
200C,
650C.
. 800C,
(~860C). 900C 1000C
C,
.
79,14 mg/g 109,36 mg/g
. ,
103,75 mg/g 140,67 mg/g.

520C. 620C 950C
N2, 780 810C
2, C4,

.
2 . 3,3 mg/g 15,3 mg/g,
5,14
mg/g 7,40 mg/g. ,
. ,
,
maceral .
vi
2 400C
(1100C)
. H2 605C 660C,
750C 800C,
CH4 ,
2. 2
,

.
(TDTGmax),
, ,
400C 408C, .
415C 432C
, TDTGmax 370C 400C.
TDTGmax
.
TDTGmax ,
.
vii
viii
ABSTRACT
The intense post-Alpine activity in Greece during Neogene and Quaternary had as a
result the formation of many intermontane and paralic basins. The largest Greek lignite
deposits were formed from Neogene to Pleistocene in intermontane basins (Ptolemais,
Florina, Drama, Megalopolis) while the lignite deposits of paralic origin are smaller in
thickness and size. Around 67% of the exploited Greek coal deposits are located in FlorinaPtolemais-Servia basin in west Macedonia while Megalopolis deposit in Peloponnesus
peninsula, in southern Greece is also under exploitation. Lignite is mined in open pits and is
used mainly for electricity production (~ 62-63% of the total energy demands).
The objective of the present doctoral thesis is to study the behavior of lignites coming
from the main Greek lignite basins under pyrolysis conditions. We emphasized on the effect
the macroscopic and coal petrographic characteristics have on the pyrolysis mechanisms and
also studied the liberation of CO, CO2, H2, CH4 and 2 during open system non-isothermal
pyrolysis. A number of analytic methods such as Fourier Transform Infrared Spectroscopy
(FTIR), Rock Eval II pyrolysis and thermal analyses (TG/DTA) were also performed in an
effort to collect more data and investigate the correlations between them.
Samples were taken from exploration wells in two basins: the Florina-PtolemaisServia basin (deposits of Komanos, Klidi, Proastio, Prosilio and Notio Pedio) in W.
Macedonia and the Megalopolis basin (deposits of Kyparissia and Marathousa) in
Peloponnesus, where the main Greek coal deposits are located and exploited by the Greek
Public Power Corporation (P.P.C.).
According to macroscopic observations matrix lignite is the dominant lithotype for
samples coming from Komanos, Proastio and Notio Pedio while those of Klidi and Prosilio
can be of either xylitic or matrix lithotype. On the other hand, samples from Kyparissia and
Marathousa mostly belong to the mineral rich lithotype.
Proximate analysis included the determination of moisture, ash and volatile matter
while the calorific value of lignites was also measured. In samples from W. Macedonia
moisture as received ranges from 31.0-64.5%, ash on dry basis is 8.7-45.5%, volatile matter
on dry basis range from 37.2% to 58.5% and calorific value on an ash-free dry basis is 3,8516,735 kcal/kg. In lignites from Megalopolis as received moisture range from 38.9-67.3%,
and ash on dry basis is 28.4% to 48.5%. Volatile matter on a dry basis range from 33.7% to
46.8% and calorific value on an ash-free dry basis is around 2,473-4,897 kcal/kg.
ix
During ultimate analysis the percentage of carbon, hydrogen, nitrogen, sulfur and
oxygen was determined. For the lignites of W. Macedonia the above values range from 32.359.3%, 2.5-5.9%, 0.5-2.2%, 0.4-3.9% and 13.0-34.3% respectively, while for the Megalopolis
lignites the values are 17.2-42.4%, 2.0-3.8%, 0.9-1.5%, 2.6-5.6% and 10.2-28.8%
respectively. From the proximate and ultimate results it was concluded that samples from W.
Macedonia are classified as lignites while those of Megalopolis are of lower maturity and can
be regarded as peat to lignite.
Mean random Eu-ulminite B reflectance (Rr) and maceral analysis was performed in
all studied samples. In lignites from W. Macedonia Rr range from 0.24-0.42%, while in
samples from Megalopolis the Rr is much lower (0.19-0.37%). Huminite is the dominant
maceral group in all studied samples (between 76 and 97vol%, mmf), Liptinite range from 318vol%, mmf and Inertinite does not exceed 7vol%, mmf. Detrohuminite maceral subgroup
prevails in all the studied samples and display values from 22-90 vol%, mmf while
Telohuminite range from 5-70 vol%, mmf. The TPI, GI and GWI, VI indices have higher
values for the samples of W. Macedonia, indicating good tissue preservation possibly as a
result of increased rate of subsidence/rise of the water table and/or the existence arboreal
vegetation. The lower values for Megalopolis samples and especially for those from
Kyparissia indicate bad tissue preservation as a result of slow burial possibly due to a low rate
of subsidence/rise of water table and/or the dominance of herbaceous plants with cell tissues
rich in cellulose.
The major elements (Al, Ca, Fe, Mg, Si, Ti), the minor elements and the trace
elements (Ni, Mn, Cr, B, Be, Co, Cu, Mo, V, Y, Zn) correlate mainly with the inorganic part
of the samples and constitute the basic elements of the minerals. Concentrations of minor
elements and trace elements are within the range reported in the literature for coals. Only the
elements Ni and Cr exhibit higher than expected values while increased is also the amount of
V and Mo for the lignite samples of Megalopolis.
The temperature of maximum rate of release of hydrocarbons (Tmax) from the
breakdown of kerogen reflects the thermal stability of the macromolecular organic matter and
range from 405C to 430C. The lower Tmax values for the xylitic lithotype samples from
Klidi and Prosilio (358-406C) can be attributed to the original vegetation which was mostly
coniferous while in all other regions lignite derived from mainly herbaceous vegetation.
Hydrogen Index (HI) values extended from 74 to 218 mg HC/g TOC while Oxygen Indices
(OI) ranged from 50 to 150 mg CO2/g TOC. According to the above results all Greek lignite
samples fall in the region of Type III organic matter meaning that they have low hydrocarbon
generation potential which is to be expected given the fact that they are all of terrestrial origin.
Fourier transform infrared (FTIR) spectra of the lignite samples reveal a great
abundance of hydroxyl, phenolic, alcoholic, ketone and ether functional groups bonded with
aliphatic chains or aromatic rings. A great similarity between the spectra of raw lignites and
their insoluble organic matter, obtained by Soxhlet, extraction was noted while the vertical
and lateral differentiation in the FTIR spectra is insignificant. Small differentiations in the
spectra of xylitic lithotype samples are attributed to the presence of lignin. In the case of
mineral rich samples intense bands due to the absorption of carbonaceous and clay minerals
overlap with those from the organic functional groups and therefore any univocal band
assignment is impossible.
The 15 values in lignite samples range from 2.92 to 3.80. Almost the same
values are observed for the solid residues of Soxhlet extraction while in the extracts 15
values are 4% to 26% lower. Small differentiation in the isotopic composition of nitrogen
possibly reflects small changes in the paleoenvironment and more particularly in the original
vegetation of the lignite basins.
The pyrograms of the individual gaseous products (CH4, CO, CO2, H2 and N2) of each
lignite sample exhibited characteristic patterns reflecting the type and composition of the
precursor entities in the complex polymer structure of the coals.
Methane is usually released in the 250C to 800C range. Maximum CH4 liberation
for the samples from Ptolemais and Servia basins is observed at around 460oC while the same
temperature for the samples of Megalopolis is 10-30C lower. Shoulders or distinct dual peaks
in the pyrograms indicate its formation from different precursor structures within the coal.
Dual methane peaks were mostly spotted on samples from Florina basin and can be attributed
to the pyrolysis of lignin which is more abundant in lignites coming mostly from wood
vegetation. The early methane peak from lignin pyrolysis is only observed in lignites and
other low-rank coals while high-rank coals do not produce methane in this relatively low
temperature region. The total amount of methane liberated from the samples of W. Macedonia
is 8.12-11.74 mg/g while it is much lower for the ones coming from Megalopolis (5.45-6.60
mg/g) which is due to their lower maturity.
Carbon monoxide together with carbon dioxide and water constitute the major oxygen
gases liberated during coal pyrolysis. Carbon dioxide is the earliest pyrolysis product to be
liberated with its generation starting around 100C and extending beyond 600C.
Characteristic CO2 peaks around 640C associated with CO peaks are indicative for small
xi
amounts of carbonate. Maximum CO2 liberation for the samples of W. Macedonia in

observed in the temperature range of 310-330C and is around 91.62-121.41 mg/g while in
Megalopolis it takes place between 305C and 310C and ranges from 63.10 mg/g to 109.49
mg/g. Carbon monoxide pyrograms show complex structures and reach their peak generation
rate at around 650C. A decrease in the CO emissions is observed for the W. Macedonia
lignites at 800C while the same phenomenon in Megalopolis is taking place at higher
temperatures (~860C). A reverse trend is observed for most samples above 900-1000C
which is possibly due to the thermal decomposition of heterocyclic oxygen compounds. The
total amount of emitted CO is 79.14-109.36 mg/g for the W. Macedonia samples and much
higher for those coming from the Megalopolis basin (103.75-140.67 mg/g).
Liberation of molecular nitrogen in all samples start at around 520C and several
peaks are observed in the temperature range from 620C to 950C. A very narrow and
conspicuous N2 peak is found in the 780 to 810C range which requires a molecular precursor
structure with a well-defined thermal stability. That sharp N2 peak is followed by an increase
of H2 liberation and in some cases by a very small increase of CH4 suggesting the organic
origin of the above gases. The total amount of N2 emitted during pyrolysis of samples from
W. Macedonia is 3.3-15.3 mg/g, while lower values are observed for the Megalopolis lignites
(5.14-7.40 mg/g). The total amounts of liberated CH4 and N2 seem to increase with the
increase of coal rank as expressed by random reflectance (Rr) of Eu-ulminite B. The increase
of methane is probably due to the increase of aromatic structures with rank and has as a result
an increase in the calorific value of coals. No correlation between CO2 and Rr was observed
due to the fact that a significant amount of CO2 is coming from the thermal decomposition of
minerals and not of organic matter. The amount of CO decreases while coal rank increases as
a result of loss of oxygen-bearing compounds with maturation. However the correlation is
very poor due to the presence of inorganic matter.
Only the yield of methane appears to be correlated with the maceral composition of
the coals. Increasing Huminite contents are associated with a decrease in CH4 yields while the
opposite is observed for Liptinite. The low amount of Liptinite in some samples that do not
follow the general trend is possibly due to depositional conditions that resulted in the
decomposition of Liptinite and the formation of small scattered Liptodetrinite particles that
impregnate the humic matter and cannot be measured on the microscope.
Liberation of H2 starts at around 400C as a result of condensation of aromatic
structures and continues after 1100C when pyrolysis experiments end. Maximum H2
liberation is observed at around 605C to 660C. In some cases a second peak is found at
xii
temperatures between 750C to 800C that is followed by a small increase of CH4 and N2
emissions. Pyrolysis of char, during which the residual kerogen and the non volatile bitumen
further decompose, can explain the presence of H2 and CH4 at such high temperatures.
The temperature TDTGmax, during which the maximum rate of weight loss is observed,
in Megalopolis, ranges from 400C to 408C while it is much higher for the samples of W.
Macedonia (415-432C) with the exception of xylitic lithotype samples where TDTGmax is
around 370C to 400C. It is concluded that TDTGmax is indicative of the thermal maturity of
the samples and tends to increase with increasing level of maturity since it also correlates well
with Rr.
xiii
xiv

........................................................................................................... i
..........................................................................................................iii
ABSTRACT .......................................................................................................... ix
1. ....................................................................................................... 1
2. .............. 5
2.1. - - ..............................................5
2.2. .........................................................................................5
3. ................................................................................. 7
3.1. - - ..............................................7
3.1.1. ..........................................................................................................................7
3.1.2. .............................................................................................8
3.1.3. ...................................................................................................................8
3.1.3.1. ..............................................................11
3.1.3.2. ..........................................................11
3.1.4. .............................................................................................................14
3.2. .......................................................................................15
3.2.1. ........................................................................................................................15
3.2.2. ...........................................................................................15
3.2.3. ....................................................................................................................16
3.2.4. .............................................................................................................19
4. ........................................................................................... 23
4.1. .......................................................................................................23
4.2. ......................................................................24
4.2.1. ..........................................................................24
4.2.2. ..............................................................................25
4.2.2.1. maceral ...............................................................................................25
4.2.2.2. ..............................................................................26
4.2.3. ..................................................................................................26
4.2.4. Rock Eval II ............................................................................................27
4.2.5. Soxhlet ......................................................................................................27
4.2.6. (FTIR) ...........................................................................28
4.2.7. 15 .............................................................................................................29
4.2.8. ..............................................................................................29
4.2.9. (TG/DTA) ...................................................................................31
5. ....................................................... 33
5.1. ..........................................33
5.2. ..........................................................35
5.2.1. ...........................................................................................35
5.2.2. ..............................................................................................37
5.2.3. ..............................................................................................38
xv
5.2.4. .........................................................................................................39
5.2.4.1. ....................................................................................39
5.2.4.2. ..............................................................................................................40
5.2.4.3. .................................................................................................................41
5.2.4.4. ....................................................................................................................42
5.2.4.5. H/C O/C........................................................................................43
5.2.5. ...........................................................45
5.3. ...............................................................47
5.3.1. maceral..................................................................47
5.3.1.1. ......................................................................................47
5.3.1.2. .....................................................................................50
5.3.1.3. ......................................................................................51
5.3.2. ..................................52
5.3.2.1. - .....................................................................52
5.3.2.2. maceral ...............................................................56
5.3.3. ..............................................................................64
5.3.3.1. Mukhopadhyay................................................................................65
5.3.3.2. TPI-GI .............................................................................................69
5.3.3.3. GWI-VI ...........................................................................................75
5.3.3.4. Singh and Singh ..............................................................................79
5.4. ...........................................................................................80
5.5. Rock Eval II ............................................................................................86
5.5.1. S1, S2 S3 ..........................................................................................86
5.5.2. Tmax..........................................................................................................................88
5.5.3. (), () (PI) ................................90
5.6. (FTIR) ...............................................................94
5.6.1. ........................................................................................................................94
5.6.2. ..........................................95
5.6.2.1. ..................................95
5.6.2.2. T ...........................................................................103
5.6.3. .................................................................................................................106
5.7. 15 .....................................................................108
5.7.1. ......................................................................................................................108
5.7.2. ..................................................................................108
5.8. ....................................................................................113
5.8.1. ......................................................................................................................113
5.8.2. .....................................................................................................115
5.8.2.1. ............................................................................................................115
5.8.2.2. ....................................................................................121
5.8.2.3. .................................................................................125
5.8.2.4. ...............................................................................................................130
5.8.2.5. ..........................................................................................................138
5.8.3.
..................................................................................................................140
5.9. (TG/DTA) ............................................................................144
5.9.1. ......................................................................................................................144
5.9.2. (TG/DTG) ................................................................144
5.9.3. (DTA).......................................................................152
6. ..................................................................................... 155
xvi
............................................................................................... 161
I ................................................................................................ 189
I............................................................................................... 199
II ............................................................................................. 217
IV ............................................................................................. 225

3.1. -
( Vinken, 1965 Okuda et al., 2002). ............................................................................................. 15
4.1. (I.C.C.P., 1993)........... 23
4.2. Soxhlet ...................................................................... 28
5.1.
................................................................................................................................... 39
5.2. macerals Stopes/Heerlen (I.C.C.P., 1963, 1971, 2001,
Skorov et al., 2005)..................................................................................................................................... 48
5.3. - (Rr)
, n: . ................................................................................................... 53
5.4. ( ppm, , *:
Swaine, 1990). ................................................................................................................................................ 80
5.5. ( ppm,
). .......................................................................................................................................................... 81
5.6. Pearson (r)
...................................................................................................................................... 82
5.7. Rock-Eval......................................................... 87
5.8. Tmax , n: .................... 90
5.9.
......................................................................................................................................... 96
5.10. ..................... 105
5.11. [] [15N vs. air] ,
Soxhlet (n: , SD:
).......................................................................................................................................... 109
5.12. CO2, CH4, CO, N2, H2
0,5K/min,
(#1,#2,#3: ). .................................................................................... 118
5.13. CH4, CO, CO2 N2
0,5K/min, (extr:
Soxhlet, HC: , CH4 vs total HC:
, C: )............................................................................... 119
5.14. (Burnham et al.,
1980, Campbell et al., 1980, Reynolds et al., 1991). .................................................................................... 121
5.15. CO/CH4, CH4/CO2, CH4/N2 CO/CO2
0,5K/min, (extr:
Soxhlet). ....................................................................................................................................................... 123
5.16. 0,1%, 0,5%, 0,9%, x
10%, 50% 90% ,
TDTGmax.......................................................................................................................................................... 146
5.17. (W) (WTotal:
)........................................................................................................................... 150
xvii

3.1. - - (
-, 1983)...........................................................................................9
3.2.
- - ( , 1997). ................................12
3.3. ( .., 1997). ....17
3.4. (
.., 1997).............................................................................................................................20
5.1. DIN ASTM
(Stach et al., 1982) (1: , 2: )....................................................................38
5.2. , .....................................41
5.3. (N) (TOC)....................................................42
5.4. H/C O/C ( : :
, : , : , : , : )
( van Krevelen, 1993). ..........................................................................................................................44
5.5. ) (HI) /C, )
(I) /C. ..........................................................................................44
5.6. ,
TOC TIC [TC] [C]. ................................................45
5.7. - (Rr)
. ...................................................................................................................................................54
5.8. ,
( % , )....................................................................56
5.9. , .
( % , ).......................................................................57
5.10. ,
( % , ).................................................................59
5.11. ,
( % , ). ...............................................................60
5.12. ,
( % , )....................................................................61
5.13. ,
( % , ).............................................................62
5.14. ,
( % , ). ...........................................................63
5.15. ABC ,
Mukhopadhyay (1986, 1989). ......................................................................................................................66
5.16. ABC ,
Mukhopadhyay (1986, 1989). ......................................................................................................................67
5.17. ABC . ,
Mukhopadhyay (1986, 1989). ......................................................................................................................68
5.18. ABC ,
Mukhopadhyay (1986, 1989). ...........................................................................................................68
5.19. GI TPI
Diessel (1986, 1992), ....................................................................................................72
5.20. GI TPI
Diessel (1986, 1992), ....................................................................................................73
5.21. GI TPI . Diessel
(1986, 1992), . ......................................................................................................................73
5.22. GI TPI
Diessel (1986, 1992), . .....................................................................................74
5.23. GWI VI
Calder et al. (1991).....................................................................................77
5.24. GWI VI
Calder et al. (1991).....................................................................................77
5.25. GWI VI .
Calder et al. (1991). ...............................................................................................................................78
xviii
5.26. GWI VI
Calder et al. (1991).....................................................................................78
5.27.
Singh and Singh (2000). ......................................................................................................................79
5.28. Singh and Singh
(2000). ..........................................................................................................................................................79
5.29. Rr Tmax . ..................................................................................89
5.30. .................................................................91
5.31. /Tmax . ..................................................................91
5.32. () (Rr)
............................................................................................................................................92
5.33. (, 1998)................................94
5.34. () () . .......102
5.35. 360 C .............................104
5.36. ,
Soxhlet.......................................................................................................................................110
5.37. (a) 15 [], (b)
N/Corg..........................................................................................................................................................110
5.38. 15 [] [%] . ..........................................111
5.39. 2 PL-7
....................................................................................................................................................112
5.40.
(0,72 Ro), 0,2K/min (Cramer,
2004)...........................................................................................................................................................115
5.41.
0,5K/min ( ). ........................................................................117
5.42. a) CH4
CH4 (Tmax), b) CH4
(). .............................................120
5.43.
0,5K/min ( ). ........................................................122
5.44. a) C2 [] b) C2
[], Rock Eval II. .........................................124
5.45.
0,5K/min ( ).......................................126
5.46. CO/C2 ...................................................128
5.47. CH4/CO2 C/C2 (a) . (b)
. .........................................................................................................................................128
5.48.
0,5K/min ( ). .............................................................133
5.49. CO,CO2 2 0,5K/min
KYP-1 SF-31........................................................................................................................................134
5.50. 2 (a) , (b)
/C..........................................................................................................................................................136
5.51. 2[mg/g] CH4[mg/g] . ..........................................137
5.52. ( Strezov et al. 2004) ..................................................138
5.53.
0,5K/min ( ). ........................................................................139
5.54. (a) CH4 (b)
. .............................................................................................................140
5.55. Rr [%] (a) N2 [mg/g], (c) CO [mg/g] (d)
CO2 [mg/g] (b) N/C. .......................................................................................................141
5.56. [Rr] CO2 [Tmax CO2]. .....142
5.57. (a) (b)
..........................................................................................................................143
5.58. (TG) . .................................145
5.59. x .....................................................145
5.60. DTG . ...................................................................................147
5.61. (TDTGmax)
(Rr). ............................................................................................................................................................148
xix
5.62. (TDTGmax)
(Tmax). .........................................................................................148
5.63. (TDTGmax)
(Tmax CH4). .........................................................................................149
5.64. WTotaloC H/C . .............151
5.65. 670C 800C (W670-800oC)
(Ca, Mg) . ..................................................................................151
5.66. DT . ...................................................................................152
xx
1.
-

.
(, , , ) ,
(, , , , , ,
) (Koukouzas et al., 1997, Christanis, 2003).

, 2,5Gt,
900Mt 100Mt
(www.dei.gr). ,
370. (Sakorafa and Michailidis, 1997).
- 67%
. (<2%)
(), ,

.
.
78,4%
(Koukouzas et al.,1997) 62-63%.
maceral (
(1993))
(Hagemann and
Hollerbach, 1979, Hagemann and Wolf, 1987, Kalkreuth et al., 1991b, Diessel, 1992).

(Cameron et al., 1984, , 1986, Kalkreuth et al., 1991a, Kaouras
et al., 1991, Antoniadis et al., 1992, 2001, 2003, 2005, 2006a,b,c, Gentzis et al., 1996, 1997,
Sakorafa and Michailidis, 1997, Papanicolaou et al., 2000, .. 2000, 2001,
Mavridou et al., 2003, , 2003, , 2004)

(Foscolos et al., 1989, Filippidis and Georgakopoulos, 1992, Filippidis et al.,

1996a,b, Papanicolaou et al., 2004, Kantiranis et al., 2005, Adamidou et al. [in press]).
,
,
(Lappas and
Vasalos, 1989, Georgakopoulos, 2000, Iordanidis et al., 2001, .. 2001, Skodras et
al., 2006).
, .

,
.
CO, CO2, H2
CH4,
(Campbell, 1977, Szab et al., 1990a,b, Ibarra and Moliner, 1991, Solomon et al., 1991,
Wjtowicz et al., 1993, Solomon and Hamblem, 1994, Charpenay et al., 1996a,b, Gaschnitz et
al., 2001, Lin et al., 2002, Charland et al., 2003, Cramer, 2004, Porada, 2004).

(Blazs et al., 1985, Carangelo et al., 1987, Serio et al., 1987,
Chu et al., 1988, Ibarra et al., 1991, Ibarra and Moliner, 1991, Kkbayrak, 1993, Otake and
Walker, 1993, Behar et al., 1995, Kopp et al., 2000, Cramer et al., 2001, Arenillas et al., 2003,
Strezov et al., 2004, MacPhee et al., 2005, Yalim et al., 2007),
.. (2001) .

CN NH3 (Solomon and Colket, 1973, Chu et al., 1988, Bassilakis et al.,
1993, Lepplahti, 1995, Thomas, 1997, Arenillas et al., 1998, 2002, Yan et al., 2005),
2 (Boudou and Espitali,
1995, Wu and Ohtsuka, 1996, 1997a,b, Friebel and Kpsel, 1999, Xu and Kumagai, 2002,
Krooss et al., 1995, 2005).

.

CO, CO2, H2, CH4 2
, . ,
2

(Serio et al., 1987, Solomon et al., 1993).

(FTIR), Rock Eval II
(TG/DTA),
. -
,
.
2.
, .

(. ), ,
(. ), (. ),

(. ).
2.1. - -
,

() , ,
.
+600m, 120km, 20km -,
.
[+2.128m], [+2.063m] () [+2.111m]
() [+2.524m] [+2.027m].
[+1.878m]
[+2.161m], .
2.2.
H , ,
[+1.900m], [+1.420m]
[+2.409m]. +400m
-. 18km
12km (, 1957, .., 1974). ,
, 2km
8km .
3.

.
,
/ .
,
,
.

. ,
. ,

(Christanis, 2003).
3.1. - -
3.1.1.

(-) (Pavlides and Mountrakis, 1987).
- -

( , 1972, Pavlides and Mountrakis, 1987).
, ,
- - - .

,
, ( .., 1979,
Pavlides and Mountrakis, 1987, Doutsos and Koukouvelas, 1998, Doutsos and Kokkalas,
2001).
3.1.2.

,
( 3.1). (
)

(, , , )
(, , ,
) (, 1960, .., 1979).
( )

( , 1972).
,
, -
( ,
1973, .., 1979).
3.1.3.

,

( , 1973, , 1986).
(Pavlides and
Mountrakis, 1987)
, .

(), (
), (),
( ) ( 3.2).

( .., 1979).
3.1. - - (
-, 1983).
10
3.1.3.1.
(1997)
,
:
:
, ,

.
():
(), , , .
135m ( )
(25m ) ,
.
, ,
,
(Steenbrink et al., 2000).
:
.
, , ,
, .
.. (1979)
, (, 1986) (Steenbrink
et al., 2000) .
3.1.3.2.
,
, (1997):
:
,
.
11
al
H.pt
Pt.cs

Pt.c.lm
Pt.s
H.cs
H.lk
Pt.c
(al) , (.cs) ,
(.lk), (. pt)
(Pt.cs) , (Pt.s)
(Pt.c) , (Pt.c.lm)

( , , )
-

(, )

(, , , )

(, , , , )
100 m
0m
3.2.
- - ( , 1997).
12
( ): ,

.
(.. , , ), .
:
, , ,
. (. , .
) ,
, .

, ( ..
, , -).
, 130m
(Kalaitzidis et al., 2004),
( , 1972): () ,
80m, ,
.
.
, ,
Theodoxus
(Calvertia) macedonicus, Neritina, ()
14m, ,
,
2-3cm () 30m
, .
(1972) Ioakim (1981)
, (Van
Vugt et al., 1998, Steenbrink et al., 1999)
5,23 3,94Ma .
13
3.1.4.

,
. ,
(, 1985).
.. (1979)

, .
,
.
,

. ,
( .., 1979, Mavridou et al., 2003):
( ):
, .
.
( ):

.
,
,
.
.
:
, ,
,
.
14
3.2.
3.2.1.
,

(, 1958)
(, 1994).
- - (, 1958, , 1961,
Okuda et al., 2002),
(, 1957). ,
(Okuda et al., 2002),
: , , ,
, ( 3.1).
3.1. -
( Vinken, 1965 Okuda et al., 2002).
()
,
,

,

,
, ,
,
, ,
3.2.2.

,
(, 1958,
.., 1974, Sakorafa et al., 1997).
,
15

(, 1985).

,
.

(
) ( .., 1974, .., 1997).

.

( .., 1997) (
3.3).
3.2.3.

( 3.4).
( .., 1974):
:
mm .
0,1m 0,5m.
:
,
, ,
.
16
3.3. ( .., 1997).
17
18
3.2.4.
.
( .., 1997):
:

.
: : )
) .
) :

,
,

( .., 1974, Okuda et al., 2002).
,
, CaCO3, ,

.
, 1m 20
m, ,
(, 1961),
. ,
( ), ( )
,

(, 1958, Sakorafa et al., 1996).

. Van Vugt et al. (2000) Mulder et al. (2000)
.
19
3.4. (
.., 1997).
20
)
,
, ,
.
:
, , ,
.
,
,
.
21
22
4.

:
4.1.

. ,
( , ,
,
) .
64 : 7
( -75), 6 (
-12), 14 ( -7), 13
( 12/00), 12
( -24), 3 ( -8) 9
( -10).
,
.
,
,
.

International Committee for Coal and Organic
Petrology ( 4.1) (I.C.C.P., 1993).
4.1. (I.C.C.P., 1993).

( )
()

Matrix

(: )
( )
()
( )
( )
()
(xylite-rich)
(charcoal-rich)
(mineral-rich)
23
4.2.
4.2.1.
10
<1mm 250m
.
(proximate) ,

American Society for
Testing and Materials (A.S.T.M.).
(...)
...

1g (<250m)
1052C 4h (ASTM D 3173-03).
ASTM D 3174-04, 1g
Barnstead/Thermolyne 30400 (1h
550C 3h 750C).
.
1g Carbolite
ELF 11/6 950C 6min (ASTM D 3175-02).
100%.
(ultimate)
, , , .
O C,H,N S, ,
C-H-N-S EAGER 200 Carlo Erba

. () :
= 100 - (C + H + N + S + + )
,
,
(Hower and Parekh, 1991, Thomas, 1992).
24

(Total Organic Carbon, TOC) (Total Inorganic Carbon,
TOC) LECO RC-412 Institute of Geology and Geochemistry of Petroleum
and Coal, RWTH-Aachen .
4.2.2.

(macerals)
. macerals
, .
4.2.2.1. maceral

<1mm
LEITZ Orthoplan Pol

.
(macerals) Stopes/Heerlen,
I.C.C.P. (1963, 1971, 2001) Skorov et
al. (2005), ().
500 maceral
( )
(point counter) Swift Prior.

, .
, ,
o,
.
.

.
25
LEITZ
Wetzlar, 50x/0,85oil 500x
(64).
4.2.2.2.

LEITZ
Orthoplan
Pol
LEITZ Wetzlar, 50x/0,85oil,

=546nm.
(64) - 50
.
4.2.3.

. Ca, Mg,
Fe
CO, CO2
(Burnham et al., 1980, Campbell et al., 1980, Charland et al., 2003), C4 (Otake
and Walker 1993). Mori et al. (1996), Wu and Ohtsuka (1996, 1997b), Friebel and Kpsel
(1999), Wu et al. (2001), Tsubouchi and Ohtsuka (2002) Xu and Kumagai (2002)
2 Fe
Ca Mg. / Mg Ca
(Ca) 2
(Otake and Walker, 1993, Lin et al., 2002). , ..
, ,
(Finkelman and Gross, 1999).

(Inductively Coupled Plasma Spectroscopy)
(FU-SAV, Bratislava,
Slovakia). 12 (360C)
26
: Al, Ca, Fe, Mg, Si, Ti,

: As, B, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, V, Y, Zn.
Mo, V, Y Zn
(Environmental
Protection Agency, US).
4.2.4. Rock Eval II

Rock-Eval
,
(Espitali et al., 1977).
Institute of Geology and Geochemistry of
Petroleum and Coal, RWTH-Aachen
(64) Rock-Eval .
(<200m) 300C 3min,

( S1 mg HC/g ).
25C/min 550C,
.
S2 ( mg HC/g
), 300C 390C
CO2 S3 ( mg C2/g ).
(max), S2
(Tissot and Espitali, 1975).
4.2.5. Soxhlet
Soxhlet 6 Institute of
Geology and Geochemistry of Petroleum and Coal, RWTH-Aachen . ,
2g (<200m) 200 ml
. 57,5C
, 47%, 23% 30%
.
27
(activated copper granulate)

.
65oC 24h.
,
.
30C 200-300mbar.
,

matrix (Solomon et al., 1992). Y
( 4.2) KL1
(55,3 mg /g ) SF-31
(30,6 mg /g ).
(. . 4.2.8),
(. . 4.2.6),
.
4.2. Soxhlet .

[g]

[mg]
[%]
KL - 1
KYP - 1
KOM - 9
PL - 7
SF - 31
PST - 3
1,9
1,9
1,9
1,9
1,9
1,9
105,0
60,8
66,1
76,5
58,2
82,4
5,5
3,2
3,5
4,0
3,1
4,3
4.2.6. (FTIR)
(FTIR)
Institute of Chemistry and Dynamics of the Geosphere, ICG V: Sedimentary Systems
Juelich .
KBr (1mg 200mg KBr)
. ,
10t, .
PERKIN ELMER 783 Infrared Spectrophotometer.
28
KBr ,
400 4000cm-1.
(FTIR)
(64 ),
360C ( ) (12
)
Soxhlet (6 )
4.2.7. 15
(15) Institute of
Chemistry and Dynamics of the Geosphere, ICG V: Sedimentary Systems
Juelich . 15, ()
Carlo-Erba CN2500,
(Isotope Ratio Mass Spectrometry,
IRMS). ,
, ,
, Holzmaar.
11 , (6 )
(6 ) Soxhlet.
4.2.8.
Institute of
Chemistry and Dynamics of the Geosphere, ICG V: Sedimentary Systems
Juelich .
(open system pyrolysis unit), ,
,
.
300mg (<200m)
, 40 ml/min. He

29
( C) (Solomon and Hamblen, 1983).

EUROTHERM PID NiCr-Ni,
(2-3mm)
.
1100C 0,5K/min, (KL-1)
0,1K/min.

(46,3vpm N2, 45,9vpm CH4, 43,7vpm CO 49,5vpm CO2).
,
2-5ml 2min
. 2, 2, C4 CO
CG
(Flame Ionisation Detector, FID), CO2
.
.

(~5-10%)
(Krooss et al., 2005).

:
(14 ),
Soxhlet (6 ).
,
(Isotope Ratio Mass Spectrometry, IRMS)
2 .

Finnigan Delta Plus XL
2 PL-7 (~10 min).
30
4.2.9. (TG/DTA)
14 .
(Thermogravimetric analysis, TG TGA)
,
, (Differential thermal analysis, DTA)
,
,
.
TG DTA
,
(Redfern, 1970).
G DT SETARAM
LabSys TG/DTA
. 8010mg (<200m)
.
He 10K/min
1100C.
In Al.
31
32
5.
5.1.
7
, 1-7.
,
. ( ,
, , ).
,
.
,
.
, .

(, , ) .
II, 1
A (2004).

(, . ) matrix,
, (.
) . (
) .
,
, ,
.

, , .
,
,
, .
33
P-4,
.
matrix,
.
,
. 1.
(Teichmller and Thomson,
1958, Kershaw and Sluiter, 1982)
. Hagemann and Hollerbach (1979), von der Brelie and Wolf (1981) Dehmer
(1989) [ Diessel (1992)]

,

(Lamberson et al., 1991).
.
, . , , .
34
5.2.
5.2.1.

, I, 2.

.

. , (
) ( 1052C).

(Orem and Finkelman, 2004).

( I, 2)
61,6% 64,5%, . 51,3% 59,0%,
37,8% 56,1%, 45,2%
54,8%, 31,0% 45,3%,
38,9% 57,6% 65,0% 67,3%.

,
matrix .
To 7,8%
16,8%, 12,8%,
16,0% 25,4%.

.
CO2, SO2 H2O
, (Ward, 1984, Thomas, 1992).
:
35
=1,1 (Standards Association of Australia formula), MM: o

: . Parr: MM = 1,08A +
0,55S, S: (Van Krevelen, 1993).
12,28% 25,71% ,
. 9,27% 45,51%,
10,85% 28,42%, 21,13% 34,88%
8,68% 45,09%.
28,39% 46,17%
31,54% 48,48%.

(Diessel, 1992).
.

38,78% 48,97%, . 37,19% 52,30%,
43,48% 52,58%, 43,25% 56,71%
33,63% 58,49%.

33,70% 45,53% 37,03%
46,84% ( I, 2).

55,82% 61,68%, . 56,15%
70,82%, 57,21% 60,75%,
66,15% 76,58%, 61,04% 67,09%,
60,78% 75,47%
64,91% 73,72%.

.

36
, ,
(Rees, 1966).
26,10%
38,76%, . 17,30% 39,16%,
28,10% 38,62%, 20,47% 25,81%,
21,29% 32,83%,
14,00% 27,29% 14,50% 24,03%.
5.2.2.
,
,
, , .
,
,

(...),
.
...
4.518kcal/kg 6.735kcal/kg, . 4.036kcal/kg
6.329kcal/kg, 3.851kcal/kg 6.276kcal/kg
5.154kcal/kg 6.573kcal/kg.
...
3.129kcal/kg 4.499kcal/kg

... ...
Neavel et al. (1986):
... = 81,5 Cdry + 316,4 Hdry - 29,9 Odry + 23,9 Sdry - 3,5 dry
, ...
37
5.2.3.

.
, ,
, .
5.1. DIN ASTM (Stach

et al., 1982) (1: , 2: ).
38

( 5.1) ,
( ) ( ).
I, 2.
5.1.
5.1.
.
:
:

(Lignite)

(Weichbraunkohle)

*
*
(Torf)
(Peat)

*:
5.2.4.
(ultimate)
, , , .

.
,
I, 3.
H/C, O/C N/C.
5.2.4.1.

. K
CO2 H2O . , CO2
o , H2O
, .
(C)
40,8% 54,3%, . 36,1% 55,3% (
39
SF-8 25,1%)
40,7% 56,3%, PST-2 31,7%.
42,4% 53,9%
32,3% 59,3%. C
30,4% 42,4%
17,2% 40,6%.
()
2,5% 4,8%, . 2,5% 5,9%,
2,9% 5,4%, 4,0%
5,1%, 3,5% 5,9%,
2,7% 3,8% 2,0% 2,9%.
5.2.4.2.
,
,
.
,
, .
.
,
(Ward, 1984).
()
17,5% 28,4%, . 13,6%
28,1% ( SF-3 SF-25,
38,5% 44,5% ), 20,0% 34,3%,
14,6% 21,5% 13,0%
28,2%.
10,2% 20,8%,
17,2% 28,8%.

. , 5.2
(r=-0,96).
40
70
RR22=0,92
= 0.92
O [%, , ]
60
50
40
30
20
10
0
30
35
40
45
50
55
60
65
70
C [%, , ]
5.2. , .
(Brown and Taylor, 1961, Gurba and

Ward, 2000).
5.2.4.3.

.

(Ward, 1984).

.
()
1,2% 1,6%, . 0,9% 1,6%
1,0% 2,2%.
0,5% 1,1% 1,0% 1,9%
PL-3 0,4%.
0,9% 1,3% 1,0%
1,5%.
41
2,5
2,0
N [%]
1,5
1,0
KL-2
KL-3
0,5
KL-4
KL-1
PL-3
0,0
10
20
30
40
50
60
TOC [%]
5.3. (N) (TOC).
5.3,
(. 5.2.5).
KL-1 KL-4 ,
PL-3 , .
Thomas (1997)
.
~85%.. .
5.2.4.4.
: )
, ) , .. )
,
(Ward, 1984).
( ).

,
(Casagrande, 1987). Chou (1990) Liu et al. (2001),

(<1%), (1-3%) (>3%).
42
(S)
0,4% 2,6%, . 2,1% 3,8% ( SF-1
0,7%), 1,7%
2,9%, 2,4% 3,5%
2,1% 3,7%.
3,4% 5,6%,
2,6% 5,2%.
,
(Given and
Miller, 1985, Hower et al., 1996, Taylor et al., 1998, Liu et al., 2001).

,
. Teichmller (1989) Markic and
Sachsenhofer (1997),

.

,
.
,
pH (Berner et al., 1979),
.
5.2.4.5. H/C O/C
H/C O/C ,
van Krevelen (1993),
. , (, , ,
)
, H/C O/C.
,
5.4,

. ,
43

. , 5.5,
(). (r = +0,5)
H/C HI ( 5.5)
(Espitali et al., 1977, 1985),
2,5
2,0
E
1,5
H/C
-4
1,0
B
0,5
A
0,0
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
O/C
5.4. H/C O/C ( : : ,

: , : , : , : ) ( van Krevelen,
1993).
250
200
200
Oxygen Index [mg OC/g org.C]
Hydrogen Index [mg HC/g org.C]
250
150
100
50
150
100
50
()
()
0
0,0
0,5
1,0
H/C
1,5
2,0
0,0
0,5
1,0
1,5
O/C
5.5. ) (HI) /C, )

(I) /C.
44
() /C ( 5.5).
-4, H/C O/C
(17,2%).
H/C O/C
.
5.2.5.
O : )
)
.
(Total Organic Carbon, TOC)
(Total Inorganic Carbon, TC), (Total
Carbon, TC) .

36,11% 48,28%, . 31,00% 47,12% (
SF-8 TOC 21,83%)
37,04% 49,97%, PST-2 27,42%.
65
55
C [%, ]
R = 0.92
R2=0,92
45
35
25
15
15
25
35
45
55
65
TC [%, ]
5.6. , TOC
TIC [TC] [C].
45
40,78% 51,11%
34,37% 54,21% PL-15, TOC
26,19%. TOC
28,57% 40,96%
15,65% 35,35%.

0,31% 1,45%, 0,10% 0,53%,
0,11% 0,94%, 0,17%
0,63%, 0,11% 0,88%,
0,07% 0,35% 0,07% 0,46%.

TOC TIC (C)
( 5.6)
(r = +0,96).
.
46
5.3.
5.3.1. maceral

(macerals) (mineral)
. macerals

.
macerals .
macerals
. , macerals

,
(Taylor et al., 1998).
Stopes/Heerlen (I.C.C.P., 1963, 1971)
(I.C.C.P., 2001, Skorov et al., 2005) macerals
, , ( 5.2).
, ,
(Teichmller, 1989, Diessel, 1992, Taylor et al., 1998).
5.3.1.1.
macerals
, , , .
, (Taylor et al., 1998)

.
(Teichmller, 1989).

()
.

.
, .
47

maceral (Cronauer et al., 1992, Stankiewicz et
al., 1996).
maceral, ,
, maceral
( 5.2).
, /
.
5.2. macerals Stopes/Heerlen (I.C.C.P., 1963, 1971, 2001, Skorov
et al., 2005).
MACERAL
MACERAL
MACERAL
MACERAL
48
MACERAL
) -
maceral
, (Stach et al.,
1982, Taylor et al., 1998).
pH
(forested peatlands) (forested raised bogs)
(Diessel, 1992).
. maceral

.
(Skorov et al., 2005).

/ .

, -
-.
Diessel (1992)
- -
- ( -)

. , - ()

(Diessel, 1992, Taylor et al., 1998).
) -
maceral,
.
(<10m), .
.

. ,
.
49
) -
maceral
,
.
.
, .
()
, .
5.3.1.2.
, , , ,
, .
( )

(Teichmller, 1989).
.
,
. maceral :

.
(sporopollenin),
(Teichmller,
1989).
.
. , ,
(cutin) .

, , .
,
. ,
. .
,
( ).
50

.

. .
maceral .
.
.
()
.
maceral ,
(Teichmller, 1989).
5.3.1.3.
maceral ,

(Taylor et al., 1998).
, (fusinitization).
(
) ,
, .

(Taylor et al., 1998). maceral
:

.
, , ,
.
- .

, .
maceral
/ .
51
, (hyphe), (mycele),
(plectenchyme), (sklerotie).

(I.C.C.P., 2001).
(vesicle) (
) . O
(<10m),
.
5.3.2.
5.3.2.1. -

(I.C.C.P., 1971).
<0,5% (Stach et al., 1982,
Mukhopadhyay, 1989),
maceral (Valceva, 1979,
Russell, 1984).
maceral
(Valceva, 1979).
.
,
,
(Orem and Finkelman, 2004). McCartney and Teichmller (1972)

.
Mukhopadhyay (1989)
- -
.
- ,
(Valceva, 1979, Mukhopadhyay, 1989, Cameron, 1991, Gentzis et al., 1996, Papanicolaou et
al., 2000, Iordanidis and Georgakopoulos, 2003, 2004)
52
(McCartney and Teichmller, 1972, Goodarzi, 1985, Marchioni,

1985).
H (Rr) -
I, 4.
Rr . 0,320,03%
0,410,03%, 0,310,04% 0,390,04%
0,330,03% 0,420,04%.
, Rr
0,250,03% 0,360,05%,
, -
0,240,02% 0,400,03%.
Rr
, 0,190,03% 0,260,04%

, Rr 0,270,04% 0,370,06%.
Carr and Williamson (1990), Suggate (1998) Nzoussi-Mbassani
et al. (2005),
(0,2%Rr 0,7%),
. Carr and
Williamson (1990)
, ,
. (0,7%Rr 3%),

.
5.3. - (Rr)
, n: .
rRr-
rRr-
(n=7)
+ 0,82
(n=6)
+ 0,87
(n=10)
+ 0,90
(n=13)
+ 0,92
(n=9)
+ 0,70
(n=13)
+ 0,89
* (n=3)
+ 0,94
*: (n=3)

.
53
160
R2 = 0.67
[m]
[m]
85
80
75
70
65
0,15
0,20
0,25
0,30
0,35
0,40
R2=0.82
PL-12
150
145
140
135
0,15
0,45
PL-15
155
0,20
0,25
0,30
Rr
500
R2 = 0.76
55
[m]
[m]
60
50
45
40
35
0,15
0,20
0,25
0,30
0,35
0,40
300
200
PST-2
0,20
0,25
0,30
[m]
[m]
175
165
145
0,25
0,30
0,40
0,45
0,35
0,40
0,35
0,40
0,45
R2=0.65
125
75
25
0,15
0,45
0,20
0,25
0,30
Rr
Rr
50
[m]
0,35
Rr
185
0,20
0,45
400
100
0,15
0,45

R2=0.85
125
0,15
0,40
R2=0.78
Rr
205
0,35
Rr
R2=0.88
48
46
44
42
40
0,15
0,20
0,25
0,30
0,35
0,40
0,45
Rr
5.7. - (Rr) .
.
( 5.1)
C (Subbituminous Coal C).
,
,
, .

(r>+0,70) -
54
( 5.3). Rr
.

(PL-12 PL-15)
(PST-2),
(. 5.7). Rr PST-2

(Diessel et al., 2000, Davies et al., 2005).
(9,6%) .
PL-12
PL-15
,
Gurba and Ward (1998), Davies et al. (2005) Ward et al. (2007)
.

.
( 2 3, I)

. PL-12 PL-15,
,

(. 5.5.3), (Bostick and
Daws, 1994). Gentzis and Goodarzi (1994)
,
.
55
5.3.2.2. maceral
)
.
I, 5
( 5.8), maceral.

84,3% 94,2%, 3,0% 9,3%,
2,6% 6,3%2.
(36,6%62,0%) (36,6%-55,8%),
21,3% -14.
, 20,0% 49,0%. (8,7%-20,8%), -
, 1,0% 5,7%. -
(3,3%-12,8%) - (2,3%-8,8%)
-14, - 17,4%.
, -15 (0,2%).
0,6% 3,2%.
80%
20%
60%
40%
40%
60%
20%
100%
80%
80%
60%
40%
20%
0%
5.8. ,
( % , ).
2
% maceral ..
56
(0,2%-1,7%),
.
(0,2%-2,0%).
(0,2%-0,4%
0,0%-0,8% )
0,3%.
maceral
(0,4%-6,0%), (0,8%-5,6%) (0,6%-2,4%).
(0,6%) (0,4%).
6,4% 48,5%.
(2,6%-21,6%), (2,6%-19,8%)
(0,4%-4,3%) (0,6%-2,4%).
)
13 .
.
I, 6
( 5.9), maceral.
H
83,6% 93,6%, 1,6%
7,2%. 3,8% 14,4%
80%
20%
60%
40%
40%
60%
20%
100%
X
80%
80%
60%
40%
20%
0%
5.9. , .
( % , ).
57
PST-3, 18,5%.

(27,0%-70,4%).
25,4% 64,4%, 20,4%
SF-25 SF-35.
, 19,2% 55,2%.
maceral - 7,4% 26,8% -
1,2% 18,8%. maceral -
2,2% 16,4% 0,0% 14,6% .
(0,8%). (1,2%-5,0%)
(2,4%), (2,4%)
(1,2%).
(4,8%),
(2,4%) (2,2%). maceral
(0,8%).
(8,2%)
maceral (3,0%), (2,8%) (1,8%).
5,7% 56,7%.
23,6% 26,5%.
(5,5%), 3,1%
3,8%.
)
14
.
I, 7 5.10,
maceral.
76,0%
93,2%, 5,6% 18,5%,
4,8% PST-2,
9,6%.
(42,8%-59,4%)
, (34,6%-55,4%)
(11,7%), PST-4 .
58
45,8% maceral . 10,6%

(5,8%), maceral (4,0%)
(3,0%).
80%
20%
60%
40%
40%
60%
20%
100%
80%
80%
60%
40%
20%
0%
5.10. ,
( % , ).
(5,0%),
(2,2%) (2,0%). maceral
(0,6%).
maceral
(1,4%-11,2%) (6,2%) maceral
(1,0%-3,5%) (2,4%).
5,8% 30%.
12,7% 10,1%.
(6,5%), 3,0%.
)
12
.
I, 8 5.11,
maceral.
59
84% 97,2%.
17,6%
70,0%, maceral - (3,4%-55,6% 6,0%29,6% ). - (7,6%),
- (7,2%).
(4,4%).
(24,8%-70,0%)
. maceral
, 0,4% 4,0%.
80%
20%
60%
40%
40%
60%
20%
100%
80%
80%
60%
40%
20%
0%
5.11. ,
( % , ).
2,8% 14,8%.
(11,2%) (8,0%) , ,
.
1,2% 6
.

34,2%, (23,7%).
(5,2%)
(3,8%).
60
.
I, 9 5.12,
maceral.

74,6% 93,6%.
(19,2%-66,8% 22,0%-62,4%),
8,6% (5,6%)
maceral. maceral -
(7,8%-46,4%) - (2,8%-13,25) -
(1,0%-10,0%). - (5,6%
5,8% ), 2,6%.
,
21,6% 47,4%, 0,4% 23,1%.
5,8% 13,6%.
(5,0%), (3,8%) (3,4%) ,
.
2,6%,
KL-5, 11,7% (. 5.12).
19,1% 39,7%.
80%
20%
60%
40%
40%
60%
20%
100%
X
80%
80%
60%
40%
20%
0%
5.12. ,
( % , ).
61
(9,5%-24,4%), (1,4%-19,4%)
(2,3%-5,2%) (4,1%).
)
3
.
I, 10
5.13, maceral.
90,4%
96,4%.
6,4%. KYP-4
25,5%, - 24,0%.
67,0% 90,0%.
56,4% 63,5%
3,5% 28,6%. 1,0%
.
3,2% 7,2%.
(2,4%-5,2%), maceral (1,5%)
(1,0%).
2,4%,
.
80%
20%
60%
40%
40%
60%
20%
100%
X
80%
80%
60%
40%
20%
0%
5.13. ,
( % , ).
62
39,2%
68,8%.
)
9
.
I, 11
5.14, maceral.

84,4% 95,4%. 3,5%
9,2%, 0,8% 3,2%.
MAR-4 MAR-10, 9,6%
5,2% .
80%
20%
60%
40%
40%
60%
20%
100%
80%
80%
60%
40%
20%
0%
5.14. ,
( % , ).
(38,4%-67,6%),
.
13,6% 48,8%. - (10,6%-37,2%), -
(2,4%-15,2%), MAR-16 (32,6%)
MAR-19 (26,9%). (2,0%)
- (1,2%).
63
maceral
(0,4%-4/0%) (1,2-3,6%).
(2,4%) (2,4%),
(1,6%).
,
,
22,2% 62,3%.
5.3.3.
macerals

(Teichmller, 1989).
. , ..
, - -
, maceral (Taylor et al., 1998, Jimnez et al.,
1999). ,
,
.
,
,
, maceral
(Crosdale, 1993, Dehmer, 1995, Wst et al., 2001, Moore and Shearer,
2003).

.

(Kalaitzidis et al., 2004).
,
, , ,
(Collinson and Scott, 1987, Scott, 2002, Moore
and Shearer, 2003).
macerals.
64
5.3.3.1. Mukhopadhyay

Mukhopadhyay (1986, 1989). ,

.
, () ,
, , , . macerals

, .
,

(Mukhopadhyay, 1989). ()
, , ,

, .
, .
, () ()
( ).

, () ()

. ()
, () .

, (Kalkreuth
et al., 1991b). (C) ,
/ ,
. >30%
, <5% .

<15% > 15%, .

,
65
, .
/
.
, ,
,
.
5.15-5.18 (), () (C)
.
C
80%
60%
40%
()
20%
40%
,

,

,

,
60%
20%
100%
Series1
Series11
Series2
Series3
80%
80%
60%
40%
20%
0%
5.15. ABC ,
Mukhopadhyay (1986, 1989).
( 5.15)
() (), Mukhopadhyay
(1989) ( ).
<5%,
,

. L-5 (C=11,7%)
( )

.
( 5.16)
() ()
66
(). (=50-100%)
,
,

.
.
-14 (=41,8%) PST-11 (47,2%),
.
-7 (6,3%), PST-2 (9,6%) PST-5 (6,0%) <5%,

. -7,
PST-2 PST-5 (5%<C<15%)
.
80%
()
60%
40%
20%
40%
,

,

,

,
60%
20%
100%
A
Series1
Series11
Series2
Series3
80%
80%
60%
40%
20%
0%
5.16. ABC ,
( 5.17)
5%, 5% 15%

(Stach et al., 1982). H
() ()
67
, ,
, .
( 5.18)
(), ,
,
(Kalkreuth et al., 1991b).
() ()
(),
( ).
C
80%
60%
()
,

,
60%
20%
100%
Series1
Series11
Series2
Series3
N.
40%
,

,

40%
20%
80%
80%
60%
40%
20%
0%
5.17. ABC . ,
C
80%
60%
40%
()
20%
40%
,

,

,

,
60%
20%
100%
Series1
Series11
Series2
Series3
80%
80%
60%
40%
20%
0%
5.18. ABC ,
68
<5%, .
AR-4 (C=9,6%),

.
5.3.3.2. TPI-GI

,
macerals,
, (Calder et al., 1991, Kalkreuth
et al., 1991a, Diessel, 1992, Calder, 1993, Markic and Sachsenhofer, 1997).

.
(TPI Tissue Preservation
Index) (GI Gelification Index),
Diessel (1986)
Kalkreuth et al. (1991a),
Markic and Sachsenhofer (1997) Kolcon and Sachsenhofer (1999).

( .., 2000, 2001, Antoniadis et al., 2001, , 2003, Mavridou et al.,
2003)
.
(TPI)
macerals,
, .
:
TPI =
+ +
+ + +
TPI ( )
,
(Diessel, 1992).
, ,
, .
69

,
.
,
(Diessel, 1992).
TPI, ,
(
)
(Lamberson et al., 1991, Markic and Sachsenhofer, 1997).
,
.
,
TPI
,
.
(Diessel, 1992) ,
Lamberson et al. (1991) , ,
,
. ,
pH .
(GI)
(TPI)
,
(GI) .
macerals :
GI =
+ +
+ +
.
GI
TPI GI
. (>1)
70
,
. GI TPI
(Lamberson et al.,
1991, Diessel, 1992).
TPI GI
Diessel 5.19-5.22.

GI (>1),

.
TPI GI
Diessel 5.19.
TPI,
.
(KL-9, PL-15) TPI>1
.
.
TPI (<1)
,
/ (Diessel, 1992).
( PL-1 PL-4) .
(TPI>1),

. , ,
TPI (TPI>1) (TPI<1)
,
.
, ,

. TPI
,

.
71
100,0
/
%
LIMNO - TELMATIC
LIMNIC
TELMATIC
KL-3
KL-1
KL-4
PL-11
10,0
FEN
WET
FOREST
SWAMP
PL-7
KL-2
KL-9
PL-10
PL-13
PL-9
GI
KL-7
PL-15
PL-3
PL-4
PL-1
PL-5
PL-2
PIEDMONT
PLAIN
KL-5
PL-12
1,0
DRY
FOREST
SWAMP
OPEN
MARSH
0,1
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
TPI
5.19. GI TPI
Diessel (1986, 1992), .
, .
( 5.20 5.21) TPI
(<1) GI (>1),

(Lamberson et al., 1991, Diessel, 1992). TPI>1
SF-1, SF-2 SF-3 .

.
TPI
PST-11 KOM-14,
.

.

( . ), .
72
100,0
/
%
LIMNO - TELMATIC
LIMNIC KOM-3
PST-9
PST-8
10,0
PST-14
PST-4
PST-7
PST-15
KOM-14
PST-11
PST-12
FEN
WET
FOREST
SWAMP
PST-5
PST-10
KOM-13
PST-3
PST-2
GI
TELMATIC
KOM-7
1,0
DRY
FOREST
SWAMP
OPEN
MARSH
0,1
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
TPI
5.20. GI TPI
Diessel (1986, 1992), .
100,0
/
%
LIMNO - TELMATIC
SF-35
LIMNIC
TELMATIC
SF-1
SF-25
10,0
SF-20
SF-23
GI
SF-8
SF-12
SF-31
SF-29
FEN
WET
FOREST
SWAMP
SF-16
SF-10
SF-2
SF-3
1,0
DRY
FOREST
SWAMP
OPEN
MARSH
0,1
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
TPI
5.21. GI TPI . Diessel (1986,

1992), .
73
100,0
/
%
LIMNO - TELMATIC
LIMNIC
TELMATIC
10,0
FEN
R-19
GI
R-6
WET
FOREST
SWAMP
R-16
1,0
R-10 R-12
R-11
R-13
R-4
KYP-3
KYP-1
R-18
DRY
FOREST
SWAMP
KYP-4
OPEN
MARSH
0,1
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
TPI
5.22. GI TPI
Diessel (1986, 1992), .
( 5.22)
. . ,

TPI ( ) GI (
).

( ) /
.
,
, MAR-19 (GI=8,0)
. GI

.
( MAR-4 GI=0,5)
.
PI
( ) .
74
5.3.3.3. GWI-VI
(GWI Groundwater Influence
Index) (VI Vegetation Index),
Calder et al. (1991). ,
.. (2000, 2001).
(GWI)

Cumberland (Calder et al., 1991, Calder, 1993)
.
,
.
macerals, ,
. A,
(Von
der Brelie and Wolf, 1981), ,
macerals.
:
GWI =
+ +
+
(VI)
( )
TPI,
( ).
,
macerals
(Calder et al., 1991, Kalkreuth et al.,
1991a, Calder, 1993). :
VI =
T + + +
+ + +
GWI VI
Calder 5.23-5.26.
75
(GW)
0,6 3,3
. Calder et al. (1991) GWI<0,5,

().

( ),

( PL1 PL4).
(VI<3).
PL-1, PL-2, PL-3, PL-4, PL-15 KL-4
,
( 5.23).
( 5.24)
(GWI>1).

<1 -14 (VI=1,4).
(PI)
/
, .
. ( 5.25)
.
,
. ,
( SF-1, SF-2 SF-3)
(
VI).
( 5.26),
,

.
(VI<1,2), .
76
10.0
Inundated
Marsh
Inundated
Forest
rheotrophic
Limnic
KL-7
PL-7
Swamp
PL-11
KL-2
KL-3
GWI
PL-12
KL-5
PL-5
KL-1
KL-9
PL-9
PL-13
PL-10
1.0
Fen
PL-15
mesotrophic
PL-1
PL-3
PL-2
KL-4
PL-4
Bog
ombrotrophic
0.1
0.0
2.0
4.0
6.0
VI
5.23. GWI VI
Calder et al. (1991).
10.0
Inundated
Marsh
Inundated
Forest
rheotrophic
PST-15
Limnic
GWI
PST-3
KOM-7 PST-9 PST-2
PST-8
KOM-13
KOM-3
PST-10
PST-5
PST-13
PST-6
1.0
Swamp
KOM-9
KOM-15
PST-12
PST-11 KOM-14
Fen
mesotrophic
Bog
ombrotrophic
0.1
0.0
2.0
4.0
6.0
VI
5.24. GWI VI
77
10.0
Inundated
Marsh
Inundated
Forest
Limnic
rheotrophic
SF-25
SF-31
SF-20
SF-8
SF-23
SF-29
Swamp
SF-12
GWI
SF-10
SF-16
1.0
SF-2
Fen
SF-35
SF-3
SF-1
mesotrophic
Bog
ombrotrophic
0.1
0.0
2.0
4.0
6.0
VI
5.25. GWI VI .
10.0
Inundated
Marsh
Inundated
Forest
rheotrophic
Limnic
GWI
Swam
KYP-1
R-4
KYP-3
1.0
R-19
R-10
Fen
R-6
R-18
R-13
R-16
R-12
R-11
mesotrophic
KYP-4
Bog
ombrotrophic
0.1
0.0
2.0
4.0
6.0
VI
5.26. GWI VI
78
5.3.3.4. Singh and Singh

Singh and Singh (2000)
macerals
,
.
, ( 5.27 5.28)
,
.
A:

: ()

C:

&
80%
20%
60%
40%
50
40%
50
60%
20%
80%
100%
80%
Series1
KOMANO
60%
50
40%
20%
0%
5.27.
Singh and Singh (2000).
A:

: ()

C:

&
80%
20%
60%
50
40%
Series1
40%
50
60%
20%
80%
100%
80%
60%
50
40%
20%
0%
5.28. Singh and Singh

(2000).
79
5.4.

,
,

.
12 ,
(360C)
: (>1.000ppm),
(100-1.000ppm) (<100ppm).
( 5.4)
: Al (0,20-4,00%), Ca (2,80-9,80%), Fe (0,26-3,10%), Mg (0,16-2,20%),
Si (0,04-0,30%) Ti (0,005-0,15%). : Ni (92336ppm), Mn (25-227ppm) Cr (63-330ppm).
5.4. ( ppm, , *:
Swaine, 1990).
KL-1 KL-5 PL-7 KOM-9 KOM-15 SF-1 SF-20 SF-31 PST-3 PST-14 MAR-16 KYP-1
Al [%]
Si [%]
Fe [%]
Mg [%]
Ca [%]
Ti [%]
B
Co
Ni
Mn
Cr
Cu
Y
V
Zn
Mo
Be
As
Sb
Pb
Cd
80
1,90
0,18
1,50
0,41
2,80
0,09
90
29
106
211
117
75
11
48
84
3,9
0,69
<60
<15
<30
<2
2,60
0,24
1,40
0,40
3,80
0,14
70
22
114
209
86
57
12
40
77
1,9
0,56
<60
<15
<30
<2
0,82
0,06
0,87
0,23
4,60
0,03
54
16
116
97
87
15
7
34
23
1,7
0,34
<60
<15
<30
<2
0,20
0,10
0,26
0,16
9,00
0,005
68
28
211
109
63
15
6
5
8
<1
<0,2
<60
<15
<30
<2
2,00
0,07
0,94
0,44
4,20
0,10
123
25
137
70
77
19
8
36
27
2,02
0,44
<60
<15
<30
<2
0,78
0,21
0,58
0,70
2,90
0,03
33
13
110
79
99
8
4
24
16
3,7
0,64
<60
<15
<30
<2
0,98
0,23
0,73
0,78
3,20
0,03
40
15
164
26
148
9
4
53
18
4,0
0,62
<60
<15
<30
<2
3,40
0,30
1,30
2,20
8,10
0,14
92
44
336
155
330
38
19
107
61
<1
0,8
<60
<15
<30
<2
1,30
0,04
0,68
0,73
3,20
0,05
38
14
92
25
98
10
4
49
25
3,4
0,34
<60
<15
<30
<2
0,79
0,07
0,66
0,51
3,30
0,03
31
13
96
36
65
12
7
3,2
20
<1
0,66
<60
<15
<30
<2
4,00
0,07
3,10
0,62
2,90
0,15
73
31
126
218
158
40
14
145
77
69,0
0,83
<60
<15
<30
<2
1,80
0,12
1,80
0,30
9,80
0,05
69
41
262
227
111
40
14
54
43
13,8
0,43
<60
<15
<30
<2
/*
0,001-0,2
5-400
0,5-30
0,5-50
5-300
0,5-60
0,5-50
2-50
2-100
5-300
0,1-10
0,1-15
0,5-80
0,05-10
2-80
0,1-3
<100ppm: B, Be, Co, Cu, Mo, V, Y, Zn, , : As, Cd, Sb Pb

.
Swaine (1990)
( 5.4). Ni Cr
. Y V Mo
, Sakorafa et al.
(1996) .
, ( 5.5)
: Al (0,33-8,20%), Ca (4,90-18,90%), Fe (0,80-6,30%),
Mg (0,36-4,60%), Si (2,00-15,80%) Ti (0,03-0,46%). :
(152-581ppm), Co (75-136ppm), Ni (320-937ppm), Mn (197-908ppm), Cr (133-789ppm),
V (142-459ppm), Zn (34-990ppm) : As, Be, Cd, , Pb, Sb .
As, Pb, Cd, Mn Cr
, . Guo et al. (2002) Pb
, Mn Cr .

(Raask, 1985, Pike et al., 1989, Karayigit et
5.5. ( ppm,
).
Al [%]
Si [%]
Fe [%]
Mg [%]
Ca [%]
Ti [%]
B
Co
Ni
Mn
Cr
Cu
Y
V
Zn
Mo
Be
As
Sb
Pb
Cd
KL-1
KL-5
PL-7
6,40
7,20
5,10
1,20
6,80
0,31
152
132
370
795
345
248
53
168
232
19
1,6
<60
<15
<30
<2
7,80
6,70
4,80
1,00
10,40
0,46
208
104
335
811
789
257
40
154
257
14
1,7
76
<15
<30
<2
2,50
7,20
4,60
0,87
14,50
0,21
354
92
445
667
482
143
22
311
96
20
2,1
<60
<15
<30
2,5
KOM-9 KOM-15
0,33
2,00
0,80
0,36
15,20
0,03
347
75
414
514
133
45
20
142
34
19
0,1
<60
<15
<30
<2
6,30
4,60
3,30
1,40
10,90
0,41
306
98
459
324
323
80
21
150
68
13
1,7
<60
28
<30
<2
SF-1
SF-20
SF-31
PST-3
2,90
4,30
4,20
4,60
18,90
0,19
360
136
937
908
645
124
31
327
163
74
3,4
108
<15
<30
<2
1,50
13,40
4,30
3,40
5,70
0,20
581
81
856
262
715
74
17
459
106
36
1,8
71
<15
<30
<2
4,50
15,80
2,30
2,10
14,60
0,35
225
130
688
391
652
4137
35
262
990
18
1,6
<60
<15
<30
3
6,20
7,50
3,80
2,80
13,50
0,32
283
111
521
197
640
64
42
390
78
33
2
<60
<15
<30
<2
PST-14 MAR-16 KYP-1

3,70
6,60
4,30
1,80
16,10
0,24
263
125
616
366
473
115
45
362
116
23
2,9
<60
<15
<30
5,5
8,20
7,60
6,30
1,30
4,90
0,36
216
97
320
487
375
91
45
411
149
175
2,2
<60
<15
<30
<2
3,40
6,00
4,30
0,64
14,10
0,18
212
107
494
820
279
109
22
223
113
51
1,3
<60
<15
<30
<2
81
al., 2000, Pollock et al., 2000, Zajusz-Zubek and Konieczyski, 2003, Hu et al., 2006).

, (Spears and Zheng,
1999). ,

(Burnham et al., 1980, Campbell et al., 1980, Otake
and Walker, 1993, Charland et al., 2003).
,
Ca Mg,
(.. ), (.. , ),
(.. ) (Baruah et al., 2003).
, Al, Fe Ti
(r+0,82) ( 5.6)
. Ti Al (r=+0,96), Fe
(r=+0,72) (Spears and Zheng, 1999),
FeTi- (arayigit et al., 2000, Hu et al., 2006).
Ti Fe
. Al (r=+0,84),
. Al
5.6. Pearson (r)

.
Al[%] Si[%] Fe[%] Mg[%] Ca[%] Ti[%]
Al[%]
Si[%]
Fe[%]
Mg[%]
Ca[%]
Ti[%]
B
Co
Ni
Mn
Cr
Cu
Y
V
Zn
Mo
Be
82
0,91
0,17
0,83
0,41
0,34
0,82
0,59
0,84
0,52
0,76
0,61
0,59
0,92
0,84
0,73
0,79
0,45
0,26
0,84 -0,01
0,48 0,60 0,08
-0,03 0,10 -0,06 0,14
0,96 0,32 0,72 0,43 -0,13
0,53 0,09 0,34 0,13 0,27
0,61 0,29 0,53 0,39 0,70
0,27 0,45 0,09 0,58 0,85
0,64 0,25 0,76 -0,03 0,31
0,63 0,61 0,33 0,93 0,25
0,59 0,35 0,60 0,03 0,04
0,82 0,37 0,69 0,49 0,43
0,88 0,19 0,83 0,53 -0,02
0,82 0,34 0,78 0,21 -0,13
0,80 -0,31 0,89 0,17 -0,07
0,56 0,51 0,46 0,51 -0,12
0,60
0,51
0,16
0,61
0,53
0,66
0,76
0,74
0,85
0,56
0,50
Co
Ni
Mn
Cr
Cu
0,66
0,35
0,47
0,26
0,52
0,57
0,31
0,47
0,09
0,11
0,81
0,72
0,60
0,57
0,87
0,55
0,53
0,44
0,34
0,30
0,70
0,11
0,62
0,32
0,07
0,08
0,24
0,24
0,86
0,78
0,49
0,82
0,45
0,33
0,23
0,68
0,71
0,40
0,69
0,57
0,69
0,37
0,93
0,18
0,35
Zn
Mo
0,67
0,75 0,63
0,54 0,97 0,45
0,48 0,54 0,51 0,62
Si Si, ,
.

,
(Querol and Chenery, 1995),
(Zajusz-Zubek and Konieczyski, 2003).

(Lindahl
and Finkelman, 1986, Clark and Sloss, 1992).

(r+0,73) , .
: Co, Mn, Mo, V, Y Zn,
(+0,45r+0,61).
()
(Eskenazy et al., 1994,
Goodarzi and Swaine, 1994, Pollock et al., 2000, Goodarzi, 2002). Goodarzi and Swaine
(1994) <50ppm ,
50ppm 110ppm ,
110ppm . 5.4
50ppm 100ppm
-15 (123ppm).

. .
Goodarzi and Swaine (1994)
,
. Beaton et
al. (1991) Pollock et al. (2000)
.
(Be)
(+0,45r+0,56),
(Roy and Chakrovarty, 1984, Gentzis and Goodarzi, 1997, Finkelman and
Gross, 1999, Karayigit et al., 2000, Goodarzi, 2002), ,
Al (Beaton et al., 1991, Finkelman 1994).
83
(Co) Ni (r=0,81) (r=0,87)

: Al (r=0,61), B (r=0,66), Ca (r=0,70), Cr (r=0,60) Mn (r=0,72)
(Karayigit et al., 2000). Finkelman (1994)
Co ,

[(Co,Ni)3S4]. ,
(Swaine, 1990, Goodarzi, 2002).
(Ni) (Querol and Chenery,
1995, Baruah et al. 2003),
: Ca (r=+0,85), Co (r=+0,81), Cr (r=+0,70) Y (r=+0,62). Ruppert et al.
(1992, 1996) 10%
, , ,
mixed-layer .
: (NiS), ((Co,Ni)3S4)
(NiSbS), Ni ,
(Finkelman, 1994). Ni
(Palmer and Lyons, 1996).
(Mn) Al (r=+0,64), Fe (r=+0,76), Ti (r=+0,61),
Co (r=+0,72), Cu (r=+0,86), Y (r=+0,78) Zn (r=+0,82). Raask (1985),
Finkelman (1995) Zhuang et al. (2000) Mn
( )
. Mn Ca
.
(Swaine, 1990, Finkelman, 1994, 1995,
Goodarzi, 2002).
(Cr) (r=0,61), Al (r=0,63), Co
(r=0,60), Mg (r=0,93), Mo (r=0,69), Ni (r=0,70), Si (r=0,61), V (r=0,71)
(r=0,68). Karayigit et al. (2000), Pollock et al. (2000) Goodarzi (2002)
Cr , Cr-
, (Querol and Chenery, 1995, Ruppert et al., 1996) Cr
Cr- .
Cr (Roy and Chakrovarty, 1984)
(Huggins et al., 1993,
Huffman et al., 1994, Goodarzi and Huggins, 2001, Orem and Finkelman, 2004).
84
(Cu) Mn (r=0,86) Zn (r=0,93),

Fe (r=0,60), Ti (r=0,66) Y (r=0,69).
Karayigit et al. (2000) Cu . Swaine
(1990) Goodarzi (2002)
Cu, Cu .
Mo, V, Y, Zn, Al
(0,80r0,88), Fe (0,69r0,89) Ti (0,56r0,85),
(Spears and Zheng, 1999), (
) (Querol et al., 1995, 1997, Alasteuy et al., 2001). Karayigit et al. (2000)
Mo V
, Zn (Raask, 1985)
(Goodarzi, 2002). V
(maceral) (Querol and Chenery, 1995).
85
5.5. Rock Eval II

Rock-Eval

(Espitali et al., 1977, 1985).
(Durand and Paratte, 1983, Teichmller
and Durand, 1983, Bertrand, 1984, Horsfield et al., 1988, Mukhopadhyay, 1989, 1991,
Suggate and Boudou, 1993, Georgakopoulos 2000, Papanicolaou et al., 2000).
10mg 20mg
(TOC) . 100mg
(Peters, 1986) TOC,
(Flame Ionization
Detector, FID)
(Georgakopoulos, 2000). Rock-Eval
5.7.
5.5.1. S1, S2 S3
P1 S1
C1 C33,
(>C33), (resins) (asphaltenes)
P2 ( S2) (Bordenave et al., 1993). S1

,
(Teichmller and Durand, 1983, Bostick and Daws, 1994). S1
2,73 8,09mg HC/g ,
(2,77-5,65mg HC/g ).
S1
1,30 2,33mg HC/g , .
1,02-3,69mg HC/g 1,37
3,88mg HC/g . S1
. ,
3,82 6,70mg HC/g , 2,27-4,50 mg
HC/g .
86
5.7. Rock-Eval.
SF-1
SF-2
SF-3
SF-8
SF-10
SF-12
SF-16
SF-20
SF-23
SF-25
SF-29
SF-31
SF-35
KL-1
KL-2
KL-3
KL-4
KL-5
KL-7
KL-9
KOM-3
KOM-7
KOM-9
KOM-13
KOM-14
KOM-15
KYP-1
KYP-3
KYP-4
MAR-4
MAR-6
MAR-10
MAR-11
MAR-12
MAR-13
MAR-16
MAR-18
MAR-19
PST-2
PST-3
PST-4
PST-5
PST-6
PST-7
PST-8
PST-9
PST-10
PST-11
PST-12
PST-13
PST-14
PST-15
PL-1
PL-2
PL-3
PL-4
PL-5
PL-7
PL-9
PL-10
PL-11
PL-12
PL-13
PL-15
Min
Max
M.O.
S1
S2
S3
[mg/g rock] [mg/g rock] [mg/g rock]
2,02
56,38
40,85
3,69
46,30
36,10
3,12
36,30
38,35
1,02
16,68
24,97
2,85
52,57
38,09
1,91
39,29
38,78
2,09
46,66
41,33
1,92
41,92
42,30
2,07
37,22
41,18
1,53
30,69
25,44
2,13
41,62
32,99
1,85
37,77
28,51
1,73
35,10
37,34
8,09
86,19
35,04
3,85
66,56
36,97
7,29
96,14
34,58
5,00
63,20
29,80
2,73
45,84
35,09
3,39
52,45
32,83
2,88
53,65
31,34
2,33
56,89
41,55
1,30
39,40
22,10
1,73
44,79
33,06
1,86
40,81
29,28
1,42
38,76
35,23
1,80
44,40
36,20
3,20
34,92
36,45
4,50
38,65
53,20
2,27
26,24
19,16
3,82
38,27
28,90
5,34
55,97
40,19
4,15
47,20
27,00
5,79
57,36
35,19
5,91
53,87
25,51
4,82
54,01
26,39
4,84
54,44
46,86
6,70
65,98
32,08
5,16
48,60
43,01
1,37
30,34
24,60
1,96
47,38
39,62
3,04
43,26
34,13
2,71
51,86
33,64
3,60
49,69
35,46
3,88
69,72
37,59
3,04
50,54
39,78
2,96
53,33
37,59
2,31
54,53
40,37
2,34
65,21
47,02
2,68
54,12
41,64
2,47
41,38
34,05
2,97
50,49
41,38
2,23
36,60
28,83
3,73
61,02
34,20
4,37
56,76
28,45
4,61
106,05
27,21
4,24
65,84
37,92
3,82
52,53
32,15
3,26
51,95
46,52
2,77
45,18
35,18
3,10
53,10
43,88
2,35
57,07
35,09
5,65
76,28
25,23
2,97
55,10
33,82
4,05
56,81
19,71
1,02
8,09
3,29
16,68
106,05
50,93
19,16
53,20
34,82
Tmax
[C]
420
410
411
421
410
418
415
420
419
427
425
428
421
364
365
363
358
390
404
406
414
430
424
425
427
425
416
407
421
421
408
405
412
405
424
417
425
413
421
421
405
411
403
409
412
416
409
418
407
421
410
420
395
414
361
400
364
420
418
424
422
393
423
420
358
430
410
TOC [%]
[mg]
OI
HI
PI
43,22
35,88
33,89
21,83
42,13
40,08
46,42
43,81
42,29
31,00
39,02
36,99
47,12
48,40
49,20
51,11
43,40
40,78
40,97
41,87
47,29
36,11
48,28
36,26
43,30
45,29
32,73
35,35
15,65
28,40
37,97
34,20
35,04
34,48
28,57
40,58
30,22
40,96
27,42
42,58
44,61
44,82
42,87
49,97
44,72
42,29
45,54
47,22
46,99
40,56
44,75
37,04
42,34
34,37
54,21
47,11
39,57
48,35
41,73
43,42
44,38
38,78
41,08
26,19
9,4
19,5
19,5
20,5
10,5
9,9
10,5
10,4
10,1
20,2
19,7
10,8
9,8
10,5
9,6
9,6
10,0
10,6
10,6
10,4
10,3
20,0
9,8
20,9
10,5
10,0
20,3
20,0
50,1
19,1
19,7
20,0
20,8
19,6
19,7
9,9
19,7
9,3
20,4
10,7
9,2
10,7
9,7
10,8
9,2
10,8
10,8
9,4
9,7
10,1
10,1
10,3
10,7
20,1
10,4
10,6
20,9
9,2
10,8
10,3
10,6
19,1
9,4
20,7
95
101
113
114
90
97
89
97
97
82
85
77
79
72
75
68
69
86
80
75
88
61
68
81
81
80
111
150
122
102
106
79
100
74
92
115
106
105
90
93
77
75
83
75
89
89
89
100
89
84
92
78
81
83
50
80
81
96
84
101
79
65
82
75
130
129
107
76
125
98
101
96
88
99
107
102
74
178
135
188
146
112
128
128
120
109
93
113
90
98
107
109
168
135
147
138
164
156
189
134
218
119
111
111
97
116
116
140
113
126
120
138
115
102
113
99
144
165
196
140
133
107
108
122
129
197
134
217
0,03
0,07
0,08
0,06
0,05
0,05
0,04
0,04
0,05
0,05
0,05
0,05
0,05
0,09
0,05
0,07
0,07
0,06
0,06
0,05
0,04
0,03
0,04
0,04
0,04
0,04
0,08
0,10
0,08
0,09
0,09
0,08
0,09
0,10
0,08
0,08
0,09
0,10
0,04
0,04
0,07
0,05
0,07
0,05
0,06
0,05
0,04
0,03
0,05
0,06
0,06
0,06
0,06
0,07
0,04
0,06
0,07
0,06
0,06
0,06
0,04
0,07
0,05
0,07
15,65
54,21
40,20
9,20
50,10
14,01
50,19
150,50
87,88
74
218
128
0,03
0,10
0,06
87
S2
,
. S2
(45,84-96,14mg HC/g ) (45,18-106,05mg HC/g
) (16,68-69,72mg
HC/g ). S2 38,27
65,98mg HC/g ,
(26,24-38,65mg HC/g ). Bordenave et al. (1993) Bostick and Daws (1994)
S2 ,
. S2

.
S3 ,
(Bordenave et al., 1993). ,
. S3
22,10-47,02mg C2/g . S3
29,80 36,97mg C2/g ,
S3 (19,71-46,52mg C2/g ).
S3 . ,
25,51 46,86mg C2/g ,
19,16 53,20 mg C2/g .
5.5.2. Tmax
max ,

S2.
max (358
406 C) ( 5.7),
.
Papanicolaou et al. (2000). Von der Dick et al. (1989) Fowler et al.
(1991)
(diterpenoid resins)
(Stefanova et al., 2005).
88
, Papanicolaou et al. (2000), Iordanidis and

Georgakopoulos (2003), .
. max 410C 428C
414C 430C ,
(403-421C). ,
max 405C 425C 407
421C . max 430C
(Espitali et al., 1985). 401427C max < 365C
.
Espitali et al. (1985), Bostick and Daws (1994) Copard et al. (2002)
Rr Tmax,
0,45
2
R =0,41
Rr [%]
Rr [%]
0,45
0,30
0,15
350
2
R =0,48
0,30
0,15
375
400
425
350
450
375
0,45
R2=0,50
Rr [%]
Rr [%]
0,45
0,30
0,15
350
375
400
425
0,15
350
450
375
Rr [%]
Rr [%]
0,30
400
Tmax [oC]
400
425
450
425
450
Tmax [oC]
0,45
375
450
0,30

2
R =0,49
0,15
350
425
R2=0,48
Tmax [oC]
0,45
400
Tmax [oC]
Tmax [ C]
425
450
MA
0,30
0,15
350
375
400
Tmax [oC]
5.29. Rr Tmax .
89

. Newman
et al. (1997) .

Rr Tmax ( 5.29)
(+0,33 r +0,71).
(r = +0,81),
.

Rr - ,
Tmax (Georgakopoulos, 2000). ,

.

Tmax ( 5.8), (+0,48 r
+0,84),
Rr.
(PST-2 PST-3) (MAR-4)
Tmax,
,
.
5.8. Tmax , n: .
(n=7)
(n=10)
(n=8)
(n=3)
RTmax-
+ 0,84
+ 0,69
+ 0,62
+ 0,56
(n=6)
(n=13)
(n=12)
RTmax-
+ 0,48
+ 0,68
+ 0,61
5.5.3. (), () (PI)

(Hydrogen Index, ) S2
(S2/TOC) mg HC/g C org. ,
(Oxygen Index, OI) S3
(S3/TOC) mg C2/g C org. Espitali et al.
(1977, 1985) H/C HI,
90
Type I
SF-1
.
KL-1
K
KOM-3
K
KYP-1
K
MAR-4
M
PST-2
PL-1
Type II
600
300
Type III
0
0
50
100
150
200
Oxygen Index [mg CO2/ g org.C]
5.30. .
900
900
Type I
SF-1
.
KL-1
K
KOM-3
K
KYP-1
K
MAR-4
M
PST-2
PL-1
Rr=0.5%
600
Type II
300
Rr=1.35%
Type III
0
340
360
380
400
420
440
460
480
500
520
o
IMMATURE
OIL ZONE
Tmax [ C]
GAS ZONE
5.31. /Tmax .
91

H/C .
(OH),
(Bordenave
et al., 1993).
HI OI H/C O/C
van Krevelen
( 5.30). ()
.
()
. ()
.
5.30
.
5.31,
max.

,
(Teichmller and Durand, 1983,
250
Hydrogen Index (HI)
200
150
100
50
0
0,15
0,20
0,25
0,30
0,35
0,40
0,45
0,50
Rr [%]
5.32. () (Rr)
.
92
Mukhopadhyay, 1986, Powell et al., 1991). ,

( 5.32).
(Production Index, PI) S1/(S1+S2)
.
<0,1 ( 5.7),
.
>0,1 Tmax>470C (Peters, 1986),
.
93
5.6. (FTIR)
5.6.1.

(functional groups) (Painter et al., 1981,
Kuehn et al., 1982, Riesser et al.,1984, Wang and Griffiths, 1985, Solomon and Carangelo,
1988, Mastalerz and Bustin, 1994, 1996, 1997, Ibarra et al., 1996, Guo and Bustin, 1998a,b).
(Ganz and
Kalkreuth, 1987, Mastalerz and Bustin, 1993, Lis et al., 2005),
(Ibarra and Moliner,
1991, Ibarra et al., 1994, de la Puente et al., 1998, Georgakopoulos et al., 2003, Sun et al.,
2003).

,
.
, .
(stretching vibrations)
/ (bending/deformation vibrations),
. ,
(symmetric asymmetric),
(scissoring),
(rocking),
(wagging)
(twisting) ( 5.33).
5.33. (, 1998).
94
4000 cm-1 400

cm-1 , (McMurry, 1998):
) 4000 2500 cm-1
() -, C-H -.
- - 3300-3600 cm-1, C-H
3000 cm-1.
) 2500-2000 cm-1 ()
. (RCN) .
) 2000 1500 cm-1 (C=O,
C=N C=C). 1650
1750 cm-1,
1610 1650 cm-1.
) 1500 cm-1
. ,
C-C, C-O, C-N C-X.
5.6.2.
5.6.2.1.
FTIR 1-10
III. ( 5.9)
(van der Maas, 1972, Painter et al., 1978b, Kuehn et al., 1982, Riesser et al., 1983,
Russell and Barron, 1984, Wang and Griffiths, 1985, Solomon and Carangelo, 1988,
Supaluknari et al., 1988a,b, Ibarra and Moliner, 1991, van Krevelen, 1993, Mastalerz and
Bustin, 1994, 1997, Guo et al., 1996, Stankiewicz et al., 1996, Guo and Bustin, 1998 a,b,
Iglesias et al., 1998, McMurry, 1998, etinkaya and Yrm 2000, Yongkang et al., 2001,
Baruah et al., 2003, Georgakopoulos et al., 2003, Lis et al., 2005).
3800 3600cm-1
3699cm-1
3701cm-1 (van Krevelen, 1993)
(Iglesias et al., 1998).
3623cm-1,
95
(van Krevelen, 1993, Georgakopoulos et al.,

2003).
3600 3000cm-1
3600-3000cm-1
~3430cm-1.
,

KBr (Solomon and Carangelo, 1982, Supaluknari et al., 1988a).
Martinez-Tarazona et al. (1994)

.
C-H
3100-3000cm-1 (Kuehn et al., 1982, de la Puente et al., 1998, Iglesias et al., 1998,
Lis et al., 2005).
, . Riesser
et al. (1984) Solomon and Carangelo (1988)
,
H/C>0,9 (Supaluknari et al., 1988b).
5.9.
.
[cm-1]
3699-3701 3623
~3430
2920
2850
1610-1620 1510-1515
1450-1420
1429 874
1383-1375
1300-1000
1080, 1031, 910
900-700
794 774
690
668
530
470
96

( )
()
(CH2)
(CH2)
(C=C)
CHx ,
.
(CH3)
C-
C-O-C
Si-O ( )
(C-H)
(CH2),
, C-S
()
Si-O ()
Si-O () S-S ()
3000 2800 cm-1

3000cm-1 2800cm-1,
(C-H) (C3) (C2) (Kuehn et al.,
1982, Wang and Griffiths, 1985, Guo and Bustin, 1998 a,b, Iglesias et al., 1998, de la Puente
et al., 1998, Yongkang et al., 2001). ,
~2920 cm-1 2850 cm-1
(asym CH2 sym CH2) (Wang
and Griffiths, 1985, van Krevelen, 1993, Guo et al., 1996, Georgakopoulos et al., 2003).
Kuehn and Davis (1991) CH3

, .
(CH3)
(.
. 5.3.3). CH2
.
1800 1500 cm-1
1750 cm-1 1650 cm-1
(C=O),

(Wang and Griffiths, 1985).
~1700cm-1,
(shoulder),
KL-1, KYP-3, KYP-4, MAR-10, MAR-12, SF-3 SF-8.

~1600cm-1
(Kuehn et al., 1982, Russell and
Barron, 1984, Solomon and Carangelo, 1988, Guo et al., 1996, de la Puente et al., 1998,
Georgakopoulos et al., 2003, Lis et al., 2005). Painter et al. (1978) Iglesias et al. (1998)
~1700cm-1
C=O
, .
(
97
C=, C-),
C- (Ruau et al., 1996).
1610-1620cm-1
(C=C) (Guo et al., 1996,
Stankiewicz et al., 1996, Guo and Bustin, 1998a),
(-) (-H )
(Solomon and Carangelo, 1988, Supaluknari et al., 1988a).
C=C
1510cm-1 1515cm-1. Russell and
Barron (1984) Guo and Bustin (1998a)
. 1510-1515cm-1

, PL-3, PL-4 PL-5 .

KYP-3, KYP-4, MAR-4, MAR-18, KOM-15,
PL-10, PST-4, PST-12, PST-15, SF-3, SF-29 SF-30. PST-2,
SF-8 SF-25, KYP-1, KOM-7 KOM-13, ,
1425cm-1.
1510-1515cm-1
- (Wagner, 1982).
1500 1300 cm-1
1500-1300cm-1 ~1450cm-1,
~1420cm-1 ~1375 cm-1. ~1450cm-1
C-H
(van Krevelen, 1993, Stankiewicz et al., 1996, de la Puente et al., 1998, Guo and Bustin,
1998a,b, Lis et al., 2005), (in-plane) C-H
(Wang and Griffiths, 1985, Yaman and
Kkbayrak, 2000). Guo and Bustin (1998a), Russell and Barron (1984) Erin and
Yrm (2003) ~1450cm-1 ~1420cm-1
C-Hx
-CO-CH2- -CO-CH3 (Wang and Griffiths, 1985).
~1450cm-1 ~1420cm-1 PL-3, PL4 PL-5 ( KL-4),
98

1420-1410cm-1. KL-4, PL-5, KYP-1, PST2, PST-3, PST-4, PST-5, KOM-7, KOM-13, KOM-14 SF-31
~1429 cm-1,

(Wang and Griffiths, 1985, Iglesias et al., 1998, Baruah et al., 2003).
1383-1375cm-1
(CH3) (Wang and Griffiths, 1985, Guo et al., 1996, Guo and
Bustin, 1998a,b, Iglesias et al., 1998, Lis et al., 2005) KL1, KL-2, KL-3, PL-3, KOM-14, MAR-11, MAR-16, MAR-18 MAR-19.
1300 1000 cm-1
1300-1000cm-1
(CO-) ,
(de la Puente et al., 1998).
1270-1265cm-1, 1220-1210 cm-1, ~1100 cm-1, ~1082cm-1 ~1031cm-1.
1270cm-1 1200cm-1
CO- , ,
(Ibarra et al., 1996, Yaman and Kkbayrak, 2000).

CO- .
1265-1270 cm-1 (OCH3) (Ibarra and
Moliner, 1991). ( MAR-4,
MAR-10, KYP-4, PST-6 SF-8),
. 1220-1210 cm-1
C-O-C (Yongkang et al., 2001, Erin and
Yrm, 2003) ,
. KL-1, KL3 PL-3 ,
~1140cm-1. Russell and Burron (1984) 1270-1265cm-1, 12201210cm-1 1140cm-1 CO- ,

.
99
1100-1080cm-1,
(shoulder) 1031cm-1,
(Riesser et al., 1984). H
1080 cm-1 KOM-13, KL-9, PL-7 KYP-4
Painter et al. (1978b), Iglesias et al. (1998) Baruah et al. (2003)
Si-O
Si-O-Si .
PL-7 (. 5.34)
CO- .
XRD ,
1080cm-1 ,
CO- .
~1031cm-1
(C-O-C) (-) (Guo et al., 1991, Georgakopoulos et al.,
2003) (Guo and
Bustin, 1998a). C-N
(McMurry, 1998), Si-O
( : , , ),

(Painter et al., 1978b, Iglesias et al., 1998, Georgakopoulos et al., 2003).
~1031cm-1
530cm-1 470cm-1 (Painter et al.,
1978b, Iglesias et al., 1998, Rubiera et al., 2002). KOM-9, PST-7, SF-16 SF35 , 1031cm-1,

. ,
530cm-1 470cm-1.
900 700 cm-1
900cm-1 700cm-1
(out-of-plane) (Painter et al., 1981, Kuehn et al., 1982, Ibarra et
al., 1994, Guo and Bustin, 1998b, Iglesias et al., 1998, Lis et al., 2005)
(Wang and Griffiths, 1985),
Rr (Mastalerz and Bustin, 1994). Guo and Bustin (1998a)
100
Erin and Yrm (2003) 870cm-1, 810cm-1

750cm-1.
(Guo and Bustin, 1998a, Iglesias et al., 1998). Kuehn et al. (1982),
Riesser et al. (1984), Stankiewicz et al. (1996) Guo and Bustin (1998a,b)
, (rocking)
CH2 CH3
. 900-700cm-1

(Riesser et al., 1984,
Wang and Griffiths, 1985, Solomon and Carangelo, 1988, Lis et al., 2005).

910, 874, 794, 774, 690 668cm-1. 910cm-1
874cm-1
(,
) (Painter et al., 1978b, Ul Hasan and Bhatti, 1991,

van Krevelen, 1993, Iglesias et al., 1998, Baruah et al., 2003).
874cm-1 (KL-4, PL-5, KYP-1, PST-2,
PST-3, PST-4, PST-5, KOM-7, KOM-13, KOM-14 SF-31),
1429 cm-1.
794cm-1 774cm-1
KL-5, KL-9, PL-2, PL-7, PL-15, PST-3, PST-15, KOM-13, SF-8, SF-25,
.
PL-7,
(rocking)
(CH2) (van Krevelen, 1993, Guo and Bustin, 1998a).

P-1. 794cm-1 774cm-1 Painter
et al. (1978b) ,

.
~690cm-1
C-S (Ul Hassan and Bhatti, 1991) /
(Baruah et al., 2003).
101
()
SF-31
KL-1
KOM-9
PST-3
KYP-1
PL-7
C-O
C=C
out-of-plane
C
asCH
Absorbance
syCH
000
4000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
()
SF-31extract
KL-1 extract
KOM-9 extract
PST-3 extract
KYP-1 extract
PL-7 extract
C-O
C=C
asCH
out-of-plane
C
syCH
Absorbance
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
5.34. () () .
102
700 400 cm-1

~668cm-1 SF-2, SF-3, SF-8, SF-10
,
MAR-16 KYP-4 ()
(Painter et al., 1978b). Georgakopoulos et al. (2003)

,
C- .
, 5.34, ~668cm-1
KYP-1 (
, ).
( 5.35)
~673cm-1
(~668cm-1),
(~673cm-1).
700cm-1 400cm-1
~530cm-1 ~470cm-1. ,
KOM-9, PST-7, SF-16 SF-35
Si-O (Painter et al., 1978b, Ul Hasan
and Bhatti, 1991, Iglesias et al., 1998, Yaman and Kkbayrak, 2000, Rubiera et al., 2002).
~470 cm-1 S-S
(Baruah et al., 2003).
5.6.2.2. T

360C FTIR.
5.35 () (), ( 5.10)
(Painter et al., 1978b, Wang and Griffiths, 1985, van
Krevelen, 1993, Iglesias et al., 1998, Jackson, 1998, Madejov and Komadel, 2001, Rubiera
et al., 2002, Baruah et al., 2003, Georgakopoulos et al., 2003).

.
103
Absorbance
KL-1ash
KL-5 ash
KOM-9 ash
KOM-15 ash
KYP-1 ash
MAR-16 ash
()
/
.
000
4000
3500
3000
2500
2000
1500
1000
500
()
Absorbance
PL-7ash
PST-3 ash
PST-14 ash
SF-1ash
SF-20 ash
SF-31ash
.
.
Wavenumbers (cm-1)
4000
000
3500
3000
2500
2000
1500
1000
Wavenumbers (cm-1)
5.35. 360 C .
104
500
~3699cm-1
3623cm-1 ( KOM-15ash, MAR-16ash SF-31ash),
,
(van Krevelen, 1993, Iglesias et al., 1998, Georgakopoulos et al., 2003).
~3445cm-1
.
1625-1630cm-1 1031-1044cm-1
~530cm-1 ~470cm-1
(Painter et al., 1978b, Iglesias et al., 1998,
Madejov and Komadel, 2001, Rubiera et al., 2002).
KOM-9ash, ~530cm-1
KL-1ash, KL-5ash L-7ash. ~913cm-1,
KYP-1ash, PST-14ash, KOM-15ash, SF-20ash SF31ash, . ~470cm-1

S-S (Baruah et al.,
2003).
~1430cm-1 ~874cm-1
( ) (Wang and Griffiths, 1985, Iglesias et al.,
1998, Baruah et al., 2003) KL-1ash MAR-16ash.
2511cm-1, 1797cm-1 710 cm-1
(Painter et al., 1978b), -9ash,
-1ash SF-31ash.
H 1110-1150cm-1 Painter et al. (1978b),
Iglesias et al. (1998) Baruah et al. (2003) Si-O
Si-O-Si .
795cm-1 774cm-1,
5.10. .
[cm-1]
3699, 3623, 1031-1044, 913, 530
470
2511, 1797, 1430, 874 710
1110-1150, 795 774
1150, 673, 609 594
470

Si-O (, ,
)
(, , )
()
S-S ()
105
KOM-9ash, PL-7ash SF-20ash.

()
~673, ~609 ~594 cm-1 (Jackson, 1998),
1150cm-1 . ,
,
KOM-15ash, KOM-9ash SF-31ash.
5.6.3.
FTIR
Georgakopoulos et al. (2003)
, (2004)
. .
( )
,
.

.
FTIR
( 5.34 ),

Soxhlet.
Soxhlet ,
(Tognotti et al., 1991), - 1:1 (Ul
Hasan and Bhatti, 1991) (Georgakopoulos et al., 2003)
( , 47%, 23%
30% ), .

matrix (Ul Hasan and Bhatti, 1991)
(65C), .
(3000-2800cm-1)
(1300-1000cm-1) (Georgakopoulos et al., 2003). ,
(2850cm-1
106
2920cm-1 )
. C- ~1080cm-1
PL-7 ,
(790700cm-1).
107
5.7. 15
5.7.1.
15
standard
:
15 () = ((15/14 / 15/14 ) -1) *1000
15 0,00361 0,00374
14 0,99639 0,99626.
Bedard-Haughn et al. (2003), De Laeter et al. (2003) Boeckx et al. (2006)
,
15 -15 +20,
, (Hgberg, 1997).

,
(De Laeter et al., 2003).

(Meckler, 2006). 15
()
[15 = +103] (Coplen et al., 2002),
3 [15 = +150] (Freyer et al., 1996). Cline
and Kaplan (1975) ,
14

. ,
15
[15 = -49] (Wada et al., 1981),

200 ,
[15 = -55] (Coplen
et al., 2002).
5.7.2.
15 3,04
3,80 ( 5.11) ( 2,96) SF-1 .
108
(5,14) PL-7 .
15 ,
, ,
. (Wada et al., 1975, Rigby and Batts, 1986, Ader et al., 1998,
Francioso et al., 2005). 15 4% 26%
15
. 5.11 5.36
KOM-9 PL-7
15, L-1 7%.
5.37
15, N/Corg
. 15
Ader et al. (1998)
. .

. Rigby and
Batts (1986) 15

15
. ,
5.11. [] [15N vs. air] ,

Soxhlet (n: , SD:
).

TN[%]
SD
15N
vs. air
SD
TN[%]
SD
15N
vs. air
SD
TN[%]
SD
15N
vs. air
SD
KYP-1
1,21
0,01
3,80
0,10
0,13
0,00
3,23
0,46
1,17
0,00
3,68
0,05
MAR-16
1,17
0,01
3,46
0,14
KOM-9
1,07
0,01
3,51
0,01
0,10
0,00
3,28
0,07
1,04
0,00
3,53
0,10
KOM-15
1,31
0,01
3,61
0,13
SF-1
1,00
0,00
2,69
0,13
SF-20
1,25
0,01
3,36
0,13
SF-31
1,01
0,00
3,18
0,00
0,17
0,00
2,79
0,27
1,06
0,02
3,06
0,03
PST-3
1,35
0,01
3,04
0,10
0,13
0,02
2,92
0,39
1,37
0,01
2,99
0,01
KL-1
0,65
0,00
3,76
0,06
0,26
0,00
2,76
0,29
0,63
0,00
4,02
0,07
KL-5
0,95
0,00
3,37
0,19
PL-7
1,43
0,01
5,14
0,16
0,15
0,00
3,82
0,14
1,39
0,01
5,17
0,08
109
5,5

15N vs. air
4,5
3,5
2,5
KYP-1 MAR-16 KOM-9 KOM-15
SF-1
SF-20
SF-31
PST-3
KL-1
KL-5
PL-7
5.36. ,
Soxhlet.
15
.
5.3.3,
SF-1, 15, ,
PL-7, 15 , .

, .
5,0
6,0
5,0
4,0
N/Corg x100
15 vs air []
4,0
3,0
2,0
KYP-3
KYP-1
3,0
PL-15
2,0
1,0
1,0
0,0
0,0
0,0
0,1
0,2
0,3
Rr [%]
0,4
0,5
0,0
0,1
0,2
0,3
0,4
Rr [%]
5.37. (a) 15 [], (b) N/Corg.
110
0,5
100
PL-7
Huminite [%]
90
80
PST-3
KL-5
70
60
0
15
[] vs air
5.38. 15 [] [%] .

15 ( 5.38).
KL-5 PL-7 PST-3
Francioso et al. (2005) 15

.
[] 1,00% 1,43%
( 5.11), KL-1 KL-5 (0,65%
0,95% ). ,

,
Soxhlet.
( 5.11)
(R2=+0,8) () C-HN-S ( 5.2.4).
15 (PL-7)
2 ( 5.39).
15 2,
Krooss et al. (2005, 2006)
. 2
111
15
450
15N
15
400
Area 28 [Vs]
10
350
300
250
0
200
-5
Area 28 [Vs]
15 []
150
100
-10
50
-15
300
400
500
600
700
800
900
1000
1100
Temperature [C]
5.39. 2 PL-7
.
0,5K/min 600C, 15 ~0
-13. 650C 15 +9
900C, +8 +9
1100C. ,

2, 2
5.8.2.4 .

(-13 +10)
.

.
112
5.8.
5.8.1.

,
,
(Cloke et al., 1999).
, ,
: ) ,
)
,

.
,
(Schaefer et al., 1990, Behar et al., 1995,
Landais and Gerard, 1996, Shuai et al., 2006).

(Gaschnitz et al., 2001).
(Serio et al., 1987,
Solomon et al., 1992, Arenillas et al., 2003): (i)
150C,
.
, -
. (ii) 150C
~500C
(), (2)

. , ,
(tar) ,
.

, (C2), ,
(C4) . (iii)
113
, (C4) , (C)
, (C)
(2) .

:
CO, CO2, H2, CH4 2. (0,5K/min
0,1K/min), ,
(Serio
et al., 1987, Solomon et al., 1993).
.
,
.
maceral.
V.
114
5.8.2.
5.8.2.1.

(Szab et al., 1990a, Cramer et al., 2001, Lin et al., 2002,
Shuai et al., 2006). Jntgen (1984), Ofosu-Assante et al. (1988) Cramer (2004)
,
( 5.40).
: () C-O C-S, () ,
() /

, (IV) .
88%
.

(Campbell et al., 1980, Serio et al., 1987, Solomon et al., 1992, Otake and
Walker, 1993, Charpenay et al., 1996a,b, Erin and Yrm, 2003). ,
,

5.40.
(0,72 Ro), 0,2K/min (Cramer, 2004).
115
(Carangelo et al., 1987, Obeng and Stock, 1996).

250oC
800oC ( 5.41). CH4
460oC,

10 30C (. 5.41 5.12).
(shoulder)
360-370C, MAR-19
,
.
CH4 (Reynolds et al.,
1991, Solomon et al., 1992).
(L-1 L-5)
CH4
(. 5.41f). L-5
385C, CH4 461C. L-1
378C 495C.
,
FTIR ( 5.6).

(Anvi et al., 1983). Serio et al. (1994)
,
,
(30 C/min).
,
(Obeng and
Stock, 1996).
(crosslinks), ,
(Serio et al., 1994).

. Obeng and Stock (1996)
(300oC - 400oC)
, ,
,
116
2.5E-06
2.5E-06
SF-1
SF-20
SF-31
SF-31 extracted
1.5E-06
1.0E-06
5.0E-07
KOM-9
KOM-9 extracted
KOM-15
2.0E-06
[mol/min/gr]
[mol/min/gr]
2.0E-06
a
1.5E-06
1.0E-06
5.0E-07
0.0E+00
0.0E+00
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
2.5E-06
700
800
900
1000
1100
1.5E-06
1.0E-06
5.0E-07
PL-7
PL-7 extracted
PL-11
2.0E-06
[mol/min/gr]
[mol/min/gr]
600
2.5E-06
PST-3
PST-3 extracted
PST-14
2.0E-06
1.5E-06
1.0E-06
5.0E-07
0.0E+00
0.0E+00
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
Temperature [ C]
2.5E-06
2.5E-06
KL-1 [0.1 K/min]

KL-1
KL-1 extracted
KL-5
MAR-16
MAR-19
KYP-1
KYP-1 extracted
2.0E-06
2.0E-06
1.5E-06
[mol/min/gr]
[mol/min/gr]
500
Temperature [oC]
Temperature [ C]
1.0E-06
5.0E-07
1.5E-06
1.0E-06
5.0E-07
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
o
Temperature [ C]
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
5.41.
0,5K/min ( ).
.
SF-1, SF-20, KOM-9, PL-11, -9
PST-3 PST-14
780C 790C,
PL-7 750C. ,
(Hodek et al., 1991, Reynolds et al., 1991, Behar et al., 1995),
Mazumdar and Chatterjee (1973) (auto-hydrogenation reactions),
.
117
(Reynolds et al., 1991)

(char)
/ ,
(Szab et al., 1990a, Cramer, 2004).
(2) (. 5.12,
#3 2).
CH4 8,12mg/g 11,74mg/g
. ,
(5,45mg/g 6,60mg/g) ( 5.12)
(Yao et al., 2006). ,
(TOC) , 18,98mg/gTOC 27,34mg/gTOC
. 13,30mg/gTOC 16,26mg/gTOC .

(Cramer et al., 2001, Yalin et al., 2007).
Soxhlet
5,1% 17,7% KL-1,
CH4
5.12. CO2, CH4, CO, N2, H2

0,5K/min, (#1,#2,#3:
).
CO2 [C]
#1
KL-1 [0,1C/min]
KL-1
KL-5
SF-1
SF-20
SF-31
PL-7
PL-11
KOM-9
KOM-15
PST-3
PST-14
303
316
320
318
336
309
331
304
#2
640
607
616
606
597
CH4 [C]
#1
355
378
385
CO [C]
#2
460
495
461
#3
463
462
458
455
464
467
462
464
465
788
790
795
750
793
781
788
782
#1
295
324
320
#2
580
597
601
320
640
607
616
606
618
605
N2 [C]
#3
620
650
647
648
650
*
640
650
*
641
652
640
#1
#2
633
730
750
620
620
670
740
450
660
700
431
640
640
*
640
750
452
: , *: #2 .
MAR-16
MAR-19
KYP-1
118
306
309
309
2 [C]
#3
790
810
783
789
791
800
800
786
780
794
785
#1
605
660
#2
626
606
802
748
605
608
778
784
651
627
. (.
KL-1[0,1K/min] 5.13)
25,6%.
CH4
Soxhlet .
CH4,
5C 15C.

( 5.13)

, Rock-Eval ( 5.5).
()
( 5.5), Waples et al. (1992) Yalin et al. (2007)
.
5.13. CH4, CO, CO2 N2

0,5K/min, (extr:
Soxhlet, HC: , CH4 vs total HC: ,
C: ).
CH4

CO2
CO
N2
TOC
CH4 vs
total HC
CH4
/ TOC
CO2
CO
N2
[mg/g]
[mg/g]
[mg/g]
[mg/g]
[%]
[%]
[mg/g TOC]
[mg/g TOC]
[mg/g TOC]
[mg/g TOC]
KL-1 [0,1K/min]
KL-1
KL-5
SF-1
SF-20
SF-31
PL-7
PL-11
KOM-9
KOM-15
PST-3
PST-14
14,74
11,74
9,05
9,23
8,31
8,12
10,93
9,38
10,76
9,46
9,96
9,64
4,41
3,31
5,16
5,83
7,74
7,40
15,30
7,79
8,07
10,93
10,27
9,95
48,40
48,40
40,78
43,22
43,81
36,99
48,35
44,38
48,28
45,29
36,42
44,75
17,11
13,62
19,75
16,37
19,84
21,49
21,03
16,44
24,02
21,31
24,57
19,09
30,47
24,25
22,20
21,35
18,98
21,94
22,598
21,14
22,28
20,89
27,34
21,54
92,81
101,66
97,79
152,30
115,06
95,23
121,41
91,62
45,28
98,42
92,78
79,14
86,47
98,29
98,49
89,37
98,88
89,18
109,36
86,23
214,74
232,05
264,38
315,00
259,25
197,25
268,08
204,73
93,55
203,34
227,52
183,11
197,38
265,72
203,70
201,37
204,80
196,90
300,27
192,70
9,11
6,83
12,66
13,48
17,68
20,02
31,64
17,55
16,71
24,14
28,21
22,23
MAR-16
MAR-19
KYP-1
6,60
5,44
6,00
109,49
63,10
89,96
103,75
134,59
140,67
5,91
5,14
7,40
40,58
40,96
32,73
12,12
11,21
17,18
16,26
13,30
18,32
269,82
154,05
274,85
255,66
328,59
429,80
14,56
12,54
22,62
KL-1 extr
SF-31 extr
PL-7 extr
KOM-9 extr
PST-3 extr
KYP-1 extr
11,64
7,70
9,23
9,14
8,20
5,23
81,15
-
91,34
90,21
85,26
85,45
80,80
119,04
3,04
6,35
9,29
7,54
6,82
7,01
48,40
36,99
48,35
48,28
36,42
32,73
24,05
20,82
19,085
18,94
22,51
15,97
167,66
-
188,72
243,88
176,34
177,00
221,84
363,71
6,27
17,17
19,22
15,61
18,72
21,41
119
30
30
25
CH4 vs total HC generation [%]
25
CH4 vs total HC generation [%]
..
20
15
10
0
400
20
15
10
0
420
440
460
Tmax CH4 [oC]
480
500
100
200
300
400
500
600
700
800
900
HI [mg HC/g TOC]
5.42. a) CH4
CH4 (Tmax), b) CH4
().
83mg HC/g TOC 178mg HC/g TOC.

. 16,37% 24,57% KL-1
, (13,62%),
(11,21%-17,18%).
CH4 (r=+0,7)
( 5.42a), (r=-0,7) (
5.42b). 5.42b,
Yalin et al. (2007)

.
120
5.8.2.2.
100C
670C ( 5.43).
,
(.. PL-11, PST-14 MAR-19) ,
, .
0,5/min,
(CO2) . 310-330C
PL-11, (340C),
305C 310C.
CO2
(Obeng and Stock, 1996, Arenillas et al., 2003).

,
,
(Campbell et al., 1980, Blazs et al., 1985, Solomon et al.,
1993, Cloke et al., 1999, Charland et al., 2003). C2
(Serio et al., 1987, Ibarra
et al., 1991, Solomon et al., 1992),
(Ibarra and Moliner, 1991, Arenillas et al., 1999).
600C 640C
(. 5.12 #2 CO2),
(Campbell et al., 1980, Reynolds et al., 1991, Solomon et al., 1992,
Charland et al., 2003, Macphee et al. 2006).
5.14.
(, ) ( 5.4),
5.14. (Burnham et al.,

1980, Campbell et al., 1980, Reynolds et al., 1991).
[C]
CaMg (CO)3
MgO + CaO + 2CO2
~600-750
MgO + CaCO3 + 2CO2

CaCO3
CaO + CO2
b
~600-750
~600-900
a: CO2, b: CO2
121
8.0E-06
8.0E-06
SF-1
SF-20
SF-31
6.0E-06
[mol/min/gr]
6.0E-06
[mol/min/gr]
KOM-9
KOM-15
4.0E-06
2.0E-06
4.0E-06
2.0E-06
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
8.0E-06
700
800
900
PL-7
PL-11
1000
1100
6.0E-06
[mol/min/gr]
6.0E-06
[mol/min/gr]
600
8.0E-06
PST-14
4.0E-06
2.0E-06
4.0E-06
2.0E-06
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
Temperature [ C]
8.0E-06
8.0E-06
KYP-1
MAR-16
MAR-19
KL-1 extracted
6.0E-06
6.0E-06
[mol/min/gr]
[mol/min/gr]
500
Temperature [oC]
Temperature [ C]
4.0E-06
4.0E-06
2.0E-06
2.0E-06
0.0E+00
0.0E+00
0
100
200
300
400
500
600
Temperature [oC]
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
5.43.
0,5K/min ( ).
( 5.3).
SF-31, KOM-9 KYP-1,
Ca Mg.
, 450C 600C.
, ,
.

(Campbell, 1978, Campbell et al., 1980).
C2 91,62mg/g 121,41mg/g
. PL-7 ,
122
152,30mg/g. C2 63,10mg/g
109,49mg/g ( 5.13).
(TOC) 197,25mg/gTOC 315,00mg/gTOC
. 154,05mg/gTOC 274,85mg/gTOC .
CH4/CO2 ( 5.15) 0,07 0,11
. , ,
0,06 0,09.

,
( 5.44a).
(Xu and Tomita,
1987, Ibarra and Moliner, 1991, Cloke et al., 1999),
,
. SF-1,SF-20,KOM-9 PST-14 ( 5.44a)
,
5.15. CO/CH4, CH4/CO2, CH4/N2 CO/CO2

0,5K/min, (extr: Soxhlet).
CO/CH4
KL-1 [0,1K/min]
KL-1
KL-5
SF-1
SF-20
SF-31
PL-7
PL-11
KOM-9
KOM-15
PST-3
PST-14
3,07
8,38
10,25
8,58
10,40
12,11
9,01
9,52
9,19
9,43
10,98
8,95
MAR-16
MAR-19
KYP-1
KL-1 extr
SF-31 extr
PL-7 extr
KOM-9 extr
PST-3 extr
KYP-1 extr
CH4/CO2
CH4/N2
CO/CO2
0,11
3,34
3,55
1,75
1,58
1,07
1,10
0,71
1,20
1,33
0,87
0,97
0,97
15,72
24,71
23,45
0,06
0,09
0,07
1,12
1,06
0,81
0,95
2,13
1,56
7,85
11,71
9,24
9,35
9,86
22,77
0,14
3,83
1,21
0,99
1,21
1,20
0,75
1,13
0,10
0,08
0,08
0,07
0,08
0,11
0,08
0,85
0,85
1,01
0,65
0,78
1,04
0,73
0,94
123
400
200
R2 = 0,72
300
CO2 [mg/g TOC]
CO2 [mg/g]
150
SF-20
100
KOM-9
SF-1
PST-14
200
100
50
0
0
10
20
30
O [%, ]
0
40
20
40
60
80
100
120
140
160
180
200
OI [mg CO2/g TOC]
5.44. a) C2 [] b) C2
[], Rock Eval II.
CO2 /

(Charland et al., 2003).
CO2,
[] Rock
Eval II ( 5.44b),
.
Rock Eval
II (
),
.
124
5.8.2.3.
(CO) (CO2)
(2) ,
(Solomon et al., 1992, Charland et al., 2003, Macphee et al., 2006).

, CO 200C,
650C (. 5.45).
CO (<600C)
(Blazs et al., 1985, Solomon et al., 1991, Otake and Walker, 1993),
(>600C)
(Campbell, 1978). CO
Boudouard (5.8.1),
(<500C) CO,
CO2 (Campbell et al., 1980, Gregg et al., 1981, Reynolds et al.,
1991).
CHx+ CO2 2CO+(x/2)H2
(5.8.1)
(~650C)
C
. ,
C (Charland et al., 2003).
(L-1 L-5)
320C, ,
L-1,
CO2 .

. DeGroot et al. (1987) Pan and Richards (1990)
CO
.
(spike)
600C 640C,
C2 (. 5.43 5.12 #2
CO2 CO ) ,
125
1.4E-05
1.4E-05
1.2E-05
KOM-9
KOM-9 extracted
KOM-15
1.2E-05
1.0E-05
[mol/min/gr]
1.0E-05
[mol/min/gr]
SF-1
SF-20
SF-31
SF-31 extracted
8.0E-06
6.0E-06
8.0E-06
6.0E-06
4.0E-06
4.0E-06
2.0E-06
2.0E-06
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
1.4E-05
700
800
900
1000
1100
PL-7
PL-11
PL-7 extracted
1.2E-05
1.0E-05
[mol/min/gr]
1.0E-05
[mol/min/gr]
600
1.4E-05
PST-3
PST-3 extracted
PST-14
1.2E-05
8.0E-06
6.0E-06
8.0E-06
6.0E-06
4.0E-06
4.0E-06
2.0E-06
2.0E-06
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
Temperature [ C]
2.8E-05
1.4E-05
KYP-1
MAR-16
MAR-19
KYP-1 extracted
2.4E-05
1.0E-05
1.6E-05
1.2E-05
8.0E-06
6.0E-06
8.0E-06
4.0E-06
4.0E-06
2.0E-06
0.0E+00
KL-1 [0.1 K/min]

KL-1
KL-1 extracted
KL-5
1.2E-05
[mol/min/gr]
2.0E-05
[mol/min/gr]
500
Temperature [oC]
Temperature [oC]
0.0E+00
100
200
300
400
500
600
700
o
Temperature [ C]
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
5.45.
0,5K/min ( ).

(Burnham et al., 1983). SF-31,
KOM-9 KYP-1, CO2
.
600C 640C , CO
650C ( 5.12), .
(KL-1
KL-5), PST-14 .
126
SF-1, SF-20, PL-11 . ,

MAR-16 MAR-19 .
.
800C,
(~860C). 900C 1000C
C,
(Jntgen, 1984), CO
(Arenillas et al., 2003).
,
. Solomon and Hamblen (1983)
CO 1000C. Chu et al. (1988)
C ~1350C,

()
. Heller-Kallai and Miloslavski (1992)

,
,
.
.

(C) (-9),
, ,
FTIR ( 5.6).

79,14mg/g 109,36mg/g . ,
103,75mg/g 140,67mg/g
( 5.13). Soxhlet C
7,91% 15,38% , PST-3
26,12%. KL-1
[0,1K/min]
54%.
O CO/CH4 ( 5.15) 8,38 12,11
. , (15,72
127
1.5
1.5
SF-1
SF-20
SF-31
KOM-9
KOM-15
1.0
CO/CO2
CO/CO2
1.0
0.5
0.5
0.0
100
200
300
400
500
600
700
800
900
1000
0.0
100
1100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
Temperature [oC]
1.5
2.5
PL-7
PL-11
PST-14
KYP-1
MAR-16
MAR-19
2.0
1.0
CO/CO2
CO/CO2
1.5
1.0
0.5
0.5
0.0
100
200
300
400
500
600
700
800
900
1000
0.0
100
1100
200
300
400
500
Temperature [oC]
600
700
800
900
1000
1100
Temperature [oC]
5.46. CO/C2 .
24,71).
Soxhlet, (0,1K/min)

CO/CH 4 63,4%. CO/C 2 .
1,04, 0,95
2,13. CO/C2 500C 800C ( 5.46)
0,12
0,12
R2 = 0,91
R2 = 0,88
0,10
CH4/CO2
CH4/CO2
0,10
SF-31
0,08
0,06
0,08
0,06
0,04
0,04
0,5
0,6
0,7
0,8
CO/CO2
0,9
1,0
1,1
0,5
0,7
0,9
1,1
1,3
1,5
1,7
1,9
2,1
2,3
CO/CO2
5.47. CH4/CO2 C/C2 (a) . (b)

.
128
, 900C
C .
. ,
CH4/CO2 C/C2 (
5.47).
(R2=0,88 R2=0,91 ). CO/C2
CH4/CO2 SF-31,

.

.
129
5.8.2.4.

C, C2, C4, 2
. 2
(Wjtowicz et al., 1995, Wu and
Ohtsuka, 1996, Arenillas et al., 2002, Tsubouchi and Ohtsuka, 2002).
(3)
(C) (Solomon and Colket, 1973, Chu et al.,
1988, Bassilakis et al., 1993, Thomas, 1997).
(2),
2 2 (Mori et
al., 1996, Wu and Ohtsuka, 1996, 1997a).

,

(Krooss et al., 1995).
,
.
(coal-N)
,
(Wallace et al., 1989, Arenillas et al., 1999). ,
, ( )
( ) (Solomon and Colket, 1973, Thomas, 1997, Wu et al., 2001).
,
(Wjtowicz et al.,
1995).
, , , , (Staczyk and Boudou,
1994, Thomas, 1997, Arenillas et al., 1999).
Wjtowicz et al. (1995)
- (pyrrolic-N) - (pyridinic-N),
.
130

-, - (Staczyk and Boudou,
1994).
, (tar) (Solomon and Colket,
1973, Xu and Kumagai, 2002),
- -
(Wjtowicz et al., 1995, Thomas, 1997).

(3) (C) (Thomas, 1997).
C, 3
(Chen et al. 1992, Wu and Ohtsuka, 1997a). Bassilakis et al. (1993) Friebel
and Kpsel (1999) 3
, C
, - .
(2)
(Boudou and Espitali, 1995, Mori et al., 1996, Wu and Ohtsuka,
1996,1997a,b, Friebel and Kpsel, 1999): () C
3 2 () 2 (char-).
char-
(3 C), ,
2 (Friebel and Kpsel, 1999,
Tsubouchi and Ohtsuka, 2002).
(char) (Neoh and
Gannon, 1984). Kidena et al. (2000) C char-
2
.
,

(Krooss et al., 1995)
(Cooper and Evans, 1983). Williams et al. (1989, 1995), Sucha et al. (1994), Ward and
Christie (1994) Buckley (1995)
, + a+
4+. , -
2 3. Oh et al. (1988, 1993)
131
10C/min
500C 3,
~700C 2 2 (5.8.2):
3
0,52 + 1,52
(5.8.2)
:
0,5/min (N2)
520C. 2
. 620C 950C
N2 (. 5.48 5.12),
N2
.
950C N2 ,
1100C .
Staczyk and Boudou (1994), Boudou and Espitali (1995) Krooss et al. (1995, 2005)
1000-1100C 2,

.
,
(Arenillas et al., 1999).
N2 620C 640C.
SF-31, KO-9, PST-3 KYP-1
C, C2 ( 5.49)
.
2: () ,
3, (5.8.2)
2, () CaO
( 5.14).
Fe Ca
2 (char-)
(Wu and Ohtsuka, 1996, 1997ab, Friebel and Kpsel, 1999,
Wu et al., 2001). Tsubouchi and Ohtsuka (2002)
132
CaO char- (CaCxNy) (

5.8.3), 2 ( 5.8.4).
CaO + char N
CaCxNy +CO
(5.8.3)
CaCxNy
CaCz + N2
(5.8.4)
PL-7, SF-31 KYP-1

700C 750C ( #2, 5.12). KOM-9, KOM-15 PST-3

( #3, 5.12).
#2 #3.
1.6E-06
1.6E-06
KOM-15
KOM-9
KOM-9 extracted
1.2E-06
[mol/min/gr]
1.2E-06
[mol/min/gr]
SF-1
SF-20
SF-31
SF-31 extracted
8.0E-07
4.0E-07
8.0E-07
4.0E-07
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
Temperature [ C]
2.0E-06
1.6E-06
PST-14
PST-3
PST-3 extracted
PL-11
PL-7
PL-7 extracted
1.6E-06
[mol/min/gr]
[mol/min/gr]
1.2E-06
8.0E-07
1.2E-06
8.0E-07
4.0E-07
4.0E-07
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
Temperature [ C]
1.6E-06
600
700
800
900
1000
1100
1.6E-06
MAR-16
MAR-19
KYP-1
KYP-1 extracted
8.0E-07
4.0E-07
KL-1 [0.1 K/min]

KL-1
KL-1 extracted
KL-5
1.2E-06
[mol/min/gr]
1.2E-06
[mol/min/gr]
500
Temperature [oC]
8.0E-07
4.0E-07
0.0E+00
0.0E+00
0
100
200
300
400
500
600
Temperature [oC]
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
5.48.
0,5K/min ( ).
133
1E-06
2.0E-05
CO
8E-07
1.6E-05
6E-07
1.2E-05
N2
4E-07
8.0E-06
CO2
2E-07
0E+00
100
CO, CO2 [mol/min/g]
N2 [mol/min/g]
KYP-1
4.0E-06
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
1E-06
2.0E-05
SF-31
8E-07
1.6E-05
6E-07
1.2E-05
N2
4E-07
8.0E-06
CO, CO2 [mol/min/g]
N2 [mol/min/g]
CO
CO2
2E-07
0E+00
100
4.0E-06
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
5.49. CO,CO2 2 0,5K/min KYP-1

SF-31.
( #3)
780C 810C.
. , PL-7,
. MAR-16 MAR-19

700C 740C,
2.
780C 810C 2
2, C4 ( 5.12),

(Boudou and Espitali, 1995).
,
134
,
. ,
Sohxlet
. 5.48f KL-1
, 2,
KYP-1 2
. , -9 ,

.
PL-7 ,
2 750C ( #2)
(780C 810C), . .
2 750
, .
, 5.7,
15
. PL-7 ( 5.48d)
, KOM-9
PST-3 ( 5.48b,c)
#3.
700C 750C
. Oh et al. (1988,
1993)
~700C 2 2.
XRD .

(Krooss et al. 2005). PST-3,
~700C .
850C 950C -9, KOM-15, PST-3 PL-7
,
-9 . 1050C,
N2.
C
, .
135
2
.
2
3,31mg/g 10,93mg/g,
PL-7 (15,30mg/g).
5,14mg/g
7,40mg/g ( 5.13).
, (TOC) ,
12,66mg/gTOC 31,64mg/gTOC . (
L-1 6,83mg/gTOC) 12,54mg/gTOC 22,62mg/gTOC
.
Soxhlet 2
KL-1, KOM-9, KYP-1 SF-31 5,4% 14,2% ,
PST-3 PL-7 33,6% 39,3% .
KL-1, [0,1K/min],
33,3%.
5.50 (2)
(R2=0,75)
( 5.2.4),
/C (R2=0,72).
O CH4/2 ( 5.15) 0,81 1,58
, L-1
2,0
0,04
R2 = 0,75
1,5
0,03
N/C
N [%, ]
R2 = 0,72
1,0
0,5
0,02
0,01
0,0
0
10
N2 [mg/g]
15
0,00
20
10
15
20
25
30
N2 [mg/g TOC]
5.50. 2 (a) , (b)

/C.
136
35
20
CH4 [mg/g]
15
KL-1
10
0
0
10
12
14
16
18
N2 [mg/g]
5.51. 2[mg/g] CH4[mg/g] .
KL-5 (3,55 1,75 ).

L-1, 2
CH4,
2 ( 5.51). Soxhlet
CH4/2 , -1 -9
~9%, 10%
40%. (0,1K/min)
2 CH4/2 6%.
137
5.8.2.5.

(2), 2
.
2
, (Otake and Walker, 1993,
Arenillas et al., 1999). 2 400C
(Arenillas et al., 2003)
(1100C)
( 5.53).

(Solomon and Hamblen, 1983, Szab et al., 1990a, Otake and Walker,
1993) ,
C-H
(Jntgen, 1984, Porada, 2004). 2 C C,
( 5.52) (Strezov
et al., 2004). Campbell et al. (1980) 500-600C 2
: ) Boudouard
(5.8.5):
CO2+CHx2CO+(x/2)H2
(5.8.5)
) (water-gas shift reaction) (5.8.6):

H2+CO2 CO+H2O
(5.8.6)
, -
5.52. ( Strezov et al. 2004)
138
2.0E-07
2.0E-07
SF-31
KOM-15
PL-7
PST-3
1.6E-07
1.2E-07
1.2E-07
[mVs]
[mVs]
1.6E-07
8.0E-08
8.0E-08
4.0E-08
4.0E-08
0.0E+00
0.0E+00
100
200
300
400
500
600
700
800
900
1000
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
Temperature [ C]
2.0E-07
2.0E-07
KYP-1
MAR-16
KL-1
KL-1 [0.1 K/min]
1.6E-07
1.2E-07
1.2E-07
[mVs]
[mVs]
1.6E-07
8.0E-08
8.0E-08
4.0E-08
4.0E-08
0.0E+00
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
Temperature [ C]
1100
100
200
300
400
500
600
700
800
900
1000
1100
Temperature [oC]
5.53.
0,5K/min ( ).
, ,
2 2. 2,
2
2 (Arenillas et al., 1999). 550C
(Reynolds et al., 1991)
2 .
H2 605C 660C, SF-31,
K-15, Pl-7 PST-3 750 C 800C
( 5.53). , 5.12 (.118),
CH4 ,
2. 2
Reynolds et al. (1991)
(char),
.
139
5.8.3.

(CH4, N2, CO CO2)
: (i) (Rr) ,
(I.C.C.P., 1971) (ii) maceral.

,
MAR-19 KL-1 ( 5.54a). Rr
( 5.54b).
CH4

(Szab et al., 1990a, Orem and Finkelman, 2004, Yao et al., 2006),
CH4 (Kopp et al., 2000). ,

(Cloke et al., 1999). CH4
Charpenay et al. (1996a,b) Shuai et al. (2006)
.
2
( 5.55a).
(C) Rr ( 5.55b).
(Boudou and Espitali,
0,5
0,5
0,4
0,4
MAR-19
MAR-19
0,3
Rr [%]
Rr [%]
0,3
KL-1
0,2
0,2
0,1
0,1
0,0
0
CH4 [mg/g]
10
12
14
0,0
400
420
440
460
480
500
Tmax CH4 [oC]
5.54. (a) CH4 (b)

.
140
1995, Krooss et al., 1995, Lepplahti and Koljonen, 1995, Ader et al., 1998),
Rr<1,0% ,
(Rr>1,0%) .
Burchill and Welch (1989) Thomas (1997)
() .
~85% (daf)
.
Solomon and Hamblen (1983), Blazs et al. (1985), Kkbayrak (1993)
Arenillas et al. (1999)
(CO2)
.
CO2 (Rr) ( 5.55d)
CO2
.
( 5.56),
0,5
0,5
R2 = 0,6
R2 = 0,7
0,4
0,3
0,3
Rr [%]
Rr [%]
0,4
0,2
0,2
KYP-1
KYP-1
0,1
0,1
0,0
0
10
12
14
16
0,0
0,00
18
0,01
0,02
N2 [mg/g]
0,03
0,04
N/C TOC
0,5
0,5
0,4
0,3
0,3
Rr [%]
Rr [%]
0,4
0,2
0,2
0,1
0,1
0,0
0
20
40
60
80
CO [mg/g]
100
120
140
160
0,0
0
20
40
60
80
100
120
140
160
CO2 [mg/g]
5.55. Rr [%] (a) N2 [mg/g], (c) CO [mg/g] (d) CO2

[mg/g] (b) N/C.
141
0,5
R2 = 0,7
PST-14
0,4
Rr [%]
0,3
KYP-1
0,2
0,1
0,0
270
290
310
330
350
370
Tmax CO2 [oC]
5.56. [Rr] CO2 [Tmax CO2].

(Xu and Tomita, 1987, Arenillas et al., 2003).
5.55c
,
.
(Chu et al., 1988, Solomon et al.,
1991, Charpenay et al., 1996a,b, Cloke et al., 1999, Kopp et al., 2000, Yao et al., 2006),
CO CO2,
C4 .

. ,
,
.

,
( 5.57). 5.57b
-9, -15, SF-31, L-1, PL-7 KYP-1.
,
,
(Diessel, 1992).
C4
142
C-H .
, C-H
(Sun and Wang, 2000, Sun et al., 2003),
maceral
. Choi et al. (1988), Cloke and Lester (1994), Guo
et al. (1996) Orem and Finkelman (2004)
maceral,
.
(2), ,
maceral.
(Thomas, 1997) ,
maceral
. Boudou and Espitalie (1995)
maceral,
( ). C C2,
maceral .

.
maceral
maceral
.
, 75% 96%.
20
100
PL-7
KL-1
15
Liptinite [%]
Huminite [%]
90
80
10
KL-1
70
KOM-15
KYP-1
60
10
15
20
CH4 [mg/g TOC]
25
SF-31
PL-7
KOM-9
30
10
15
20
25
30
CH4 [mg/g TOC]
5.57. (a) (b)

.
143
5.9. (TG/DTA)
5.9.1.
(hermogravimetry, TG)
(Derivative thermogravimetry, DTG) ,
. ,
,
. ,
,
(Cumming and McLaughlin,
1982, Benfell et al., 1996).

(fingerprint)

(Kkbayrak, 1993).
(Differential thermal analysis, DTA)
,

, .

, , ,
, , , , ,
, (Wendlandt, 1986).
, ,
, ,
.
5.9.2. (TG/DTG)
(TG)

. TG ( 5.58),

144
, x
(Rosenvold et al., 1982, Yongkang et al., 2001):
wo wt
wo w f
x=
(5.9.1)
wo , wt
wf .
x 5.59,
300C 600C.
SF-31
SF-20
SF-1
KOM-15
KOM-9
PST-14
PST-3
Weight Loss [%]
Weight Loss [%]
KYP-1
MAR-16
MAR-19
PL-7
PL-11
KL-5
KL-1
100
200
300
400
500
600
700
800
900
1000 1100
100
200
300
400
500
600
700
800
900
1000 1100
Temperature [oC]
Temperature [oC]
1,0
1,0
0,9
0,9
0,8
0,8
0,7
0,6
0,5
0,4
KYP-1
MAR-16
MAR-19
PL-7
PL-11
KL-5
KL-1
0,3
0,2
0,1
0,0
Pyrolysis fractional conversion x
Pyrolysis fractional conversion x
5.58. (TG) .
0,7
0,6
0,5
0,4
SF-31
SF-20
SF-1
KOM-15
KOM-9
PST-14
PST-3
0,3
0,2
0,1
0,0
100
200
300
400
500
600
700
Temperature [oC]
800
900
1000 1100
100
200
300
400
500
600
700
800
900
1000 1100
Temperature [oC]
5.59. x .
145
5.16
0,1%, 0,5%, 0,9%, x 10%, 50% 90%
. 10%
110C 130C KYP-1 ,
0,1% 10C . 0,5% 361C
408C KYP-1 (427C), 0,9%
x 90% 674C 779C. Yongkang et al. (2001)

.
(DTG) ,
TG. DTG
TG
TG (Wendlandt, 1986).
DTG ( 5.60)
. , 120C 140C,
(Cumming and McLaughlin, 1982,
Serio et al., 1987, Szab et al., 1990a, Solomon et al., 1992, Ozbas et al., 2000)
(Arenillas et al., 2003) /
(Borah et al., 2005, Vijayakumar et al., 2006).
5.16. 0,1%, 0,5%, 0,9%, x
10%, 50% 90% , TDTGmax.
146
T0,1% [oC]
T0,5% [oC]
T0,9% [oC]
TDTG max [oC]
KL-1
KL-5
SF-1
SF-20
SF-31
PL-7
PL-11
KOM-9
KOM-15
PST-3
PST-14
131
128
110
118
119
131
133
125
124
125
129
389
402
361
370
408
396
403
390
395
398
398
674
754
675
691
750
707
699
712
719
726
711
370
387
432
429
425
400
440
415
423
428
421
MAR-16
MAR-19
KYP-1
125
130
140
391
398
427
728
779
763
408
405
400

.
TDTGmax,
,
(Cumming and McLaughlin, 1982, Kkbayrak, 1993, Arenillas et al., 1999, Das, 2001).
( ) TDTGmax ( 5.16)
400C 408C, .
415C 432C
L-1, KL-5 PL-7, TDTGmax 370C, 387C 400C
. TDTGmax

. TDTGmax (R2=0,72)
,
( 5.61)
L-1 L-5
,
S1
Rock-Eval ( 5.5), L-1 (8,09mg
HC/g ) . (
1,73 3,26mg HC/g ). TDTGmax
KYP-1
MAR-16
MAR-19
PL-7
PL-11
KL-5
KL-1
100
200
300
400
500
600
700
o
Temperature [ C]
800
900
1000 1100
DTG signal [mg/min]
DTG signal [mg/min]
, Rock-Eval
KOM-15
KOM-9
PST-14
PST-3
SF-31
SF-20
SF-1
0
100
200
300
400
500
600
700
800
900
1000 1100
Temperature [oC]
5.60. DTG .
147
0,5
R2 = 0,72
Rr [%]
0,4
0,3
KL-5
KL-1
KYP-1
0,2
0,1
350
360
370
380
390
400
410
420
430
440
450
TDTGmax [ C]
5.61. (TDTGmax) (Rr).
450
R2=0,70
Tmax [oC]
430
410
390
370
KL-1
350
350
360
370
380
390
400
410
420
430
440
450
TDTGmax [ C]
5.62. (TDTGmax)
(Tmax).
148
500
2
R = 0,74
Tmax CH4 [oC]
450
400
350
350
360
370
380
390
400
410
420
430
440
450
TDTGmax [ C]
5.63. (TDTGmax)
(Tmax CH4).
(Tmax).
5.62,
(Arenillas et al., 2003)
(
) .
TDTGmax (L-1 L-5)

(.
5.8). 5.63
(R2=0,74) TDTGmax
.
5.60 DTG
TDTGmax, 250C
600C. Smutkina et al. (1982) DTG

.
.
5.17
. 160C
149
. 160C 250C
(Cypres and Soudan-Moinet, 1980, Kneller, 1986, Das, 2001),

(de la Puente et al., 1998, Arenillas et al., 2003, Borah
et al., 2005). (W160-250 C) ,
o
3,1% 6,8% (.
5.8), .
250C 600C (W250-600 C)
o

. W250-600 C 17,95% 38,88%,
o
45% 65% .
(Podder et al., 1995, de la Puente et al., 1998, Iordanidis et al., 2001, Pietrzak and
Wachowska, 2004, Borah et al., 2005)
.
600C
, (char) (Szab et al.,
1990a, Das, 2001, Arenillas et al., 2003).
800C,
1100C 2% 4%.
(WTotal C) 50%
o
P-1, WTotal C
o
5.17. (W) (WTotal:

).
W0-160 oC [%] W160-250 oC [%] W250-600 oC [%] W600-800 oC [%] W160-800 oC [%] WTotal oC [%]
8,18
3,11
38,88
6,80
48,79
59,07
KL-1
8,83
4,41
28,75
7,10
40,26
53,09
KL-5
14,68
5,93
29,64
6,45
42,02
61,11
SF-1
13,68
6,80
28,92
6,93
42,65
58,89
SF-20
10,61
4,40
24,08
9,58
38,06
51,24
SF-31
9,44
5,82
32,32
7,25
45,39
57,60
PL-7
8,89
6,01
29,18
6,69
41,88
53,06
PL-11
11,02
6,40
29,86
8,03
44,29
57,71
KOM-9
10,67
6,06
28,08
7,25
41,39
55,04
KOM-15
10,08
5,38
28,86
7,36
41,6
54,69
PST-3
9,51
5,72
29,91
6,99
42,62
54,98
PST-14
MAR-16
MAR-19
KYP-1
150
8,81
8,44
6,99
4,38
5,13
3,25
29,32
23,32
17,95
6,32
6,61
7,54
40,23
40,02
28,74
52,00
53,31
36,38
(. 5.2.5) .

(Das, 2001).
5.64 (R2=0,7)
WTotal C H/C .
o
H/C ,
.
80
2
R =0,7
WTotal C [%]
60
40
20
0,7
0,9
1,1
1,3
1,5
H/C
5.64. WTotaloC H/C .

8
R2 = 0,9
SF-31
6
W670-800 C [%]
KYP-1
KOM-9
2
0
10
12
14
Ca + Mg [%]
5.65. 670C 800C (W670-800oC)

(Ca, Mg) .
151

DTG, 670C 800C
KYP-1, SF-31 -9.
( )
(Burnham et al. 1983, ten Brink et al., 1996, Ozbas et al., 2000, Charland et al., 2003)
(.
5.8.2.2).
(R2=0,9) 670C 800C
( 5.65).
5.9.3. (DTA)
(DTA)
(
120-150, 500-550 670-800C) ( 350450 850-950C) ( 5.66).

DTA ,
.

Endo
PL-7
PL-11
MAR-16
MAR-19
KL-5
KL-1
KYP-1
0
100
200
300
400
500
600
700
Temperature [oC]
800
900
1000 1100
KOM-15
KOM-9
PST-14
PST-3
SF-31
SF-20
SF-1
Endo
Heat Flow [V]
Heat Flow [V]
Exo
Exo
(Gorman and Walker, 1971, Yariv, 2004), Markova et al. (1985) Podder
100
200
300
400
500
5.66. DT .
152
600
700
Temperature [oC]
800
900
1000 1100
et al. (1995) . To
DTG
.
350C 450C
.
850C 950C,

,
.
.
Gorman and Walker (1971,1973), Earnest et al. (1985) Yariv (2004)
, ,
,
.

,
. ,
Rosenvold et al. (1982), Kneller (1986), Solomon et al. (1992)
Strezov et al. (2004) DTA .
:
(120-150C) Markova
et al. (1985), Podder et al. (1995), etinkaya and Yrm (2000) Borah et al.
(2005) , (Iordanidis et al., 2001)
.
(350-450C) Elder and

Harris (1984), Podder et al. (1995), Iordanidis et al. (2001) Borah et al. (2005)
, Markova et al. (1985), Hefta et al. (1986)
Strezov et al. (2004) .

, ,

(Strezov et al., 2004).
153
154
6.
:
, , . , ,
( )
(Weichbraunkohle) ,
(Lignite).

.
,

. O/C H/C
.
, .
matrix ,
, matrix ,
.
-
matrix
.
.
.
matrix
. ,
. ,
,

.
maceral ,
T.
,
.
155
, ,
, ,
.
.

.
,
.

.
(F.T.I.R.)
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186

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, . 1986. (). ..., XVIII: 111-130.
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188
1
2
3
4
5
6
7
189
190
1. -12 () .
191
2. 12/00 (. ) .
192
3. -7 () .
193
4. -24 () .
194
5. -75 () .
195
6. -8 () .
196
7. -10 ()
197
198
199
200
1. .
X
X
X
X
SF-35
X
X
SF-31
SF-25
SF-29
SF-23
SF-20
SF-16
X
X
SF-12
SF-10
SF-8
SF-2
SF-1
KOM-15
KOM-14

SF-3
KOM-9
KOM-13
()
KOM-7
KOMANO
KOM-3
. .
.
-
.

Stratified
Matrix
Unstratified
X
X
X
X
X
X
X
X
X
X
X
X
X
?
?
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Xylite - Rich Coal

Charcoal - Rich Coal
Mineral - Rich Coal
201
1 (). .
202
PST-15
PST-14
PST-13
PST-12
PST-11
PST-10
PST-9
PST-7
PST-6
PST-5
PST-4
PST-8
()
PST-3
PST-2
. .
Stratified
Matrix
Unstratified
Xylite - Rich Coal

Mineral - Rich Coal
X
X
X
X
X
X
X
X
1 (). .
KL-9
KL-7
X
X
.
-
.

Stratified
Matrix
Unstratified
KL-5
X
. .
KL-4
KL-3
X
X
X
KL-2
KL-1
PL-13
PL-12
PL-11
PL-7
PL-5
PL-4
PL-3
PL-15
PL-9
PL-10
()
PL-2
PL-1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Xylite - Rich Coal
X
X
X
X
X

Mineral - Rich Coal
203
1 (). .
204
. .
Stratified
Matrix
Unstratified
X
X
X
X
X
X
X
X
R-19
R-18
R-10
R-16
R-6
KYP-4
R-13
R-12
R-4
R-11
()
KYP-3
K
KYP-1
X
X
X
X
X
Xylite - Rich Coal

Mineral - Rich Coal
2. .
,
[m]
[m]
' '
[%]
' ,
' [%]
Y [%]
A... ' '

[kcal/kg]
A... ' ,
' [kcal/kg]
[%]
(750 oC)
[%]
C [%]
A...
[kcal/kg]
[%]
C [%]
A...
[kcal/kg]
KOM-3
39,30 - 39,50
0,20
62,00
65,03
14,99
1672
1754
12,28
48,97
38,76
4400
55,82
44,18
5016
KOM-7
42,00 - 43,50
1,50
61,60
71,20
12,95
1678
1940
35,12
38,78
26,10
4370
59,77
40,23
6735
KOM-9
46,00 - 46,60
0,60
64,50
69,17
13,57
1431
1535
19,03
49,94
31,03
4031
61,68
38,32
4978
KOM-13
54,30 - 54,70
0,40
63,20
69,03
13,36
1606
1754
22,94
46,50
30,56
4364
60,35
39,65
5663
KOM-14
55,20 - 55,70
0,50
60,40
64,62
14,53
1494
1598
16,49
48,70
34,81
3773
58,31
41,69
4518
KOM-15
56,00 - 57,00
1,00
63,30
69,89
13,34
1691
1867
25,71
45,09
29,20
4608
60,69
39,31
6202
SF-1
139,00 - 139,60
0,60
58,20
60,99
15,00
2321
2432
10,94
51,45
37,61
5553
57,77
42,23
6234
SF-2
147,60 - 148,00
0,40
52,50
63,05
12,19
1894
2275
35,22
45,88
18,90
3987
70,82
29,18
6155
SF-3
148,00 - 150,50
2,50
52,80
56,25
14,17
2003
2134
12,99
52,30
34,71
4244
60,11
39,89
4877
SF-8
157,00 - 158,00
1,00
51,30
64,47
11,80
1615
2030
41,94
40,27
17,79
3316
69,37
30,63
5712
SF-10
160,10 - 162,30
2,20
55,50
61,92
13,60
1999
2230
23,30
49,18
27,52
4492
64,13
35,87
5857
SF-12
163,00 - 165,00
2,00
59,00
64,16
14,11
2027
2204
19,61
46,04
34,36
4944
57,26
42,74
6150
SF-16
169,00 - 170,00
1,00
58,00
61,21
15,35
2199
2321
12,47
49,15
38,38
5236
56,15
43,85
5982
SF-20
175,00 - 177,50
2,50
57,00
60,08
15,93
2270
2393
11,93
50,40
37,67
5279
57,23
42,77
5994
SF-23
178,50 - 181,00
2,50
51,90
57,51
16,21
1894
2099
20,28
48,15
31,57
3938
60,40
39,60
4939
SF-25
185,90 - 187,00
1,10
55,70
59,03
15,86
1919
2034
12,74
52,06
35,20
4332
59,66
40,34
4964
SF-29
192,00 - 193,00
1,00
58,00
63,05
14,89
2151
2338
19,07
50,56
30,37
5121
62,48
37,52
6329
SF-31
195,30 - 196,00
0,70
53,70
64,24
11,17
1205
1442
35,51
37,19
27,30
2603
57,66
42,34
4036
SF-35
199,20 - 200,00
0,80
56,80
59,17
15,71
2098
2186
9,27
51,56
39,16
4856
56,84
43,16
5353
PST-2
170,00 - 170,50
0,50
51,90
60,12
12,40
1915
2218
28,42
43,48
28,10
3981
60,75
39,25
5562
PST-3
182,30 - 183,90
1,60
56,10
60,85
12,96
1490
1616
17,80
48,35
33,86
3394
58,81
41,19
4129
PST-4
215,00 - 215,70
0,70
47,80
50,67
12,97
2305
2443
10,85
52,58
36,57
4416
58,98
41,02
4953
PST-5
244,30 - 245,50
1,20
51,80
54,93
13,19
2450
2598
11,82
50,45
37,73
5083
57,21
42,79
5764
PST-6
271,80 - 273,00
1,20
52,90
56,36
12,53
2540
2706
13,03
50,11
36,86
5393
57,61
42,39
6201
PST-7
275,00 - 276,10
1,10
51,10
53,74
12,80
2290
2408
10,06
51,32
38,62
4683
57,06
42,94
5207
PST-8
312,00 - 313,60
1,60
49,00
53,76
11,63
2455
2693
17,35
49,21
33,44
4814
59,54
40,46
5824
PST-9
319,90 - 321,80
1,90
45,30
50,05
12,23
2330
2574
17,36
47,55
35,09
4260
57,53
42,47
5154
PST-10
322,30 - 323,50
1,20
50,20
54,36
12,30
2645
2864
15,37
50,41
34,22
5311
59,56
40,44
6276
PST-11
334,90 - 336,00
1,10
47,80
51,52
12,40
2550
2748
13,82
51,33
34,85
4885
59,56
40,44
5668
PST-12
383,50 - 384,50
1,00
47,60
51,83
12,77
2525
2749
15,58
48,34
36,08
4819
57,26
42,74
5708
PST-13
472,10 - 473,50
1,40
37,80
41,46
12,67
2055
2254
14,20
49,61
36,19
3304
57,82
42,18
3851
PST-14
478,40 - 479,40
1,00
13,38
12,99
50,67
36,34
58,24
41,76
PST-15
493,30 - 494,00
0,70
11,70
24,31
45,47
30,22
60,07
39,93
205
[m]
[m]
' '
[%]
' ,
' [%]
Y [%]
[%]
(750 oC)
[%]
C [%]
A...
[kcal/kg]
[%]
C [%]
A...
[kcal/kg]
A... ' '

[kcal/kg]
A... ' ,
' [kcal/kg]
2 (). .
KL-1
69,50 - 70,00
0,50
54,80
62,00
14,66
1731
1958
25,69
53,84
20,47
3830
72,46
27,54
5154
KL-2
70,00 - 71,50
1,50
49,30
55,41
14,13
2495
2804
21,76
52,73
25,51
4921
67,39
32,61
6290
KL-3
71,50 - 73,20
1,70
51,20
57,41
13,66
2301
2580
22,16
56,71
21,13
4715
72,85
27,15
6058
KL-4
75,60 - 76,00
0,40
48,50
54,42
12,14
2528
2837
21,13
53,05
25,81
4909
67,27
32,73
6224
KL-5
76,00 - 77,20
1,20
49,80
58,48
12,73
2324
2729
29,57
46,59
23,84
4629
66,15
33,85
6573
KL-7
78,10 - 79,00
0,90
45,20
55,88
13,00
1795
2219
34,88
43,25
21,87
3276
66,41
33,59
5030
KL-9
81,00 - 81,30
0,30
47,30
55,91
10,81
2407
2845
29,23
48,07
22,70
4567
67,93
32,07
6454
PL-1
138,90 - 140,05
1,15
31,00
39,62
8,38
31,54
37,30
29,16
54,48
45,52
PL-2
140,90 - 141,80
0,90
41,00
48,36
9,41
25,80
49,05
25,15
66,10
33,90
PL-3
142,60 - 143,20
0,60
43,90
46,15
11,10
8,68
58,49
32,83
64,05
35,95
PL-4
143,20 - 143,50
0,30
45,30
51,26
11,33
21,26
48,47
30,27
61,56
38,44
PL-5
143,65 - 144,05
0,40
40,40
48,36
11,79
27,61
48,56
23,82
67,09
32,91
PL-7
145,20 - 146,40
1,20
43,70
48,09
13,54
16,20
51,15
32,65
61,04
38,96
PL-9
150,20 - 151,00
0,80
41,40
51,52
11,49
33,52
42,13
24,34
63,38
36,62
PL-10
151,00 - 151,80
0,80
45,60
52,44
12,80
23,98
48,24
27,78
63,46
36,54
PL-11
151,80 - 152,90
1,10
38,20
44,97
12,69
24,35
46,33
29,32
61,24
38,76
PL-12
152,90 - 153,55
0,65
43,30
55,26
9,64
38,17
37,77
24,06
61,08
38,92
PL-13
154,25 - 154,65
0,40
38,00
46,11
11,92
28,37
46,43
25,20
64,82
35,18
PL-15
155,80 - 156,25
0,45
37,30
52,00
7,82
45,09
33,63
21,29
61,23
38,77
MAR-4
34,50 - 36,00
1,50
55,10
69,51
11,00
1049
1323
46,17
38,86
14,97
2336
72,18
27,82
4340
MAR-6
59,10 - 61,00
1,90
54,80
62,87
12,00
1339
1536
28,39
44,33
27,29
2962
61,90
38,10
4137
MAR-10
74,60 - 75,00
0,40
38,90
53,06
9,40
1077
1469
43,67
41,23
15,10
1763
73,20
26,80
3129
MAR-11
98,00 - 99,00
1,00
51,40
63,85
9,26
1083
1345
40,13
37,79
22,08
2228
63,13
36,87
3722
MAR-12 112,00 - 112,80
0,80
48,10
62,45
8,81
1183
1536
44,27
41,05
14,68
2279
73,66
26,34
4090
MAR-13 114,60 - 115,50
0,90
45,80
60,38
9,13
1228
1619
44,56
33,70
21,74
2266
60,78
39,22
4086
MAR-16 118,00 - 119,50
1,50
54,10
64,99
8,78
1240
1490
36,50
44,46
19,04
2702
70,02
29,98
4255
MAR-18 124,00 - 125,70
1,70
54,40
68,84
9,45
1108
1402
46,00
40,00
14,00
2430
74,07
25,93
4499
MAR-19 125,70 - 128,00
2,30
57,60
68,19
11,00
1138
1347
36,63
45,53
17,84
2684
71,85
28,15
4236
KYP-1
41,35 - 43,09
1,74
65,00
74,51
16,05
550
630
36,46
46,84
16,70
1571
73,72
26,28
2473
KYP-3
43,95 - 44,35
0,40
66,10
74,01
25,35
750
840
31,54
44,44
24,03
2212
64,91
35,09
3232
KYP-4
44,55 - 47,35
2,80
67,30
79,98
22,22
825
980
48,48
37,03
14,50
2523
71,86
28,14
4897
206
3. (C,H, N, S,O) (TOC)

(TIC) (TC: ).
[%]
, [%]
C H N S O TOC TIC
TC
H N S
O TOC
H/C O/C N/C
KOM-3
54,3
4,8
1,6
1,2
25,8 47,29
0,31
47,60
61,9
5,5
1,8
1,4
29,4
53,91
1,06
0,36
0,025
KOM-7
40,8
2,5
1,2
1,0
19,4 36,11
0,64
36,74
62,9
3,9
1,8
1,5
29,9
55,66
0,74
0,36
0,025
KOM-9
51,7
3,4
1,3
0,4
24,1 48,28
0,34
48,61
63,9
4,2
1,7
0,4
29,8
59,63
0,79
0,35
0,022
KOM-13 42,5
3,9
1,3
1,0
28,4 36,26
1,45
37,72
55,2
5,0
1,7
1,3
36,8
47,05
1,08
0,50
0,026
KOM-14 52,4
4,0
1,2
2,6
23,3 43,30
0,71
44,01
62,7
4,8
1,5
3,1
27,9
51,85
0,92
0,33
0,020
KOM-15 50,1
4,7
1,3
0,6
17,5 45,29
0,41
45,70
67,5
6,4
1,8
0,9
23,5
60,96
1,12
0,26
0,023
SF-1
53,8
5,9
1,2
0,7
27,4 43,22
0,22
43,43
60,4
6,7
1,4
0,8
30,7
48,53
1,31
0,38
0,020
SF-2
42,7
3,9
0,9
3,3
14,0 35,88
0,29
36,16
65,9
6,0
1,4
5,1
21,7
55,39
1,08
0,25
0,019
SF-3
39,9
3,7
1,1
3,8
38,5 33,89
0,23
34,12
45,8
4,2
1,3
4,3
44,3
38,95
1,09
0,73
0,025
SF-8
25,1
2,5
0,9
2,3
27,2 21,83
0,39
22,23
43,3
4,4
1,6
4,0
46,8
37,60
1,21
0,81
0,031
SF-10
50,2
4,5
1,4
2,8
17,8 42,13
0,19
42,31
65,4
5,9
1,9
3,7
23,2
54,93
1,07
0,27
0,024
SF-12
52,1
4,8
1,4
2,8
19,3 40,08
0,10
40,18
64,8
6,0
1,7
3,5
24,0
49,86
1,11
0,28
0,022
SF-16
52,5
4,1
1,4
2,7
26,9 46,42
0,17
46,59
59,9
4,7
1,6
3,0
30,7
53,03
0,93
0,39
0,023
SF-20
52,8
4,9
1,5
2,5
26,4 43,81
0,10
43,92
60,0
5,5
1,7
2,8
30,0
49,74
1,10
0,38
0,025
SF-23
49,6
2,9
1,3
2,1
23,8 42,29
0,50
42,79
62,2
3,7
1,6
2,7
29,9
53,05
0,70
0,36
0,022
SF-25
36,1
3,5
1,1
2,1
44,5 31,00
0,32
31,32
41,3
4,0
1,3
2,4
51,1
35,53
1,15
0,93
0,026
SF-29
44,4
4,0
1,6
2,9
28,1 39,02
0,16
39,18
54,9
4,9
1,9
3,5
34,7
48,22
1,07
0,47
0,030
SF-31
44,0
3,5
1,1
2,4
13,6 36,99
0,53
37,51
68,2
5,4
1,7
3,7
21,0
57,36
0,95
0,23
0,021
SF-35
55,3
5,0
1,5
2,2
26,7 47,12
0,26
47,37
61,0
5,5
1,6
2,5
29,4
51,94
1,08
0,36
0,023
PST-2
31,7
2,9
1,0
1,7
34,3 27,42
0,94
28,36
44,3
4,0
1,4
2,4
47,9
38,31
1,09
0,81
0,027
PST-3
47,8
4,4
1,5
2,5
26,0 42,58
0,30
42,87
58,1
5,4
1,8
3,1
31,6
51,80
1,10
0,41
0,027
PST-4
51,8
3,7
1,5
2,6
29,5 44,61
0,49
45,10
58,1
4,2
1,7
2,9
33,1
50,04
0,86
0,43
0,026
PST-5
54,0
3,6
1,8
2,0
26,8 44,82
0,49
45,31
61,2
4,0
2,1
2,3
30,4
50,83
0,79
0,37
0,029
PST-6
50,0
4,2
1,8
2,9
28,1 42,87
0,23
43,09
57,5
4,8
2,1
3,3
32,3
49,29
0,99
0,42
0,031
PST-7
55,3
3,9
1,9
2,0
26,9 49,97
0,11
50,08
61,4
4,3
2,1
2,2
29,9
55,56
0,84
0,36
0,030
PST-8
53,2
4,1
2,0
2,9
20,6 44,72
0,15
44,87
64,3
4,9
2,4
3,5
24,9
54,11
0,91
0,29
0,032
PST-9
49,4
3,9
1,9
2,4
25,0 42,29
0,31
42,6
59,7
4,8
2,3
2,9
30,3
51,17
0,95
0,38
0,033
PST-10
53,9
4,3
1,9
2,7
21,9 45,54
0,18
45,72
63,7
5,1
2,2
3,1
25,9
53,81
0,95
0,31
0,030
PST-11
56,3
5,4
2,2
2,3
20,0 47,22
0,22
47,44
65,3
6,3
2,5
2,7
23,2
54,79
1,15
0,27
0,033
PST-12
52,3
5,1
2,1
2,3
22,6 46,99
0,16
47,15
62,0
6,0
2,5
2,7
26,8
55,66
1,15
0,32
0,034
PST-13
47,8
3,9
1,6
2,6
29,8 40,56
0,17
40,73
55,7
4,5
1,9
3,1
34,8
47,27
0,97
0,47
0,029
PST-14
51,1
3,0
1,7
2,1
29,1 44,75
0,17
44,92
58,8
3,5
1,9
2,4
33,4
51,43
0,70
0,43
0,028
PST-15
40,7
3,3
1,3
2,4
28,0 37,04
0,53
37,57
53,7
4,4
1,7
3,2
37,0
48,93
0,97
0,52
0,028
KL-1
50,4
4,7
0,5
3,5
15,2 48,40
0,26
48,66
67,8
6,3
0,7
4,7
20,5
65,14
1,11
0,23
0,009
KL-2
53,1
4,8
0,8
2,4
17,1 49,20
0,50
49,69
67,9
6,2
1,1
3,0
21,8
62,88
1,08
0,24
0,014
KL-3
53,9
5,1
0,8
2,5
15,5 51,11
0,63
51,74
69,2
6,5
1,0
3,3
20,0
65,66
1,12
0,22
0,012
KL-4
49,7
4,2
0,5
3,0
21,5 43,40
0,20
43,60
63,0
5,3
0,6
3,8
27,3
55,03
1,00
0,33
0,008
KL-5
45,2
4,3
1,0
2,4
17,5 40,78
0,26
41,05
64,2
6,1
1,4
3,5
24,9
57,90
1,12
0,29
0,019
KL-7
42,4
4,3
1,1
2,7
14,6 40,97
0,18
41,15
65,2
6,6
1,6
4,2
22,4
62,91
1,20
0,26
0,022
KL-9
47,9
4,0
1,0
2,9
15,0 41,87
0,17
42,05
67,7
5,6
1,4
4,1
21,2
59,16
0,99
0,23
0,017
207
3 (). (C,H, N, S,O)

(TOC) (TIC) (TC: ).
[%]
, [%]
C H N S O TOC TIC
TC
H N S
O TOC
H/C O/C N/C
PL-1
45,2
4,3
1,5
2,9
14,6 42,34
0,19
42,52
66,0
6,3
2,1
4,2
21,3
61,84
1,14
0,24 0,028
PL-2
38,4
4,0
1,0
2,7
28,2 34,37
0,29
34,66
51,7
5,3
1,3
3,6
38,0
46,32
1,23
0,55 0,022
PL-3
59,3
5,9
0,4
2,3
23,4 54,21
0,12
54,33
65,0
6,4
0,4
2,5
25,6
59,36
1,18
0,30 0,006
PL-4
53,2
5,4
1,1
2,1
17,0 47,11
0,24
47,35
67,6
6,9
1,4
2,6
21,6
59,83
1,21
0,24 0,018
PL-5
44,5
4,2
1,0
3,7
19,0 39,57
0,31
39,87
61,5
5,8
1,3
5,2
26,3
54,66
1,12
0,32 0,018
PL-7
52,8
4,8
1,5
2,9
21,8 48,35
0,88
49,22
63,0
5,7
1,8
3,4
26,0
57,70
1,08
0,31 0,024
PL-9
44,4
3,7
1,1
2,8
14,5 41,73
0,14
41,88
66,8
5,6
1,7
4,1
21,8
62,77
0,99
0,25 0,022
PL-10
50,4
4,8
1,5
2,3
17,0 43,42
0,13
43,55
66,3
6,4
1,9
3,0
22,4
57,11
1,15
0,25 0,025
PL-11
50,0
4,9
1,3
2,2
17,4 44,38
0,23
44,61
66,0
6,5
1,7
2,8
23,0
58,66
1,17
0,26 0,021
PL-12
40,6
4,2
1,4
2,8
13,0 38,78
0,24
39,02
65,6
6,7
2,2
4,5
21,0
62,72
1,22
0,24 0,029
PL-13
48,7
4,2
1,9
3,4
13,5 41,08
0,11
41,18
67,9
5,8
2,7
4,7
18,8
57,35
1,03
0,21 0,034
PL-15
32,3
3,5
1,0
2,9
15,3 26,19
0,43
26,52
58,8
6,3
1,8
5,3
27,8
47,69
1,27
0,36 0,026
MAR-4
31,8
3,1
1,1
3,7
14,2 28,84
0,26
29,10
59,0
5,7
2,1
6,8
26,4
53,58
1,16
0,34 0,030
MAR-6
41,7
3,8
1,1
4,2
20,8 37,97
0,33
38,30
58,3
5,3
1,6
5,8
29,0
53,02
1,08
0,37 0,023
MAR-10 37,8
3,1
1,0
4,2
10,2 34,20
0,18
34,38
67,2
5,5
1,9
7,4
18,1
60,71
0,97
0,20 0,024
MAR-11 35,5
3,2
1,3
4,3
15,6 35,04
0,22
35,26
59,3
5,3
2,1
7,2
26,0
58,53
1,06
0,33 0,031
MAR-12 35,7
3,2
1,1
5,4
10,3 34,48
0,14
34,61
64,1
5,8
1,9
9,7
18,4
61,87
1,07
0,22 0,026
MAR-13 30,4
2,7
0,9
3,4
18,1 28,57
0,24
28,80
54,7
4,9
1,7
6,1
32,6
51,53
1,06
0,45 0,027
MAR-16 41,8
3,2
1,0
4,4
13,0 40,58
0,14
40,72
65,8
5,1
1,6
7,0
20,5
63,91
0,92
0,23 0,021
MAR-18 33,1
3,2
1,2
4,4
13,1 30,22
0,35
30,57
60,2
5,9
2,2
8,0
23,8
54,94
1,17
0,30 0,031
MAR-19 42,4
3,8
1,0
5,6
10,6 40,96
0,07
41,03
66,9
5,9
1,5
8,8
16,8
64,64
1,06
0,19 0,020
KYP-1
38,8
2,7
1,2
3,7
17,2 32,73
0,24
32,98
61,1
4,2
1,9
5,8
27,0
51,51
0,82
0,33 0,026
KYP-3
40,6
2,9
1,5
5,2
18,3 35,35
0,07
35,42
59,3
4,2
2,2
7,6
26,7
51,63
0,85
0,34 0,031
KYP-4
17,2
2,0
1,0
2,6
28,8 15,65
0,46
16,11
33,3
3,8
1,9
5,1
55,9
30,38
1,36
1,26 0,048
208
.. [%]
Rr [%]
.. [%]
.. [%]
Rr [%]
.. [%]
KL-1
0,20
0,32
0,25
0,030
PST-2
0,33
0,47
0,42
0,036
KL-2
0,20
0,36
0,27
0,041
PST-3
0,22
0,45
0,33
0,049
KL-3
0,25
0,43
0,34
0,044
PST-4
0,25
0,47
0,34
0,041
KL-4
0,24
0,36
0,30
0,024
PST-5
0,25
0,46
0,37
0,058
KL-5
0,21
0,40
0,30
0,038
PST-6
0,28
0,43
0,34
0,034
KL-7
0,25
0,39
0,33
0,035
PST-7
0,31
0,48
0,38
0,040
KL-9
0,30
0,46
0,36
0,049
PST-8
0,34
0,53
0,40
0,042
PL-1
0,23
0,37
0,31
0,038
PST-9
0,29
0,49
0,38
0,050
PL-2
0,23
0,34
0,32
0,025
PST-10
0,28
0,48
0,39
0,051
PL-3
0,24
0,44
0,32
0,047
PST-11
0,30
0,49
0,40
0,047
PL-4
0,26
0,44
0,35
0,048
PST-12
0,31
0,53
0,41
0,044
PL-5
0,28
0,37
0,32
0,019
PST-13
0,31
0,53
0,41
0,049
PL-7
0,24
0,43
0,34
0,046
PST-14
0,33
0,48
0,42
0,040
PL-9
0,28
0,43
0,37
0,040
PST-15
0,33
0,48
0,42
0,036
PL-10
0,30
0,46
0,38
0,043
KOM-3
0,24
0,44
0,31
0,045
PL-11
0,37
0,49
0,40
0,032
KOM-7
0,22
0,43
0,35
0,052
PL-12
0,21
0,39
0,28
0,040
KOM-9
0,27
0,44
0,34
0,040
PL-13
0,27
0,44
0,37
0,047
KOM-13
0,27
0,45
0,35
0,045
PL-15
0,20
0,29
0,24
0,023
KOM-14
0,31
0,47
0,39
0,044
SF-1
0,25
0,39
0,32
0,034
KOM-15
0,29
0,44
0,38
0,030
SF-2
0,23
0,41
0,34
0,047
MAR-4
0,20
0,39
0,28
0,043
SF-3
0,27
0,45
0,34
0,041
MAR-6
0,21
0,37
0,27
0,041
SF-8
0,28
0,48
0,35
0,044
MAR-10
0,21
0,42
0,29
0,053
SF-10
0,23
0,43
0,36
0,043
MAR-11
0,21
0,44
0,31
0,052
SF-12
0,28
0,48
0,38
0,049
MAR-12
0,21
0,44
0,30
0,050
SF-16
0,30
0,49
0,38
0,040
MAR-13
0,23
0,37
0,31
0,034
SF-20
0,30
0,45
0,38
0,037
MAR-16
0,20
0,39
0,32
0,044
SF-23
0,29
0,46
0,37
0,043
MAR-18
0,22
0,40
0,33
0,049
SF-25
0,32
0,46
0,40
0,034
MAR-19
0,25
0,46
0,37
0,055
SF-29
0,30
0,49
0,40
0,045
KYP-1
0,14
0,32
0,20
0,042
SF-31
0,30
0,45
0,38
0,036
KYP-3
0,15
0,29
0,19
0,029
SF-35
0,36
0,47
0,41
0,026
KYP-4
0,17
0,34
0,26
0,037
KY
MA
KOMANO
KI
4. - (..:
, ..: , Rr: ).
209
5. ( % ) (
). ..: , ..: , ..: .
T
T A
T B
T- A
T- B
- A
- B
TPI
GI
GWI
VI
A
B
C
210
KOM-3
KOM-7
KOM-9
KOM-13
KOM-14
KOM-15
E.T.
M.T.
M.O.
90,8
34,0
0,0
0,0
34,0
1,0
15,8
11,4
5,8
56,2
0,4
55,8
0,6
0,0
0,2
0,4
6,6
0,4
2,8
0,6
0,0
1,2
0,2
1,4
2,6
0,2
0,2
0,2
0,0
0,0
2,0
6,4
2,6
0,0
0,4
2,6
0,6
0,2
0,6
30,1
1,8
0,6
38,2
59,0
2,6
84,3
20,0
0,0
0,0
20,0
5,7
8,7
3,3
2,3
62,0
21,3
40,7
2,3
0,7
0,0
1,7
9,3
0,3
1,3
0,3
0,0
1,3
0,0
6,0
6,3
0,3
2,0
0,0
0,0
0,3
3,7
48,5
21,6
0,0
4,3
19,8
2,4
0,3
0,3
2,3
2,2
0,3
23,7
70,0
6,3
94,2
42,6
0,0
0,0
42,6
4,8
18,2
10,8
8,8
50,8
5,8
45,0
0,8
0,4
0,2
0,2
3,0
0,2
1,6
0,2
0,0
0,6
0,0
0,4
2,8
0,4
1,0
0,4
0,0
0,0
1,0
23,8
8,1
0,9
1,2
11,7
0,9
0,9
0,8
10,3
1,4
0,9
44,8
52,4
2,8
92,2
28,4
0,0
0,0
28,4
3,4
15,6
4,6
4,8
61,2
13,6
47,6
2,6
1,6
0,4
0,6
5,2
0,0
1,4
0,2
0,0
1,0
0,0
2,6
2,6
0,4
0,4
0,0
0,2
0,0
1,6
31,1
12,8
0,1
1,4
15,3
1,2
0,3
0,5
4,9
1,9
0,5
30,6
66,8
2,6
88,6
49,0
0,0
0,0
49,0
2,0
17,0
12,6
17,4
36,6
0,0
36,6
3,0
1,4
1,2
0,4
8,4
0,2
5,6
0,0
0,0
1,0
0,0
1,6
3,0
0,4
1,0
0,8
0,0
0,0
0,8
10,4
3,0
0,0
1,3
4,5
1,1
0,5
1,2
29,5
1,0
1,4
55,2
41,8
3,0
91,0
44,0
0,0
0,2
43,8
2,2
20,8
12,8
8,0
43,8
3,8
40,0
3,2
0,8
1,2
1,2
4,8
0,0
0,8
0,0
0,0
2,4
0,0
1,6
4,2
0,4
1,0
0,2
0,2
0,0
2,4
18,6
10,4
0,0
1,0
4,2
1,8
1,1
0,9
10,6
1,3
0,9
46,0
49,8
4,2
84,3
20,0
0,0
0,0
20,0
1,0
8,7
3,3
2,3
36,6
0,0
36,6
0,6
0,0
0,0
0,2
3,0
0,0
0,8
0,0
0,0
0,6
0,0
0,4
2,6
0,2
0,2
0,0
0,0
0,0
0,8
6,4
2,6
0,0
0,4
2,6
0,6
0,2
0,3
2,3
1,0
0,3
23,7
41,8
2,6
94,2
49,0
0,0
0,2
49,0
5,7
20,8
12,8
17,4
62,0
21,3
55,8
3,2
1,6
1,2
1,7
9,3
0,4
5,6
0,6
0,0
2,4
0,2
6,0
6,3
0,4
2,0
0,8
0,2
0,3
3,7
48,5
21,6
0,9
4,3
19,8
2,4
1,1
1,2
30,1
2,2
1,4
55,2
70,0
6,3
90,2
36,3
0,0
0,0
36,3
3,2
16,0
9,3
7,9
51,8
7,5
44,3
2,1
0,8
0,5
0,7
6,2
0,2
2,3
0,2
0,0
1,3
0,0
2,3
3,6
0,4
0,9
0,3
0,1
0,1
1,9
23,1
9,8
0,2
1,6
9,7
1,3
0,6
0,7
14,6
1,6
0,8
39,7
56,6
3,6
6. ( % ) . (
). ..: , ..: , ..: .
SF-1 SF-2 SF-3 SF-8 SF-10 SF-12 SF-16 SF-20 SF-23 SF-25 SF-29 SF-31 SF-35 E.T. M.T. M.O.
87,2
T
55,2
T A
0,0
T B
0,0
55,2
T- A 3,2
T- B 24,6
- A
12,8
- B
14,6
27,0
1,6
25,4
5,0
0,2
2,4
2,4
93,2
50,2
0,0
0,0
50,2
1,2
26,8
14,0
8,2
41,0
13,0
28,0
2,0
0,6
0,2
1,2
89,2
32,0
0,0
0,4
31,6
18,8
10,4
2,4
0,0
55,2
10,4
44,8
2,0
0,4
0,4
1,2
88,2
39,4
0,0
0,0
39,4
6,8
13,2
12,2
7,2
47,6
14,2
33,4
1,2
0,4
0,0
0,8
86,6
29,2
0,0
0,0
29,2
1,8
10,2
10,8
6,4
55,0
9,8
45,2
2,4
0,2
0,2
2,0
89,6
40,8
0,0
0,0
40,8
4,4
12,6
16,4
7,4
45,8
6,8
39,0
3,0
0,8
0,6
1,6
87,6
23,8
0,0
0,0
23,8
3,2
7,4
9,2
4,0
62,2
5,4
56,8
1,6
0,0
0,2
1,4
88,8
22,4
0,0
0,0
22,4
1,4
8,2
7,4
5,4
64,4
8,6
55,8
2,0
0,0
0,6
1,4
88,8
22,0
0,4
0,0
21,6
5,2
9,6
5,6
1,2
64,4
0,0
64,4
2,4
1,2
0,4
0,8
89,0
19,6
0,0
0,0
19,6
4,0
11,0
3,8
0,8
67,4
20,2
47,2
2,0
0,4
0,0
1,6
91,2
19,2
0,0
0,0
19,2
1,2
12,4
4,0
1,6
70,4
20,4
50,0
1,6
0,0
0,0
1,6
93,6
52,4
0,8
0,0
51,6
1,6
24,0
14,2
11,8
39,6
0,0
39,6
1,6
0,0
0,6
1,0
83,6
19,2
0,0
0,0
19,2
1,2
7,4
2,4
0,0
27,0
0,0
25,4
1,2
0,0
0,0
0,8
10,6
0,0
8,2
0,0
0,0
1,6
0,0
0,8
3,8 10,8 5,2

0,4 0,2 0,4
1,0 5,4 1,2
0,0 0,4 0,8
0,0 0,0 0,0
0,8 2,2 1,2
0,0 0,0 0,0
1,6 2,6 1,6
10,2
0,4
2,6
1,8
0,0
2,4
0,6
2,4
7,4
0,0
3,4
0,4
0,0
0,4
0,2
3,0
4,2
0,2
1,0
0,0
0,2
1,0
0,0
1,8
6,6
0,2
1,6
0,0
0,4
2,8
0,4
1,2
5,2
0,2
1,2
0,0
0,0
1,4
0,0
2,4
4,0
0,4
1,2
0,8
0,0
0,8
0,0
0,8
3,8
0,2
0,6
0,2
0,0
0,6
0,0
2,2
4,0
0,4
0,0
0,4
0,0
0,4
0,4
2,4
4,8
0,0
1,4
0,4
0,0
2,2
0,0
0,8
3,8 10,8 6,2

0,0 0,4 0,2
0,0 8,2 2,2
0,0 1,8 0,4
0,0 0,4 0,0
0,4 2,8 1,4
0,0 0,6 0,1
0,8 3,0 1,8
2,2
1,0
0,8
0,0
0,0
0,0
0,4
3,0
0,2
1,2
0,4
0,0
0,0
1,2
5,6
1,8
2,2
0,2
0,0
0,0
1,4
5,6
1,2
1,6
0,4
0,0
0,0
2,4
1,6
0,0
1,0
0,0
0,0
0,0
0,6
6,0
0,6
1,4
0,2
0,0
0,0
3,8
6,2
1,2
1,4
0,0
0,0
0,2
3,4
5,8
0,4
2,2
0,8
0,0
0,0
2,4
6,0
0,4
1,6
0,4
0,0
0,2
3,4
7,2
2,4
0,8
0,4
0,0
0,0
3,6
7,2
0,8
1,4
0,0
0,0
0,2
4,8
4,8
0,4
0,8
0,0
0,0
0,0
3,6
1,6
0,4
0,6
0,0
0,0
0,0
0,6
1,6
0,0
0,6
0,0
0,0
0,0
0,4
12,0
4,2
0,0
0,7
6,7
0,2
0,2
2,0
22,5
0,7
2,2
65,8
32,0
2,2
32,2
14,2
0,4
3,1
11,7
0,9
1,8
1,2
5,0
1,0
1,2
52,8
44,2
3,0
18,0
9,5
0,0
1,0
7,2
0,3
0,0
1,2
4,7
0,9
1,2
51,2
43,2
5,6
45,9
23,6
0,0
1,9
15,8
3,7
0,9
0,6
4,8
2,2
0,6
35,6
58,8
5,6
33,5
19,3
0,0
2,0
10,0
1,9
0,4
0,8
4,7
1,3
0,9
45,0
52,8
1,6
13,3
7,5
0,2
1,4
1,9
1,7
0,7
0,5
4,9
1,6
0,6
35,0
58,8
6,0
9,9
5,6
0,0
1,4
1,6
0,7
0,5
0,9
6,4
1,1
0,9
43,8
50,0
6,2
12,6
10,8
0,0
1,0
0,2
0,2
0,3
0,4
7,3
2,4
0,4
27,4
66,4
5,8
15,5
9,0
1,2
0,8
1,4
1,9
1,4
0,4
5,5
2,4
0,4
25,2
68,8
6,0
5,7
1,5
0,0
0,4
1,9
0,8
1,1
0,4
11,6
3,3
0,4
25,2
67,6
7,2
17,2
8,9
0,2
1,3
2,6
1,3
2,8
0,3
2,5
1,7
0,3
22,2
70,6
7,2
56,7
15,9
3,8
1,0
26,5
5,5
3,8
0,3
2,8
2,7
0,3
21,6
73,2
4,8
11,8 5,7 56,7 21,9

3,2 1,5 23,6 10,3
0,0 0,0 3,8 0,4
1,2 0,4 3,1 1,3
6,2 0,2 26,5 7,2
0,5 0,2 5,5 1,5
0,7 0,0 3,8 1,1
1,0 0,3 2,0 0,8
38,7 2,5 38,7 9,3
1,0 0,7 3,3 1,7
1,3 0,3 2,2 0,8
55,2 21,6 65,8 38,9
43,2 32,0 73,2 56,1
1,6 1,6 7,2 4,8
TPI
GI
GWI
VI
A
B
C
83,6
43,8
0,6
0,4
42,8
3,8
17,2
11,2
10,6
37,4
9,0
28,4
2,4
0,4
0,6
1,4
93,6
55,2
0,8
0,4
55,2
18,8
26,8
16,4
14,6
70,4
20,4
64,4
5,0
1,2
2,4
2,4
7,2
2,4
2,2
0,8
0,0
0,2
4,8
89,0
34,6
0,1
0,1
34,4
4,4
14,4
9,5
6,1
52,1
9,2
42,9
2,2
0,4
0,5
1,4
4,8
0,8
1,3
0,2
0,0
0,0
2,4
211
212
PST-3
PST-4
PST-5
PST-6
PST-7
PST-8
PST-9
PST-10
PST-11
PST-12
PST-13
PST-14
PST-15
T
T A
T B
T- A
T- B
- A
- B
TPI
GI
GWI
VI
A
B
C
PST-2
7. ( % ) (
). ..: , ..: , ..: .
76,0
21,2
0,6
0,2
20,4
2,8
2,4
8,6
6,6
44,2
9,6
34,6
10,6
4,0
5,8
0,8
14,4
0,2
6,2
0,8
0,4
2,4
1,0
3,4
9,6
2,0
2,2
0,4
0,0
0,0
5,0
23,7
11,6
0,0
1,2
9,8
1,1
0,0
0,4
3,3
2,2
0,6
29,6
59,8
9,6
77,1
18,5
0,5
0,2
17,7
10,5
3,7
2,2
1,2
55,6
11,7
43,9
3,0
0,5
0,0
2,5
18,5
0,0
0,7
1,5
1,0
3,5
0,5
11,2
4,5
0,7
1,2
0,0
0,0
0,0
2,5
30,0
9,6
0,0
6,5
10,1
3,0
0,9
0,4
3,8
2,5
0,3
24,2
70,8
4,5
88,8
34,4
0,0
0,0
34,4
8,0
11,0
6,6
8,8
49,0
0,0
49,0
5,4
0,8
1,6
3,0
8,4
0,2
0,8
0,6
0,2
2,2
0,4
4,0
2,8
0,2
1,4
0,4
0,0
0,2
0,6
5,8
3,4
0,0
0,2
0,0
0,8
1,5
0,7
31,7
1,8
0,7
39,2
57,6
2,8
82,6
35,2
2,4
0,0
32,8
15,2
10,4
3,4
3,8
44,2
3,6
40,6
3,2
0,6
0,4
2,2
11,4
0,6
0,0
2,4
1,0
2,0
0,2
5,2
6,0
0,4
2,0
0,6
0,0
0,2
2,8
9,9
7,2
0,0
1,8
0,0
0,5
0,4
0,8
6,4
1,4
0,8
41,4
52,4
6,0
89,2
39,2
1,4
0,0
37,8
13,6
18,2
3,2
2,8
46,6
4,8
41,8
3,4
0,8
0,0
2,6
8,4
0,6
0,4
1,0
0,2
1,4
0,0
4,8
2,4
0,0
0,4
0,6
0,0
0,0
1,4
8,4
5,7
0,0
1,1
0,0
1,6
0,0
0,9
9,7
1,2
0,8
44,0
53,6
2,4
86,8
32,8
0,6
0,0
32,2
6,2
5,0
9,2
11,8
48,8
1,8
47,0
5,2
2,2
1,8
1,2
12,4
0,0
4,2
0,4
0,0
3,2
0,4
4,2
0,8
0,0
0,2
0,4
0,0
0,0
0,2
12,0
8,3
0,0
0,5
2,3
0,4
0,5
0,6
26,4
1,9
0,7
38,6
60,2
0,8
90,6
32,0
0,2
0,6
31,2
11,0
12,2
4,6
3,4
54,2
3,8
50,4
4,4
1,0
0,4
3,0
8,4
0,4
0,8
0,4
0,4
2,4
0,0
4,0
1,0
0,2
0,2
0,0
0,0
0,0
0,6
19,1
10,7
0,0
1,5
5,8
0,5
0,6
0,6
15,4
2,1
0,6
37,0
62,0
1,0
89,8
28,4
0,2
0,0
28,2
12,0
7,6
5,0
3,6
58,4
3,0
55,4
3,0
0,4
0,4
2,2
9,0
0,0
1,8
0,8
0,4
1,6
0,2
4,2
1,2
0,2
0,4
0,0
0,0
0,0
0,6
12,3
6,5
0,0
1,4
3,3
0,2
0,9
0,5
19,7
2,3
0,5
33,6
65,0
1,2
91,0
28,0
0,4
0,4
27,2
8,8
9,4
4,0
5,0
59,4
11,2
48,2
3,6
1,4
0,4
1,8
5,6
0,0
0,8
0,2
0,4
1,6
0,0
2,6
3,4
0,4
1,6
0,2
0,0
0,0
1,2
19,4
12,7
0,0
1,9
2,6
1,3
0,8
0,5
5,1
1,8
0,5
31,2
65,4
3,4
90,6
45,8
0,2
0,0
45,6
10,8
16,0
10,6
8,2
42,8
3,8
39,0
2,0
0,0
0,2
1,8
9,4
0,0
4,4
0,6
0,2
2,8
0,0
1,4
0,0
0,0
0,0
0,0
0,0
0,0
0,0
13,6
8,3
0,0
1,9
2,4
0,5
0,5
1,1
21,7
1,1
1,0
52,8
47,2
0,0
93,2
42,0
0,0
0,2
41,8
9,2
19,2
8,6
4,8
47,8
5,8
42,0
3,4
1,0
0,4
2,0
5,8
0,0
1,6
0,0
0,8
1,0
0,0
2,4
1,0
0,0
0,4
0,0
0,0
0,0
0,6
13,8
8,8
0,0
0,5
4,1
0,3
0,0
0,9
12,5
1,2
0,9
46,4
52,6
1,0
88,0
41,4
0,2
0,0
41,2
6,2
18,6
8,8
7,6
44,4
5,2
39,2
2,2
0,4
1,0
0,8
10,0
0,2
0,6
0,4
0,0
1,2
0,0
7,6
2,0
0,2
0,6
0,4
0,0
0,0
0,8
18,0
10,7
0,0
5,4
0,0
1,5
0,5
0,9
11,2
1,3
0,8
43,4
54,6
2,0
86,2
31,6
0,4
0,0
31,2
8,8
9,2
6,8
6,4
50,6
1,8
48,8
4,0
1,6
0,4
2,0
13,6
0,6
2,8
0,8
0,0
2,0
0,0
7,4
0,2
0,0
0,0
0,0
0,0
0,0
0,2
10,4
2,7
0,0
1,4
0,0
1,8
4,5
0,6
35,0
1,9
0,6
37,8
62,0
0,2
84,4
21,0
0,0
0,0
21,0
7,0
5,2
4,2
4,6
57,4
3,6
53,8
6,0
1,6
3,0
1,4
10,8
0,4
0,6
1,8
0,0
2,8
0,0
5,2
4,8
0,6
2,0
0,2
0,0
0,0
2,0
22,4
8,7
0,5
0,6
2,5
1,4
8,7
0,4
9,6
3,3
0,4
25,2
70,0
4,8
E.T. M.T. M.O.

76,0
18,5
0,0
0,0
17,7
2,8
2,4
2,2
1,2
42,8
0,0
34,6
2,0
0,0
0,0
0,8
5,6
0,0
0,0
0,0
0,0
1,0
0,0
1,4
0,0
0,0
0,0
0,0
0,0
0,0
0,0
5,8
2,7
0,0
0,2
0,0
0,2
0,0
0,4
3,3
1,1
0,3
24,2
47,2
0,0
93,2
45,8
2,4
0,6
45,6
15,2
19,2
10,6
11,8
59,4
11,7
55,4
10,6
4,0
5,8
3,0
18,5
0,6
6,2
2,4
1,0
3,5
1,0
11,2
9,6
2,0
2,2
0,6
0,0
0,2
5,0
30,0
12,7
0,5
6,5
10,1
3,0
8,7
1,1
35,0
3,3
1,0
52,8
70,8
9,6
86,7
32,2
0,5
0,1
31,6
9,3
10,6
6,1
5,6
50,2
5,0
45,3
4,2
1,2
1,1
1,9
10,4
0,2
1,8
0,8
0,4
2,1
0,2
4,8
2,8
0,4
0,9
0,2
0,0
0,0
1,3
15,6
8,2
0,0
1,9
3,1
1,1
1,4
0,7
15,1
1,9
0,7
37,5
59,5
2,8
8. ( % ) (
). ..: , ..: , ..: .
PL-1 PL-2 PL-3 PL-4 PL-5 PL-7 PL-9 PL-10 PL-11 PL-12 PL-13 PL-15 E.T. M.T. M.O.
T
T A
T B
T- A
T- B
- A
- B
TPI
GI
GWI
VI
A
B
C
94,0
68,4
4,0
2,8
61,6
55,6
6,0
0,0
0,0
24,8
17,6
7,2
0,8
0,0
0,0
0,8
6,0
0,0
0,4
0,4
0,4
2,0
0,0
2,8
0,0
0,0
0,0
0,0
0,0
0,0
0,0
55,8
23,7
0,0
0,7
30,6
0,9
0,0
2,8
2,9
0,7
2,4
70,4
29,6
0,0
89,6
62,8
3,2
2,4
57,2
38,8
16,4
2,0
0,0
26,4
24,4
2,0
0,4
0,0
0,0
0,4
10,4
0,4
0,4
0,4
0,0
0,8
0,4
8,0
0,0
0,0
0,0
0,0
0,0
0,0
0,0
51,6
20,2
0,0
5,2
25,0
0,8
0,4
2,4
2,0
0,6
1,8
64,4
35,2
0,0
92,0
61,8
3,4
1,0
57,4
27,8
21,8
5,0
2,8
28,0
4,4
23,6
2,2
0,0
0,0
2,2
7,2
0,0
2,4
0,0
1,0
2,6
0,2
1,0
0,8
0,0
0,4
0,2
0,0
0,0
0,2
14,7
8,2
0,0
2,7
2,6
0,0
1,2
2,3
8,7
0,6
2,1
67,4
31,6
0,8
97,2
70,0
2,4
1,2
66,4
36,4
29,2
0,8
0,0
25,2
10,8
14,4
2,0
0,0
0,0
2,0
2,8
0,0
0,4
0,4
0,4
0,4
0,0
1,2
0,0
0,0
0,0
0,0
0,0
0,0
0,0
29,6
0,8
0,0
0,8
26,5
0,8
0,6
2,9
5,8
0,6
2,7
73,2
26,8
0,0
91,2
35,2
4,4
1,2
29,6
14,8
14,0
0,8
0,0
54,8
20,4
34,4
1,2
0,0
0,0
1,2
8,4
0,8
0,8
0,8
0,8
2,0
0,0
3,2
0,4
0,0
0,0
0,4
0,0
0,0
0,0
39,2
19,0
0,0
0,5
17,0
1,5
1,2
0,7
2,5
1,3
0,6
39,6
60,0
0,4
95,8
24,8
0,2
0,2
24,4
11,2
12,0
1,2
0,0
70,0
12,4
57,6
1,0
0,0
0,0
1,0
4,0
0,0
0,0
0,0
0,4
0,8
0,0
2,8
0,2
0,0
0,0
0,0
0,0
0,0
0,2
21,8
17,4
0,0
1,9
1,6
0,6
0,3
0,4
6,4
2,2
0,3
26,2
73,6
0,2
86,4
46,4
2,8
1,6
42,0
21,2
18,0
1,6
1,2
38,8
14,0
24,8
1,2
0,0
0,0
1,2
12,8
0,0
2,4
1,6
1,2
2,8
0,4
4,4
0,8
0,0
0,0
0,0
0,0
0,0
0,8
50,7
12,6
0,0
1,4
34,1
1,8
0,8
1,2
3,5
1,3
1,1
52,8
46,0
0,8
86,8
42,0
0,4
0,4
41,2
8,0
22,4
7,6
3,2
40,8
17,2
23,6
4,0
0,0
0,0
4,0
13,2
0,0
0,8
1,6
2,4
2,0
0,0
6,4
0,0
0,0
0,0
0,0
0,0
0,0
0,0
31,9
16,9
0,3
0,5
10,1
3,8
0,3
1,1
3,8
1,0
1,0
50,8
49,2
0,0
86,4
29,6
0,0
0,0
29,6
6,4
12,4
3,6
7,2
55,6
6,4
49,2
1,2
0,0
0,0
1,2
12,8
0,0
8,0
0,0
0,0
2,8
0,0
2,0
0,8
0,0
0,0
0,8
0,0
0,0
0,0
24,7
19,9
0,0
0,0
3,3
1,5
0,0
0,6
11,1
2,1
0,6
38,8
60,4
0,8
84,0
17,6
0,0
0,4
17,2
10,4
6,0
0,8
0,0
63,2
36,8
26,4
3,2
0,0
0,0
3,2
14,8
0,0
0,0
1,2
1,2
1,2
0,0
11,2
1,2
0,0
0,0
0,0
0,0
0,0
1,2
58,7
19,3
0,0
1,8
33,9
1,2
2,5
0,3
1,2
1,6
0,3
23,2
75,6
1,2
96,2
41,6
0,2
1,8
39,6
3,4
29,6
4,6
2,0
53,0
20,2
32,8
1,6
0,0
0,0
1,6
3,8
0,0
0,4
1,2
0,6
1,0
0,2
0,4
0,0
0,0
0,0
0,0
0,0
0,0
0,0
35,7
18,8
0,0
3,1
13,2
0,3
0,4
0,8
3,3
1,1
0,8
45,4
54,4
0,0
96,4
64,0
0,4
1,2
62,4
43,6
18,4
0,4
0,0
32,0
9,2
22,8
0,4
0,0
0,0
0,4
3,6
0,0
0,4
1,2
0,4
0,4
0,0
1,2
0,0
0,0
0,0
0,0
0,0
0,0
0,0
44,8
9,5
0,0
0,9
34,2
0,0
0,2
2,0
7,9
0,9
2,0
66,4
33,6
0,0
84,0
17,6
0,0
0,0
17,2
3,4
6,0
0,0
0,0
24,8
4,4
2,0
0,4
0,0
0,0
0,4
2,8
0,0
0,0
0,0
0,0
0,4
0,0
0,4
0,0
0,0
0,0
0,0
0,0
0,0
0,0
14,7
0,8
0,0
0,0
1,6
0,0
0,0
0,3
1,2
0,6
0,3
23,2
26,8
0,0
97,2
70,0
4,4
2,8
66,4
55,6
29,6
7,6
7,2
70,0
56,8
57,6
4,0
0,0
0,0
4,0
14,8
0,8
8,0
1,6
2,4
2,8
0,4
11,2
1,2
0,0
0,4
0,8
0,0
0,0
1,2
58,7
23,7
0,3
5,2
34,2
3,8
2,5
2,9
11,1
2,2
2,7
73,2
75,6
1,2
91,3
47,0
1,8
1,2
44,1
23,1
17,2
2,4
1,4
42,7
17,8
24,9
1,6
0,0
0,0
1,6
8,3
0,1
1,4
0,7
0,7
1,6
0,1
3,7
0,4
0,0
0,0
0,1
0,0
0,0
0,2
38,3
15,5
0,0
1,6
19,3
1,1
0,7
1,4
4,9
1,2
1,3
51,6
48,0
0,4
213
9. ( % ) (
). ..: , ..: , ..: .
T
T A
T B
T- A
T- B
- A
- B
TPI
GI
GWI
VI
A
B
C
214
KL-1
KL-2
KL-3
KL-4
KL-5
KL-7
KL-9
E.T.
M.T.
M.O.
93,3
48,9
1,0
1,2
46,7
31,0
13,2
2,0
0,6
41,8
3,0
38,9
2,6
0,4
0,0
2,2
5,9
0,2
1,0
0,8
0,0
0,6
0,0
3,4
0,8
0,6
0,0
0,2
0,0
0,0
0,0
30,6
10,3
1,4
4,5
7,8
4,1
2,6
1,2
14,9
1,4
1,1
53,1
46,2
0,8
87,2
34,8
5,8
1,6
27,4
22,0
2,8
2,0
0,6
48,4
6,6
41,8
4,0
1,2
0,0
2,8
11,2
0,8
2,8
1,2
0,2
1,8
0,6
3,8
1,6
0,2
1,2
0,0
0,0
0,0
0,2
24,8
9,5
0,0
2,7
11,6
0,3
0,8
0,8
4,7
1,7
0,8
42,6
55,2
1,6
89,0
38,4
1,2
0,4
36,8
27,8
5,6
1,0
2,4
42,8
2,8
40,0
7,8
2,2
0,0
5,6
9,4
0,6
2,4
0,6
0,2
2,2
0,2
3,2
1,6
0,2
0,6
0,2
0,0
0,0
0,6
19,1
11,0
0,0
2,8
4,5
0,5
0,3
1,0
14,1
1,6
0,9
47,8
50,4
1,6
93,6
66,8
2,4
2,6
61,8
46,4
5,8
6,6
3,0
22,0
0,4
21,6
4,8
1,0
0,8
3,0
5,8
0,2
0,8
0,0
0,6
1,2
0,2
2,8
0,6
0,4
0,0
0,2
0,0
0,0
0,0
19,5
10,0
0,0
5,2
1,4
0,3
2,6
2,9
14,7
0,7
2,7
71,4
27,8
0,6
74,6
20,5
0,4
0,2
19,9
11,3
4,2
3,1
1,3
49,7
23,1
26,6
4,4
1,5
0,4
2,5
13,6
0,4
3,8
0,6
0,2
3,4
0,2
5,0
11,7
2,3
3,8
0,4
0,2
0,6
4,4
32,9
18,0
0,0
2,3
12,7
0,0
0,0
0,5
1,4
1,5
0,5
28,1
60,0
11,7
86,8
19,2
0,0
0,0
19,2
7,8
4,4
4,8
2,2
62,4
15,0
47,4
5,2
2,6
0,8
1,8
10,6
1,2
2,0
0,0
0,0
2,6
0,2
4,6
2,6
0,4
2,0
0,0
0,0
0,0
0,2
39,7
24,4
0,0
3,6
11,3
0,4
0,0
0,3
4,1
2,7
0,4
24,2
73,0
2,6
89,4
42,4
0,8
2,0
39,6
19,4
4,6
10,0
5,6
38,4
11,8
26,6
8,6
3,4
1,8
3,4
9,2
0,2
1,8
1,2
0,6
1,2
0,2
4,0
1,4
0,0
0,2
0,0
0,0
0,0
1,2
35,3
13,6
0,0
2,3
19,4
0,0
0,0
1,0
4,7
1,3
1,0
49,6
48,8
1,4
74,6
19,2
0,0
0,0
19,2
7,8
2,8
1,0
0,6
22,0
0,4
21,6
2,6
0,4
0,0
1,8
5,8
0,2
0,8
0,0
0,0
0,6
0,0
2,8
0,6
0,0
0,0
0,0
0,0
0,0
0,0
19,1
9,5
0,0
2,3
1,4
0,0
0,0
0,3
1,4
0,7
0,4
24,2
27,8
0,6
93,6
66,8
5,8
2,6
61,8
46,4
13,2
10,0
5,6
62,4
23,1
47,4
8,6
3,4
1,8
5,6
13,6
1,2
3,8
1,2
0,6
3,4
0,6
5,0
11,7
2,3
3,8
0,4
0,2
0,6
4,4
39,7
24,4
1,4
5,2
19,4
4,1
2,6
2,9
14,9
2,7
2,7
71,4
73,0
11,7
87,7
38,7
1,7
1,1
35,9
23,7
5,8
4,2
2,2
43,6
8,9
34,7
5,3
1,8
0,5
3,0
9,4
0,5
2,1
0,6
0,3
1,8
0,2
3,8
2,9
0,6
1,1
0,1
0,0
0,1
0,9
28,8
13,8
0,2
3,3
9,8
0,8
0,9
1,1
8,4
1,6
1,0
45,2
51,6
2,9
10. ( % ) (
). ..: , ..: , ..: .
T
T A
T B
T- A
T- B
- A
- B
TPI
GI
GWI
VI
A
B
C
KYP-1
KYP-3
KYP-4
E.T.
M.T.
M.O.
96,4
6,4
0,8
0,0
5,6
3,2
2,4
0,0
0,0
90,0
62,0
28,0
0,0
0,0
0,0
0,0
3,2
0,4
0,0
0,0
0,0
0,4
0,0
2,4
0,4
0,0
0,4
0,0
0,0
0,0
0,0
58,0
23,4
1,7
12,9
18,5
0,5
1,0
0,1
0,5
1,3
0,1
6,8
92,8
0,4
90,4
4,8
0,6
0,0
4,2
3,4
0,8
0,0
0,0
85,0
56,4
28,6
0,6
0,0
0,0
0,6
7,2
0,4
0,2
0,0
0,0
1,4
0,0
5,2
2,4
0,2
0,6
0,2
0,0
0,0
1,4
39,2
19,0
0,0
10,6
6,8
1,3
1,5
0,1
0,6
1,1
0,1
6,0
91,6
2,4
93,5
25,5
0,5
0,0
25,0
24,0
0,5
0,5
0,0
67,0
63,5
3,5
1,0
0,0
0,0
1,0
5,0
0,0
0,0
1,0
0,0
1,5
0,0
2,5
1,5
0,0
0,5
0,0
0,0
0,0
1,0
68,8
22,9
0,8
1,4
39,3
2,8
1,6
0,4
0,5
0,8
0,4
27,5
71,0
1,5
90,4
4,8
0,5
0,0
4,2
3,2
0,5
0,0
0,0
67,0
56,4
3,5
0,0
0,0
0,0
0,0
3,2
0,0
0,0
0,0
0,0
0,4
0,0
2,4
0,4
0,0
0,4
0,0
0,0
0,0
0,0
39,2
19,0
0,0
1,4
6,8
0,5
1,0
0,1
0,5
0,8
0,1
6,0
71,0
0,4
96,4
25,5
0,8
0,0
25,0
24,0
2,4
0,5
0,0
90,0
63,5
28,6
1,0
0,0
0,0
1,0
7,2
0,4
0,2
1,0
0,0
1,5
0,0
5,2
2,4
0,2
0,6
0,2
0,0
0,0
1,4
68,8
23,4
1,7
12,9
39,3
2,8
1,6
0,4
0,6
1,3
0,4
27,5
92,8
2,4
93,4
12,2
0,6
0,0
11,6
10,2
1,2
0,2
0,0
80,7
60,6
20,0
0,5
0,0
0,0
0,5
5,1
0,3
0,1
0,3
0,0
1,1
0,0
3,4
1,4
0,1
0,5
0,1
0,0
0,0
0,8
55,3
21,8
0,8
8,3
21,5
1,6
1,3
0,2
0,5
1,1
0,2
13,4
85,1
1,4
215
11. ( % ) (
). ..: , ..: , ..: .
R-4 R-6 R-10 R-11R-12 R-13 R-16R-18 R-19 E.T. M.T. M.O.
T
T A
T B
T-
A
T-
B
- A
- B
TPI
GI
GWI
VI
A
B
C
216
84,4
13,6
0,0
0,0
13,6
88,8
48,8
0,8
0,4
47,6
88,0
37,6
0,8
0,8
36,0
90,0
47,2
0,4
0,4
46,4
91,6
45,6
2,0
0,0
43,6
95,2
38,8
2,0
0,4
36,4
91,2
44,8
0,0
0,4
44,4
87,6
28,0
0,0
0,0
28,0
95,4
42,7
0,0
0,0
42,7
84,4 95,4 90,2

13,6 48,8 38,6
0,0 2,0 0,7
0,0 0,8 0,3
13,6 47,6 37,6
10,8
37,2
28,0
30,8
32,8
30,4
10,6
16,8
15,0
10,6 37,2 23,6
2,4
10,0
7,2
15,2
10,4
4,8
32,6
11,2
26,9
2,4
32,6 13,4
0,4
0,0
67,6
54,4
13,2
3,2
0,0
0,0
3,2
6,0
0,0
0,4
0,4
0,0
1,2
0,0
4,0
9,6
1,6
2,8
0,0
0,0
0,0
5,2
62,3
45,1
0,0
4,4
7,8
3,6
1,4
0,3
0,5
1,2
0,2
17,6
72,8
9,6
0,4
0,0
38,4
12,8
25,6
1,6
0,0
0,0
1,6
9,2
0,8
2,0
1,6
0,0
2,4
0,0
2,4
2,0
1,2
0,0
0,0
0,0
0,0
0,8
35,2
28,0
0,0
1,6
3,1
2,3
0,3
1,3
4,7
1,0
1,2
54,8
43,2
2,0
0,4
0,4
46,4
30,8
15,6
4,0
0,4
0,4
3,2
6,8
1,2
1,2
0,0
0,0
2,0
0,0
2,4
5,2
1,2
0,8
0,8
0,0
0,0
2,4
52,6
39,1
0,2
1,5
9,5
1,3
0,9
0,8
1,5
1,1
0,8
43,2
51,6
5,2
0,0
0,4
42,0
35,6
6,4
0,8
0,0
0,0
0,8
8,8
0,8
0,4
1,2
0,0
3,6
0,0
2,8
1,2
0,0
0,8
0,0
0,0
0,0
0,4
47,9
26,7
0,0
4,0
14,6
1,9
0,8
1,1
1,4
0,7
1,0
50,4
48,4
1,2
0,4
0,0
43,2
35,6
7,6
2,8
0,0
0,0
2,8
7,6
0,0
2,4
0,4
0,0
2,0
0,0
2,8
0,8
0,0
0,0
0,8
0,0
0,0
0,0
48,5
19,6
0,0
4,9
18,4
4,5
1,0
1,1
1,4
0,7
1,0
51,2
48,0
0,8
1,2
0,0
53,2
45,6
7,6
3,2
0,0
0,0
3,2
3,6
0,4
0,8
0,4
0,0
1,6
0,0
0,4
1,2
0,0
0,4
0,0
0,0
0,0
0,8
57,3
36,5
0,0
2,6
15,4
2,4
0,5
0,8
1,0
0,8
0,7
43,6
55,2
1,2
0,6
0,6
43,4
23,2
20,2
3,0
0,2
0,0
2,8
6,8
0,2
1,0
0,8
0,0
1,8
0,0
3,0
2,0
0,2
1,2
0,6
0,0
0,0
0,0
30,9
10,4
1,4
4,6
7,9
4,1
2,6
1,1
2,6
0,8
1,0
49,6
48,4
2,0
0,0
0,0
58,8
49,2
9,6
0,8
0,0
0,0
0,8
9,2
2,4
0,0
0,0
0,0
3,6
0,0
3,2
3,2
0,0
0,0
0,4
0,0
0,0
2,8
59,8
47,9
0,5
1,3
6,6
2,4
1,1
0,5
0,7
0,9
0,4
31,2
65,6
3,2
0,8
0,0
51,9
9,6
42,3
0,8
0,0
0,0
0,8
3,5
0,0
0,8
0,0
0,0
1,5
0,0
1,2
1,2
0,0
0,0
0,4
0,0
0,0
0,8
22,2
8,7
0,3
3,9
7,5
0,6
1,2
0,8
8,0
1,2
0,8
44,2
54,6
1,2
0,0
0,0
38,4
9,6
6,4
0,8
0,0
0,0
0,8
3,5
0,0
0,0
0,0
0,0
1,2
0,0
0,4
0,8
0,0
0,0
0,0
0,0
0,0
0,0
22,2
8,7
0,0
1,3
3,1
0,6
0,3
0,3
0,5
0,7
0,2
17,6
43,2
0,8
1,2
0,6
67,6
54,4
42,3
4,0
0,4
0,4
3,2
9,2
2,4
2,4
1,6
0,0
3,6
0,0
4,0
9,6
1,6
2,8
0,8
0,0
0,0
5,2
62,3
47,9
1,4
4,9
18,4
4,5
2,6
1,3
8,0
1,2
1,2
54,8
72,8
9,6
0,5
0,2
49,4
33,0
16,5
2,2
0,1
0,0
2,1
6,8
0,6
1,0
0,5
0,0
2,2
0,0
2,5
2,9
0,5
0,7
0,3
0,0
0,0
1,5
46,3
29,1
0,3
3,2
10,1
2,6
1,1
0,9
2,4
0,9
0,8
42,9
54,2
2,9
FTIR
1
2-3
4
5
6
7-8
9-10
II
217
218

KL-1
KL-2
KL-3
KL-4
KL-5
KL-7
KL-9
C-O
C=C C
asCH
out-of-plane
C
Absorbance
syCH
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
1. .
C-O
PL-1
PL-2
PL-3
PL-4
PL-5
PL-7
Absorbance
asCH
out-of-plane
C
syCH
000
4000
C=C
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
2. ( ).
219
C-O
PL-9
PL-10
PL-11
PL-12
PL-13
PL-15
C=C
out-of-plane
C
asCH
Absorbance
syCH
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
3. ( ).
C-O
MAR-4
MAR-6
MAR-10
MAR-11
MAR-12
MAR-13
MAR-16
MAR-18
MAR-19
asCH
Absorbance
syCH
4000
000
C=C
3500
3000
2500
2000
1500
out-of-plane
C
1000
Wavenumbers (cm-1)
4. .
220
500
KYP-1
KYP-3
KYP-4
C-O
C=C
out-of-plane
C
Absorbance
asCH
syCH
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
5. .
KOM-3
KOM-7
KOM-9
KOM-13
KOM-14
KOM-15
C-O
C=C
Absorbance
out-of-plane
C
asCH
syCH
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
6. .
221
C-O
PST-2
PST-3
PST-4
PST-5
PST-6
PST-7
PST-8
C=C
4000
000
out-of-plane
C
asCH
Absorbance
syCH
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
7. ( ).
PST-9
PST-10
PST-11
PST-12
PST-13
PST-14
PST-15
C-O
C=C
C
Absorbance
asCH
syCH
4000
000
out-of-plane
C
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
8. ( ).
222
SF-1
SF-2
SF-3
SF-8
SF-10
SF-12
SF-16
C-O
C=C
asCH
Absorbance
out-of-plane
C
syCH
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
9. . ( ).
SF-20
SF-23
SF-25
SF-29
SF-31
SF-35
C-O
C=C
asCH
Absorbance
syCH
out-of-plane
C
4000
000
3500
3000
2500
2000
1500
1000
500
Wavenumbers (cm-1)
10. . ( ).
223
224
IV
1-3
4-6
7-8
9-10
11-12
13-14
15
IV
225
226
5.0E-07
7E-07
Methane
Nitrogen
Carbonmonoxide
4.0E-07
355 oC
KL-1 (0.1 K/min)

460 oC
6E-07
620 oC
3.0E-07
4E-07
295 C
3E-07
2.0E-07
CO [mol/min/g]
CH4, N2 [mol/min/g]
5E-07
2E-07
1.0E-07
790 oC
1E-07
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
1. KL-1 ( 0,1K/min).
2.0E-06
Methane
Nitrogen
Carbon monoxide
KL-1
6E-06
CH4, N2 [mol/min/g]
495 oC
650 oC
5E-06
1.2E-06
4E-06
3E-06
8.0E-07
324 oC
CO [mol/min/g]
1.6E-06
7E-06
378 oC
2E-06
4.0E-07
810 oC
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
2. KL-1 ( 0,5K/min).
227
2.0E-06
7E-06
Methane
Nitrogen
Carbon monoxide
1.6E-06
KL-5
6E-06
647 oC
461 oC
1.2E-06
385 C
4E-06
3E-06
8.0E-07
320 oC
CO [mol/min/g]
CH4, N2 [mol/min/g]
5E-06
2E-06
783 oC
4.0E-07
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
3. KL-5 ( 0,5K/min).
2.0E-06
7.0E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
463 C
6.0E-06
648 oC
CH4, N2 [mol/min/g]
303 oC
5.0E-06
1.2E-06
789 oC
4.0E-06
3.0E-06
8.0E-07
CO, CO2 [mol/min/g]
1.6E-06
SF-1
o
2.0E-06
4.0E-07
1.0E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
4. SF-1 . (
0,5K/min).
228
2.0E-06
7E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
650 C
6E-06
316 oC
462 oC
CH4, N2 [mol/min/g]
791 oC
5E-06
1.2E-06
4E-06
3E-06
8.0E-07
CO, CO2 [mol/min/g]
1.6E-06
SF-20
2E-06
4.0E-07
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
5. SF-20 . (
0,5K/min).
2.0E-05
2.0E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
1.6E-05
640 oC
458 C
CH4, N2 [mol/min/g]
1.8E-05
1.4E-05
1.2E-05
1.2E-06
1.0E-05
8.0E-07
8.0E-06
800 oC
o
730 C
320 oC
6.0E-06
640 C
4.0E-07
CO, CO2 [mol/min/g]
1.6E-06
SF-31
4.0E-06
2.0E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
6. SF-31 . (
0,5K/min).
229
2.0E-06
CH4, N2 [mol/min/g]
1.6E-06
750 oC
607 oC
PL-7
9E-06
318 C
8E-06
7E-06
6E-06
1.2E-06
5E-06
4E-06
8.0E-07
3E-06
CO, CO2 [mol/min/g]
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
1E-05
455 oC
320 oC
4.0E-07
2E-06
607 C
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
7. PL-7 (
0,5K/min).
2.0E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
1.6E-06
464 oC
7E-06
650 oC
PL-11
336 oC
6E-06
800 C
1.2E-06
4E-06
3E-06
8.0E-07
CO, CO2 [mol/min/g]
CH4, N2 [mol/min/g]
5E-06
o
2E-06
4.0E-07
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
8. PL-11 (
0,5K/min).
230
2.0E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
1.2E-05
616 oC
KOM-9
1.0E-05
8.0E-06
1.2E-06
6.0E-06
786 C
309oC
8.0E-07
4.0E-06
CO, CO2 [mol/min/g]
1.6E-06
CH4, N2 [mol/min/g]
471 oC
940 C
4.0E-07
2.0E-06
616 oC
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
9. KOM-9 (
0,5K/min).
2.0E-06
331 oC
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
KOM-15
606 C
6E-06
CH4, N2 [mol/min/g]
780 oC
5E-06
1.2E-06
4E-06
3E-06
8.0E-07
CO, CO2 [mol/min/g]
1.6E-06
7E-06
462 C
2E-06
4.0E-07
606 oC
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
10. KOM-15 (
0,5K/min).
231
2.0E-06
1.2E-05
Methane
Nitrogen
Carbon monoxide
PST-3
464 C
o
618 C
1.0E-05
8.0E-06
1.2E-06
794 oC
6.0E-06
8.0E-07
CO [mol/min/g]
CH4, N2 [mol/min/g]
1.6E-06
4.0E-06
4.0E-07
2.0E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
11. PST-3 (
0,5K/min).
2.0E-06
7E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
6E-06
465 C
605 C
CH4, N2 [mol/min/g]
785 oC
5E-06
304 C
1.2E-06
4E-06
3E-06
8.0E-07
700 oC
CO, CO2 [mol/min/g]
1.6E-06
PST-14
2E-06
597 oC
4.0E-07
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
12. PST-14 (
0,5K/min).
232
2.0E-06
7E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
1.6E-06
MAR-16
o
670 C
6E-06
306 C
1.2E-06
4E-06
3E-06
8.0E-07
665 oC
730 oC
CO, CO2 [mol/min/g]
CH4, N2 [mol/min/g]
5E-06
450 oC
2E-06
790 oC
4.0E-07
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
13. MAR-16 (
0,5K/min).
2.0E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
1.6E-06
7E-06
660 oC
MAR-19
6E-06
1.2E-06
4E-06
309
431 oC
3E-06
8.0E-07
CO, CO2 [mol/min/g]
CH4, N2 [mol/min/g]
5E-06
2E-06
700 oC
4.0E-07
1E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0E+00
1100
Temperature [C]
14. MAR-19 (
0,5K/min).
233
2.0E-05
2.0E-06
Methane
Nitrogen
Carbon monoxide
Carbon dioxide
KYP-1
1.8E-05
1.6E-05
1.4E-05
1.2E-05
1.2E-06
452 oC
1.0E-05
8.0E-06
8.0E-07
750 oC
6.0E-06
640 oC
309 oC
CO, CO2 [mol/min/g]
1.6E-06
CH4, N2 [mol/min/g]
640 oC
4.0E-06
4.0E-07
2.0E-06
0.0E+00
0
100
200
300
400
500
600
700
800
900
1000
0.0E+00
1100
Temperature [C]
15. -1 (
0,5K/min).
234

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2007

Ralf Littke Dr. Bernhard Krooss, Institute of Geology and

Dr. Andreas Lcke Dr. Anne Richter, Institute of Chemistry and

Dr. Peter Svec, Department of Metal Physics, Institute of Physics, Slovac

8,7% 45,5%, 37,2% 58,5%

amounts of carbonate. Maximum CO2 liberation for the samples of W. Macedonia in

(Foscolos et al., 1989, Filippidis and Georgakopoulos, 1992, Filippidis et al.,

) ( .., 1974, .., 1997).

3.3. ( .., 1997).

LEITZ Orthoplan Pol

LEITZ Wetzlar, 50x/0,85oil,

: Al, Ca, Fe, Mg, Si, Ti,

4.2.4. Rock Eval II

(activated copper granulate)

( C) (Solomon and Hamblen, 1983).

(Orem and Finkelman, 2004).

=1,1 (Standards Association of Australia formula), MM: o

5.1. DIN ASTM (Stach

(Brown and Taylor, 1961, Gurba and

5.3. (N) (TOC).

5.4. H/C O/C ( : : ,

Oxygen Index [mg OC/g org.C]

Hydrogen Index [mg HC/g org.C]

5.5. ) (HI) /C, )

(Skorov et al., 2005).

(McCartney and Teichmller, 1972, Goodarzi, 1985, Marchioni,

45,8% maceral . 10,6%

Mukhopadhyay (1986, 1989). ,

5.21. GI TPI . Diessel (1986,

5.3.3.4. Singh and Singh

5.28. Singh and Singh

<100ppm: B, Be, Co, Cu, Mo, V, Y, Zn, , : As, Cd, Sb Pb

PST-14 MAR-16 KYP-1

5.6. Pearson (r)

(Co) Ni (r=0,81) (r=0,87)

(Cu) Mn (r=0,86) Zn (r=0,93),

5.5. Rock Eval II

, Papanicolaou et al. (2000), Iordanidis and

5.5.3. (), () (PI)

Oxygen Index [mg CO2/ g org.C]

Hydrogen Index [mg HC/g org.C]

Hydrogen Index [mg HC/g org.C]

Hydrogen Index (HI)

Mukhopadhyay, 1986, Powell et al., 1991). ,

4000 cm-1 400

(van Krevelen, 1993, Georgakopoulos et al.,

3000 2800 cm-1

Erin and Yrm (2003) 870cm-1, 810cm-1

) (Painter et al., 1978b, Ul Hasan and Bhatti, 1991,

700 400 cm-1

KOM-9ash, PL-7ash SF-20ash.

[15 = -49] (Wada et al., 1981),

5.11. [] [15N vs. air] ,

15N vs. air

5.37. (a) 15 [], (b) N/Corg.

(Carangelo et al., 1987, Obeng and Stock, 1996).

KL-1 [0.1 K/min]

(Reynolds et al., 1991)

5.12. CO2, CH4, CO, N2, H2

5.13. CH4, CO, CO2 N2

CH4 vs total HC generation [%]

CH4 vs total HC generation [%]

Tmax CH4 [oC]

HI [mg HC/g TOC]