Journal O/Southeast Asian L2trth Sciences, Vol. 5, Nos 1-4, pp. 345-347, 1991 0743-9547/91 $3.00 + 0.

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Printed in Great Britain Pergamon Press plc

Study on the geochemical thermodynamic nature of C O 2 - C H 4 and

CO2 rich gas
QIAN FUWEI

Geological Research Institute, East China Bureau of Petroleum Geology, Yangzhou, Jiangsu,
People's Republic of China

Abstract--A marine Paleozoic CO 2 gas field with of CO2-CHa, CO 2 rich, and other types of gas reservoirs, located
in the Yangtze paraplatform, is taken for a case study. By studying the geochemical and thermodynamic nature
of these reservoirs on the basis of their geologic settings and origins, the phases and thermodynamic equilibrium
conditions have been determined. The results have been used in gas prospecting, resulting in new technical designs
for gas-well testing, and providing theoretical bases for the establishment of new geochemical-thermodynamic
prospecting techniques.

GEOLOGIC FEATURES OF THE GAS characterized by a CO 2 content of 52-78%, higher C H 4

RESERVOIR
THE CASEstudy in this paper is of a marine Paleozoic CO2
gas field of carbonate and detrital rocks, located in
Huangqiao, Taixing county, north Jiangsu. The gas field
is in the Yangtze paraplatform. Its regional structure
comprises a large-scale, overthrust nappe zone. The
marine Paleozoic strata in this gas field are extensive and
are very thick. In the platform facies, the carbonate
rocks are rich and associated with detrital rocks. The
gas-production beds are in the Lower Permian Qixia Fm
(P~q), Upper Carboniferous Tsansan Fm(C3c), Upper
Devonian Wuton Fm(D3w ), Upper Silurian Maosan
Fm(S3m), Mid Silurian Fentou Fm(S2f) and Lower
Ordovician Honghuayuan Fm(O~h). The marine gas-
production beds are Pd, C3c and D3w, which are com-
posed of marine limestones or sandstones. The reservoirs
are in fractured limestones, vugged limestones, fractured
sandstones and pore-fractured sandstones. The con-
trolling factors for CO2 in the gas reservoir are the deep
faults cut by multifaults, and the enclosed blocks. Local
highs (or anticlinal traps) cause the gas to be further
concentrated (Fig. 1).
THE ORIGIN OF THE GAS
Compositions and contents of gas reservoirs
The compositions and contents of each main gas-pro-
duction horizon are listed in Table I. Table 1 shows that
the gas reservoir is divided into two types, based on the
characteristics of gas compositions and contents. The
first type is a CO2 rich gas reservoir, represented by Ptq
l i m e s t o n e , D3w sandstone, and S3m sandstone reservoirs,
and are characterized by their high CO2 content of
over 95% (up to 99.6%) and low contents of hydro-
carbon as well as non-hydrocarbon gases. The other
type is a mixed C O 2 - C H 4 gas reservoir. There are several
S2f sandstone gas reservoirs of this type. They are
content averaging 11.65% (up to 36.3%) which can
burn on ignition and has a higher content of N2
(8.56-16.36%).
Stable carbon isotopic composition
The stable carbon isotopic composition of the gas is
listed in Table 2, which shows that the value of P~q
limestone gas is similar to that of the O3w sandstone
(-3.00 to -3.30%0 P.D.B.), and that of the S2f sand-
stone reservoir has been changed to -5.5%o P.D.B.
Thermal evolution of gas
The average burial depths range from 1800 to 2800 m,
and condensate or light oils have been found in the main
production beds. The measured R0 and calculated R0
from ,,~'3Cco2-Jx0" relationship plots coincide with each
other, ranging from 0.9 to !.9%. 6,3c-~--~CO2 and 6 '3Cc, 4 for
Saf gas samples are -5.50%o P.D.B. and -38.6%o
P.D.B. respectively. Based on the above characteristics
and the abnormally high temperature zone, it can be
concluded that the CO2-CH4 gas and highly rich CO2 gas
reservoirs are at a high maturity level, mainly at the
catagenesis stage.
Origin
Stable carbon isotopic composition and pyrolysis
simulation experiments for carbonate rocks were made
Fig. 1. Structure m a p of a gas reservoir. C)--location for gas well.

345
346 QIAN FUWEI

Table 1. Compositions and contents of each main gas production horizon

Gas composition %
Type of
Horizon gas reservoir CO2 CH4 C2H~- N2 Gravity
Plq Fractured limestone 95.7 3.25 1.515
D 3w Fractured sandstone 97.17 1.061 0.056 2.54 1.513
S 3m Pore-fractured sandstone 96.49 2.020 0.060 1.46 1.510
s~f Pore-fractured sandstone 77.93 11.65 0.730 0.44 1.355

Table 2. Characteristics of stable carbon isotopic composition in The compressibility coeffÉcients for CO2 and the
different reservoirs
CO2-CH4 gas mixture was determined by plotting data
Lithology from P.V.T. testing and using the above equation. The
of gas 6 t3Cco,°/oo Sampling
Horizon reservoirs (P.D.B.) condition dynamic equilibrium of CO2 phases was also determined
by plotting. It is concluded that the critical values of
P~q Limestone -3.30 Moving gases in
testing process temperature, pressure and specific volume are 31.1°C
D~ w Sandstone - 3.00 Moving gases in (abs.), 75.28 atm. (abs), and 0.002 m 3kg -m, respectively.
testing process When the conditions of CO2 in the gas well surpass the
Sj Sandstone --5.50 Moving gases in
testing process critical points, the CO2 cannot be liquidized, and remains
in the gas phase. In order to have normal production, it
is therefore necessary to keep the temperature above
and the results shown in Table 3 and Fig. 2. These results
indicate that marine Paleozoic CO2 gas reservoirs are (a)
mainly of an inorganic complex origin; (b) composed of
pyrolysis gas sources related to marine carbonate rocks
and deep gas sources related to magma activities; and (c) B. 9nO*(
associated with hydrocarbons and non-hydrocarbons 24

formed by the pyrolysis of kerogens in source rocks.

I0"(
12 10*C
PHASES AND THERMODYNAMIC o

EQUILIBRIUM C ~)*C
nn
In the dynamic equilibrium system for COz-HzO a 10*C
13..
phases under various temperatures and pressures, the 0
¢,1
,12
~J
CO2 phase undergoes complicated changes, while the (.9
change in the water phase is relatively simple.
Based on the thermodynamic nature of CO2 gas the -12
gas equation is

PV=0.0815 z M
-24
where

P = gas pressure (Kg cm 2 abs.)

V = g a s v o l u m e ( m 3) -36
Z = compressibility coefficient
M = w e i g h t o f g a s (kg) -90 -60 -30 0
u = g a s m o l e c u l a r w e i g h t ( C O , m o l e = 4 4 g) 813 CcH4(PDB) • O,'oo
T = gas temperature (K abs.)
Fig. 2.6 t3Cco., vs 6 ~3Ccn, plot. (I---CH 4 and CO2 zone from mantle and
CO2 g a s c o n s t a n t CO, zone from mantle; II--biogenetic CH4 and CO2; III---CH4 and
CO2 from organic metamorphism; 0 - - 6 ~C value from CO2 gas well
= 0.0815 atm pressure m 3 kg ~ m o l - ~ " C - ~. in Fentou Fm, Middle Silurian.)

Table 3. 6 ~3r
~C02 ranges for different origins
3 ~3C%o Primitic carbon Origin of CO 2
< -30 Organic carbon (1) Coalification products of organism
(2) Not enough micro-organisms of CH 4 bacteria
- 30 to - 22 Terrestrial organism Burning of plants and coals
- 7 Young magma Activities of basic magma (?)
2 to + 2
- Marine Pyrolysis of marine limestone
- 10 to + 10 Organic origin Micro-organisms associated with enough CH4
(After Stahl 1971).
 Geochemical thermodynamic nature of CO2-CH 4
31.1°C (abs.). If the temperature is lower than 31°C, the
pressure must be lowered, to gasify the CO2. Hence, a
key problem was resolved.
Testing reveals that thermodynamic indices, such as
compressibility coefficient, change regularly. The data
provided important indices for evaluating CO2 gas
resources and calculating gas reserves under both static
and flow state conditions. The study of geochemical
and thermodynamic natures of the gas reservoir
therefore provides a theoretical basis for geochemical-
thermodynamic prospecting methods.
GEOCHEMICAL-THERMODYNAMIC
PROSPECTING METHOD
A new prospecting method based on the application
of geochemical thermodynamics has been developed.
Geochemical-thermodynamic surveys accompanied by
geologic surveys have been conducted. Maps such as the
composite abnormal geochemical map, the geothermal
gradient contours map, and maps of magma and fault
distribution were plotted. Based on these maps, abnor-
mal zones such as abnormal hydrocarbon zone and
abnormal CO,, and rare gases zones, associated with
abnormal geothermal zones, were found.
By means of the study of abnormal geochemi-
cal-thermodynamic zones, the exploration design was
determined. In the overthrust-nappe zone, adjacent to
the deep fault side, within the NE-trending high
block-anticline zone, the geochemical abnormality was
found to coincide with the abnormal higher geothermal
gradient zone, and this zone has now become a major
area for exploration. By selecting the best local traps
347
associated with the above local abnormal features, gas
reservoirs were discovered. Thus, a new prospecting
technique--monostage controlled flowing process was
developed and the multistage controlled flowing process
was improved during the CO2 gas well testing to avoid
formation of an ice block inside and outside the gas pipe.
The advantages of this method include the ability to
maintain stable pressures, to gasify the CO2 under a
stable temperature and a lower pressure, to make the gas
flow in monophase (gas phase) with a low friction factor
and to eliminate the ice block problem inside and outside
the pipes. It is favourable to take readings of
temperature, pressure and amounts of gas, water and oil
accurately and they can be used in various gas wells of
different production capacities.
During the early survey stage, a quantitative method
is now available for evaluating the CO2 gas reserves
based on the high content of CO: and CO2-CH4 gas
reservoirs. The application of a CO2 phase plot of a gas
reservoir and a plot of CO2 compressibility coefficient
will make the calculation more practical and accurate.
CONCLUSIONS
With the development of prospecting, the information
for both static and flow states of gas reservoirs can be
obtained. Geologic, geochemical and thermodynamic
indices can be used to establish mathematical and
geochemical-thermodynamic discriminating models for
finding natural gas reservoirs more rapidly and
effectively.
Acknowledgement--The author is especially grateful to the co-
operation of Gao Huanzhangin this study.