SPE 71460
Application of Plasma Technology to Fracture Tight Formations
Muftah El-Naas and Abdulrazag Y. Zekri, United Arab Emirates University
Copyright 2001, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2001 SPE Annual Technical Conference and
Exhibition held in New Orleans, Louisiana, 30 September –3 October 2001.
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstr act submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers is
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
Abstract
Tight formations are normally fractured using different fluids
under high pressure to improve well permeability and
consequently improve productivity. In this paper, a new
sophisticated technique is proposed to treat tight formations,
especially those containing large deposits of heavy oil. The
technique consists of exposing the wellbore to an argon
plasma jet to insure instantaneous and efficient heat transfer to
the surrounding wellbore rocks. The high temperature
associated with the plasma jet changes the basic properties of
the rock resulting in a significant increase in its porosity and
permeability. In this study the effect of high temperature on
the carbonate rock porosity and permeability is investigated.
Limestone rocks were subjected to high temperatures ranging
from 800 to 1200 °C. At temperatures beyond 600 °C, the
carbonate rock decomposes to form calcium oxide and carbon
dioxide. TGA analysis of carbonate samples indicated that the
rate of decomposition at atmospheric pressure depended
mainly on reaction temperature. At low temperatures, the rate
of reaction was so slow that only 5% of the carbonate
converted to calcium oxide in a period of one hour, while at
1000 °C complete conversion was achieved in five minutes.
The changes of the pore structure under different temperatures
were also observed using Scanning Electron Microscope
(SEM). Porosity & permeability analysis of heated carbonate
samples indicated that the porosity and permeability increased
by 100% and 4500 % respectively at 1000 °C.
Introduction
Thermal recovery processes tend to focus on reducing oil
viscosity that results in alleviating the reservoir flow
resistance. Thermal recovery processes used by the oil
industry nowadays falls into two classes: those in which a hot
fluid is injected into the reservoir and those in which heat is
generated within the reservoir itself. Thermal recovery
processes also can be classified as thermal drives or
stimulation treatment. In thermal drives, fluid is injected
continuously to displace the heavy oil toward the production
wells. Thermal stimulation processes decrease resistance to
flow and, thus, allow the driving forces present in the oil
reservoir to increase crude oil production. The reduction in
flow resistance is achieved by heating the reservoir area near
by the wellbore. One mechanism of thermal stimulation is a
reduction in the viscosity of the crude oil and of the water;
reducing the viscosities tends to reduce the flow resistance. A
second mechanism is wellbore cleanup, in which one of the
flowing might occur: clays may be stabilized; the absolute
permeability may be increased by the high temperature,
organic solids near a wellbore may be melted or dissolved, or
fines that could be inhibiting flow may be flushed away.
Thermal stimulation nowadays is the most effective
treatment for heavy oil reservoirs with poor lateral continuity.
Thermal stimulation improves oil production very quickly due
to the fact that its effects are confined to the neighborhood of
the wellbore. The thermal stimulation consists of the following
three categories: hot fluid injection; combustion; and wellbore
heating. In hot fluid injection, steam is injected into the
formation for a few weeks, wait for few days to let the heat
soak in and allow the steam to condense, and then put the well
on production (Hong and Jensen 1; Rivero and Heintz2 ). Other
fluids can be used instead of steam, but non have been found
as effective. A hot water soak was reported by Dietrich and
Willhite3 . In hot water stimulation, a large volume of water is
normally injected per unit of heat and that resulted in higher
water saturation around the wellbore. This can affect the well
producing oil cut significantly. Cyclic steam injection is very
effective in improving the oil recovery. Production response
to cyclic steam is obtained quickly and amount of recovered
oil per amount of steam injected is higher than steam drive.
Combustion is normally used to burn solid organic matter,
stabilize clay, and increase the permeability of formation near
the wellbore of production well. White and Moss 4 reported on
the use of high temperature to stimulate oil recovery. In
wellbore heating, the producing interval is normally heated.
The general practice is to alternate the heating and production
cycles. Thermal conduction countercurrent to the transfer of
heat out of the reservoir by the produced fluids heats
the reservoir.
2 MUFTAH EL-NAAS, ABDULRAZAG Y. ZEKRI
The wellbore usually is heated either by using a gas fired
downhole burner or a downhole electrical heater hanging on
electrical power cable or by circulating fluids heated at the
surface. Albernethy5 proposed to use electrical current as a
source of energy to generate heat. DePriester and Pantaleo6
reported an increase of oil production rate obtained with
downhole gas burner. Chakma et al.7 introduced heat to the
reservoir through electromagnetic heating. They conducted
laboratory experiments on using combination of
electromagnetic heating and gas injection with horizontal
wells. The main objective of Chakma work is to minimize the
heat losses associated with other thermal methods in addition
to lowering heavy oil viscosity and improving overall
recovery. No investigation in the effect of ultra-high
temperature on the rock properties had been reported in the
literature. Wang et al.8 studied the effect of ultra high
temperature on the ceramics. They used ceramic materials to
simulate the effects of sever thermal loading associated with
nuclear fusion reactors and supersonic transport.
In the present study, the effect of ultra-high temperature on
the basic rock properties was investigated. The main purpose
of using ultra-high temperature is to stimulate the area around
the wellbore, and hence improve the permeability. This
technique could be used in the case of tight carbonate
formation instead of other normally used fracturing
techniques. The intensity of heat could be easily controlled
and treatment location could be precisely targeted. The control
of heat will result in controlling the degree of improvement in
permeability. An argon plasma jet is used as the source of
ultra-high temperature to insure instantaneous and efficient
heat transfer to the surrounding wellbore rocks. Controlling
the power input to the plasma torch can control the plasma jet
enthalpy and temperature. In addition, argon plasma is an
inert medium that will not have any detrimental effect on the
surrounding environment.
Plasma can be defined as an ionized gas containing molecules,
atoms, ions, electrons and photons, where the negative and
positive charges are approximately equal making it neutral
overall (Fauchais et al.9 ). Langmuir first used the term “Plasma”
in 1928 to denote gases in the Ionization State. Gases in the
plasma state usually posses’ different chemical and physical
properties, and therefore plasma is sometimes referred as the
fourth state of matter. Plasma can be classified as thermal
(equilibrium) plasma, where the electron temperature is
approximately equal to that of the heavy particles, or non-
thermal (non-equilibrium) plasma, where the electron
temperature is much higher than that of the heavy particles.
Over the past decade, thermal plasma technology has seen
considerable advances and growth both in industrial applications
and in scientific research. This growth is mainly stimulated by
the need of industries for improved and economical
manufacturing methods as well as the need for environmental
friendly processes to comply with environmental regulations that
are becoming more stringent every year. Processes utilizing
thermal plasma technology have several advantages over
conventional ones. The high energy associated with plasma
allows increase production using smaller installations with less
SPE 71460
capital costs. In addition, the use of electrical energy improves
process control by allowing separate control of the thermal input
into the process from its chemistry.
Thermal plasma has been applied to numerous processes,
including spraying, extractive metallurgy, chemical vapour
deposition, thermal decomposition, and synthesis of fine
powders as well as spheroidization and sintering of powders
(Boulos et al.10 ). Several studies have been carried out on the
use of plasma in the pyrolysis of coal (Baumann et al.11 ),
vitrification of nuclear waste (Munz and Chin 12 ), pyrolysis of
medical waste (Camacho13 ), pyrolysis of heavy oil residues (El-
Naas et al.14 ), production of fumed silica (Addona and
Munz15 ), and synthesis of calcium carbide (El-Naas et al.16 ). In
this paper a new application of thermal plasma technology is
proposed. A high-energy inert plasma jet is considered as a
heating source to enhance the porosity and consequently the
permeability of tight rock formations. This paper focuses on the
effect of ultra high temperature on the structure, porosity and
permeability of calcium carbonate rocks. Experimental results
for thermal heating of carbonate rocks through direct exposure to
argon plasma will be published in upcoming paper.
Materials and Methods
Carbonate Samples . Limestone cores, obtained from
outcrops at Hafeet Mountains (Al-Ain, UAE), were used to
prepare calcium carbonate samples for porosity as well as
TGA analysis. For porosity analysis, the carbonate rocks were
cut into six small disks 25.4 mm in diameter and 5 mm in
thickness. Five of these samples were heated separately at a
different temperatures ranging from 800 to 11 00 °C for a
period of one hour to examine the effect of temperature on the
porosity and structure of the samples. After heating, the
samples were removed and placed in a desiccator to cool
down. The sixth sample was kept at room temperature to
determine the initial porosity of the limestone cores. Each
sample was then divided into two parts: one part is used for
porosity analysis using Mercury Porosimetery, and the second
part is used for SEM analysis. Additional cylinderical core
samples were heated seperately at a different temperatures
ranging from 800 to 1100 °C for a period of one hour and
permeability measurments prior and after heating were taken
to assses the effect of heat on the permeabvility of the cores.
Thermogravimetric Analysis. A thermogravimetric analyzer
TGA (Model 7 Berkin Elmer) was used to examine the rate of
decomposition of calcium carbonate at different temperatures.
Small particles of about 10 mg, collected from the limestone
cores described above, were heated in the TGA unit at
temperatures ranging from 650 to 950 °C at atmospheric
pressure and under continuous flow of pure nitrogen.
Scanning Electron Microscope (SEM). SEM was used in
this study to characterize pore size and pore structure of the
calcium carbonate samples prior to and after exposure to ultra-
high temperatures. The SEM generates an electron beam from
SPE 71460 APPLICATION OF PLASMA TECHNOLOGY TO FRACTURE TIGHT FORMATIONS
the electron gun. This beam is focused and illuminated on the
specimen. As the beam is scanned over the specimen surface
in both X and Y directions, secondary electrons backscattered
are detected. Amplifying these electron signals and
modulating their brightness on the observation cathode ray
tube display a specimen image displayed on the cathode
ray tube.
Mercury Porosimetery (MP). The Rusk Universal
Porometer, Model 1053-801, was used to determine the
porosity of the core samples. Cores were subjected to
complete evacuation followed by fillling the void space by
mercury in the entire porometer system. The system pressure
is raised to 5175 kPa (750 psi) to force the mercury to
penetrate the pore space and the pore volume is read directely
on the pore space scale.
Plasma Device. Plasma is usually generated by applying a high
frequency, high voltage electric field to a gas. This can be
achieved through generating devices that have electrodes, which
are characterized by the presence of a cathode and an anode like
plasma arcs or electrodeless devices, which use inductive or
capacitive coupling. There are two types of plasma arcs that are
widely used in the industry and research: transferred arcs and
non-transferred arcs. The plasma device proposed in this paper
will have a non-transferred DC arc, where an electric arc is
created between two water-cooled copper electrodes. The
cylindrical cathode, which has a conical tungsten tip, is
positioned inside a cooper anode. Argon at about 50 liters/min
and 345 kPa (50 psi) is injected between the two electrodes,
where it is heated and ionized by the high temperature arc,
resulting in a high enthalpy plasma jet. The efficiency of these
types of thermal arcs exceeds 85%.
Results and Discussion
Decomposition of Calcium Carbonate. An important factor
in understanding the effect of ultra high temperature on
carbonate rock formation is the decomposition reaction of
calcium carbonate. Although it is not the objective of this
paper to study the kinetics of the reactions of calcium
carbonate, it is essential to examine the decomposition of
calcium carbonate at different temperatures and to investigate
the effect of reaction temperature on the generation of pore
volume within the rock. Calcium carbonate (limestone)
decomposes at atmospheric pressure to form calcium oxide
(quick lime) and carbon dioxide according to the
following reaction:
CaCO3 ↔ CaO + CO2 (1)
Johnston 17 and Mitchell18 determined the equilibrium
temperature at which calcium carbonate dissociates at
atmospheric pressure to be 1171 K. Both the decomposition
temperature and reaction time affect the physical properties of
the formed calcium oxide. A high burning temperature and
3
long calcination time yield a hard-burned quicklime that has
high density and low porosity; whereas a low burning
temperature and short burning duration yield soft-burned lime
with low density and high porosity (Boynton 19 ).
A low burning temperature is the reaction temperature that is
high enough for the Calcination to reach high conversion but
less than the Tammann temperature of the produced calcium
oxide, where the rate of sintering is expected to rise sharply.
Sintering here refers to the phenomenon by which a porous
solid increases its bulk density and hence decreases its
porosity as a result of being held at high temperature. The
Tammann Temperature is usually about 0.4-0.5 times the
melting point in the absolute scale (Szekely et al.20 ). The
melting point of calcium oxide is 3172 K (Barin 21 ) and the
therefore its Tammann Temperature is about 1500 K El-
Naas 22 and El-Naas et al.23 reported that heating calcium oxide
particles in a plasma fluid bed reactor beyond 1373 K resulted
in lowering the porosity of these particles by 22 %.
The change in Gibbs free energy (∆G) for Reaction (1) was
found to be zero at 1170 K, and the reaction approaches
completion at about 1573 KPa. A plot of the equilibrium
composition as a function of temperature for the reaction is
shown in Figure 1. Azbe24 investigated the changes in the
carbonate structure that occur due to calcination at low
burning temperature. He reported that the release of carbon
monoxide during the decomposition reaction results in
creating voids representing about 57% of the solid volume.
This indicates that a calcium carbonate rock can achieve high
porosity and hence high permeability if it is exposed to high
temperatures ranging between 1200 and 1500 K.
An equilibrium analysis has been carried out on calcium
carbonate using HSC Chemistry thermochemical software
(Roine25 ) to determine the equilibrium composition as a
function of temperature for the calcination reaction. The HSC
program uses Gibbs energy minimization to evaluate the
equilibrium composition for any reaction at specific
temperature and pressure. Figure 2 shows the coversion as
function of time for different exposure temperatures. At
temperature of 650 °C, the rate of coversion is quite slow and
it takes 20 mintues to reach a 10% conversion. As indicated in
figure 2 the conversion rate increases drasticaly with
increasing the temperature where 100% conversion is
achieved in less than 2 mintues at 950 °C.
Pore Formation. According to Reaction (1), as the heating
temperature increases the amount of carbon dioxide at
equilibrium increases as shown in Figure 1. This would
clearly indicate that the higher the temperature the more CO2
released and the more voids or pores are created within the
carbonate rock until the reaction reaches completion. One can
then relate the change of porosity of a rock with a volume V
and an initial density ρ to the change in density (∆ρ)
as follows:
4 MUFTAH EL-NAAS, ABDULRAZAG Y. ZEKRI
∆ρ
φ (T ) = φ i + (2)
ρ pressure (P) through the Washburn equation (Washburn 26 :
Where φ(T) is the rock porosity at any temperature and φi is
the initial porosity. Assuming that the rock overall volume V
does change with reaction, the change of density can be
related to the change of mass which is the mass of carbon
dioxide released. Thus, the porosity as a function of
temperature can be written as:
M CO 2
φ (T ) = φi + X (T ) (3)
M CaCO 3
where MCO2 and MCaCO3 are the molecular weights of carbon
dioxide and calcium carbonate respectively. X(T) is the
equilibrium conversion of calcium carbonate to carbon dioxide
at any temperature. Although pressure is not an important
factor for this study since heating is always considered at
atmospheric pressure, the amount of carbon dioxide released
by Reaction (1) can be highly affected by the pressure.
Increasing the pressure would force the reaction to the left,
resulting in less formation of CO2 at any temperature.
The equilibrium conversion X(T), which is obatined by
thermodynamic analysis for Reaction (1), can be related to
temperature by the following equation:
0.98
X (T ) =  T −1168 
(4)
− 
1+ e  65 
Combining Equations 3 and 4, yeilds the following equation
for porosity as a function of temperature:
 
M CO 2  0 . 98  The substantial improvement in permeability is attributed to
φ (T ) = φ i +  T −1168  (5)
−  
M CaCO 3    addition to pore generation. A comparison of the experimental
1 + e  65
 results with predictions by Equation (6) is shown in Figure 5.
Experimental results of porosity analysis of heated limestone
samples samples indicated that the beyond the temperature of
1000 °K, porosity increased more or less linearly with
increasing temperature. Porosity of rock samples increased
from 14.7% @ 25 °C to 30% @ 1000 °C, which is around
100% improvement as a result of heating. A comparison of the
experimental results with predictions by Equation (3) is shown
in Figure 3. Clearly, Equation (3) overestimated the porosity
change with temperature. This can be attributed to the fact
that some calcium carbonate rocks may not react as predicted
thermodynamically and hence less CO2 (less porosity) is
formed at any temperature. Another important factor is that
the experimental measurements did account for all pores
formed. The Mercury Porosimeter used for measurements
could only push the mercury up to 5175 kPa and therefore
SPE 71460
mercury might have not been able to reach fine pores less than
0.02 µm. The pore diameter (D) is related to the applied
4γ cos ϕ
D=− (6)
P
where γ is the surface tension of mercury and φ the solid-
mercury contact angle. This equation is based on the capillary
law and assumes cylindrical pores. The generally accepted
value for γ is 485 dynes/cm and that of the contact angle (ϕ
ϕ ) is
130. A mercury porosimeter that uses high pressure up to 207
MPa (Micromeritics PoreSizer 9320) can push mercury into
pores as small as 0.0066 µm (El-Naas, 1996). The
permeability is related to porosity through the follwing
equation obtained from plotting (k vs. φ ) as shown in
Figure 4 :
k = 0.411e 0.2547φ (7)
Combining Equations 5 and 7, yeilds the following equation
for permeability as a function of temperature:
 
ki M CO 2  0 .98 
+ ∗ 
. 0411 3 . 926 M CaCO  T −1168 
3  −  
k =e +  
 1 e 65

(8)
Experimental results of permeability analysis of heated
limestone samples samples indicated again that the beyond the
temperature of 1000 °K, permeability increased more or less
linearly with increasing temperature. Permeability of rock
samples increased from 1.8 md @ 25 °C to 93 md @ 1000 °C,
which is around 5000% improvement as a result of heating.
the creation of micro-fractures (as shown in Figure 8) in
The differences between experimental and theoretical
estimation of permeability is due to the same phenomena that
affected porosity measurements and was discussed in the
previous section. Carbonate rock consist of fine nonporous
grains closely compacted, micro photo of these grains prior to
ultra-high temperature exposure is shown in Figure 6. As
samples of these rocks exposed to ultra-high temperature,
grain structure started to change due to generation of CO2
according to the reaction presented in equation 1. The
calcinations reaction commence at approximately 650 °C as
can been seen in Figure 1. The rock samples were exposed to
different temperatures of 800, 900, 1000 and 1100 for the
same period of time (60 minutes). Figure 6 shows the effect
of 800 °C on the grains of limestone rock. It can clearly be
seen that pores were generated within each grain, which
confirm the decomposition phenomena. The size and number
SPE 71460 APPLICATION OF PLASMA TECHNOLOGY TO FRACTURE TIGHT FORMATIONS
of generated pores increase with increasing temperature as
shown in Figures 7 & 8. The optimum temperature is around
1000 °C beyond which defragamentation of the rock material
was observed as shown in Figure 9. Exposing of rock to ultra-
high temperatures resulted in creation of micro-fractured in
additional to pore generation as indicated in Figure 6. The
creation of micro-fracture resulted in substantial improvement
in rock permeability. Therefore using plasma to simulate tight
carbonate rock by generating ultra-high heat is a feasible
process. The proposed process has three fold advantages: 1) It
is simple process, does not require complicated equipment. 2)
The process is friendly to the environment since inert gas is
employed in the process. 3) Good control on the degree of
improvements could be obtained based on applied heat
(temperature). 4) No propping agent is requited to keep the
fractures or pores open after the process is completed as the
case with typical current used fracturing techniques.
Conclusions
Ultra -high heat proven to improve the porosity and
permeability of tight carbonates rocks. Porosity &
permeability analysis of heated carbonate samples indicated
that the porosity and permeability increased by 100% and
5000 % respectively at 1000 °C. Plasma is proposed to be
used as ultra-high heat source to stimulate the tight carbonate
rocks. Equations are presented to predict porosity and
permeability as function of ultra-high heat. The process is
environmently friendly and can be applied to oil wells easily.
The proposed process could be applied to tight heavy oil
reservoirs where dual benefits of the process could be
obtained: permeability improvement and viscosity reduction,
that will result in substantial improvements in overall
oil recovery.
Nomenclature
D pore diameter
M molecular weight
P pressure
T temperature, K
X conversion
Greek sympoles
φ porosity
γ surface tension
ϕ contact angle
ρ density
∇ρ change in density
Subscripts
i initial
Acknowledgments
The paper was written as part of a research grant provided by
the Abu Dhabi National Oil Company (ADNOC). We thank
Engineers Ali Dewadar Ibrahim El-Magrahbi, Sami Abdullah
for performing the experimental work.
5
References
1. Hong, K. C., and Jensen, R. B.. 1969. Optimization of
multicycle steam stimulation. Soc. Of Pet. Eng. J.
(Sept.), 357-367.
2. Rivero, R. T., and Heintz, R. C.. 1975. Resteaming time
determination case history of a stem soak well in
Midway Sunset. J. Pet. Tech. (June), 665-671.
3. Dietrich, W. K., and Willhite, G. P.. 1966. Steam soak
results, Cat Canyon Field, Santa Barbara County. Paper
presented at Pet. Industry Conf. on Thermal Oil
Recovery. L.A., Calif. (June).
4. White, P. D., and Moss, J. T.. 1965. High temperature
thermal technique for stimulating oil recovery. J. Pet.
Tech. (Sept.), 1007-1011.
5. Albernethy, E. R.. 1976. Production increase of heavy oil
by electromagnetic heating. J. Cdn. Pet. Tech. (July), 91-
97.
6. DePriester, C. L., and Pantaleo, A. J.. 1963. Well
stimulation by downhole gas-air burner. J. of Pet. Tech.
(Dec.), 1297-1302.
7. Chakma, Amit, Jha, K. N.. 1992. Heavy-oil recovery
from thin pay zones by electromagnetic heating. SPE
24817, presented at the 67th Annual Technical
Conference and Exhibition. Washington D.C. (Oct.) 4-7.
8. Wang, B. L., Han, J. C., Du, S. Y.. 2000. Crack problems
for functionally graded materials under transient thermal
loading. Journal of Thermal Stresses. Vol. 23. pp 143-
168.
9. Fauchais P., Boulos M. and Pfender E., “Physical and
Thermodynamic Properties of Thermal Plasma”, Chapter
3 in Plasma Technology in Metallurgical Processing, Ed.
by Feinman J., Iron and Steel Society, Inc., 1987.
10. Boulos, M. I., P. Fauchais and E. Pfender, Thermal
Plasmas: Fundamentals and Applications. Volume I,
Plenum Press, New York, 1994.
11. Baumann H., Bittner D., Beiers H. -G., Klein J. and
Juntgen H., “Pyrolysis of Coal in Hydrogen and Helium
Plasmas”, Fuel, Vol. 64, No. 8, 1988, PP. 1120 -1123.
12. Munz, R.J. and Chen, G.Q. "Verification of Nuclear
Waste in a Transferred Arc Plasma Melter", J. Nuclear
Mat. 161 , pp. 140-14 (1989).
13. Camacho,S. L., “Plasma Pyrolysis of Medical Waste”
Proceeding of the First International EPRI Plasma Symp.,
1990.
14. EL-Naas, M.H., RJ. Munz and D. Berk, "Pyrolysis of
CANMET Coprocessing Residue in Argon/Hydrogen
Plasma", Canadian Journal of Chemical Engineering,
Vol. 71, pp. 866-872, 1993.
15. Addona, T. and Munz, R.J. "Thermal Plasma Production
of Fumed Silica: The Effect of Quench Conditions on
Thickening and Thixotropic Ability", Can. J. Chem. Eng.
72 pp. 476-483 (1994)
16. EL-Naas, M. H., R. J. Munz and F. Ajersch, “Solid
Phase Synthesis of Calcium Carbide in a Plasma
Reactor”, Plasma Chemistry and Plasma Processing, Vol
18, No 3 (1998), PP. 409- 427.
6 MUFTAH EL-NAAS, ABDULRAZAG Y. ZEKRI SPE 71460

17. Johnston, J., “The Thermal Dissociation of Calcium the equilibrium conversion to CO2 at any temperature and
Carbonate”, J. Am. Chem. Soc., Vol. 32, PP.938-946 pressure through:
(1910).
18. Mitchell, J. , J. Am. Chem. Soc., Vol. 45 (1923) [Cited ′ 3 X (T , P )
N CO 2 (T , P ) = N CaCO (4)
in Boynton, 1980].
19. Boynton, R. S., Chemistry and Technology of Lime and
Limestone, John Wiley & Sons, New York, 1980. Combining Equations (3) and (4) then substituting
20. Szekely, J. , J. W. Evans and H. Y. Sohn, Gas-Solid in Equation (2) yields the following equation for the
Reactions, Academic Press, New York, 1976. porosity as a function of calcination temperature
21. Barin, I., Thermochemical Data of Pure Substances, and pressure.
VCH Verlags Gesellschaft, Weinheim, 1989.
22. EL-Naas, M.H., “ Synthesis of Calcium Carbide in a
M CO 2
Plasma Spout Fluid Bed” Ph.D. Thesis, McGill φ (T , P ) = φ i + X (T , P ) (5)
University, 1996. M CaCO 3
23. EL-Naas, M. H., R. J. Munz and F. Ajersch, “Effect of
Calcium Oxide Structure on the Solid Phase Synthesis
of Calcium Carbide”, The 49th Canadian Chemical
Engineering Conference, Saskatoon, Canada, 1999.
24.Azbe, V. J., “Science and Engineering in Lime-
Burning” Industrial and Engineering Chemistry, Vol.
19, No. 5, 1927.
25 Roine, A., “Outokumpu HSC Chemistry for Windows”,
Ver. 4.1, User’s guide, Outokumpu Research Oy, 2000.
26. Washburn, E. W., "Note on a Method of Determining
the Distribution of Pore Sizes in a Porous Material",
Proc. Nat. Acad. Sci., Vol. 7 (1921) PP 115-116.

Appendix- Porosity as function of conversion

The change in porosity for a piece of calcium carbonate rock
with volume V and initial mass Μ and density ρ can be related
to the change in density as follows:

∆ ρ
φ (T ) = φ i + (1)
ρ
Where φ(T) is the porosity at any temperature and φi is the
initial porosity. The change in density ∆ρ is basically the
change of mass ∆Μ divided by the volume V. Assuming that
the volume of the rock does change with reaction, the porosity
can be written as:

∆Μ ( T )
φ (T ) = φi + (2)
Μ
The change of mass is equivalent to the mass of carbon
dioxide released at any temperature, and it can be related to
the moles of CO2 at equilibrium NCO2 (T) as follows:

∆Μ ( T ) M CO 2 N CO 2 ( T )
= (3)
Μ M CaCO 3 N ′CaCO 3

where M CO2 and M CaCO3 are the molecular weight of carbon

dioxide and calcium carbonate respectively. ′ 3 is the
N CaCO
initial number of moles of calcium carbonate. The number of
moles of carbon dioxide at equilibrium can be easily related to
SPE 71460 APPLICATION OF PLASMA TECHNOLOGY TO FRACTURE TIGHT FORMATIONS 7

1.0
CaCO3
CaO, CO2

Equilibrium Composition
0.8

0.6

0.4

0.2

0.0
600 800 1000 1200 1400 1600

Temperature (K)

Fig. 1- Equilibrium composition as a function of temperature at 1 Bar

1.0

950 C 850 C
0.8
Conversion

0.6

0.4

0.2

650 C

0.0
0 2 4 6 8 10 12 14 16 18 20

Time(min)

Fig. 2- Decomposition of CaCO3 at 1 Bar.

8 MUFTAH EL-NAAS, ABDULRAZAG Y. ZEKRI SPE 71460

0.6

Predicted Porosity
0.5 Experimental Porosity

Porosity
0.4

0.3

0.2

0.1

0.0
200 400 600 800 1000 1200 1400 1600 1800 2000

T e m p e r a t u r e ( K )

Fig. 3- Experimental and theoratical estimation of porosity vs. temperature

35

30
Permeability (mD)

25

20

15

10

0
0 5 10 15 20 25 30

Porosity

Fig. 4- Permeability vs. porosity

SPE 71460 APPLICATION OF PLASMA TECHNOLOGY TO FRACTURE TIGHT FORMATIONS 9

1e+5

Predicted Max Permeability

1e+4

Permeability (mD)
Experimental

1e+3

1e+2

1e+1

1e+0
200 400 600 800 1000 1200 1400 1600 1800 2000

Temperature (K)

Fig. 5- Experimental and theoratical estimation of permeability vs. temperature.

pore

Grain

Fig. 6- Microphoto of the rock sample before heating, T= 25°C. (x= 4000).
10 MUFTAH EL-NAAS, ABDULRAZAG Y. ZEKRI SPE 71460

Fig. 7- Microphotograph of the rock sample after heating, T = 800 °C. (x = 4000).

Fig. 8- Microphotograph of rock sample after heating, T = 900 °C. (x = 4000).

SPE 71460 APPLICATION OF PLASMA TECHNOLOGY TO FRACTURE TIGHT FORMATIONS 11

Fracture

Fig. 9- Microphotograph of rock sample after heating, T = 1000 °C. (x = 4000).

Fig. 10- Microphotograph of rock sample after heating, T = 1100 °C. (x =

4000).