SPE 86549
Periodic Effect of Pressure and Temperature on Flow Phenomena in Porous Media
I. Lakatos, SPE, J. Tóth, J. Lakatos-Szabó, and B.H. Rayes, SPE, Research Institute of Applied Chemistry, U. Miskolc,
and M. Hlatki, and Á. Vágó, Hungarian Oil and Gas Co., Upstream Division, Szolnok, Hungary
Copyright 2004, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium and Exhibition
on Formation Damage Control held in Lafayette, Louisiana, U.S.A., 18–20 February 2004.
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Abstract
The paper deals with the effect of pressure and temperature
fluctuation characteristic in underground gas storage facilities
on gas permeability of natural sandstone cores. Primary aim of
the laboratory studies was to develop an appropriate method
which might simultaneously restrict water imbibition and
improve rock stability in vicinity of both producing and
injection gas wells. The hypothetical method is based on
hydrophobization of rock surface by different silicone
compounds and asphaltenes or asphaltene-containing natural
hydrocarbons. The paper provides new information for
behavior of treated and non-treated cores, particularly for their
gas permeability as a function of cycle number, absolute gas
permeability and type of treating agents. It is also
demonstrated that water content (saturation) of the porous
media fundamentally influences the adsorption of asphaltenes,
and hence, the efficiency of hydrophobization, wettability
alteration. Despite substantial progress in the topic, some
questions remained open and these “white spots” must be
answered if a reliable and efficient well treatment methods
should be developed for stabilization of gas wells operating in
gas fields and underground gas storage facilities.
Introduction
During the operation of gas wells the disintegration of
reservoir rocks leading to accumulation and production of
sand is a frequently observed phenomena. That problem has
got to the forefront of attention over many years since the sand
formation might be detrimental not only from technical, but
economic points of view because it may seriously influence
the storage capacity, gas deliverability, injectivity, produc-
ibility, and hence, the cost of operation. Therefore, recognition
of sand formation in prematured state and its inhibition are
fundamental in optimization of technology maximizing thus
the cash-flow at gas fields and underground gas storage
facilities. The importance of such activity and preventive
actions well demonstrated by a general survey in 1993 which
has shown that roughly 5 % of gas deliverability has been
annually lost in the USA on account of sand formation in gas
wells and all probability this figure is underestimating the real
damage at wider industrial scale. Converging experimental
results and practical observation prove that the detrimental
effect of pressure and temperature fluctuation are in the
background of pheanomena1,2.
The underground gas storage systems are mostly in
sandstone formation not only worldwide, but also in Hungary.
These storage systems were originally gas fields operating
with active water encroachment. Majority of gas wells have
double functions, viz. they are used for both injection and
production. Consequently, the pressure and temperature are
changing in a measurable extend through the cycle: the
pressure and the temperature are fluctuating on average by 40-
60 bar and 20-30 °C, respectively. In addition, the vapor
content of the injected/produced gas is not constant either and
the flow direction of the gas is also annually diverted. Thus, it
is evident that these periodic effects often evoke rock fatigue
which appears as sand formation. According to the Hungarian
field experiences the sand formation appears to cause
detrimental impacts on well performance after 15-20 years of
continuous operation. Henceforward, however, the severe
effect of cyclic pressure and temperature fluctuation is
accelerating which is accompanied by substantial surplus cost
in well maintenance. In case of wells located at the rim of the
storage system these problems are indicated even earlier on
account of more extensive water fingering, frontal break-
through and unfavorable geological, lithological formation
conditions.
Restriction or prevention of formation damage in gas wells
has outstanding importance in practice. Therefore, it is easy to
understand why so many papers and efforts had been focused
on mitigation of the lost injectivity, producibility,
deliverability etc. problems during the past decades. Although
physical methods, like bottom-hole filters, liners may
temporarily ease the difficulties, the real and long-lasting
solutions were mainly searched in direction of chemical
treatments. These methods are based on creation of chemically
bound films over pore surface which might prevent
disintegration of minerals (mostly clays) and migration of
mobile fines3,4. The polymer films, simply adsorbed, in-situ
cross-linked or polymerized on surface, can be quite different
in chemical nature, but their effect must be beneficial for the
well performance.
2 SPE 86549
The present laboratory studies are based on the fact that
hydrophobization of the vicinity of gas wells by asphaltenes
can be beneficial for both the hydrodynamic processes
hampering the spontaneous water imbibition and the
stabilization of the clay minerals minimizing the extend of
swelling/shrinking interactions. Taking the otherwise
detrimental effects of asphaltene adsorption, precipitation in
oil bearing formations into account a hypothetical idea was
studied which is based on injection of asphaltene-containing
solution into the gas wells with the aim at improving the well
performance and hence, lowering the maintenance and
operation cost. Therefor the paper gives an overview of the
detailed laboratory study of adsorption and asphaltene-rich
materials derived from different sources, then the effect of
periodic pressure and temperature will be discussed using the
original and the asphaltene treated sandstone cores. Finally,
the potential of such treatments is outlined critically evaluating
the obtained results and experimental observations.
Results and discussion
Adsorption of asphaltenes on reservoir rocks. In recent pa-
pers5,6 a detailed comparative study of asphaltenes adsorption
on reservoir rocks was reported. The laboratory measurements
were extended to different n-pentane asphaltenes precipitated
from crude oils, dist. residues and solid materials precipitated
in stock tanks (Table 1). A crushed reservoir rock (Algyő
field, Hungary) in its original form and enriched then by
montmorillonite and calcite were used as basic adsorbents.
Pure clay and calcite were also applied as models. The ad-
sorption tests were performed under static (batch type) and
dynamic (column elution) conditions. Dependence of the ad-
sorption loss on concentration was described by the Tóth’s
isotherm. The main conclusions of the measurements and the
asphaltene adsorption/retention listed in Table 2 can be sum-
marized as follows:
1. The basic trends of the asphaltenes adsorption were
similar in all cases, but the highest adsorption loss was
measured for the asphaltene precipitated from the heavy
oil, while the least one for the asphaltene obtained from
the ultra light oil. Generally, however, the adsorption of
asphaltenes, independently of their origin, was in the
same range and close to each other.
2. The least adsorbed amount was measured on pure calcite,
the values were between 1 and 2 mg/g in all cases. As
expected, the calcite-rich formation rock adsorbed less
asphaltene than the original formation rock did. These
observation can be attributed to the solid, crystalline
structure and hence, the smaller specific surface area of
calcite. The surface energy and surface charge density of
this mineral might also play, however, fundamental role
in weaker ionic interaction between the asphaltenes and
the rock.
3. The highest adsorption was found on montmorillonite.
The extremely high adsorption capacity of clay minerals
can be explained partly by the high specific surface area,
ionic character of surface and partly by mechanical
penetration of asphaltene particles (molecules) into the
layered structure of clays, etc.
4. Since the montmorillonite adsorbs much more asphaltenes
as any other minerals, the clay rich adsorbent retains also
more asphaltene as the original formation rock.
5. These experimental results are fully converging with
those observation which are mentioned in literature. The
only new finding might be that some isotherms,
particularly those ones which were obtained on calcite,
may show an inversion (negative adsorption) phenomena.
This is accepted as a weak indication of a competitive
adsorption process.
6. In the low concentration range the measured data could be
described correctly with the Tóth’s isotherm. The only
exception was the adsorption of asphaltene precipitated
form an ultra-light oil on pure calcite. The inconsistency
of that case can also be attributed to a competitive
adsorption process over 0.3 mg/ml asphaltene concentra-
tion.
7. According to the interaction parameter of the Tóth’s
isotherm we could detect a strong intermolecular
interaction among the molecules in the adsorbed layer.
Namely, we may state that strong asphaltene−solid
surface interaction is in the background of the sorption
phenomena when the rock contains high amount of
montmorillonite or calcite. However, the silicate type
formation rocks (e.g. low clay-containing sandstones)
weakly adsorb the asphaltenes and the adsorbed layer, if
forms anyway, can easily be removed or desorbed under
certain conditions.
8. The above mentioned observations and conclusions might
be crucial in respect to the efficiency of wettability
alteration by asphaltene adsorption. As reported in
literature, the carbonate or dolomite type reservoir rocks
rapidly lose their native water-wet character and become
oil-wet in contact with oils, while sandstones with high
silicate contents remain water-wet or intermedier
character even after long oil/rock contact.
9. Comparing the “dynamic adsorbed amounts” with the
static and the theoretically calculated values we may
conclude that a good agreement exists among the data and
the basic trends are also supported by these results.
10. In certain cases slight curve inversion was observed. The
curve inversion is a direct consequence of an experimental
fact: in the final period of the measurements the effluent
solution contained more asphaltene than the original
solution added to the top of the column. Since the excess
amount of asphaltene in the effluent may derive only from
desorption (of the previously adsorbed asphaltenes), the
cumulative curves start slightly to decline. From physico
chemical point of view the phenomena are classified as
“negative adsorption”.
11. The existence of even a slight competitive adsorption in
asphaltene/rock or crude oil/rock systems has far reaching
effects and consequences. First, we may firmly suspect
that the adsorbed layer is of composite character: the
interface consists of different molecules, aggregates,
particles which are bound to the surface by diverse
interaction forces. Second, the composition of the
adsorbed layer significantly depends on the type of oils,
SPE 86549
rocks, asphaltenes, etc. Now we have to add, as a new
aspect, that the character of the interfacial layer, and
hence the wettability is also depending on the amount of
asphaltene contacted with the solid material even in case
of the same oil or asphaltene.
The static and dynamic adsorption tests didn’t provide
adequate answer for the effect of the water content of
adsorbent which might be fundamental under reservoir
conditions if asphaltenes are used for bottom hole
hydrophobization. Therefore, a special test series were carried
out with the aim at elucidating the role of mobile and residual
water saturation in non-consolidated porous media. The
dynamic tests were performed as earlier, however, additional
adsorbent parameters were measured to enhance the
explanations. Thus, the laboratory studies were performed
using the following experimental conditions:
Adsorbent type : crushed reservoir rock
particle size : 0.2-30.0 µm
specific surface : 466 cm2/g
weight : 15 g
Water content : 0.1-8.0 cm3
saturation : 1.25-3.12-6.25-12.5-100 %
Asphaltene : precipitated for heavy oil
Asphaltene solution : 0.5 g/l in toluene
The cumulative adsorbed amount (absolute weight of
asphaltene retained by the adsorbent under dynamic
conditions) obtained on different water-containing adsorbent
are shown in Fig. 1. As expected, the asphaltene adsorption
strongly depends on water content and this predominant effect
is characteristic already in range of the low water saturation.
In Fig. 2 the cumulative adsorbed amount is plotted as a
function of the absolute water content and it is clear from this
curve that over 1 g water content in 15 g reservoir rock the
adsorbed asphaltene amount reduced practically to zero. More
convincing conclusions can be drawn by transformation (re-
calculation) of the primary data:
1. The specific asphaltene adsorption decreased by 95 % in
range of water saturation of 0-12.5 % (see Fig. 3).
2. More general message of the phenomena is that the
adsorbed amount calculated for unity of surface (84
mg/m2) in water-free system drops to less than 10 mg/m2
if the water saturation in the porous system increases up
to 12.5 % (Fig. 4).
3. By the specific surface area of the adsorbent the total
surface of the model could be calculated. Thus, the
average thickness of the water film over the adsorbent
surface can also be obtained. Plotting the specific
adsorbed asphaltene mount as a function of that film
thickness the curve in Fig. 5 characterize the sorption
barrier or penetration efficiency of asphaltene molecules
(aggregates) into aqueous phase. As shown, the
asphaltenes are not able to reach the rock surface if the
water film is thicker than some hundreds (300-500) nm.
4. On the basis of the mentioned experimental findings we
may definitely predict that contacting of asphaltenes or
asphaltene-containing solutions with reservoir rocks the
3
wettability alteration becomes highly questionable if the
surface is partially or fully covered by water films.
Consequently, in originally water-wet porous systems,
where the residual water saturation is usually exceeding
10-15 %, any dynamic treating techniques aimed at
modification of wetting properties might be questionable
and inefficient.
The last conclusions forecast an uncertainty for relative
permeability and capillary pressure measurements where the
treatment of cores were carried out by injection of asphaltene-
containing toluene and aromatic organic solvents. Similar
results have been obtained by different silicone compounds
which were detailed in two earlier papers9, 10. This inadequate
method was, however, justified by the native character and the
practice of gas fields.
Effect of asphaltene adsorption on wettability. The wet-
tability of a smooth carbonate rock having homogeneous and
heterogeneous surface were used as a model material for
evaluation of the asphaltene treatments. First the contact angle
of water on carefully cleaned rock plates was determined as a
function of time. After this step the same plates were im-
mersed into asphaltene containing toluene solutions for 24 h.
The treated rock plates were then rinsed with solvent and dried
at 80 °C in vacuum oven. In a parallel test the treatment was
carried out with a solution which contained not asphaltene but
the original oil in the same concentration. Results of the wet-
tability tests are detailed in Refs 5 and 6 and the main conclu-
sions drawn by the experimental results can be summarized as
follows:
1. Equilibrium contact angles on both heterogeneous and
homogeneous surfaces were set after 10 min in all cases.
2. The contact angle on heterogeneous surfaces was always
higher than those measured on homogeneous surfaces.
The difference between the values, characteristic on
untreated surfaces, is around 30°.
3. Treating the rock plates by asphaltene solutions the
contact angle increased to 120° and that change did not
depend on type of asphaltenes. Namely, the asphaltenes
from a heavy and a light oils, and even from dist. residue
and stock tank precipitate, were equally effective in
wettability alteration.
4. It is worth mentioning that the native difference of
homogeneous and heterogeneous surface was also
suppressed by the asphaltene adsorption. Namely, the
surface character of the treated rocks became completely
asphaltene dependent.
5. Using an oil solution as a treating agent only the heavy oil
proved to be effective. In this case the degree of
wettability alteration was nearly the same as in case of the
asphaltene solution. This is attributed to the extremely
high asphaltene content of the oil. Basically similar results
were obtained for the medium oil, dist. residue and stock
tank precipitate.
6. The ultra-light oil in toluene solution was not effective at
all either of the homogeneous nor the heterogeneous rock.
That experimental finding is explained by its very low
asphaltene concentration.
4 SPE 86549
7. The results of representative measurements carried out by
asphaltene solutions prepared by mixture of aromatic
solvents (refinery by-product, aromatol) were identical.
The mentioned conclusions might be important in
technological utilization of asphaltenes or asphaltene-contain-
ing solutions for wettability alteration.
Effect of asphaltene adsorption on hydrodynamic proper-
ties. The absolute, effective, relative and normalized relative
permeability of cores were determined with the aim at charac-
terizing the flow properties of water and gas in the original
and the asphaltene treated cores. In the present case the so
called “displacement” type procedure developed by Tóth et
al.7,8 was applied. The absolute permeability of cores was de-
termined by nitrogen using the Klinkenberg’s technique. The
protocol and sequence of relative permeability measurements
jointly with other experimental conditions are described in an
earlier paper5.
The treatment method may influence significantly the final
results. The dynamic treatment procedure is probably close to
the reality met under field conditions, however, at present we
wanted to overemphasis the effects of asphaltene treatment.
Therefore, such a method was applied which resulted in an
immense and full contact between the core surface and the
asphaltene compounds. Since the vacuum saturation
corresponds best to the mentioned requirements, that
procedure technique was used without controlling residual
water saturation after drying the core overnight in a vacuum
oven at 70 °C. On the basis of experimental data obtained by
the effect of asphaltene adsorption on relative permeability
changes the following important conclusions were drawn:
1. Effect of asphaltene treatment on porosity is negligible.
The data obtained by He-porosimetry and water saturation
measurements show, however, opposite tendency: higher
porosity was measured by the former method, while lower
values were obtained by the latter procedure. The 1.5-2.7
% increase in porosity registered by He-porosimetry is
attributed to removal of some toluene-soluble organic
matter from the core during the treatment. In the other
case the 4.5-6.8 % increase in porosity is traced back to
changes of the capillary forces (wettability alteration) and
partial blocking of the smallest pore throats by the large
asphaltene molecules and aggregates. These experimental
observations suggest that flowing crude oils or solutions
having high asphaltene content through the core the
adsorption and entrapment of asphaltenes might
significantly decrease the accessible pore volume in low
permeable porous systems.
2. The absolute gas permeability of cores decreased by 12-
35 % after asphaltene treatments. Parallel with this change
the Klinkenberg constant multiplied and became more
uniform among the cores than it was before treatment. On
the basis of these experimental findings we may get to a
conclusion that the smallest pores and capillaries were
really blocked, and as a result, the average pore size
increased, meanwhile the tortuosity and the free flow
cross-section decreased after asphaltene treatment.
3. The impact of asphaltene treatment on effective water
permeability is controversial: the permeability often
increased, but in some cases decreased in treated cores. At
the moment, the number of experiments is not enough to
draw statistically correct conclusion in this respect.
Despite these deficiency we may accept as a fact that the
asphaltene treatment may result in both positive and
negative modification in effective water permeability.
Since the effective permeability of different fluids is a
resultant property determined jointly by the effective
porosity, number and size of pores and capillaries,
tortuosity, wettability, friction forces, local vortex
formation, etc. and these parameters might be influenced
in different extend and directions by asphaltene sorption
and entrapment, the final outcome of the treatment is hard
to predict and neither the positive, nor the negative
consequences can be excluded.
4. Evaluation of water saturation data obtained before and
after asphaltene treatments clearly indicated a
hydrophobization effect in all cores . In general, the
residual saturation measured after gas injection decreased
by 4-6 %. On the other hand, the residual gas saturation or
maximal water saturation at the end of water injection
seemed to be increased a little, but rather we may say that
the values are close to 100 % and the change is within the
relative standard deviation of measurements.
5. The relative permeability curves, presented in Figs 6-9 as
characteristic examples, support the earlier statements.
The curves obtained after treatment and in drainage
direction may run either below or above the original ones,
and as proved in Figs 6 and 8, or they even can intersect
each other. Thus, the asphaltene treatment may have both
positive and negative effect on relative gas permeability
depending on the core structure and fluid saturation. The
reasons and explanations of that behavior are the same as
mentioned in respect to the effective water permeability in
the previous paragraph.
6. The normalized relative permeability curves shown in
Figs 7 and 9 reflect similar behavior as the original ones
do. Since the curves are not coinciding we may suspect
that the actual flow path of gas and water in cores are
different in the original and the treated cores. Once again,
the reasons must be searched in the hydrophobization and
its consequences, namely modifications in porosity,
tortuosity, capillary forces, etc.
The practical message of these experimental results is that
the water production in gas wells might be restricted by
hydrophobization (e.g. asphaltene treatment) only until water
break-through retarding thus the spontaneous imbibition
process. After water break-through, particularly at high water
saturation, however, the effect is doubtful and hard to predict:
the relative gas permeability might be higher, lower or even
equal compared to the values characteristic the native, water-
wet porous cores.
Effect of asphaltene adsorption on capillary pressure. In
the present research program the centrifugal methods were
routinely used. Here only two representative examples of the
serial measurements are presented which well demonstrate the
effect of asphaltene treatment on capillary pressure curves.
The cores were the same as those used in the relative perme-
SPE 86549
ability measurements and similar methods were applied to
characterize the pore structure, porosity, absolute and relative
permeability, etc. Unfortunately, evaluation of the primary
data and interpretation of capillary pressure curves obtained by
centrifugal technique under reservoir condition often face with
serious problems. One of the crucial difficulties hard to over-
come is that the measurements are made on small core sam-
ples which represent only an extremely small part of the reser-
voir. Therefore, the so called J-function was also used for
characterization of the effect of asphaltene adsorption on cap-
illary properties of rock before and after the treatment. The
main conclusions of the capillary pressure measurements can
be summarized as follows:
1. Both the normal and the normalized J function curves run
below the original ones after asphaltene treatment (Figs
10-13). At low water saturation the curves may intersect
each other, however, they are practically approaching the
same limiting residual values. Thus, the effective
hydrophobization could not be predicted by the residual
water saturation and this fact apparently contradict to the
conclusions which might be drawn by the modification of
capillary and threshold pressure data. The phenomena are
explained by the small size and end effect of cores and the
native properties of the centrifugal technique.
2. After asphaltene treatment the threshold pressure
considerably decreased: 7-19 % fall was indicated by the
normal capillary pressure curves , meanwhile 31-41 %
reduction was calculated by the normalized J functions.
These experimental results definitely indicate a strong
hydrophobization after treatment not only in the initial
period of water drainage by gas, but through almost the
whole process (down to 30 % water saturation which is
close to the residual value).
3. Although the capillary pressure curves fall very close to
each other, the difference of water saturation belonging to
constant capillary pressure and J values is remarkable. As
shown in Figs 14 and 15 that difference rapidly decreases
with the capillary pressure and reaches zero as the
drainage gets to the final stage. Anyhow, the asphaltene
adsorption resulted in an accelerated water drainage in
both cores, or in other words, identical water saturation
could be obtained at lower capillary pressure after
asphaltene treatment.
On the basis of the capillary pressure measurements we
may outline further beneficial effect of asphaltene (and
silicone9,10) treatments in gas/water systems or gas production.
Supposing that water coning is responsible for high water
production in gas wells, not only the water imbibition (rapid
water cone development) can be restricted after
hydrophobization, but retreat of cone, if it already exists, is
also accelerated under the effect of gravitational forces in the
rest (shut-in) period. The new experimental findings discussed
here unambiguously proved the earlier theoretical
considerations and conclusions which suggested a capillary
depression or negative capillary forces when asphaltenes
adsorbed and precipitated in formation cores and rocks. Now,
we have to add: the phenomena may have not only detrimental
but sometimes beneficial effect on production characteristics,
5
particularly when the phenomenon is deliberately utilized as a
basis of a technology in oil/gas production.
Effect of cyclic pressure and temperature fluctuation on
permeability and rock stability of sandstone cores. As men-
tioned previously fundamental goal of the present study was
the evaluation of pressure, temperature and vapor content fluc-
tuation on permeability of natural sandstone cores. Since the
vapor content of gas had negligible effect on the measured pa-
rameters only the simultaneous pressure and temperature
changes were tested systematically. The porosity of the origi-
nal cores was in the range of 0.14-0.28, while the permeability
varied between wide, 1 and 120 mD limits. The geometrical
parameters of the models were practically identical (diameter:
3.7 cm, length: 7 cm). Hassler mounting was applied in all
cases. The prepared cores were placed into a temperature-
controlled air chamber (thermostate). Parallel tests were per-
formed with a non-treated and a treated core selected by their
absolute permeability. First, the absolute gas permeability of
cores was determined at 25 °C using 2.78-27.8 volumetric gas
rates. The cycle upper and lower limits were 80 bar, 100 °C
and 30 bar, 50 °C. Consecutively 10 cycles were measured
maintaining the setting first the new pressure and then the
temperature limit. Conditioning of the cores lasted 24 h at
each limits. Thus, a full test program was carried our through
nearly one month (minimum 20 days) if the core was not dete-
riorated earlier. The final step of the experiment was depres-
surizing and cooling of the core to ambient temperature and
repeated measurement of the gas permeability. The linearized
Forchheimer equation was used for evaluation of the experi-
mental results and determination of a and b constants:
p12 − p 22 = aq g + bq g2
p12 − p 22
= a + bq g
qg
From a the gas permeability characteristic at average flow
pressure was obtained by the following relationship:
l ⋅ µ g ⋅ pg 1
kg = ⋅
A a
This gas permeability was compared to the original value
obtained at ambient conditions (zero cycle). This relative
value is expressed in percentage on the vertical axes of
figures. In Figs 16-22 the odd cycle numbers represent the
upper limit (80 bar and 100 °C). If the cycle number is less
than 20, the core was severely damaged as a result of the
pressure and temperature fluctuation. Since the sequence of
measurements were defined earlier and the research program
lasted nearly two years, the presented results are not grouped
in a logical line, viz. the figures contain the parallel tests. The
treatment methods and the absolute gas permeability of cores
are listed in Table 3, but the applied treating agents are also
indicated in the caption of the figures. On the basis of the
experimental findings the following conclusions were drawn:
1. Generally, the gas permeability of cores, independently of
the treating agent (and also in case of non-treated cores),
is much lower at 80 bar and 100 °C than the values
6 SPE 86549
obtained at ambient conditions. The difference is
apparently permeability dependent: in case of low
permeable cores the reduction of gas permeability may
exceed the 90 %, while for medium and high permeability
cores the difference is between 40 and 60 %.
2. Comparing the gas permeabilities obtained at the upper
and the lower pressure and temperature limits a
systematic difference was found in all cases: the gas
permeability characteristic at 30 bar and 50 °C, similarly
as the values obtained at ambient conditions, is always
higher than those values which were measured at 80 bar
and 100 °C. These phenomena is attributed to the
compaction effect (elastic properties, thermal expansion
of cores) induced by the high pressure and temperature.
3. As the number of cycles is increasing the amplitude of the
gas permeability changes is gradually decreasing. This
tendency indicates certain stabilization of the core
structure, flow path, accessible pore volume, tortuosity,
etc. Parallel with this positive consequences of cyclic
pressure and temperature effects the average gas
permeability slightly decreases with the cycle number.
We may say that flow of gas (or any fluids) through the
porous cores becomes “smooth” and less sensitive to
external conditions after a given number of extreme
structure modifying effects. The damage cores, however,
represent exceptions of that behavior: the gas permeability
usually has shown hectic fluctuation and the average
values rather increased instead of the decreasing tendency
as the test went on.
4. According to the statistical data 4 cores were not treated,
4 cores treated with different silicone compounds, 3 cores
with heavy oil, 1-1 core with asphaltene form heavy oil,
dist. residue and stock tank precipitate. On account of
core damage the tests were terminated at the following
cycle numbers:
8. cycle : 2 cores (all silicone)
13. cycle : 4 cores (2 silicone, 1-1 heavy oil and non)
15. cycle : 2 cores (1-1 heavy oil and asphaltene)
21. cycle : 6 cores (2 asphaltene, 1 heavy oil, 3 non)
As shown, 8 cores of the tested 14 ones were damaged
before the end of the cyclic treatments. Independently
whether the cores were treated or non-treated, we may
conclude that there is 60 % probability that the formation
rocks in the vicinity of wells undergo severe damage
after 10 cycles or 10 years of operation in underground
gas storage facilities.
5. As the original (absolute) permeability of cores is
concerned we may conclude that close correlation doesn’t
exist between the stability and permeability of cores. It is
supposed, however, that defective crystal structures,
micro fissures, fractures, mineral heterogeneities play
important role in deterioration of cores under pressure
and temperature fluctuation.
6. On the basis of the statistical data we may conclude that it
is hard to set-up a close correlation between the stability
of cores and the type of treating agents. Although all
silicone treated cores were seriously damaged and proved
unstable against the pressure and temperature fluctuation
and those cores maintained their physical stability which
were treated with asphaltenes and high asphaltene-
containing crude oil, some non-treated cores also belong
to this category. Thus, in the present phase of the research
program it is premature to draw a final conclusion on
benefits of asphaltene treatments in respect to formation
stabilization in gas wells.
The accomplished research activity provided valuable new
data on behavior of reservoir rocks under cyclic pressure and
temperature effects. On the other hand, it is clear that the
available information left some open questions to be answered
in the future and additional laboratory study is needed to
elucidate all processes and phenomena which may provide
sufficient arguments to outline new well treatment methods
aiming at stabilizing gas well and hence, increase profitability
in gas fields and underground gas storage systems.
Conclusions
The laboratory studies of pressure and temperature fluctuation
on gas permeability of natural formation cores provided a firm
basis to draw the following important conclusions:
1. The gas permeability of cores is much lower at 80 bar and
100 °C than the values obtained at ambient conditions.
The difference is apparently permeability dependent: the
reduction of permeability may exceed the 90 % for low
permeability cores, while for medium and high perm
cores the difference is less than 60 %.
2. The gas permeability characteristic at low pressure and
temperature is always higher than those values which
were measured at 80 bar and 100 °C. These phenomena is
attributed to the compaction effect induced by the high
pressure and temperature.
3. As the number of cycles is increasing the amplitude of the
gas permeability changes is gradually decreasing. This
tendency indicates certain stabilization of the core
structure, flow path, accessible pore volume, tortuosity,
etc. Parallel with this positive consequences of cyclic
pressure and temperature effects the average gas
permeability slightly decreases with the cycle number.
We may say that flow of gas (or any fluids) through the
porous cores becomes “smooth” and less sensitive to
external conditions after a given number of extreme
structure modifying effects.
4. The damage cores represent exceptions of the behavior
mentioned in point 4.: the gas permeability usually has
shown hectic fluctuation and the average values rather
increased instead of the decreasing tendency as the test
went on.
5. Close correlation could not be found between the stability
and the permeability of cores. Thus, it is supposed that
defective crystal structures, micro fissures, fractures,
heterogeneities play important role in deterioration of
cores under pressure and temperature fluctuation.
6. According to the experimental results 8 cores of the tested
14 ones were damaged before the end of the cyclic
treatments. Independently whether the cores were treated
or non-treated, we may conclude that there is 60 %
SPE 86549
probability that the formation rocks in the vicinity of
wells undergo severe damage after 10 cycles or 10 years
of operation in underground gas storage facilities.
7. It is hard to set-up a close correlation between the stability
of cores and the type of treating agents. Although all
silicone treated cores were seriously damaged and proved
unstable against the pressure and temperature fluctuation
and those cores maintained their physical stability which
were treated with asphaltenes and high asphaltene-
containing crude oil, some non-treated cores also belong
to this category.
8. One of the crucial problems might be the inefficient
hydrophobization of porous cores. As clearly sown by the
adsorption studies the water content (saturation) of cores
radically influences the adsorbed amount, and hence the
efficiency of wettability alteration. According to the
experimental results the asphaltene retention in cores
drops down practically to zero over 10 % water content,
which is far below the value of the residual water
saturation characteristic under formation conditions.
The accomplished research activity provided valuable new
data on behavior of reservoir rocks under cyclic pressure and
temperature effects. The available information, however, left
some open questions to be answered in the future and
additional laboratory study is needed to elucidate all processes
and phenomena which may provide sufficient arguments to
outline new well treatments aiming at stabilizing gas well and
hence, increase profitability in gas fields and underground gas
storage systems.
Acknowledgements: The authors wish to acknowledge the
technical assistance of K. Bauer, F. Fedor and I. Horváth in
carrying out the capillary pressure and porosity measurements.
References
1. Aggour, M.A., Malik, S.A.: “Effect of Cyclic Formation Pressure
Changes on Permeability”, SPE Reservoir Engineering, Feb. pp
91 (1989)
7
2. Al-Awad, M.N.J.: “The Mechanism of Sand Production Caused
by Pore Pressure Fluctuation”, Oil and Gas Science and
Technology – Rev. IFP, 56:339-345 (2001)
3. Sharma, B.G., Sharma, M.M.: “Polymerizable Ultra-Thin Films:
A New Technique for Fines Stabilization”, paper SPE 27345
presented at the SPE Int. Symposium on Formation Damage
Control held in Lafayette, 7-10 Feb. (1994)
4. Maberry, L.J., Ali, S.A., McConnell, S.B., Hinkel, J.J.: Formation
Fines Stabilization Using Adsorption Polymerization”, paper
49102 presented at the SPE Annual Technical Conference and
Exhibition held in New Orleans, 27-30 Sept. (1998)
5. Rayes, B.H., Pernyeszi, T., Lakatos, I., Tóth, J.: „Comparative
Study of Asphaltene Adsorption on Formation Rock under Static
and Dynamic Conditions”, paper 80265 presented at the SPE Int.
Symposium on Oilfield Chemistry held in Houston, 5-8 Feb.
(2003)
6. Rayes, B.H., Lakatos, I., Pernyeszi, T., Tóth, J.: “Adsorption of
Asphaltenes on Formation Rocks and Its Effect on Wettability”,
paper 81470 presented at the SPE 13th Middle East Oil Show
and Conference held in Bahrain, 5-8 April (2003)
7. Tóth, J., Bódi, T., Szűcs, P., Civan, F.: “Analytical Techniques for
Determination of Relative Permeability from Displacement
Experiments”, in Lakatos, I. ”Novelties in Enhanced Oil and Gas
Recovery”, Progress in Mining and Oilfield Chemistry Vol. 2.,
pp. 91, Akadémiai Kiadó Ltd., Budapest (2000)
8. Tóth, J., Bódi, T., Szűcs, P. and Civan, F.: “Convenient Formulae
for Determination of Relative Permeability from Unsteady-State
Fluid Displacement in Core Plugs”, J. Petroleum Geoscience and
Engineering, 35:33 (2002)
9. Lakatos, I., Tóth, J., Lakatos-Szabó, J., Kosztin, B., Palásthy, Gy.,
Wöltje, H.: “Application of Silicone Microemulsions for
Restriction of Water Production in Gas Wells”, paper 78307
presented at the SPE 13th European Petroleum Conference held
in Aberdeen, 29-31 Oct. (2002)
10. Lakatos, I., Tóth, J., Bauer, K., Lakatos-Szabó, J., Kosztin, B.,
Palásthy, Gy., Wöltje, H.: “Comparative Study of Different
Silicone Compounds as Candidates for Restriction of Water
Production in Gas Wells”, paper 80204 presented at the SPE Int.
Symposium on Oilfield Chemistry held in Houston, 5-8 Feb.
(2003)
8 SPE 86549

TABLE 1−Origin of different asphaltenes used as hydrophobization agent

Material Asphaltene content, %
Heavy crude oil 19.04
Medium crude oil 2.21
Ultra-light crude oil 0.56
Distillation residue 16.60
Stock tank precipitate 27.80

TABLE 2−Dependence of the adsorbed amount on asphaltenes and adsorbent type

Asphaltene from Static, mg/g Calculated by isotherm, mg/g Dynamic, mg/g

Formation Rock
Heavy oil 3.8 3.6 4.2
Medium oil 3.1 2.9 3.1
Ultra-light oil 2.8 2.8 2.8
Dist. residues 3.5 3.3 3.1
Stock tank residue 3.2 3.1 2.9
Formation Rock + Calcite
Heavy oil 3.4 3.2 4.5
Medium oil 2.7 2.1 2.4
Ultra-light oil 2.5 2.9 2.6
Dist. residue 3.1 3.0 2.7
Stock tank residue 2.9 2.7 2.5
Formation Rock + Montmorillonite
Heavy oil 5.1 5.0 6.5
Medium oil 5.5 5.5 5.3
Ultra-light 4.5 4.5 5.2
Dist. residue 5.4 5.3 5.1
Stock tank residue 5.2 5.3 5.1

TABLE 3−Permeability and treating agent of cores tested by the cyclic method
Core Absolute gas permeability, mD Treatment method*
A993-1 22.06 asphaltene (heavy oil)
A993-2 23.89 heavy oil
S2.2. 13.36 silane
S3.2. 22.54 siloxane
A993-3 42.70 silicone resin
SA-6 1.05 siloxane
A993/1.1. 40.53 heavy oil
A993/1.2. 35.67 non-treated
A993/2.1. 21.66 asphaltene for stock tank
A993/1.3. 27.73 non-treated
A985/5.6. 119.90 heavy oil
A985/5.7. 115.93 non-treated
A2003/2. 26.72 asphaltene for dist. residue
A2203/3. 29.22 non-treated
*All treating agents (asphaltene, heavy oil, silicone compounds) have the same concentration (5 g/l)
in the injected solutions (toluene, aromatic mixture, IPA and heptane)
SPE 86549 9

0.07 0.07

0.06 0.06

Cum. ads. amount, g

Adsorbed amount, g

0.05 0.05

0.04 0.04

0.03 0.03
water-free
0.02 0.1 ml 0.02
0.25 ml
0.5 ml
0.01 1.0 ml 0.01
100% water saturation
0 0
0 50 100 150 200 250 0 2 4 6 8 10
Cum . volum e, m l Water content, m l

Fig. 1−Cumulative adsorption of asphaltenes at reservoir rock Fig. 2−Effect of water content of adsorbent on cumulative
containing different amount of water (dynamic test) adsorption of asphaltenes at reservoir (dynamic test)

5 Specific adsorption, mg/m2 100

Specific adsorption, mg/g

4 80

3 60

2 40

1 20

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Water saturation, % Water saturation, %

Fig. 3−Effect of water saturation of adsorbent on specific Fig. 4−Effect of water saturation of adsorbent on specific
adsorption of asphaltenes at reservoir (dynamic test) adsorption of asphaltenes at reservoir (dynamic test)

100 1000
Specific adsorption, mg/m2

before
80 100
after

60 10
krw/krg

40 1

20 0.1

0
0.01
0 2 4 6 8 10 12 0 0.2 0.4 0.6 0.8 1
Thickness of water film, 10E-3 mm Sw, -

Fig. 5−Dependence of the specific adsorption of asphaltenes on Fig. 6−Effect of asphaltene treatment on relative permeability
thickness of water film over the surface of the reservoir rock (Sample 1, drainage direction)
(dynamic test)
10 SPE 86549

1000 1000
before before
100 after 100 after

10 10

krw/krg
krw/krg

1 1

0.1 0.1

0.01 0.01
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
S*, -
Sw, -
Fig. 7−Effect of asphaltene treatment on normalized relative Fig. 8−Effect of asphaltene treatment on relative permeability
permeability (Sample 1, drainage direction) (Sample 2, drainage direction)

1000 10

before before
100 after after
1
10
Pc, bar
krw/krg

1
0.1

0.1

0.01
0.01
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1
Sw, -
S*, -
Fig. 9−Effect of asphaltene treatment on normalized relative per- Fig. 10−Effect of asphaltene treatment on capillary pressure
meability (Sample 2, drainage direction) curve (Sample 1, centrifugal technique)

10 10
before before
after after
1 1
Pc, bar
J, -

0.1 0.1

0.01 0.01
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
S*, - Sw, -

Fig. 11−Effect of asphaltene treatment on normalized capillary Fig. 12−Effect of asphaltene treatment on capillary pressure curve
pressure curve (Sample 1, centrifugal technique) (Sample 2, centrifugal technique)
SPE 86549 11

10 0.5
before SB-6
after 0.4
SB-10
1

Diff. Sw, -
0.3
J,-

0.2
0.1
0.1

0.01 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6
S*, - Pc, bar

Fig. 13−Effect of asphaltene treatment on normalized capillary Fig. 14− Difference of water saturation at constant capillary pres-
pressure curve (Sample 2, centrifugal technique) sure caused by asphaltene treatment
(Sample 1&2, centrifugal technique)

0.5

SB-6
0.4 SB-10

0.3
Diff. S*, -

0.2

0.1

0
0 0.2 0.4 0.6
J, -

Fig. 15− Difference of normalized water saturation at constant J function caused by asphaltene treatment
(Sample 1&2, centrifugal technique)

100

80
S A -6. co re

60
kg/kg0, %

40

20
A 9 93-3. core

0
0 1 2 3 4 5 6 7 8 9 10
C yc le n u m b e r
Fig. 16−Effect of cycle number on relative gas permeability of cores
(Treatments SA-6: siloxane, A993-3: silicone resin)
12 SPE 86549

100

80

S 3.2. core
60
kg/kg0, %

40

20 S 2.2. c ore

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
C yc le n u m b e r
Fig. 17−Effect of cycle number on relative gas permeability of cores
(Treatments S3.2: siloxane, S2.2.: silane)

120

100

80
kg/kg0, %

A 9 9 3 -1 .
60

40

A 9 9 3 -2 .
20 c o re

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
C yc le n u m b e r
Fig. 18−Effect of cycle number on relative gas permeability of cores
(Treatments A993-1: asphaltene from heavy oil, A993-2: heavy oil)

100

80

60
kg/kg0, %

A 99 3 /1 .3. c ore

40

A 9 9 3/2 .1 . co re
20

0
0 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 14 1 5 1 6 17 18 1 9 20 21
C yc le n u m b e r
Fig. 19−Effect of cycle number on relative gas permeability of treated cores
(Treatments A993/1.3.: non, A993/2.1.: asphaltene for stock tank)
SPE 86549 13

100

80

60
kg/kg0, %

40 A 9 9 3 /1 .1 . c o re

20
A 9 9 3 /1 .2 .

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13
C yc le n u m b e r
Fig. 20−Effect of cycle number on relative gas permeability of treated cores
(Treatments A993/1.1.: heavy oil, A99/1.2.: non)

100

80

60 A985/5.6. core
kg/kg0, %

40

A 9 8 5 /5 .7 .
20 c o re

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
C yc le n u m b e r
Fig. 21−Effect of cycle number on relative gas permeability of treated cores
(Treatments A985/5.6.: heavy oil, A985/5.7.: non)

100

80

60 A 2 0 0 3 /3 . c o re
kg/kg0, %

40

A 2 0 0 3 /2 . c o re
20

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
C yc le n u m b e r
Fig. 22−Effect of cycle number on relative gas permeability of treated cores
(Treatments A2003/3: asphaltene from dist. residue, A2003/3: non)