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THE USE OF NON-NEWTONIAN FLUIDS IN OIL RECOVERY

Abstract Résumé
The flow properties of non-Newtonian fluids are Les caractéristiques d’écoulement des liquides non-
shear dependent and, in many instances, also time Newtoniens dépendent du cisaillement et souvent aussi
dependent. Most non-Newtonian fluids used in oil du temps. La plupart des liquides non-Newtoniens
recovery are pseudo-plastic in nature. Their use in oil utilisés dans la récupération du pétrole sont de nature
recovery generally falls into two categories, i.e. well pseudo-plastique. On les utilise généralement dans les
stimulation fluids and as secondary and tertiary oil deux cas suivants, soit comme fluides de stimulation
recovery fluids. des puits, soit comme fluides de récupération secon-
In well stimulation they are used in hydraulic daire et tertiaire.
fracturing fluids and also in the form of micellar Dans la stimulation des puits, ils sont utilisés pour
solutions as water injection well stimulating fluids. les opérations de fracturation hydraulique, et aussi sous
The purpose here is to increase relative permeability forme de solution micellaires dans les puits d’injection
to water by injecting small volumes of micellar d’eau. L’injection de petits volumes de solution
solution into the well bore. In addition, the micellar micellaire dans la formation a pour but d’augmenter
solution helps clean up the well, thereby eliminating la perméabilité relative à l’eau. De plus la solution
skin effects. micellaire aide à nettoyer la formation aux abords du
Studies are being conducted on the use of foams, puits éliminant ainsi les effets pariétaux.
polymer solutions, emulsions and micellar solutions Des études sont en cours sur l’utilisation des
as oil displacement agents. However, only polymer mousses, des solutions polymères, des émulsions, et
solutions and micellar solutions have been applied as des solutions micellaires comme agents de déplace-
oil displacement agents in the field. High molecular ment du pétrole. Sur le champ, cependant, on n’a
weight, water soluble, polymers are being used in- utilisé que les solutions micellaires. Les polymères de
creasingly in the field for mobility control in secondary grand poids moléculaire solubles dans l’eau sont
waterflood operations. Micellar solution flooding is utilisés de plus en plus sur le champ pour contrôler la
just emerging from the field and test development mobilité dans les opérations d’injection d’eau secon-
stage. The solutions are used to recover oil by a daires. L‘injection des solutions micellaires vient
miscible-type waterflooding process. seulement d’être expérimentée sur le champ. On
utilise les solutions pour récupérer le pétrole par un
procédé d’injection d’eau présentant les caractères
d’un déplacement miscible.

1. INTRODUCTION in the oil industry occurred with the advent of


hydraulic fracturing in 1948. This was the first large-
The use of non-Newtonian fluids in the U.S. oil scale commercial use of a non-Newtonian fluid in an
industry is not new. The first and probably quite oil recovery process, albeit, a stimulation treatment.’
successful use of a non-Newtonian fluid was as a Micellar solutions (also known as soluble oils and
drilling fluid when Captain Lucas drilled his well in microemulsions) have recently been proposed as
Spindletop in 1901, although the literature suggests water injection well stimulants. The purpose is to
the use of adding materials such as clay to drilling increase relative permeability to water by injecting
water as early as 1887. small volumes of micellar solutions into the well bore.
The second large-scale use of non-Newtonian fluids In addition, the micellar solution helps clean up the
well, thereby eliminating skin effects.
by W. B. GOGARTY and FRED H. POETTMANN, Recently, the industry’s attention has turned to the
Marathon Oil Company, use of non-Newtonian fluids in secondary recovery
Littleton, Colorado, U.S.A. operations. Considerable studies are being carried out
281
288 Recovery of Hydrocarbons Beyond the Primary Stage

on foams, polymer solutions, emulsions and micellar PSEUDOPLASTIC


solutions as oil displacement agents.
To the authors' knowledge, of those listed only
polymer solutions and micellar solutions have been
applied as oil displacement agents in the field. In the
case of polymer solution floods, many have become
commercial. Micellar solution flooding is, at the
present, just emerging from the field and test develop-
ment stage.

2. CHARACTERISTICS OF NON-NEWTONIAN
FLUIDS
du/dy SHEAR RATE
In the case of Newtonian fluids, the flow property,
i.e. viscosity, is constant under all flow conditions at Fig. 1-Time independent Newtonian andnon-Newtonian
Jluids.
constant temperature and pressure, whereas the vis-
cosity of non-Newtonian fluids is shear dependent and,
in many instances, also time dependent. Flow pro- Pseudo-plastic fluids
perties of fluids are represented by curves of shear
stress vs. rate of shear. These curves are obtained by By far the largest number of non-Newtonian fluids
properly designed viscometers. The shear stress, z, is the are found in this category. These fluids are character-
stress per unit area in the plane parallel to the direction ised by the fact that the apparent viscosity decreases
of flow. Non-Newtonian fluids which are viscoelastic as the shear rate increases. Examples are polymer
are characterised by unequal normal stresses. The solutions and micellar solutions. The fluids at low
shear rate is the velocity gradient, duldy, perpendicular shear rate quite often act as though they are Newtonian
to the plane of shear. in character, i.e. the curve is linear at low shear rates.
The viscosity of a Newtonian fluid is the slope of the
curve through the origin. The apparent viscosity of a
non-Newtonian fluid is the slope of a line from the Dilatant fluids
point on the curve through the origin.
Figure 1 illustrates the various time independent These fluids exhibit an increasing apparent viscosity
shear stress us. rate of shear curves for a Newtonian with increasing shear rate. They are far less common
and non-Newtonian fluid. than pseudo-plastic fluids. Most suspensions of solids
in water exhibit dilatancy.

Newtonian fluids

As illustrated in Fig. 1, the flow curve for a New-


tonian liquid is a straight line through the origin. One
flow property, i.e. viscosity, describes these fluids.
Most of the fluids in the oil fields, such as hydrocar-
bons and water, are Newtonian in character.
0 4"x 1/32"
A I' x 1/32"
4" a 2/32"
Bingham plastic fluids + 200" x 3/32"
I
100 ipoo - woo ~ O W
These fluids exhibit a yield stress as illustrated in SHEAR RATE D I S E C "
Fig. I , i.e. below a certain stress, zo, no flow occurs, AVERAGE
while at a shear stress above z o the fluid will flow like
a Newtonian liquid. A fluid illustrative of the Bingham Fig. 2-Variation of viscosity with shear rate for a
plastic fluids is oil well drilling mud. dilatant solution.
Recovery of Hydrocarbons Beyond the Primary Stage 289

Figure 2 shows the rheological data for an aqueous 3. NON-NEWTONIAN FLUIDS IN POROUS
solution of 1.0% by weight of a mixture of sodium MEDIA
salts of hydrocarbon sulphonic acids and 0.125 % by
weight of an ethylene oxide polymer having a molecu- Most non-Newtonian fluids used in oil recovery are
lar weight of approximately 5000000. As is shown, pseudo-plastic in nature. In order to calculate the flow
this solution exhibits a dilatant character above a conditions of a non-Newtonian fluid in a porous
shear rate of about 1000 sec-’. media, effective viscosities of the fluid must be deter-
Figure 3 illustrates time dependent non-Newtonian mined. These effective viscosities are dependent on the
fluids. The flow properties of time dependent materials rock properties and the flowing conditions. A number
change with the history of treatment of the fluid. of studies have been made on the behaviour of pseudo-
plastic fluids in porous
In the case of most pseudo-plastic fluids, the
apparent viscosity obeys the power law. That is,
// THIXOTROPIC

where p a = apparent viscosity, du/dy = shear rate,


n = constant, K = consistency constant.
The effective viscosity in a core is defined by Darcy’s
equation :
kA AP
Pe = -
qL
where p e = effective viscosity, k = permeability,
- SWEAR RATE A = area, AP = pressure drop, q = volumetric flow
rate, L = length.
Fig. 3-Time dependent non-Newtonian fluids. Experimentally determined effective viscosities for a
micellar solution in Berea cores of three different
permeabilities have been studied. At low frontal
Thixotropic fluids velocities the micellar solutions behaved in a New-
tonian manner. In order to theoretically calculate the
The shear stress of these fluids decreases with time effective viscosity, a relationship must be established
under the influence of a constant shear rate. Drilling between the average shear rate in a core and the
muds exhibit thixotropic properties as well as a yield frontal velocity in the core. In addition, the effect of
stress. High pour-point hydrocarbons are in this same permeability on the shear rate-frontal velocity relation-
category. ship must also be established. Gogarty, in papers
dealing with both polymer solutions and micellar
Rheopectic fluids solutions, has developed such a relation~hip.’.~
By using the relationship for obtaining the average
These fluids are rare in occurrence. As illustrated, shear rate in a core, the effective viscosity of the
they increase in shear stress with time when held at a micellar solution for the different permeability cores
constant shear rate. referred to above agreed well with apparent viscosities
measured in a viscometer.
In the case of some polymer solutions, an added
Viscoelastic fluids factor enters into the flow behaviour in that some
polymer is retained within the porous media, thus
Viscoelastic fluids exhibit both viscous and elastic reducing the permeability to some stabilised value.
properties. Viscoelastic fluids will both flow and This effect can be important in mobility control. The
deform when subjected to stress. Examples of visco- mobility of a fluid flowing in a porous media is defined
elastic fluids are gels and bitumens. Many polymer as :
solutions under certain flow conditions exhibit k
viscoelastic properties. -
Because of the elastic characteristics of viscoelastic Pe
fluids, the behaviour of these fluids is usually character- where k is the permeability, and p e the effective
ised by a relaxation parameter, viscosity. Some polymer solutions can give effective
290 Recovery of Hydrocarbons Beyond the Primary Stage

mobility control by both reducing the permeability Both synthetic and natural polymers have been
and increasing the effective viscosity. used as friction-reducing agents in fracturing fluids.
Contrary to the micellar solutions, polymer solu- These agents are dissolved in a base fluid, usually
tions consisting of a high molecular weight, partially water, along with suspending and fluid-loss agents.
hydrolysed polyacrylamide polymer indicate a New- The degree of friction reduction is the per cent change
tonian behaviour at high frontal velocities. This in the pressure drop with and without the additive
behaviour is attributable to the viscoelastic character present. Figure 4 shows the friction reduction for a
of the polymer solution. modified guar gum in fresh water at 80°F.’ As is
shown, the per cent of friction reduction depends on
the polymer concentration and reaches a maximum
4. EXAMPLES OF THE USE OF value at a concentration of 5.5 lb/1000 gal.
NON-NEWTONIAN FLUIDS IN OIL RECOVERY Synergistic effects can be obtained by using a
STIMULATION thickening agent in combination with the friction
reducing agent. The thickening agents cause little or
Hydrofrac Fluids no friction reductions by themselves; with thickening
In 1948, Stanolind Oil and Gas Company (now Pan agents present, results are improved over those
American Petroleum Corporation) announced to the obtained only with the friction reducing agents.
Toms’ was the first to observe that the frictional
pressure drop in pipe flow is reduced by addition of
small quantities of a high molecular weight polymer.
In his first experiments he used tens of parts per
million of polymethylmethacrylate in monochloro-
benzene. The polymer addition to the solvent in high
Reynolds number turbulent flow reduced the pressure
drop substantially below that of the solvent alone at
the same flow rate. Since that time this phenomenon
has been observed with many other polymers, both in
water and hydrocarbon solvents. The Polyethylene
oxide (PE0)-water system is typical of the ones
I # , 1 1 1 1 , I I I which have been studied; for example, a 33 % pressure
0.2 o5 1.0
20 50 10.0 20.0 5ao reduction over water alone is possible by adding
-
CONCENTRATION POUNDS/ 1000 GALLONS
18 ppm of P E 0 with molecular weight 0.76 x IO6.
Fig. 4-Frictional pressure reducing properties of a The turbulent drag reduction characteristics of
mod$ed guar gum at 80°F. polymeric additives are reported to be the result of
their viscoelastic properties by Metzner and Park.
industry the original concept of the hydraulic fractur- These workers showed that polymer-solvent combina-
ing technique in which crude oil or kerosene thickened tions that exhibit drag reduction also display, in
with napalm soap is used as a fracturing fluid.’ The higher concentrations, viscoelastic effects. The turbu-
thickened fluid was used as a carrier for sand in the lent flow characteristics of these non-Newtonian fluids
process. This process created fractures in the forma- are generally similar to the Newtonian fluids. They also
tion, thus permitting additional drainage of fluid into showed that with drag reducing fluids the tran-
the well bore. Many variations of the process developed, sitional value of the Reynolds number may be in-
from the use of specially refined oils having low fluid creased to beyond 10000 for tube flow.
loss characteristics to the use of acid as fracturingfluids. The reduction in friction factor serves to illustrate
Napalm and other gels initially used in hydraulic the drag reduction behaviour. At a Reynolds number
fracturing had sufficient viscosity or gel strength to of 50000 the friction factor is reduced by more than a
hold the sand in suspension without appreciable factor of four from the value for a Newtonian fluid.
settling. This technique, however, was soon replaced These significant reductions in friction factors result
by a technique wherein Newtonian fluids, both oil and in a large reduction in pumping costs. Also larger
water and of varying viscosity, were injected at high volumes of fluids can be delivered through a given size
velocity in order to keep the sand from settling out. pipe with a fixed pressure gradient. These considera-
The flow characteristics of a gelled kerosene and water tions led to the use of friction-reducing agents in
solution are Bingham plastics in nature. Other non- fracturing operations where large quantities of fluids
Newtonian fluids have been used from time to time in are pumped rapidly in wells.
hydraulic fracturing. It is estimated that 10% of all recoverable reserves
Recovery of Hydrocarbons Beyond the Primary Stage 29 1

in North America can be attributed to hydraulic sodium sulphate. A specific example of an oil external
fracturing. micellar solution employed in a well stimulation fluid
is as follows’ : ’
Micellar Solutions
During the last few years, micellar solutions have
been successfully employed in the stimulation of Volume, %
water injection wells.’ Maintaining injectivity of water
injection wells is critical and affects the flood life and Ammonium sulphonate (80 % active) 10.0
thus the economics of the oil recovery process. Since Crude column overhead 55.3
water displaces oil immiscibly, a residual oil saturation Water 32.2
exists around the water injection well. This residual oil Isopropanol 2.0
saturation reduces the relative permeability to the n-Nonyl phenol 0.2
flow of water. The injection into the formation of small Sodium hydroxide about 1-0
quantities of micellar solutions displaces the residual
oil. The micellar solution in turn is displaced by the The component types and composition of the
water in a miscible manner. As a consequence, the micellar solution can be adjusted to make the solution
water flows as a single phase at 100 % relative perme- compatible with the reservoir fluids. For stimulation
ability in the vicinity of the well bore. purposes, the viscosity of the micellar solutions should
Injectivity increases resulting from improved relative be less than the effective viscosity of the flowing oil
permeability depend on the depth of treatment. and water for best results.
Theoretically, injectivity will increase by 100% when Because the micellar solution effectively increases
depth of treatment equals about 15 ft. Since micellar the relative permeability of the flowing water by
solutions have proven to be excellent cleaning agents, removing the residual oil saturation, the stimulation
added improvements can be obtained as a result of effect is permanent for water injection well stimulation.
the micellar solutions cleaning the sand face or However, periodic repeated treatments can be effec-
removing emulsion blocks. tive for cleaning up well bore damage due to oil carry-
Micellar solutions are translucent to transparent over in the injection water and other damaging
and thermodynamically stable. The word “micelle” carryover. Both oil external and water external
describes the aggregation of surfactant molecules micellar solutions have been employed. The process is
dissolved in the solvent (oil or water). These micelles patented’ ’ and is offered as a service by the Dowell
have the ability of swelling in order to accommodate Division of Dow Chemical Company under the
fluids other than the solvent, for example, water in an trade name “Clean Sweep”.
oil external micellar solution. Stimulation treatments usually consist of one to
The micellar solution used for well stimulation three barrels of an oil external micellar solution per ft
consists primarily of surfactant, hydrocarbon and of formation. Table I shows some typical results for
water. Small amounts of electrolyte and cosurfactants ’
stimulating water injection wells. In initially appiy-
are employed in order to impart specific properties. ing the process, Dowell reports that in the first 181
Commercial petroleum sulphonates are usually em- treatments covering 27 fields, a success ratio of over
ployed as the surfactant. Crude column overhead and 80% was achieved. These were all sandstone reser-
crude oil are examples of the hydrocarbon employed. voirs. Application to carbonate reservoirs has been
Isopropyl alcohol, amy1 alcohol and hexanol are limited.
examples of cosurfactants employed. Useful electro- Both oil external and water external micellar
lytes include sodium chloride, sodium hydroxide and solutions have been patented for stimulating oil
TABLE I
TYPICAL WELL STIMULATION RESULTS USING
OIL EXTERNAL MICELLAR SOLUTIONS 1 3
Injection rates
Sand Average Average and pressures
Well thickness @ Kair Treatment size (bd at p i g ) Inj. Increase
no. (fi) (%) (md) (brl) (brllf) Before After (bd) (%I
1 35 19.6 203 50 1.5 37 at 600 121 at 607 84 255
2 24 19.4 135 60 2.5 110at 610 515at 620 405 368
3 29 19.9 194 84 2.9 107at 570 136at 580 29 27.1
4 26 19.9 253 124 48 100at475 140at485 40 40.0
5 29 19.2 123 70 2.4 67at 590 160at 580 93 139
292 Recovery of Hydrocarbons Beyond the Primary Stage

producing well^.'^*'^ The micellar solution is dis- Results have been reported on injecting foam into a
placed into the reservoir by crude oil. However, as reservoir under field conditions.’ The purpose of the
can be surmised, after injection of the micellar solution test was to determine the effectiveness of foam in
it is produced back as the well is put in production; reducing gas and water flow in a reservoir. After
if the well produces both oil and water, the improve- 6 % of a pore volume of a 1 % foaming agent solution
ment in relative permeability is not lasting and im- had been injected, the mobility to injecting air alone
provement in production is only temporary ; whereas, was reduced by 50% and to injecting water was re-
if the well produces dry oil, the effect should last duced by 35%. During the foam injection test, the
longer. However, the micellar solution can be quite average water-oil ratio of wells in the pilot area
effective in cleaning up the well bore and in removing dropped from fifteen to twelve.
emulsion blocks. The use of stable foam prepared at the surface as a
calculating fluid for completion and remedial operations
has been reported to cut job costs by 50%.’6 In one
Oil recovery processes area, the economic gain using foam amounted to
324700 dollars on 244 jobs.
Foams
Many claims have been made for the use of foams Polymer Solutions
in oil recovery operations. Foam is effective in High molecular weight, water-soluble polymers are
restricting the flow of both gas and liquid.I6,l7 The being used increasingly in the field for mobility control
use of foam has been suggested for secondary oil in secondary waterflood operations. The largest
recovery in reservoirs with either an underlying water- polymer flood reported to date is by Ecopetrol in the
bearing strata or a gas cap. ”* ’’ Stable, tenacious La Cira field of Colombia.27 In this field, 40000 to
foams are placed in either the gas cap or the water 50000 bd of polymer solution will be injected into
strata and serve as a method of diverting injected and fifty-four wells on a 2010 acre segment of the field.
produced fluids through the oil-bearing formation. Dow Chemical Company’s partially hydrolysed
For improved thermal recovery, water is injected into polyacrylamide polymer will be used in this flood at a
the formation concurrently with the combustion sup- concentration of 300 ppm. Studies indicate that oil
porting gas. A foaming agent is mixed with the gas and recovery will be increased by 50 %.
water to keep them together.” Results on sixty-one polymer field projects initiated
Foam drives have been reported as being applicable during the period 1964-1969 have been reported by
for displacement operations in secondary re- Dow Chemical Company. ’ The sixty-one projects

covery. 1 7 s 2 Mobility conditions are improved with represent more than 95 % of all field operations where
a foam drive over a normal gas or water drive so that polymer solutions have been used for waterñooding.
both sweep and displacement efficiencies are increased. Of the sixty-one projects considered, twenty-nine
The rheology of foam has been studied in a capillary were reported in one group as being the type from
viscometer using tubes of different diameters.’ The’ which significant information could be obtained.
apparent viscosity of the foam was determined as a The remaining thirty-two projects were in a second
function of the shear stress and decreases with increas- group and were such that conclusions could not be
ing shear stress. This situation is representative of drawn either because of some gross reservoir defect
pseudo-plastic fluid. Tests showed that the foam or because the project was initiated too recently to be
exhibited a measurable yield stress at zero shear rate. interpreted. Of the twenty-nine projects in the first
This condition is indicative of the Bingham plastic group, fifteen were considered unsuccessful because no
character reported for foams. expansion was contemplated. A total of sixteen of the
Analysis of data indicates that in a capillary tube thirty-two projects in the second group were in
the high viscosity foam flows concurrently with a unsuitable reservoirs. All these projects used Dow’s
solvent layer around the tube wall. This analysis partially hydrolysed polyacrylamide polymer.
accounts for the flow characteristics of the foam Four polymer pilot waterñoods in the Mid-
varying with tube diameter and shows that the foam Continent area have been reported by Calgon Cor-
flows as a viscous fluid. Studies in porous media poration as producing more than 96000 barrels of
indicate that foam does not flow as a single fluid extra oil at a cost of 19 cent~/barrel.’~ Calgon’s 16 to
even when the liquid and gas are injected as a foam. 18 % hydrolysed, highly cross-linked polyacrylamide
Liquid moves through the porous medium via the film polymer was used in these floods. The projects
network of bubbles and gas moves progressively covered a wide range of rock and fluid properties as
through the system by breaking and reforming shown in Table II. The response of a producing well in
bubbles. Flood B is shown in Fig. 5. The water-oil ratio
Recovery of Hydrocarbons Beyond the Primary Stage 293

TABLE II
ROCK PROPERTIES, GEOGRAPHY AND FLUID PROPERTIES
OF FOUR POLYMER PROJECTS29
~~

Flood A Flood B Flood C Flood D


Permeability average, md 4.3 90 235 1200
Permeability range, md 1.1-1 1.2 30-150 10-2400 100-2500
Porosity, % 16.8 21 15.0 20
Connate water, % PV 45 25 35 25
Residual oil, % PV 21 20 20 25
Oil viscosity, CP 3 7.5 6 2.5
Formation Temp., "F 90 100, 85 95
Formation type Bartlesville Lansing- Spar Mt. Bruhlrneyer
Sand Kansas City (Rosiclare) Sand
Lime Sand
Formation thickness, ft 16 10 10 30
Original oil in place (BAF) 640 1040 812 1000

decreased significantly after polymer injection. This control mobility by viscous dissipation. Higher values
behaviour is typical of a successful polymer flood. of apparent viscosity cause lower values of mobility.
As the water-oil ratio decreases, the daily oil produc- As mentioned earlier, the polymer solutions exhibit
tion increases. The additional oil from polymer pseudo-plastic non-Newtonian character so that
flooding is the incremental oil produced above the increases in shear rate (flow rate) cause decreases in
normal decline curve. the apparent viscosity. The second mechanism for
Mobility control forms the basis for using polymers mobility control is that of permeability reduction.
to improve secondary waterflood operations. With the
addition of polymer to the flood water, a greater TABLE DI
percentage of reservoir volume is swept. The improve- CORES USED IN DETERMINING THE EFFECT
ment in sweep efficiency results from both improved O F PERMEABILITY ON MOBILITY 2
vertical and area1 conformance. The polymer solution
does not improve the unit displacement in the rock, Solution Original Reduced
concentration permeability Porosity permeability
but reduces the water injection requirement to produce (PP4 (md) (md)
a given amount of oil, i.e. the oil is produced with less
1400 polymer 466 0.21 114
water cycling. 1400 polymer 145 0.20 23
Polymer solutions exert mobility control in a for- 1400 polymer400 NaCl 438 0.21 104
mation by any or all of three mechanisms. The most 1400 polymer400 NaCI 140 0.20 12
- -
common of these is the resistance caused by the
viscous dissipation. The apparent viscosity of the
polymer solution is a measure of its capability to This reduction has been reported to take place by
adsorption and mechanical entrapment of polymer
in the rock. Results of this study are shown in Table III
for Berea cores using a partially hydrolysed poly-
HICKMAN LEASE acrylamide polymer. The reduced permeabilities in the
table were determined after flushing large volumes of
water through cores saturated with polymer solution.
hjecîed miym mi z Viscoelastic effects in polymer solution flow are
(thni ûecember,'7û) Z O , ~ O ~ 0
5oæ
5 responsible for the third mechanism of mobility
control. Additional resistance is provided in porous
40s
300-
media by polymer solutions which exhibit viscoelastic
2 character. o
200 Numerous polymers are reported in the literature
2 as being effective mobility control agents. Poly-
10 B acrylamide polymers are the only ones on which field
4 6 8 IO i2 14 16 18 x) 22 24 26
CUMULATIVE OIL RECOVERY, BBLS. x 1000 results have been reported. This type of polymer has
been investigated extensively in the laboratory. 2,
Fig. 5-Response of producing well after polymer Mobility control with this polymer takes place by
treatment of injection well. Estimated extra oil recovery means of both viscosity and permeability reduction.
due to polymer treatment is about 21000 brl. Recent studies survey the variables which determine
294 Recovery of Hydrocarbons Beyond the Primary Stage

the behaviour of this polymer for mobility control.36 fifty United States patents issued with some bearing on
Polyethylene oxide and polysaccharides are two the subject.
other types of polymer which have been considered for The micellar solution completely removes oil from
use in secondary waterñooding operations. These two the portion of the reservoir it contacts. As in the case
polymers are reported to depend only on their viscosity of micellar stimulation fluids, the micellar solution for
for mobility control, i.e. they cause no permeability oil recovery consists of a hydrocarbon, surfactant and
reduction of the porous media.23*36Also, the vis- water, along with small or trace quantities of electro-
cosity of the Polyethylene oxide and polysaccharide lytes and cosurfactants to impart specific properties.
polymers are less sensitive to salt than are the poly- Most of the micellar solutions employed to date have
saccharides. been oil external.
In addition to these polymers, the patent literature Micellar solution properties of most concern to the
abounds with others which are suggested as thickening process are stability to phase separation, proper
agents for water. Some of these include polyvinyl
alcohol sulphate, poly(glucosylglucan), copolymer FIELD L I F D c
of methyl vinyl ether and maleic anhydrideY3' mix-
tures of sulphonated poly(2,6-dialkylphenol) with B
either soluble poly (N-vinyl-2-pyrrolidone) or poly- 1964

(N-vinyl-5-R-2-oxazolidinone) '
for synergistic effects,
and copolymer of hydrolysed vinyl methyl ether-
maleic anhydride grafted with p~lyacrylamide.~' A
1963
Besides these different polymers, the patent literature
also teaches the use of an aqueous solution of a
water-thickening agent and water soluble surfactant
for improved r e c o ~ e r y . ~ ~ . ~
With the advent of polymer flooding, mathematical
models have been developed to predict field per-
SWG SIZE-PERCENT PORE VOWME
formance and to study the effects of different para-
meters. A 2-D, two-phase, non-communicating layer Fig. 6-Displacement efJiciency of micellar solution
computer program is available for handling both slugs.
waterñood and polymer flood conditions.
viscosity so that mobility control can be maintained
Micellar Solutions and compatibility with the oil, water and rock. The
Since 1962, micellar solutions have been used effect of component type and concentration on the
successfully in the field in the secondary and tertiary physical properties of micellar solutions has been
-
recovery of oil. 3 9 - These solutions are used to reported in the literature. 3 *
recover oil by a miscible-type waterflooding process. The displacement efficiency of a given micellar
The process consists of injecting a micellar solution solution depends on the reservoir water and crude oil
into the reservoir. The micellar solution displaces the being displaced, along with the nature of the reservoir
oil and most of the water. The micellar solution in rock. The design of a specific micellar solution for a
turn is displaced by a mobility buffer. The mobility given reservoir, having specific crude, water and rock
buffer can be either a water external emulsion or a characteristics, is a semi-empirical process. Small
water solution containing apolymer. Presently, polymer changes in the concentration and the chemical type of
solutions are more economical. The purpose of the the various micellar solution components can have a
mobility buffer is to protect the micellar solution from very marked effect on the displacement efficiency of
the drive water invasion which is used to propel the the micellar solution.
micellar solution and the mobility buffer through the Figure 6 shows the progress that has been made
reservoir. It is important that a favourable mobility since 1963 on the design of micellar solutions for oil
relationship exists between the reservoir fluids being recovery. It shows the oil recovery efficiencies in
displaced and the micellar solution and mobility buffer laboratory displacements using micellar solution slugs
solution. actually employed in field trials. All examples of slug
To the authors' knowledge, eleven field trials of the shown were applied under tertiary conditions. As can
process have been conducted or are in the process of be seen for the most recent slugs, those larger than 5 %
being conducted since 1962. They have demonstrated pore volume recovered 100% of the oil in place.
the technical feasibility of the process with reservoir Although the larger slugs recovered more oil, the most
spacings for 0.75 acres to 40 acres. There are at least efficient size slug will usually be between 2 and 4 % of a
Recovery of Hydrocarbons Beyond the Primary Stage 295

five-spot using 5 % pore volume micellar solution slug.


As can be seen, the oil recovery is unaffected so long
as approximately 50% pore volume or more of
mobility buffer is used. The mobility buffer in case (1)
was a 1200ppm Dow Polymer #530 in 500ppm
sodium chloride water; and, in case (2), 800 ppm Dow
Polymer $700 in 700 ppm total solids water. The Dow
polymer is a water soluble polyacrylamide. The
micellar solution slugs used in each case were different.
The problem of surfactant absorption does not
appear to be serious as long as the micellar solution is
properly designed. Apparently the interaction between
C O .4 .ô 1.2 1.6 2.0 2.1 28
the surfactant, cosurfactant, hydrocarbon and water
C U M U L A M FUIID INJECTED in the micellar solution reduces and minimises the
PORE VOLUMES adsorption effect on the displacement mechanism so
Fig. 7-Micellar solution flood performance. Isolated far as the efficiency of the process is concerned. Both
inverted $ve-spot. field and laboratory analyses indicate that surfactant
adsorption with properly designed micellar solutions
does not affect the displacement efficiency.
pore volume. Efficiency is defined as maximum Both laboratory and field experiments indicate that
dollar return on oil recovered per dollar of slug micellar solution flooding does not follow the mix-
injected. Some of the micellar solutions used in oil ing laws or rules associated with miscible flooding when
recovery contained as much as 70 % water and were using either alcohol or LPG flooding. Instead, oil
still oil external. recovery appears to be independent of the length of
Figure 7 shows the oil recovery curve and the path travelled so long as the per cent pore volume of
average oil cut for a 0.75 acre isolated inverted five- slug is held constant, whereas in the case of propane,
spot pattern field test as a function of pore volume for example, the longer the path travelled the smaller
total fluid injected. Individual well oil cuts, in some the amount of propane necessary for the same oil
instances, rose as high as 50%. For developed pat- recovery in terms of per cent pore volume injected.
terns, this process should not require more than 1 to However, because of poor mobility control and slug
13pore volumes of total fluid injected. efficiency, it takes in the order of 100 to 200% of a
Figure 8 shows the effect of mobility buffer size on pore volume propane slug to recover the same amount
recovery efficiency. The displacements presented were of oil recovered by 2 4% of a pore volume of properly
all tertiary floods in (1) a 3-in. diameter, 4-ft long designed micellar solution. In addition, field experience
Berea sandstone core using 5 % pore volume micellar indicates that permeability stratification may not
solution slug, and (2) a 2-ft by 2-ft by 2-in. thick present as serious a problem in micellar solution
Berea sandstone slab representing a quarter of a flooding as it does in alcohol or LPG flooding because
of wetting and interfacial tension effects. These and
other characteristics require considerable further study.
The economics of the micellar solution flooding
process appear very promising at the present time.
High displacement efficiencies using small slug sizes
of 2 to 4 %, along with potentially low cost component
costs, for the micellar solution and decreasing mobility
buffer costs, should result in an economic process. In
addition, because of mobility control, the process
should have a wider range of applicability than
waterflooding.
Y
a 40- -
2 Emulsions
O
Surfactants were suggested in the early 1930s as a
means of recovering additional oil by waterñooding.
Excessive adsorption has been cited as an argument
against the use of wetting agents or surfactants.
Doane used emulsions in a laboratory investigation as
296 Recovery of Hydrocarbons Beyond the Primary Stage

a method of increasing oil recovery with surfactants 3. W. B. GOGARTY and W. C. TOSCH, Trans. AIME,
1968, 243, 1407.
while overcoming the adsorption problem.44 4. W. B. GOGARTY, Trans. AIME, 1967,240, 149.
The rheological properties of emulsions are reported 5. British Patent 1,162,414, 1969.
to depend on (1) viscosity of the external phase; 6. W. E. HASSEBROEK and A. B. WATERS, J. Petrol.
Technol., 1964, 16, 760.
(2) volume concentration of the dispersed phase; 7. T. C. BUECHLEY, J. A. DER.BY and L. L. MELTON,
(3) viscosity of the internal phase; (4) nature of paper presented at the British Society of Rheology,
the surfactant; and (5) particle-size distribution. Sept. 19, 1967, at Swindon, Wilts., United Kingdom.
8. J. L. LUMMIS and B. V. RANDALL, United States Patent ..
Emulsions exhibit a wide range of non-Newtonian 3,472,769, Oct. 14, 1969.
rheological properties, including pseudo-plasticity, 9. B. A. TOMS, Proc. 1st Intern. Congr. Rheo., 1948, 2, 135.
10. A. B. METZNER and M. G. PARK, J. Fluid Mech., 1964,
thixotropy, and Bingham plasticity. Crude oil in 20, 291.
water emulsions are pseudo-plastic in nature and 11. W. B. GOGARTY, United States Patent 3,467,188, Sept. 16.
can be described by the power law 1969.
12. W. B. GOGARTY and S . C. JONES, United States Patent
Viscosity of o/w and w/o emulsions and “apparent 3,474,865, October 28, 1969.
miscibility” of w/o emulsions have been cited as the 13. W. B. GOGARTY, W. L. KINNEY and W. B. KIRK,
important characteristics of these fluids in oil dis- Soc. Petrol. Engrs., Paper No. 2412, presented at
Improved Oil Recovery Symposium, Tulsa, Oklahoma,
placement. 4 7 - 4 9 April 13-15, 1969.
Different techniques have been suggested for using 14. W. L. KINNEY, United States Patent 3,470,958, Oct. 7.
emulsions in waterflooding. One process specifies the 1969.
15. W. L. KINNEY and S. C. JONES, United States Patent
use of an emulsion in combination with thickened 3,467,194, Sept. 16, 1969.
waterfiooding for improved mobility control. 50Another 16. S . H. RAZA, Soc. Petrol. Engrs., Paper No. 2421 pre-
sented at Improved Oil Recovery Symposium, Tulsa,
teaches the grading of the emulsion to lessen the Oklahoma, April 13-15, 1969.
ability of drive water to penetrate the emulsion. 17. W. L. JACOBS and G. G. BERNARD, United States
Still another describes the use of LPG-aqueous Patent 3,330,346, July 11, 1967.
18. H. H. FERRELL, M. FELSENTHAL and C. L.
liquid emulsions to improve the vertical conformance JACOCKS, United States Patent 3,366,175, Jan. 30,
in heterogeneous reservoirs. No results have been -.--.
196R
published on using emulsions for oil displacement and 19. D. C. BOND and G. C. BERNARD, United States Patent
3,369,601, Feb. 20, 1968.
recovery in the field. 20. W. T. STRICKLAND, Jr., United States Patent 3,448,807.
Recently, emulsion technology has been used to June 10, 1969.
assist in production operations. In one method the 21. M. FELSENTHAL, J. W. QUINN and C. L. JACOCKS,
United States Patent, April 9, 1968.
formation is treated with an o/w emulsion capable of 22. A. DAVID and S. S. MARSDEN, Jr., Soc. Petrol. Engrs.,
oil wetting the formation. The procedure prevents Paper No. 2544, presented at the 44th Annual Meeting
swelling of clays and improves the response of the of the Soc. Petrol. Engrs., Sept. 28-Oct. 1, 1969, Denver,
Colorado.
formation to waterflooding. A method has also been 23. J. C. REED, paper presented at 23rd Annual Oklahoma
mentioned for enhancing the movement of a heavy Meeting of AIChE, Bartlesville, Oklahoma, March 3,
1969.
crude oil through the reservoir. Ammonium soaps 24. L.W:-HOLM, Trans. AIME, 1968, 243, 359.
are introduced into the oil in the presence of water 25. L. W. HOLM, Soc. Petrol. Engrs., Paper No. 2750, pre-
and cause the formation of an o/w emulsion having a sented at 40th Annual California Regional Meeting of the
SPE of AIME, San Francisco, California, Nov. 6-7, 1969
viscosity lower than that of the oil. Flow conditions 26. S . O. HUTCHISON, Wld. Oil, 1969, 169 (6), 73.
into wells and penetrating thief zones are reported to 27. Petrol. Engr., 1969, 41 (6), 59.
be improved with the use of o/w emulsions. Here the 28. R. L. JEWETT and G. F. SCHURZ, Soc. Petrol. Engrs.,
Paper No. 2545, presented at the 44th Annual Meeting
emulsion is mixed on the surface and injected into the of the SPE of AIME, Sept. 28-Oct. 1, 1969, Denver,
thief zone. Colorado.
A downhole emulsification process has been 29. B. SLOAT, Wld. Oil, 1969, 168 (4), 44.
30. G. L. LEVY, Ph.D. Dissertation, University of Denver.
developed to improve the productivity of wells that 1969.
produce viscous crude^.^^ In the process, surfactant 31. S. CHAIN, MS Dissertation, The Pennsylvania State
University, 1965.
is introduced into the wellbore and converts high 32. T. D. CLAY, MS Dissertation, University of Oklahoma.
viscous crude and w/o emulsions to low viscosity o/w 1965.
emulsions. In one field test using three wells, surfactant 33. D. J. PYE, Trans. AIME, 1964,231,911.
34. B. B. SANDIFORD, Trans. AIME, 1964,231,917.
injection increased oil production 34 % for a surfactant .. J. M. SPITZL. MS Dissertation, The Pennsylvania State
35. -.-
cost of 12 centslbarrel of incremental oil produced. University, 1965.
36. F. W. SMITH, Soc. Petrol. Engrs., Paper No. 2422, pre-
sented at Improved Oil Recovery Symposium, Tulsa,
Oklahoma, April 13-15, 1969.
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Recovery of Hydrocarbons Beyond the Primary Stage 297

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