ENHANCED OIL RECOVERY

TECHNIQUES

JNTU
IV YEAR B.TECH PETROLEUM ENGINEERING
UNIT-IV

A Doraiah, M.Tech (Chem. Engg.)

Retired GM(P)/Surface Manager, ONGC
Mobile: 9490817598, E-mail: [email protected]
 ENHANCED OIL RECOVERY TECHNIQUES
Syllabus

UNIT-IV (Chapter 9, page 219-251)

• Alkaline flooding: Introduction- Types of caustic used-

Entrapment of residue oil- Displacement mechanisms in
alkaline flooding- Crude oil properties-Alkali consumption-
pH of injected caustic- Effect of sodium ions and sodium
chloride- Effect of divalent ions- Reservoir selection-
Documented alkaline flooding field’s tests.
 ENHANCED OIL RECOVERY TECHNIQUES
ALKALINE FLOODING
INTRODUCTION:
 Alkaline water flooding is an EOR process where the pH of the
injection water is increased by the addition of alkaline agents ,
sodium carbonate, sodium silicate, sodium hydroxide and
potassium hydroxide in an effort towards IOR (improved).
 Alkaline flooding has started because of its low cost, simple
process and availability of suitable alkaline chemicals.
 In this process, the alkali reacts with the acidic constituents in
the crude leading to lower water-oil interfacial tension (IFT),
emulsification of oil & water, solubilization of interfacial films.
 The alkali may react with the reservoir rock, leading to
wettability alternation. All of these mechanisms will potentially
increase oil recovery .
 TYPES OF CAUSTIC USED:
 In alkaline materials used in flooding are sodium hydroxide and
sodium orthosilicate. Campbell described the orthosilicate form is
slightly more effective in cases where Calcium ions are available in
the injection fluids.
 Other alkali materials proposed and studied include sodium
carbonate, ammonium hydroxide, polyphosphate and hydroxyl
amine. These do not seem to offer any improvement over NaOH
 Table 9.1 lists the properties and costs of the major alkalis used.
ENTRAPMENT OF RESIDUAL OIL: The factors which determine the
entrapment & release of oil from a rock matrix are
1. The geometry of the pore network and the microscopic
heterogeneities of the porous medium.
2. Fluid-fluid properties; IFT, phase behavior and viscosities.
3. Fluid-rock properties; wettability, adsorption, dissolution
reactions.
4. Applied pressure gradients and gravity.
o During primary depletion, the contained fluids appear in the form of gas-cap
drive, water drive, compaction drive, solution-gas drive.
o Below the bubble pt, solution gas is released from the oil within the reservoir.
The gas phase thus created is much less viscous and bypasses (fingering,
channelling, override, etc.) the oil.
o Interfacial instability is also another mechanism for oil isolation or Haines jump
(reversible saturation changes called isons & sudden irreversible pressure
changes called rheons) occurs.
o Fig. 9.1 shows a converging-diverging pore in a porous media consisting of
spherical rock particles.
• The capillary pr as a function of
the non-wetting phase
penetration is shown in Fig. 9.2. .
• The non-wetting phase enters
the pore when its pr exceeds
the pore entry pr (A). It then
encounters decreasing capillary
prs and enters in completely
until it reaches the pore wall at B.
• The non-wetting phase then
enters the pores & the capillary
pr increases. On reaching the
critical pore saturation, the
capillary pr drops
discontinuously from C to D.
• The passage of the interface
from pore pendular ring shape
takes place in one
discontinuous movement,
termed Haines jump.
 Water flooding represents the secondary stage of production. It
improves recovery mainly through two mechanisms:
1) It provides the pressure energy to overcome the capillary
forces that entrap the oil.
2) It results in improved mobility ratio as compared to the
solution-gas drive the reservoir was subject to depletion in
the primary production.
 The displacement of oil from the pores by water also occurs
through a series of rheons and isons.
 The non-wetting phase, oil, is left behind as discontinuous blobs
and filaments adhering to the pore surface.
 This mechanism accounts for only a part of the residual OIP
after a waterflood. Poor areal and vertical sweep efficiencies
resulting from reservoir heterogeneities and gravity override
effects may reduce recovery efficiencies from 55-70% to 30-35%
DISPLACEMENT MECHANISMS IN ALKALINE FLOODING:
 The first stage involves the mobilization of the residual oil by
configurational changes like emulsification and wettability
alteration.
 The second stage involves the modification of the microscopic
production characteristics of the mobilized oil phase. The
recovery efficiency may be increased by mobility control.
The mechanisms by which alkaline flooding may improve
recovery of acidic crudes from partially depleted reservoirs:
1. Emulsification and entrainment,
2. Emulsification and entrapment,
3. Wettability reversal from water-wet to oil-wet,
4. Wettability reversal from oil-wet to water-wet
5. Lowering of interfacial tension,
6. Solubilization of rigid, interfacial films
 Conventional water
floods operate generally
at or near a capillary no.
of 10-6 .
Fig. 9.4 shows the
improvement of oil
recovery (to decrease
residual oil saturation),
the capillary no. must be
increased to 10-4 .

Lowering of interfacial tension:

 The IFT between water and certain California crudes was extremely low at certain ranges of
water pH. Their results are shown in Fig. 9.3.
 Instead, the lowest IFT is obtained for an optimum concentration
 The alkaline and surfactant solutions used alone only produced 1-3% additional oil, but the
mixture removed all of the residual oil virtually.
 The concept of capillary number, Nc = νµ/σ …9.1 where ν = darcy velocity of the displacement
front; µ = viscosity of the flowing fluid; σ = IFT
 Emulsification and flow:
.
 Researchers noted oil-in-water(oiw)
. emulsions were produced in the core & a
reduction in water mobility during
displacement tests.
 Fig.9.6 is an example of oiw emulsion. The
pseudophase diagram, neither caustic nor
water are soluble in the oil. Hence all
tielines pass through the oil corner of the
ternary diagram.
 Also it is assumed that neither relative
permeabilities nor viscosities are affected
by the presence of the alkali.
 The dispersed-oil lag factor, row is defined
as ratio of the volumetric rate at which the
oil component in the water phase moves to
the volumetric rate of movement of water.
 a) row =1 → oil droplets behave like a true
dissolved component; b) row =0.7 & row =0.3
represent a fine & course emulsion, rsply;
row = 0 → where the droplets are too large
& the IFT is too high for them to move at
all.
Emulsification and flow: (Continued)
There are two mechanisms in the emulsification process:
1) Emulsification and entrainment:
 Residual oil undergoing mobilization is emulsified and entrained into the
alkaline solution, produced as a fine emulsion. It is pointed that the alkali
conc. & pH should be such that stable in oiw emulsions are formed in the
emulsification and entrainment process.
 This mechanism is more applicable for low caustic content. The actual
movement of the oil may be described better coalescence behavior than by
entrainment.
2) Emulsification and entrapment:
 The emulsified oil is trapped again downstream in the porous medium at
pore throats that are too small for the emulsion droplets to penetrate,
forcing the injection water into pores that have not been previously
displaced.
 This results in reduction in the mobility of the aqueous phase. The
improvement in oil recovery is only due to improved areal & volumetric
sweep efficiencies. The viscosity of wio emulsions is higher than that of oiw
emulsions.
Wettability alteration:
 The success of a caustic flood
depends on the initial
distribution of residual oil in pore
spaces that is controlled by the
reservoir wettability and also on
the ability to alter wettability.
 The heavier components have a
greater effect on the rock
wettability, causing it to become
oil wet.
 The main idea is to reduce the
capillary forces holding the oil in
porous matrix. A change in pH  The pore becomes gradually oil-wet (9.7b)
can result in wettability change on arrival of wettability reversal agent
through reaction with surface- (caustic). This results, the decrease of
active materials in the crude capillary resistance & IFT reduction too.
adsorbed on the rock surface.  When the caustic conc. decreases &
 Fig.9.7a shows an oil droplet water-wetness returns, the oil clinging to
trapped at the pore throat under the rock under oil-wet conditions will
water-wet conditions. tend to be displaced. Fig. 9.7c,d)
 Alkaline flooding recovered more oil than plain water flooding. This aspect was
emphasized through controlling certain crude components.
1. Wettability reversal from oil-wet to water-wet: It is changed by the reaction
between the caustic and acidic polar compounds attached to the oil-wet
reservoir rock, resulting a favorable increase in the oil/water relative
permeability ratio & increase in displacement efficiency.
2. Wettability reversal from water-wet to oil-wet: The alteration of wettability to
oil-wet causes the discontinuous non-wetting residual oil phase to a continuous
wetting phase. Simultaneously, the IFT induces the formation of an alkali-in-oil
emulsion that plugs the flow paths & induces locally high pr gradients.
Solubilization of rigid interfacial films:
o Some crudes form insoluble films at oil-water interface. These films will
be lodged during transport at the pore constrictions, resulting in a rigid,
insoluble, immobile film and affecting the displacement efficiency in
heterogeneous porous media.
o The film forming constituents are mainly resins & asphaltenes and also
aldehydes, ketones, carboxylic acids, esters & organic nitrogen.
CRUDE OIL PROPERTIES:
 The crude components directly responsible for lowering of IFT are: 1.
Carboxylic acids, 2. carboxyphenols, 3. porphyrins 4. asphaltenes.
 A minimum acid no. (the no. of milligrams of KOH required to neutralize
1 gm of the crude oil to pH=7) needed for successful alkaline flooding, a
value of 0.5 or greater is favorable. Most oils have acid no. less than 1.
 The concept of the equivalent alkane carbon no. (EACN) to correlate IFT
behavior of crude oil-surfactant systems is under use.
 No single definitive criteria for crude properties needed for alkaline
flooding exist. Also crude oil handling affects the recovery enhancement
in core floods.
 TABLE 9.II

ALKALI CONSUMPTION:
• Alkali consumption is one of the most critical design parameters in flooding.
The injected alkali reacts with reservoir rock clays and minerals (Table 9.II).
• The consumption was found to increase with time, then level off with no
further consumption even at infinite time.
• Caustic reaction with the rock may be responsible for wettability changes. Too
high a reactivity can affect the process in two ways:
1. mechanisms like emulsification and entrainment and wettability reversal from
water-wet to oil-wet are vulnerable to high rock reactivity
2. the economics of the caustic flooding may be severely impaired due to higher
alkali consumption for a lower oil production.
• The alkali consumption comprises two types: reversible & irreversible.
• Reversible reactions or the ion-exchange type reactions seem to dominate at
high flow rates and include several mineral reactions.
• The most important irreversible reaction is the dissolution of the siliceous
material in the rock. The dissolution process is affected by the flow rate,
surface area/unit volume ratio, composition & alkali concentration and its
composition.
• Permeability damage or core plugging may sometimes occur due to reactions
with alkali. This may happen due to: clay swelling, and migration of fines.
• Permeability damage may not be a serious problem in Caustic flood in general.

•
pH OF INJECTED CAUSTIC
Fig.9.10 shows the influence of pH level on secondary recovery and Fig. 9.11 shows the effect
in the case a tertiary flood.
At a lower pH, less surfactant is produced from the oil & consequently a lesser amount of oil
is mobilized. Also at the lower pH, the ion-exchange is high enough to reduce oil production.
So it should be done at a high pH to overcome the chromatographic ion-exchange retardation
of the alkali.
EFFECT OF SODIUM IONS AND SODIUM CHLORIDE:
• The presence of sodium chloride reduces the bulk alkaline conc. required
to achieve low IFT.
• The conc. of NaOH at the interface will, however, approach the bulk conc.
• IFT is reduced when the interfacial pH reaches the pKa value of the native
acids in the crude, which are thus ionized to form interfacially-active,
charged acid species.
• Addition of salt lowers the bulk alkali conc. or the bulk pH needed to
achieve the onset of the IFT drop, i.e., the point where the interfacial pH is
equal to the pKa values of the acids in the crude.
• NaCl can be used to promote ultra-low IFT of crude oils at a lower onset
bulk aqueous pH. This is very useful in cases where too high an alkali conc.
is undesirable due to economic, environmental reasons.
• An optimum NaCl concentration may then be identified (Fig.9.12) where a
reasonably broad alkali response range is achieved without sacrificing too
much in IFT.
EFFECT OF DIVALENT IONS:
 The presence of multivalent cations, (Mg or Ca), in reservoir brines can
profoundly affect the oil recovery efficiency of an alkaline slug.
 The precipitation of Ca2+ & Mg2+ (hardness) ions delays hydroxide
transport and reduces the oil recovery efficiency. It can be avoided by
using a soft brine preflush. The detrimental effects of divalent ions on
interfacial activity have also been shown.
 On some studies, the reduction of activity the cations in the reservoir
brine will lead to more surfactant activity, resulting in lower IFT values
 The divalent ion effect depends upon: 1) ion exchange isotherm, 2) the
divalent ion concentration, 3) injection pH and salinity, 4) the solubility
product of the precipitated salt.
 Where the value of the dimensionless Damkohler number is very low,
very little of the precipitated material redissolves.
 In the field, where flow rates are low and flow lengths are extremely
large, resulting in a high Damkohler number, precipitate redissolution
is probably complete.
RESERVOIR SELECTION:
General caustic flooding experience indicates the basic criteria
presented below to identifying reservoirs suitable for alkaline flooding
Oil :
 Amount of residual oil-in-place: The amount of residual oil is
fundamental to the design and evaluation of any recovery mechanism.
Mungan suggested the residual OIP should at least be 400 bbl/ acre-ft
with a residual oil saturation of 40%.
 Viscosity-gravity: Chemical floods are applicable to oils the viscosities to
about 100 cP. Gravity may be in the range of 13-35 0 API for best results.
 Chemical character of the oil: It influences the IFT. In caustic flooding the
oil must have acidic components, an acid no. of 0.5 & a minimum acid
no. of 0.1-0.2 mg KOH/g oil. Preferably no acid gases like H 2S & CO2 .
 Compressibility: Highly compressible oils are more suitable candidates
for miscible flooding and should be generally avoided.
Formation Factor:
 Connate water Saturation: A high value of the connate water saturation
usually implies a tight reservoir, a clay- shaley formation or both. So,
connate water saturation may be less than 50%.
 Formation water salinity: In an avg. situation, a formation water salinity
less than 200, 000 ppm is desirable.:
 Formation water chemistry: Besides NaCl, there are several other
chemical species in the water that can strongly influence the behavior of
all chemical floods.
Rock mineralogy :
 Carbonate reservoirs enriched in Ca2+ & Mg2+ are unsuited for alkaline
flooding and only sandstone reservoirs are candidates for this process.
Clays, Ca, Mg, CaSo4 , gypsum etc should have minimal amount.
Laboratory Studies:
Lab core flooding helps in the selection of suitable reservoirs and
provides data essential to the design of the caustic flooding operation.
 Screen tests:
1) Acid number: The oil samples must be free from emulsion
breakers, inhibitors and other oilfield chemicals. The two most
popular techniques of measuring the acid no. are a) Color indicator
titration, b) potentiometric titration.
2) IFT measurements: The spinning drop instrument at ambient pr-
temp conditions with dead-oil, or with the pendant drop apparatus
at the reservoir pr-temp conditions with the live oil.
3) Wettability alterations: Imbibition studies or contact angle
measurements can be undertaken to determine the wettability of
the rock and its change on addition of caustic.
4) Emulsion Formation: They are studied using standard API testing
techniques
5) Brine-crude oil interaction: The formation of rigid films can be
studied using contact angle and IFT measurements.
Lab displacement tests :
After applying the screening criteria, positive results lead to the
laboratory tests on reservoir core samples.
The lab evaluation program also includes thin-section studies on
1. Untreated reservoir samples
2. Cores that have been water flooded
3. Cores that have been caustic flooded
4. Cores that have been water flooded-caustic flooded-water flooded.
5. Sand-packed Hele-Shaw models
Comparison between these studies provide valuable insight into
1. Behavior of fines
2. In-situ emulsification
3. Adsorption of various materials on grains
4. Behavior & response of various clays to the injected waters
5. Formation of various precipitates in situ.
DOCUMENTED ALKALINE FLOODING FIELD TESTS:
 A partial list of documented known field tests complied is shown in Tables
9.III & 9-IV.
 Results of these tests vary greatly from one field to another, because of
the differences in injection chemical, injection rate and quality of the
chemical, nature of the reservoir, nature of the crude oil, etc.
 Several important observations can be made from these published results
of alkaline flooding field applications.
1. Oil recovery in the field has been lower than that predicted on the basis of
the lab studies. Reservoir heterogeneities are responsible for this.
2. A caustic consumption in the field has been higher than that measured in
the lab. Lab investigations have to be made under more realistic conditions,
simulating the reservoir conditions more closely.
3. At the injection end, lab studies have shown injectivity problems and
permeability damage that has not been seen in the field. Such problems in
the field. Such problems in the field have been almost absent.
4. At the producing end in the field, scaling and plugging problems have been
encountered; no such problems occurred in the lab.