Alkaline Flooding

 Alkaline agents such as sodium hydroxide could react with naturally

occurring organic acids in crude oil to produce soaps at the water-oil
interface. The effect produced in a reservoir appears to be similar to
that of micellar solutions. The difference is that alkaline flooding
reduces the interfacial tensions (IFT) with surfactants generated in
situ.
 Despite the fact that alkaline agents are less expensive, the benefits
expected from alkaline flood have not been confirmed by firm field
results and still remain a possibility.
 Indeed, the major difficulty is that the process appears to be highly
dependent on minerals on the surface of reservoir rock, which are not
chemically inert, and on the crude oil and injection fluid
characteristics.
 Efforts have been made, to understand better the recovery
mechanisms generated in alkaline flooding. Since alkaline agents are
cost-efficient materials, their use, along with surfactant and/or
polymer, could reduce the amount of high-cost surfactant and
cosurfactant required in micellar flooding.
 A reevaluation of alkaline flooding is taking place in order to find ways
to reduce the reaction of alkaline agents with reservoir minerals and to
take advantage of the combined alkaline/surfactant mixture effect.
Displacement Mechanisms
 Several mechanisms have been suggested regarding oil displacement
by alkaline flooding. The publication of Johnson's review (1976) gives a
description of four different mechanisms based on oil emulsification
and wettability reversal.
 It is known that fluid distribution within the pore spaces of a rock
reservoir during (alkaline) waterflood depends upon the wetting and
non wetting phase saturation and upon the direction of the saturation
change.
 In a water-wet rock reservoir, the injected water increases the wetting
phase saturation, the residual oil being the discontinuous phase. In an
oil-wet rock reservoir, the injected water decreases the wetting phase
saturation, the residual oil being the continuous phase.
  It was observed also that residual oil saturation always depends on the
dimensionless ratio of viscous to capillary forces defined as the
capillary number: Nc = vμ/σ
(velocity x viscosity of the displacing water) / (interfacial tension between water
and oil phases).
 When the capillary number value can be increased from 10-6 - 10-7
(conventional waterflood) to 10-4 or more, the residual oil saturation
decreases.
Four different mechanisms
1. The alkaline solutions increase the capillary number value by
reacting with the organic acids present in some crude oil to form
emulsifying soaps. The petroleum soap or surfactant formed emulsifies
oil and water and reduces the interfacial tension by two or three
orders of magnitude.
2. When the displacement takes place in an oil-wet reservoir where
residual oil is a continuous phase, the alkaline agent changes the
injection water pH and the rock wettability is reversed from oil-wet to
water-wet. This mechanism is defined as wettability reversal. As a
consequence the water-oil relative permeability and the water-oil
mobility ratio are lowered, with evident benefits on oil recovery.
3. Even in the water-wet reservoirs the discontinuous, nonwetting
residual oil phase can be changed to a continuous wetting phase if
proper conditions of reservoir temperature, pH, and salinity of the
alkaline solution are met. The mechanism is referred as wettability
reversal from water-wet to oil-wet. The presence of water droplets in
the continuous oil-wet phase raises the pressure gradient of the flow
through porous medium. The capillary forces are overcome and
residual oil saturation is reduced.
4. A fourth mechanism, emulsification and entrapment, explains that
additional oil could be produced because of the entrapment of the oil
emulsion droplets by small pores. Because the flow is diverted into
poorly swept or unswept areas, it improves the volumetric sweep
efficiency, especially in waterflooded viscous oil reservoirs or in
heterogeneous reservoir.
 Although other displacement mechanisms have been identified, the
principal mechanism considered in alkaline flooding is the reduction of
the oilwater interfacial tension. The chemical reactions involving the
 alkaline solution and in-place crude oil form a surfactant that reduces
the IFT.
Method Description
 The basic alkaline flooding process starts with a softened water
preflush injection followed by the injection of an alkaline solution of
about 10 to 30 percent PV and by continuous injection of drive water.

 Numerous variations have been proposed. The injection of a polymer

slug behind the alkaline solution to control mobility and to improve
sweep efficiency is desirable if it is cost effective.
 Because of the complexity of the mineralogy and lithology of
petroleum reservoirs the possible reactions between rock-alkaline
solution-saline water and oil in the existing conditions of pressure and
temperature are considerable. This explains the effort put into
laboratory alkaline flooding tests and field trials to design properly the
best system for specific reservoir conditions.
 The state-of-the-art techniques for alkaline flooding utilize alkaline
agents in combination with low concentrations of synthetic surfactant
and polymer for mobility control.
Design Considerations
 The principal goal in designing an alkaline system is to achieve a
minimum IFT in the reservoir. The corresponding alkali concentration
is then considered optimum.
 In the laboratory, the alkali concentration yielding the minimum IFT
was very low, often less than 0.1 wt % in some of the early flood
designs. In the field, this concentration did not survive far from the
wellbore because of reaction with the rock and consumption.
 Results from even the earliest laboratory experiments have shown
that salinity plays an important role in determining optimum alkali
concentration. For instance, minimum IFT could be achieved with
distilled water and a wide range of NaOH concentrations, between 0.1
and 0.8 wt % .
 With brine from Whittier field, California, where a field trial of caustic
flooding was conducted , the lowest IFT was obtained over a very
narrow range of NaOH concentrations (0.18-0.27 wt % ).
 Adding alkali to increase concentration and to keep the effect of
alkaline solution far from the injection wellbore increased the salinity
of the system and the IFT value.
 Core samples waterflooded to residual oil saturation and then injected
with polymer, alkali-polymer, or alkali-surfactant-polymer showed that
the last combination was the most efficient .
  The alkali-surfactant-polymer system reduces the residual oil
saturation to its lowest value in comparison with the other two
systems. The low amount of surfactant (0.1 wt %) added to an
alkalinepolymer system can have the same efficiency in displacing oil
that a micellarpolymer system has, but at a lower chemical cost.
 Although the laboratory tests and studies reported encouraging
results, the process will have to be proven by an increasing number of
field pilots and by commercial development.

Screening Criteria
 The general screening criteria including temperature (less than 200 °F),
permeability (between 50 and 250 md), oil viscosity (less than 150 to
200 cp), and low brine salinity are the same as the limits characterizing
chemical flooding using surfactants or polymers.
 As with other injection solutions, reservoirs with large gas-cap areas
and extensive aquifers should also be avoided when considering the
use of alkaline flooding.
 There are other special aspects to consider when screening reservoirs
for alkaline flooding such as the mineralogy of the reservoir rock, the
C02 content of the petroleum reservoir, and the crude oil's acid
number.
 Gypsum. Reservoirs with gypsum (anhydrite) content greater than 0.1
percent should be rejected as candidates for alkaline flooding. The
gypsum reacts and consumes the alkali agent. For instance, 1%
gypsum in a reservoir can consume 10 PV of a 1 percent solution of
NaHC03.
 Kaolinite. Reservoirs that contain appreciable amounts of kaolinite
could be candidates for alkaline flooding only with low-pH (about 8.2-
10) alkalis. The presence of kaolinite is a serious deterrent to flooding
with higher-pH alkalis.
 Montmorillonite. The montmorillonite content of rock reservoir,
because of its large surface area and very high cation exchange
capacity, can consume much of the injected alkali by adverse
precipitation reactions. Reservoirs with a montmorillonite content
higher than 1 percent and 0.4 wt % divalent ions in the brine are not
good alkaline flooding candidates.
  Sandstone. Sandstone reservoirs are preferred. High-pH alkalis are
reactive with limestone.
 Crude oil. It is important for the crude oil to have a high acid number
(Acid number is the number of milligrams of potassium hydroxide
required to neutralize 1 gram of crude oil to pH = 7.0) to achieve low
IFT in alkaline flooding, when the system does not include synthetic
surfactant. However, even with crude oil with a low acid number, the
alkaline flood can still be successful as a result of mechanisms other
than IFT lowering.
 Carbon dioxide. The CO2 content of a petroleum reservoir is now
considered a strong screening criteria parameter. Reservoirs with high
CO2 content, mole fraction of CO2 (in produced gas) higher than 0.01,
or a pH less than 6.5 are not good candidates for alkaline flooding.
FIELD TRIALS
 Two field trials of caustic flooding (Whittier oil field and Wilmington
Ranger zone, California), where the published field results were
combined with laboratory data, are presented next.
Whittier oil field. Reservoir characteristics.
 The project was started as a simultaneous flood in both productive
second and third zones of the 63-acre project area at an average
subsea depth of 1500 ft and 2100 ft, respectively. Other reservoir and
fluid characteristics were

Project implementation.
 Approximately 1.6 million bbl of a solution composed of 20 percent PV
of 0.2 wt % sodium hydroxide in water were injected through four
initial injectors over a period of 10 months. The concentration of 0.2
 wt% NaOH is within the range which corresponds with the lowest
interfacial tension value.
 Results. As we observe, the caustic flood produced more oil than
could have been expected from the continuation of waterflood. The
response to caustic flooding showed drops in WORs also.

Comments.
 What is interesting to point out is that the injectors were located
upstructure . A high-dip oil reservoir with a very good permeability
exhibits a strong gravitational effect even when the crude oil viscosity
is 40 cp. When the reservoir is moderately to highly heterogeneous,
there are high permeability layers, referred to as thief channels,
through which the gravitational flow of fluids rapidly reaches the
downstructure producers.
 Indeed, tracers were detected a short time (8 to 16 days) after the
start of injection into downstructure producers, and injection into two
wells was stopped.
 The alkaline flood injection was started upstructure, probably to avoid
the high water saturation existing downstructure where the
waterflood was supposed to take place.
  Nevertheless, it is very important to consider carefully the reservoir
geometry and recovery mechanisms so that the way in which the
method is implemented will give maximum benefit.
Wilmington Field Ranger Zone, California, United States
 The alkaline demonstration pilot project is comprised of two rows of
four injectors each, which enclose the Block 9 pattern area in the
Ranger Zone of Wilmington Field.
 There are two reasons why alkaline flooding was considered for
Wilmington-the first is the low recovery efficiency obtained by
waterflooding a reservoir which has permeability variations and an
unfavorable mobility ratio; the second was the high content of organic
acids in the crude oil.
 The injection was started in the 91 acres pilot project area with 10.2
percent PV softened freshwater with 1 percent salts, followed by 67
percent PV of alkaline solution (0.39 wt % sodium orthosilicate) and by
a postflush of softened water with 0.75 percent salts.
The main results of this study. Reservoir characteristics.
 The productive formation lies at a depth of 2225 to 2800 ft and
consists of six to eight intervals or subzones of 305 ft total average
thickness of interbedded shales and unconsolidated to
semiconsolidated sands.
 The main reservoir and fluid characteristics in the alkaline pilot area
are

Laboratory work.
• Detailed laboratory studies were performed using core samples
recovered in frozen plastic pipe. Special core analysis tests showed an
 average displacement efficiency with waterflood of 49.4 percent of the
oil in place and a cation exchange capacity from 2.6 to 11.5
milliequivalents per 100 grams.
• The acid number of Ranger Zone crude oil varied from 0.86 to 2.5
milligrams of KOH per gram of oil and measurements of interfacial
tension indicated a lower value obtained with sodium orthosilicate than
with sodium hydroxide.
• The consumption tests performed showed alkali consumption ranged
from 8.6 to 16.9 milliequivalents of alkali per 100 grams of rock at
reservoir temperature and over a test period of 36 days.
 The reservoir contained a significant amount of clays and also gypsum.
The laboratory displacement tests with alkaline solution indicated an
average incremental recovery over waterflooding of about 6 percent
of OOIP. The concentration of ions in the produced water suggested
that during alkaline waterflooding the alkali was consumed and the
core material was undergoing dissolution.
Simulation.
 A simulator model with the ability to represent the effects of the
alkaline fluids by changes in the relative permeabilities was used in a
one-dimensional form to simulate laboratory tests, a two-dimensional
form to represent a limited area of the field, and a three-dimensional
form to represent the entire project.
 The pilot area simulation (three-dimensional model) predicted an
incremental oil recovery of about only 1.9 percent of OOIP compared
with 7.25 percent of OOIP predicted from the smaller two-dimensional
pattern. This disappointing result appears to be the effect of the long-
term consumption of alkaline fluids and of the larger surface area.
Minifield test.
 A two-month, one-well injectivity test was conducted before the start
of the full scale pilot and satisfactory results were obtained regarding
fluids injectivity and the operation of the surface facilities in handling
the chemicals.
Project implementation.
 The alkaline slug injection started in March 1980. After the 10.2
percent PV preflush injection, 49,927,000 bbl (67 percent PV) of
alkaline solution were injected over a period of 34 months at an
average rate of 30,000 bbl/day.
  Scale deposition in producing wells after the breakthrough of alkaline
solutions has been a major problem. Numerous workovers were
conducted to overcome the plugging effects of scale in producing
wells. The scales composed of calcium carbonate, magnesium silicate
and amorphous silica were treated with a combination of acid and
scale inhibitor injections.
Evaluation of results.
 The alkaline solution injection did not seem to have an impact on
production data.
 The water-oil ratio did not appear to be practically influenced,
although a reduced water production was observed in some of the
wells. The plot of the oil cut versus cumulative oil recovery indicates
that there was no improvement in oil recovery compared to
waterflooding.
 The high consumption of chemicals and the wellbore plugging
problems were the main reasons this project proved to be
unsatisfactory, not to mention the lower than expected oil recovery .
Comments.
 The Wilmington Field Ranger Zone alkaline flood project is an example
of how a very-well-prepared, developed, and executed project still did
not produce the expected results in the field. It is very important to
evaluate the complex reactions of alkaline chemicals with the reservoir
rock and fluid content.
 Losses from chemical consumption observed in laboratory tests, when
transferred to the field scale, can be the main reason for failure.
 Another important aspect is reservoir geometry. The Ranger Zone
consists of several subzones separated by impermeable shale barriers.
Even if these shale barriers are continuous, they are in hydrodynamic
communication through the producers, each opening up at least six
subzones.