Dr. Ir.

Dedy Kristanto, MT
Petroleum Engineering Department
UPN “Veteran” Yogyakarta

CHEMICAL FLOODING
CHEMICAL METHODS

Chemical EOR methods utilize:

- Alkaline
- Surfactants
- Polymer
- Combinations of such chemicals
• ASP (Alkaline-Surfactant-Polymer) flooding
• MP (Micellar-Polymer) flooding
• SS (Smart / Super Surfactant) flooding

DK - 2 -
OBJECTIVES OF CHEMICAL
FLOODING
 Increase the Capillary Number Nc to
mobilize residual oil
 Decrease the Mobility Ratio M for better
sweep
 Emulsification of oil to facilitate
production

DK - 3 -
Relationship between Capillary Number
and Oil Recovery
Figure 1

RELATIONSHIP BETWEEN CAPILLARY NUMBER

AND OIL RECOVERY

100
Nc =  µ /
80
% Oil Recovered

Nc = Capillary Number
60  = Darcy Velocity
µ = Viscosity
40
 = Interfacial Tension

20

0
1.E-06 1.E-05 1.E-04 1.E-03 1.E-02
Capillary Number

Chatzis and Morrow, SPEJ, (1994) 561.

DK - 4 -
Chemical Flooding -
GENERAL LIMITATIONS

 Cost of chemicals
 Excessive chemical loss: adsorption, reactions
with clay and brines, dilution
 Gravity segregation
 Lack of control in large well spacing
 Geology is unforgiving
 Great variation in the process mechanism, both
areal and cross-sectional

DK - 5 -
ALKALINE FLOODING
 Process depends on mixing of alkali and oil
- Oil must have acid components
 Emulsification of oil, drop entrainment and
entrapment occur
- Effect on displacement and sweep efficiencies
 Polymer slugs used in some cases
– Polymer alkali reactions must be accounted
 Complex process to design
Mixing zones

low
caustic water
drive IFT
water slug zone
oil
residual oil

Alkaline Flood
DK - 6 -
CHARACTERISTICS OF ALKALINE
FLOODING

 A solution of inorganic alkaline substance (NaOH,

KOH) is injected into the reservoir.
 NaOH Na+ + OH-
KOH K+ + OH-
OH- + Acid hydrocarbon components Surfactants
 In-situ generated surfactants reduce interfacial
tension and hence lowering Sor.
 May alter the wettability towards water wet.
 Help form emulsions near the displacement front.

DK - 7 -
SURFACTANT FLOODING
 Variations
- Surfactant-Polymer Flood (SP)
- Low Tension Polymer Flood (LTPF)
 Adsorption on rock surface
 Slug dissipation due to dispersion
 Slug dilution by water
 Formation of emulsions
- Treatment and disposal problems
mixing zone

drive surfactant slug water

water

oil
residual oil
DK - 8 -
Surfactant Flood
CHARACTERISTICS OF
SURFACTANT FLOODING
 A surface active agents which reduce interfacial
tension at the oil-water interface.
 Formation of emulsions
- These are anionic compounds, where:
Surfactant + Water  (Inorganic Cation)++ +
(hydrocarbon sulfonate anion)--
- They resist adsorption
- More stable than cationic surfactants
- Easier and cheaper to manufacture

DK - 9 -
CHARACTERISTICS OF
SURFACTANT FLOODING

 Water salinity (specially divalent cations such as

Ca++ and Mg++) play an important role in
performance.
 Minimum interfacial tensions occurs at optimal
salinity at which an optimum microemulsions is
developed and the surfactant is equally soluble in
water and oil.

DK - 10 -
SURFACTANT FLOODING
Surfactant Injection Water Separation and Production Well
Solution From Well Injection Storage Facilities
Mixing Plant Pump

3 2 1

1 Oil Zone Surfactant Drive Water

2 3

DK - 11 -
SURFACTANT FLOOD

Injector Producer

DK - 12 -
SURFACTANT FLOOD

Injector Producer

DK - 13 -
SURFACTANT FLOOD

Injector Producer

DK - 14 -
SURFACTANT FLOOD

Injector Producer

DK - 15 -
SURFACTANT FLOOD

Injector Producer

DK - 16 -
SURFACTANT FLOOD

Injector Producer

DK - 17 -
SURFACTANT FLOOD

Injector Producer

DK - 18 -
Surfactant Flooding
Description

 Consists of injecting a slug containing water,

surfactant, electrolyte (salt), usually a co-solvent
(alcohol), and possibly a hydrocarbon (oil), followed
by polymer-thickened water

Mechanisms That Improve Recovery Efficiency

 Interfacial tension reduction (improves

displacement sweep efficiency)

 Mobility control (improves volumetric sweep

efficiency)

DK - 19 -
Surfactant Flooding
Limitations
 Areal sweep more than 50% for waterflood is desired
 Relatively homogeneous formation
 High amounts of anhydrite, gypsum, or clays are undesirable
 Available systems provide optimum behavior within narrow
set of conditions
 With commercially available surfactants, formation water
chlorides should be < 20,000 ppm and divalent ions (Ca++ and
Mg++) < 500 ppm
Challenges
 Complex and expensive
 Possibility of chromatographic separation of chemicals
 High adsorption of surfactant
 Interactions between surfactant and polymer
 Degradation of chemicals at high temperature DK - 20 -
Surfactant Flooding
Screening Parameters
 Gravity > 25° API
 Viscosity < 20 cp
 Composition light intermediates
 Oil saturation > 20% PV
 Formation type sandstone
 Net thickness > 10 feet
 Average permeability > 20 md
 Transmissibility not critical
 Depth < 8,000 feet
 Temperature <  225 ° F
 Salinity of formation brine < 150,000 ppm TDS
DK - 21 -
Surfactant flood -
FIELD PERFORMANCE

Glenn Pool Field, Oklahoma

OIL
1,000

100
WOR
10
1984 85 86 87 88 89 90 91 92
DK - 22 -
POLYMER FLOODING

 Loss to rock by adsorption, entrapment, salt

reactions
 Loss of injectivity
 Lack of control of in situ advance
 High velocity shear (near wellbore), ageing, cross-
linking, formation plugging
 Often applied late in waterflood mixing zone

drive water
polymer slug
water

oil
residual oil

Polymer Flood
DK - 23 -
POLYMER FLOODING

Polymer Injection Water Separation and Production

Solution From Well Injection Storage Facilities Well
Mixing Plant Pump

3 2 1

1 Oil Zone 2 Polymer Solution 3 Drive Water

DK - 24 -
CHARACTERISTICS OF
POLYMER FLOODING

 Polymer solutions have high viscosity, hence

improve the mobility ratio.
 Some polymers are used for reducing the rock
permeability due to their retention and
viscoelastic properties. Hence, could be used as
plugging agents for profile control.
 Increasing sweep efficiency.

DK - 25 -
Polymer Flooding
Description
 Consists of adding water soluble polymers to water before it
is injected in reservoir
Mechanisms That Improve Recovery Efficiency
 Mobility control (improves volumetric sweep efficiency)
Limitations
 High oil viscosities require higher polymer concentration
 Results normally better if polymer flood started before water-
oil ratio becomes excessively high
 Clays increase polymer adsorption
 Some heterogeneity is acceptable, but avoid extensive
fractures
 If fractures are present, crosslinked or gelled polymer
techniques may be applicable
DK - 26 -
Polymer Flooding

Challenges
 Lower injectivity than with water can adversely
affect oil production rates in early stages of
polymer flood
 Acrylamide-type polymers loose viscosity due to
sheer degradation, or it increases in salinity and
divalent ions
 Xanthan gum polymers cost more, are subject to
microbial degradation, and have greater potential
for wellbore plugging

DK - 27 -
POLYMER RETENTION

 Polymer solutions are retained mainly by adsorbtion

and sometimes by pore trapping in reservoir rocks.
 Pore trapping is significant in low permeability rocks.
 Undesirable for polymer flood but desirable for
profile control and thief zone plugging.
 Field observation indicates retention in the range of
7-150 g/m3 of rock.
 Acceptable retention level is less than 20 g/m3 of
rock.
 Polyacrilamides show higher retention level than bio-
polymer due to their ionic nature and shear
thickening.

DK - 28 -
ESTIMATING POLYMER
CONCENTRATION

 Polymer concentrations depends on type and

required solutions viscosity.
 Required viscosity is determined from
maximum mobility ratio and shear rate.

DK - 29 -
ESTIMATING POLYMER
CONCENTRATION

DK - 30 -
ESTIMATING POLYMER
CONCENTRATION

DK - 31 -
ESTIMATING POLYMER SLUG SIZES

DK - 32 -
REQUIRED POLYMER SLUG SIZES

DK - 33 -
Polymer Flooding

Screening Parameters
 Gravity > 18° API
 Viscosity < 200 cp
 Composition not critical
 Oil saturation > 10% PV mobile oil
 Formation type sandstone / carbonate
 Net thickness not critical
 Average permeability > 20 md
 Transmissibility not critical
 Depth < 9,000 feet
 Temperature <  225 ° F
DK - 34 -
Polymer Flood -
FIELD PERFORMANCE

Sanand Field, India

125 650

100 620
EOR OIL
75 590
Projected

50 560

25 530

0 500
1989 1991 1993 1995

DK - 35 -
ASP: ALKALINE-SURFACTANT-
POLYMER FLOODING

 Several variations: water

Surfactant
drive oil

alkaline
water polymer bank
- ASP Injected as oil

- SAP premixed slugs

or in sequence ASP Flood
- PAS

 Field tests have been encouraging

 Successful in banking and producing
residual oil
 Mechanisms was fully understood

DK - 36 -
ASP CHEMICAL CONTENTS
 Alkaline
Type of Alkaline for ASP is Sodium Hydroxide (NaOH) and Sodium
Carbonate (Na2CO3)

 Surfactant
Type of surfactant in ASP are:
1. Alkyl Benzene Sulfonates
2. Petroleum Sulfonates
3. Lignosulfonates
4. Petroleum Carboxylates
5. Biologically Produced Surfactants

 Polymer
In ASP flooding, types of polymer is Hydrolyzed Polyacrylamide
(HPAM)
DK - 37 -
SCREENING CRITERIA ASP
FLOODING
- Preferred for sandstones reservoir
- Reservoir Temperature less than 200 °F
- Lower Ca++ and Mg++ contents
- Formation relatively homogeneous
- Oil Viscosity < 35 cp and API Gravity > 20 °API
- Oil composition is light to intermediate components
- Oil Saturation > 35 % PV
- Average Permeability > 10 md
- Reservoir Depth less than 9000 ft.

DK - 38 -
ASP PILOT – Daqing, China

100

Oil Rate
50

Oil Cut

20

10
1993 1994 1995 1996

DK - 39 -
MICELLAR FLOODING

 Utilizes microemulsion and polymer

buffer slugs
 Miscible-type displacement
 Successful in banking and producing
residual oil
 Process Limitations:
- Chemical slugs are costly
- Small well spacing required
- High salinity, temperature and clay Micellar Flood
mixing
- Considerable delay in response zone
water

polymer
water
oil

drive
- Emulsion production bank oil

micellar mixing zone

slug
DK - 40 -
MICELLAR FLOODING PROCESSES

Injection Well Producer Well

Chase Mobility Polymer Micellar Preflush Reservoir

Water Taper Slug Slug Solution Fluids
Displacement

 Chase water, to displace injected fluids

 Mobility taper, to achieve gradual decrease in viscosity of displacing
fluids.
 Polymer slug, for mobility control.
 Micellar slug, to reduce the interfacial tension and hence lowering the
residual oil saturation (Sor).
 Preflush solution, to precondition the reservoir and obtain optimal
salinity.
DK - 41 -
MICELLAR FLOODING

DK - 42 -
MICELLAR FLOODING

DK - 43 -
MICELLAR FLOODING

DK - 44 -
MICELLAR FLOODING

DK - 45 -
 ASP vs MICELLAR FLOOD -
Lab Results – Mitsue Oil Core Floods

Micellar Flood ASP Flood

100 100
Slug 5% Buffer 50% Alkali 5%,Surfactant 10%,Polymer 60%
92% OIP

Oil Cut,%; Cum. Recovery,% OIP

Oil Cut,%; Cum. Recovery,% OIP

80 80
Soi 32% Soi 38% 80% OIP
60 60

40 40
Oil Cut Oil Cut
20 20

0 0
0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5
Pore Volumes Injected Pore Volumes Injected

Earlier oil breakthrough and quicker recovery in micellar flood

DK - 46 -
Micellar flood –
TYPICAL PERFORMANCE

Bradford Special Project No. 8

1,000 10

Oil Cut

100 1

Oil Rate

10 0.1
Dec. 81 Dec. 82 Dec. 83 Dec. 84 Dec. 85
micellar
injection

DK - 47 -
Micellar floods – FIELD TESTS

100
Henry S
Henry E & Henry W
80 119-R

60 Wilkins

40

Dedrick
20

0
0 2 4 6 8 10 12 14
Micellar Slug Size, %PV
DK - 48 -
SMART SURFACTANT (SS)
 Super Effective
- Ultra-Low concentration required (0.02% - 0.3%)
- Provides ultra-low IFT
 Super Convenient
- No alkali is required
- No water treatment is required
 Super Tolerant
- High TDS brine
- High divalent cations
- High temperatures
 Super Savings
- Water treatment
- Sludge disposal
- Surface equipment
- Potential scale formation
- Equipment maintenance DK - 49 -
 Interfacial Tension-
SMART SURFACTANT (SS)

SS in High Salinity Brine SS in High Temperature

TDS ~190,000ppm, Heavy Crude
Ca, Mg ~ 95,000 ppm TDS ~ 250 ppm,
Temp. ~ 50 C, API Gravity ~ 35 Temp. ~ 100 C, API Gravity ~ 15

1 1.0000
IFT, mN/m

0.1 0.1000

IFT, mN/m
0.0100
0.01
0.0010
0.001
0.0001
0 0.05 0.1 0.15 0.2 0.25 0.00 0.05 0.10 0.15 0.20 0.25
SS 6-105, % Wt. SS-B2550, WT%
DK - 50 -
Relationship between
Capillary Number vs Oil Recovered
Surfactant Alkali Oil IFT, mN/m @ 60 min

0.1% SS B8020 None Q-22 0.00106

0.1% SS B8020 None P 0.00102
Figure 1

RELATIONSHIP BETWEEN CAPILLARY NUMBER

AND OIL RECOVERY

100
Nc =  µ /
80
% Oil Recovered

Nc = Capillary Number
60  = Darcy Velocity
µ = Viscosity
40
 = Interfacial Tension

20

0
1.E-06 1.E-05 1.E-04 1.E-03 1.E-02
Capillary Number

Chatzis and Morrow, SPEJ, (1994) 561.

Surfactant Mechanisms on Porous Media
(Wetability Change due to Surfactant on Oil-Water Surface)
SMART SURFACTANT

Injector Producer

DK - 53 -
SMART SURFACTANT

Injector Producer

DK - 54 -
SMART SURFACTANT

Injector Producer

DK - 55 -
SMART SURFACTANT

Injector Producer

DK - 56 -
SMART SURFACTANT

Injector Producer

DK - 57 -
SMART SURFACTANT

Injector Producer

DK - 58 -
SMART SURFACTANT

Injector Producer

DK - 59 -
Oil Recovery Comparisons
35000 TDS, 1700 Ca/Mg
0.1% surfactant
0.3% smart surfactant

80
70
% Recovery OOIP

60
15 PV surfactant
50 13 PV water %OOIP
40
CUM,%
30
20 2 PV smart surfactant
15 PV water
10 15 PV water
0
0 25 50 75
PV Injected
SPE 84075
DK - 60 -
Recycling Surfactant Effluent

 Residual surfactant present in the effluent

 Process identifies surfactant in effluent and
recycles back to reservoir
 Savings on surfactant costs
 Savings on disposal and treatment costs
 Recovers additional oil

SPE 84075
DK - 61 -
REASONS FOR FAILURE
 Low oil prices in the past
 Insufficient description of reservoir geology
- Permeability heterogeneities
- Excessive clay content
- High water saturation
- Bottom water or gas cap
- Fractures
 Inadequate understanding of process
mechanisms
 Unavailability of chemicals in large quantities
 Heavy reliance on un-scaled lab experiments
DK - 62 -
SCALE-UP METHODS

 Require:
- Knowledge of process variables or complete
simulation description
- Model experiments
- Scale-up of model results to field
 Greater confidence to extend lab results to field

DK - 63 -
RESULTS:
PREDICTION vs ACTUAL

60
Actual
Oil Recovery, %OIP

50

40

30
Predicted
20

10

0
0 0.2 0.4 0.6 0.8 1 1.2
Pore Volumes Produced
DK - 64 -
CHEMICAL EOR AND HEAVY OIL
 Applicable methods:
- Surfactant flooding unsuccessful
- Alkaline flooding unsuccessful
- CO2 immiscible; cyclic stimulation Limited
success with WAG
 Problems:
- Unfavourable mobility ratio
- Gravity segregation
- Rock-fluid reactions, chemical loss, dilution
- Lack of scaling criteria, inadequate simulation
- Often used where steam is not suitable
DK - 65 -
EOR SCREENING CRITERIA FOR
CHEMICAL FLOODING
Most important: geology and mineralogy

 Oil viscosity < 35 cp  Formation sand stone preferred

 Oil API gravity > 30 API  Thickness 20-30 ft
 Permeability ≥ 100 md  Stratification desirable
 Porosity ≥ 15%  Clay content < 5%
 Temperature < 150 F  Salinity < 20,000 ppm
 Depth < 9,000 ft  Hardness < 500 ppm
 Pressure not critical  Oil composition Light,
intermediates & organic acids
 Oil saturation ≥ 45% desirable
 Oil in place at process start ≥  No bottom water or gas cap
600 Bbl/acre-ft

DK - 66 -
COMPARISON OF CHEMICAL
FLOODING USAGE
Properties ASP AP SP
Surfactant 0.1 – 0.2% 0% 0.1 – 0.2%
Concentration

Interfacial Tension  10 –2 ~10 0 - 10 –1  10 -2

(mN/m)

Alkali Requirement Yes Yes No

Potential Alkali 2NaOH + Ca+2 2Na+ + Ca OH)2 Same as ASP None

reaction in
2NaOH + Mg+2 2Na++ Mg(OH)2
formation
Na2CO3 + Ca+2 2Na+ + Ca CO3 
Na2CO3 + Mg+2 2Na+ + Mg CO3
Polymer ~1,000 ppm – 2,000 ppm. The Same as ASP ~ 500 -1,000
concentration polymer concentration needs to ppm
be adjusted based on the alkali
conc. and the brine salinity. In
general, 1% alkali will reduce the
polymer viscosity by 50%. This
means more polymer will be
needed.

DK - 67 -
COMPARISON OF CHEMICAL
FLOODING USAGE

Properties ASP AP SP
Water Treatment Yes Yes No
for higher divalent
cations brine
Water treatment High High None
cost
Additional cost due Yes Yes No
to the use of alkali Including water Same as
treatment, alkali cost, ASP
shipping, storage,
equipment, water
treatment, hazardous
material handling,
potential scale/
emulsion/ corrosion
problems. More polymer
is required, etc.

DK - 68 -
COMPARISON OF CHEMICAL
FLOODING USAGE
Properties ASP AP SP
Adsorption onto Na2CO3 will be Same as ASP In general, the
Formation preferentially adsorbed surfactant
due to its common ion adsorption of SP
onto the formation and is higher than ASP
reduce the polymer and due to the
the surfactant adsorption. absence of alkali.
NaOH will also be The adsorption
adsorbed and reduce the problem can be
adsorption of the polymer minimized by
and surfactant but to a proper design of
lower extent the surfactant
structures and
also the flood
injection design
Potential corrosion Yes Yes Minimized to none
/scale problems in
the pipeline and
equipment
Note : ASP (Alkaline-Surfactant-Polymer); AP (Alkaline-Polymer)
SP (Surfactant-Polymer)
DK - 69 -
HOW TO PLAN A FLOOD ?
 Choose a process likely to succeed in a candidate
reservoir
 Determine the reasons for success or failure of
past projects of the process
 Research to “fill in the blanks”
- Determine process mechanisms
- Derive necessary scaling criteria
- Carry out lab and simulation studies
 Field based research
 Establish chemical supply
 Financial incentives essential
DK - 70 -
HOW TO REACH SUCCESS ?

 Select the proper project

 Utilize the expertise of all involved
 Chemical optimization
 Cost efficiency
 Evaluate the lab and simulation results
 Select the best process
 Start the pilot project

DK - 71 -
DETAIL STUDY ACTIVITIES

 Data colecting, evaluating and analysis

 Review and update the Geophysics and Geology Study
previously and QC
 Detail Study of Reservoir Engineering
 Laboratory Core Analysis (Routine and SCAL)
 Chemical Laboratory Flooding Test
 Detail Study of Production Engineering
 Reservoir Simulation
 Economic Analysis
 Recommendations

DK - 72 -
IMPLEMENTATION STEPS

 Integrated Reservoir Model

- Geological Model (Static Data)
- Production History (Dynamic Data)
- Fluid and Rock Properties (Laboratory Data)
 History Matching
- Validating the Geological Model
- Predicting the Present Fluid Distributions
 Forecasting Future Performance
- Evaluating the Method
- Optimizing Injection Schemes
DK - 73 -
PROCESS EVALUATION

- Compare field results with lab (numerical)

predictions
- Relative permeability changes ?
- Mobility control ?
- Fluid injectivity ?
- Extent of areal and vertical sweep ?
- Oil saturations from post-flood cores ?

DK - 74 -
COST OF CHEMICALS
 As the oil prices rise, so does the cost of chemicals,
but not in the same proportion

 Typical Costs:
- Polymer - $3/lb
- Surfactant - $1.20/lb
- Crude oil - $60/bbl
- Caustic - $0.60/lb
- Isopropanol - $20/gallon
- Micellar slug - $25/bbl

 Process Efficiency: volume of oil recovered per unit

volume (or mass) of chemical slug injected
DK - 75 -