Chemical Flooding

Secondary and Tertiary Oil Recovery

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 OUTLINE

• Elementary mechanisms
• Alkaline flooding
• Surfactant/Micellar flooding
• Polymer flooding
• AS flooding
• AP flooding
• SP flooding
• ASP flooding
• Case studies
• Screening criteria
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 Objectives of Chemical EOR

• Increase the Capillary Number (Nc) to mobilize

the residual oil.
• Reduce the mobility ratio (M) for better
sweep.
• Emulsification of oil to facilitate production.

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 Elementary mechanisms
Surfactant/Micellar
Alkaline flooding Polymer flooding
flooding
1. The injected 1. Surfactant reduces 1. High MW
alkaline chemical the IFT between polymers
reacts with the displacing increase the
certain liquid and oil. viscosity of the
component in 2. Oil drops deform injected water.
the oil to create as a result of low 2. The high water
surfactant in situ. IFT, and are viscosity reduces
2. Change the displaced through the mobility ratio
wettability of the the pore throats. to a favorable
rocks. 3. Coalescent of oil range.
3. Reduce the drops results in oil 3. The favorable M
adsorption of bank. (<1) will prevent
surfactant. viscous fingering.

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ALKALINE FLOODING

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 1. How injected alkaline generate in
situ soap??

Schematic of in situ soap generation by deZabala et al. (1982)

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 Malaysia crude oil characteristics

Varies due to its reservoir’s place of origin, depth and age

For this reason, several classification systems of characterization

crude oil for EOR chemical formulation were proposed based on
many criteria such as viscosity, density (specific gravity or API
gravity), pH, surface tension and interfacial tension.

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Area\Charac Aromatic Total Acid
teristic Saturates s Resins Asphasltene Number Issues
Terengganu
A high high asphasltene deposition
Terengganu Friction of 1:1 leads to wax and gums deposition
B 1 1 occurs

highest solvency and less problematic in flow

Sabah A high low assurance issues during production and transportation
biograded crude, high TAN lead to naphthenic acid
corrosion (NAC),formation of
naphthenates(naphthenic acid salts) which can either
precipitate of form interfacial active salts (soaps) that
Sarawak A high high are prone to stabilize emulsions

highest solvency and less problematic in flow

Sarawak B high low assurance issues during production and transportation

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 1. How injected alkaline change the
wettability of the rock??
• Alkaline – rock surface (ion exchange and dissolution)
• Alkaline – formation brine (precipitation)

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 2. How injected alkaline reduce
surfactant adsorption??

Retention

Phase
precipitation Adsorption*
trapping

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2. How injected alkaline reduce
surfactant adsorption??

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2. How injected alkaline reduce
surfactant adsorption??

Pre-
condition/pre-
flush
Surface
charge of
the rock

Electrostatic
repulsion

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 Screening Criteria

• Clay content should not exceed 15% to 20%

• High acid number in crude oil
• Formation permeability should be greater than 100 md
• Oil viscosity 50 to 100 cp
• Low formation salinity

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 ALKALINE FLOODING Limitation

• 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 for
• Complex process to design
mixing
zones

low
drive caustic IFT water
water slug zone
oil
residual oil

Alkaline Flood
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 Alkaline flooding -
FIELD PERFORMANCE

Field Slug Size Conc. Oil Satn. Consum. Oil Rec.

% PV wt% %PV mg/g rock %OIP
1 Whittier 8 0.2 51 2.4-11.2 4
2 Singleton 8 2.0 40 - 5
3 N. Ward Estes 15 4.9 64 17.2 8
4 L. A. Basin 5 0.4 30 - 3
5 Orcutt Hill 2 0.42 50 0.5 2
6 Van 12 0.14 25-35 0.6-1.2 3
7 Kern River 48 0.15 52 1.3 none
8 Harrisburg 9 2.0 30-40 - 6
9 Brea-Olinda 1.2 0.12 50-60 - 2

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 Surfactant/Micellar solution
• complex chemical system
containing:
– a surfactant (usually a
petroleum sulfonate)
– co-surfactant (alcohol)
– oil
– electrolyte
– water
• surfactant slug typically
10% PV
• CMC (Critical Micellar
Concentration)

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Surfactant/Micellar solution

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Decrease of Interfacial Tension (IFT)

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 Surfactant Adsorption

• The type of surfactant and the specific properties of

the molecule
• The solvent conditions, such as pH, salinity (Na+, CL-)
and hardness (Ca2+ , Mg2+)
• The surface nature of the adsorbing substrate, such as
surface area, type of surface (silica, calcium
carbonate, clay, etc) and surface charge
• The environment of the aqueous phase, temperature,
redox environment and flow rate in the reservoir

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 Ways to reduce surfactant
adsorption

• Matching surfactant type to specific reservoir rock by

surface charge
• Application of surfactant mixtures
• Sacrificial adsorbate

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 Surfactant flood -
FIELD PERFORMANCE
Glenn Pool Field, OK

OIL
1,000

100
WOR
10
1984 85 86 87 88 89 90 91 92

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 SURFACTANT FLOODING Limitations

• 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 water

water slug
residual oil oil

Surfactant Flood

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 Polymer types
• PARTIALLY HYDROLYZED POLYACRYLAMIDES (PHPA)

• PARTIALLY HYDROLYZED POLYSACCARIDES (PHPC)

• CELLULOSE

• BIOPOLYMERS (XANTHANS)

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Advantages & Disadvantages

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 Factors affecting polymer flooding

• POLYMER TYPES – AFFECTS STABILITY AND ADSORPTION

• POLYMER CONCENTRATION

• RESERVOIR FLUID PROPERTIES LIKE SALINITY OF RESERVOIR

WATER (BRINE) AND CRUDE OIL VISCOSITY

• RESERVOIR CONDITIONS LIKE TEMP AND PRESSURE

• RESERVOIR ROCKS PROPERTIES; ROCK TYPES, MINERALOGY,

PERMEABILITY

• FLUIDS SATURATIONS : Sw and So

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 Screening criteria for polymer flooding
(rough guide)

• RESERVOIR TEMP SHOULD BE LESS THAN 180 oF (82 oC)

• PERM SHOULD BE MORE THAN 50 mD

• WOR LIMITS BETWEEN 0.5 AND 10

• OIL VISCOSITIES BETWEEN 20 TO 100 cP (mPa.s)

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 Polymer
Polymer Flood -Flood -
FIELD
FIELD PERFORMANCE
PERFORMANCE
SanandSanand Field, India
Field, India

125 650

100 620
EOR OIL
75
Projected 590

50 560

25 530

0 500
1989 1991 1993 1995

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 Polymer Flood – FIELD PROJECTS
Project Flood Type Formation Polymer Rec., %OIP
1 Taber Manville South Secondary Sandstone PAA 2
2 Pembina " " " 0
3 Wilmington " " " 0
4 East Colinga " " Biopolymer 0
5 Skull Creek South " " PAA 8
6 Skull Creek Newcastle " " " 10
7 Oerrel " " " 23
8 Hankensbuettel " " " 13
9 Owasco " " " 7
10 Vernon " " " 30
11 Northeast Hallsville " Carbonate " 13
12 Hamm " Sandstone " 9
13 Sage Spring Cr. Unit A " " " 1.2
14 West Semlek " " " 5
15 Stewart Ranch " " " 8
16 Kummerfeld " " " 6
17 Huntington Beach " " " 4
18 North Stanley Tertiary " " 1.1
19 Eliasville Caddo Tertiary Carbonate " 1.8
20 North Burbank Tertiary Carbonate " 2.5

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 POLYMER FLOODING Limitations

• 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, making it largely
ineffective
mixing zone

drive polymer slug water

water
oil
residual oil

Polymer Flood

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 Synergy: Alkaline – Surfactant Flooding

• Reduced surfactant adsorption

• In situ soap generation
• Synergy between in situ generated soap and injected
surfactant
• Wettability alteration attributable to the injected alkali
• Ability of the alkali to work as a sacrificial agent by
reacting with the divalent

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Synergy: Alkaline – Surfactant
Flooding

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Synergy: Alkaline – Surfactant
Flooding

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 Synergy: Alkaline – Surfactant
Flooding (Limitation)

Lack of mobility control

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 Synergy: Alkaline – Polymer
Flooding
• Alkaline – Polymer can reduce polymer adsorption and alkali
consumption as well
• Polymer makes the alkaline – polymer solution more viscous to
improve sweep efficiency. Thus, polymer “brings’ alkaline solution
to the oil one, where the alkaline cannot go without polymer. More
oil can be displaced by lowered IFT owing to alkaline-generated
soap. In other words, alkaline and polymer work together to
improve both sweep efficiency and displacement efficiency
• The alkaline – polymer environment may decrease biodegradation
• Alkaline may reduce polymer viscosity in the near wellbore region
so that injectivity is improved

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 ALKALINE-POLYMER FLOOD
David Field, Alberta

1000 100
Oil Cut

100 10

10 Oil Rate
1

Waterflood Alkaline-Polymer
Primary Flood
1 0.1
1969 1974 1979 1984 1989 1994 1999 2004

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 Synergy: Surfactant – Polymer
Flooding

• Surfactant – polymer interaction or incompatibility (SPI)

• Polymer injected before surfactant – serve as sacrificial agent for
adsorption or for conformance improvement
• Polymer injected after surfactant – to avoid water fingering
• Factors affecting SP interaction: Electrolyte concentration, Alcohol
(Cosolvent), Oil, Polymer concentration, Competitive adsorption
and polymer inaccessible pore volume (IPV) and phase trapping

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 Synergy: Surfactant – Polymer
Flooding
REASON WHY CHEMICAL FLOODING could never be started from the beginning of the
field development ??

• A chemical flood requires a relatively long preparation time, including

laboratory study and facility installment
• More technical skills and competence are needed to run a chemical
flood project. Designing the project takes longer
• More time is needed to get the project approved
• An early waterflood history is required for the reservoir
characterization. This is the key justification for the late start of a
chemical flood

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 MICELLAR POLYMER FLOODING
Limitations

• 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
– Considerable delay in response Micellar Flood

– Emulsion production mixing

zone
water

polymer
oil

water
drive
bank oil

micellar mixing zone

slug

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 Synergy: Alkaline – Surfactant –
Polymer Flooding

• Increased capillary number effect to reduce residual oil saturation

because of low to ultralow IFT
• Improved macroscopic sweep efficiency because of the viscous
polymer drive
• Improved microscopic sweep efficiency and displacement efficiency
as a result of polymer viscoelastic property. Oil in the dead ends is
pulled out, and the oil films on the pore walls are “peeled” off owing
to the high velocity gradient
• Emulsification, entrainment and entrapment of oil droplets because
of surfactant and alkaline effects
• Improved sweep efficiency by emulsions

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 ASP: ALKALI-SURFACTANT-POLYMER
FLOODING

• Several variations:
drive oil water

alkali
polymer
– ASP water bank

Surf
oil

– SAP Injected as ASP Flood

– PAS premixed slugs
– Sloppy Slug or in sequence

 Field tests have been encouraging

 Successful in banking and producing residual oil

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 ASP: ALKALI-SURFACTANT-POLYMER
FLOODING Problems

• Produced Emulsions
• Precipitation and Scale problem
• Formation damage
• Chromatographic separation of Alkali, Surfactant and Polymer

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ASP Case Study

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Screening Criteria

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