Petroleum Geology

Petroleum Systems

EOR 101
 Summary

Petroleum system
What is a reservoir ? 04
Formation of hydrocarbons 05

About the reservoirs

Resources 06

Enhanced Oil Recovery (EOR)

Why consider EOR ? 08

Chemistry
Principles of Polymer Injection 10
Polymer solvent interaction 12
Polymer degradation and strategies to minimize it 14
Use of surfactants and alkali in EOR 16

SNF in Enhanced Oil Recovery

Multi-purpose Engineering Services 18
Projects 20
 Petroleum system

What is a reservoir ?

A petroleum reservoir, or oil and gas reservoir, is a Clastic rocks

subsurface pool of hydrocarbons contained in po- formed from pre-existing rocks by erosion,
rous or fractured rock formations. The naturally transport, transformation and deposition.
occurring hydrocarbons, such as crude oil or na- These include sandstones, conglomerates, sils-
tural gas, are trapped by overlaying rock forma- tones and shales.
tions with lower permeability. The vast majority
of hydrocarbons are trapped within sedimentary Carbonates
rocks, formed at the earth surface though several rocks formed from organic constituents and
process including weathering, precipitation and chemical precipitates; including limestones,
biogenic activity. We can distinguish: dolomites and chalks.

Oil bearing Abundance Production

Lithology
reservoirs of rock type by rock type
Sandstone 60% 21% 37%

Carbonate 30% 37% 61,5%

Other (shale...) 10% 42% 2,5%

Drilling rig

25 cm

Cores are drilled to study the reservoir

5 cm 100 µm
4
 Petroleum system
Formation of hydrocarbons

The petroleum system consists of a mature

source rock, migration pathway, reservoir rock,
trap and seal. Appropriate relative timing of
formation of these elements and the processes
of generation, migration and accumulation are
necessary for hydrocarbons to accumulate and
be preserved.
Hydrocarbons are generated from the thermo-
cracking of organic matter accumulated in a
source rock. It requires temperature (>50°C) and
time.

Surface

Biogenic methane
Many types of hydrocarbon traps exist:
Diagenesis

Anticline, Fault, Stratigraphic trap, Salt dome, ...

+

Biomarkers
Immature zone

Anticline Fault
Catagenesis

Depth

Oil
oil window

Stratigraphic trap Salt dome

+

Wet gas
Gas window

Dry gas
Metagenesis

Porous rock
Non-porous rock
Salt
Graphite Gas
+

+ Oil
Quantity of hydrocarbons generated

5
 About the reservoirs

Resources

Characteristics of oil and gas generated depend

on the type of organic matter and the maturation
process. People also make a distinction between
conventional and unconventional resources:
unconventional plays require specific and often
expensive techniques to be produced.

Unconventional resources: Acronyms

example of tight gas reservoirs
In tight gas reservoirs, the pores are irregularly
OOIP : Original Oil in Place
distributed and poorly connected by very narrow
capillaries resulting in very low permeability. Gas IOR : Improved Oil Recovery
flows through these rocks at generally low rates EOR : Enhanced Oil Recovery
and special methods are necessary to produce Chem EOR : Chemical EOR
this gas such as hydraulic fracturing.
PF : Polymer Flooding
Unconventional play SP : Surfactant and Polymer Flooding
By opposition with conventional systems, un- ASP : Alkaline Surfactant Polymer Flooding
conventional resources are not easily producible PAM : Polyacrylamide
with existing technologies (low permeability re-
HPAM : Partially Hydrolized Polyacrylamide
servoirs or viscous oil)
MW : Molecular Weight
Source-rock hydrocarbons Da : Dalton (MW unit of measure)
Shale Oil or Shale Gas directly extracted from the IFT : Interfacial tension
source rock by fracturation.
PSU™ : Polymer Slicing Unit
Asia & PIU™ : Polymer Injection Unit
Oceana
3%
Africa North
9% 16% America

Middle 56%
East Central &
8% South America

1% Europe

7%
Eurasia

Data source :
US Energy Information Administration from Oil and Gas Journal (2007)
Oil includes crude oil and condensate

6
Conventional Reservoirs Gas
Small Volumes, Oil
Easy to Develop

Coal Bed Methane

Accesibility
Gas Shales

Cost
Tight Gas Sands
Unconventional Tight Oil
Reservoirs Heavy Oil
Large Volumes, Bituminous Sands
Hard to Develop

Gas Hydrates

Huge Volumes, Oil Shale

Difficult to Develop

Resource pyramid

Tight gas sandstone : (voids in blue).

7
 Enhanced Oil Recovery ( EOR)

Why consider EOR ?

The production of hydrocarbons is usually to exploration & extraction increase (ultra-deep

divided into 3 stages : offshore, artic circle...). As such, increasing the
recovery factor by 1% would translate into 60
Primary depletion billion extra barrels.
Oil is naturally produced thanks to the energy EOR applies to known reservoirs, infrastructure is
initially stored within the reservoir; already in place and the market for hydrocarbons
, is available.
Secondary production Polymer flooding is a proven, cost-effective EOR
In order to maintain the production and the
pressure in the reservoir, water (or sometimes
gas) is injected to push the hydrocarbons;

injection
Polymer
Oil Production rate

Incremental
Tertiary production EOR

Injection of specific substances to increase

recovery (gas, chemicals, steam...).
Primary production
Natural flow and artificial lift Gas
CO2, Nitrogen, Air Time
techniques (pumps)
technique with over 40 years of commercial
Thermal
Steam In Situ combustion,
application that allows recovering from 5 to 15%
Secondary recovery Hot water of additional oil. The best commercial projects
Water flooding or pressure
maintenance Chemical
have produced about 1 incremental barrel of oil
Polymers (PF) for each $1 to $3 of polymer (onshore).
Surfactant Polymer (SP)
Alkaline reagents (ASP)
The addition of water-soluble polyacrylamides
Tertiary recovery increases water viscosity and helps push bypassed
Enhanced Oil Recovery me- Other oil more efficiently. A first step consists in
Microbial
thods evaluating the potential through a pilot injection.
A pilot is a good way to prove the efficiency:
35% of Oil Originally In Place (OOIP) is produced
Fast deployment (skid-mounted systems)
after primary and secondary productions.
It means that 65% of oil remains after secondary Low costs
recovery, trapped into pores by different forces. Low risks

There is little doubt that the worldwide demand Injection fluid Injection pump

for oil will increase in the long term. But reserves

are not generally replaced and it would require Injection well Production well
the discovery of new «giant» fields.

Drilling alone is expensive: it requires a large

capital investment, and drilling rate is inversely
correlated with discovery rate. The costs linked

8
 Enhanced Oil Recovery (EOR)

Modular injection systems can be tied-in to History of chemical EOR projects

existing injection lines: no need to build new
infrastructure, use of available water for polymer 1976 - 1982
injection. More than 320 chemical injections
After this stage, full-field deployment can be in the US
considered. East Coalinga
Polymer flooding reduces costs related to water Taber – Manville
West Yellow Creek
handling. The process requires less water to North Burbank
recover the same amount of oil, so the costs
linked to water treatment & handling are 1989 - 2000
Large success in China
Daqing : world’s largest polymer injection, resulting in
a 12% increase in recovery of the OOIP.

2010 - 2015
More than 50 polymer injections.
More than 170 projects.
China (Daqing cont’d)
Oman PDO Marmul
Suriname
reduced. Produced water containing polymer can Indonesia
Canada (more than 30 polymer inj.)
be reused for further injection. In the long-term, Russia & Kazakhstan
polymer flooding can be less expensive than Europe
waterflooding. Preferable conditions for polymer Latin America
India
injection are light to medium-heavy oil, low
salinity, medium to high reservoir permeability,
low temperature (below 100°C). Even though,
new polymers can resist harsh conditions: 140°C
and around 200g/L total salinity.

The earlier, the better: implementing polymer

flooding early in the life of a field helps increase
the final amount of oil recovered. Modular systems tied-in to existing injection lines

% Recovery factor Primary and Secondary oil recovery factor

80

60

40 Worldwide Average RF ~35%

20 40 to 50 % 40 to 50 % 20 to 30 %
Water or gas Water Water
injection injection injection
5 to 20 % Water injection
+
0.11 10 100 103 Oil viscosity (cp)

% Recovery factor Tiertiary oil recovery factor

80

RF ~60%
60
+10 to 20 %
Alkaline / Surfactant / Polymer
40
+5 to 15 %
Polymer only

20 30 to 40 % 30 to 40 % 20 to 30 % +5 to 15 %
Water or gas Water Water Polymer only
injection injection injection
5 to 15 % Water injection
+
0.11 10 100 103 Oil viscosity (cp) 9
 Chemistry

Principles of Polymer Injection

Polymer injection =
viscous waterflood limited risk
Water Flooding
Polymer injection applies when the mobility ratio
during a waterflood is unfavorable or when the
reservoir is heterogeneous (even with favorable
PAM Flooding
mobility ratio) to recover bypassed oil.
Some key figures:
How to design a successful pilot ? Polymer is injected over 5 to 25 years.
The main criteria to look at when designing a
Typical injection concentrations range
pilot injection are:
from 1000 to 1500 ppm active.
Short spacing /residence time between injection Injection of at least 0.3 pore volume:
and production well to accelerate the response the more the better.
Good connectivity between wells Injection of high viscosity slug
Pattern with surrounding offset producers where recommended in some cases.
incremental oil from polymer injection can be Incremental oil with polymer ranges
isolated for calculation from 5% to 15% OOIP.
Good water injectivity good polymer injectivity
Injectivity Test Pilot Full Field
Tests to check maximum rates Validation of flow Validation of Large scale
and viscosity accepted by reservoir parameters Key technology development
learnings Evaluation of
Micro-fractures can be used to improve recovery factors
the overall efficiency Timeframe
1 to 3 6 to 18 5 to 25
Relatively high oil saturation months months years
( residual oil saturation) Installations
Turn-Key systems
Portable Skids Turn-Key
Pilot injection can start very quickly using On-site injection
injection unit systems
standard equipment. plants
Critical parameter
Logistics
Dissolution/
Portable Polymer supply
Injection
selection Storage
equipment
Dissolution

Can be run in parallel and shortened

(order of weeks) if using standard skids

Polymer Laboratory Equipment Field installation Operation

selection studies Engineering Design Commissioning start-up Maintenance
2 weeks 1-6 months 6-8 months 8 months 5 - 25years

10
 Chemistry

SNF chemistry

( )
O O H H H H
Caustic soda
C C C C
n + m
H H NH2 H C O-
NH2 HO n,m
Acrylamide Acrylic acid O O
Anionic polyacrylamide
Example of an anionic co-polymer of acrylamide and acrylic acid

Advantages Disadvantages
Two families of polymers:
Excellent injectivity and
- Biopolymers
propagation
-HPAM: Partially Hydrolyzed Polyacrylamide
(synthetic polymers)
High viscosifying power Shear sensitive
Fine-tuning chemistry can help to limit shear and
salt sensitivities of synthetic polymers.
Good and long stability Salt and temperature
in mild reservoir condi- sensitive
SNF develops and manufactures tailor-made
tions
polymers based on acrylamide. High molecular
weight hydrosoluble polymers are mainly used to
Cost-effective, high Sensitive to chemical
increase viscosity.
production capacity degradation
worldwide
Polymer / Solvent Interaction
Important factors to understand properties of
Non toxic Low biodegradability
polymers into solution.
A polymer is able to increase the viscosity of the
medium only if the chains are uncoiled: this is a HPAM characteristics
medium where the polymer « feels comfortable».
What does this mean? It means that the
polymer / solvent interactions should be
better on from an energy point of view than
polymer / polymer interactions.

HPAM characteristics

11
 Polymer solvent interaction

Polymer chemistry needs to be carefully selected

Importance of brine characteristics.
Polymer/solvent interactions describe the
conformation (physical aspect) of the polymer
chains (coil) in solution Efficiency.
If the interactions are good , the macromolecular
chain unravels into the medium.
Expanded polymer chain high viscosity

Collapsed chain Expanded chain

Polymer-Polymer interaction Good solvent Polymer- Solvent interaction

Low viscosity High viscosity

1% Polyacrylamide in H2O

(viscosity brookfield) η = 5.000 to 6.000 mPa.s

Collapsed polymer (Brookfield UL @6 rpm )
(MW = 8.106 Da)
Water is a good solvent.

H2O

1% Polyacrylamide in H2O+Ethanol (70/30)

η = 700 to 800 mPa.s __

Collapsed polymer (Brookfield UL @6 rpm )
(MW = 8.106 Da)
The medium H2O/Ethanol is not as good a solvent.
The polymer « feels less comfortable ».
70%H2O The macromolecular chain uncoils partially.
30%Ethanol

1% Polyacrylamide in Ethanol

η = η of ethanol __
Collapsed polymer (Brookfield UL @6 rpm )
(MW = 8.106 Da)
Very bad interactions.
The polymer « feels very uncomfortable ».
Ethanol

Viscosity depends on solvent

12
 Chemistry

Polyelectrolytes Associatives Polymers

Polyelectrolyte is a polymer containing Associative thickener
electrostatic charges into the macromolecular Associative polymers are hydrophilic polymers
structure. containing some hydrophobic groups. A network
In a polar medium like H2O, the polymer is able is created by hydrophobic interactions in water.
to expand due to internal electrostatic repulsions These interactions create a physical network and
(stretching of the chains). It results in a high very high viscosities can be obtained.
viscosity.

But if salts are present/added, viscosity decreases

because of a «screen effect» :
- decrease of repulsions
- the macromolecular chains retract
Hydrophobic group
- viscosity decreases
Water soluble polymer chain
Hydrophobic interaction

1% Polyacrylamide in H2O

η = 5.000 to 6.000 mPa.s

(Brookfield UL @6 rpm )
Collapsed polymer
(MW = 8.106 Da)

H2O

1% Copolymer Acrylamide /AMPS in H2O

η = 20.000 to 25.000 mPa.s

Collapsed polymer (Brookfield UL @6 rpm )
(MW = 8.106 Da)
Expansion of the macromolecular chain
by electrostatic repulsion
H2O

13
 Polymer degradation
and strategies to minimize it

The value of adding polymer to a waterflood can

be explained by considering the mobility ratio
equation with the aim to reach a value close to
1 so that oil and water have the same mobility
inside the reservoir. The easiest way is to increase
water viscosity as shown by the equation below.
Polyacrylamides are sensitive to mechanical,
thermal and chemical degradations. Guidelines
exist and have to be implemented to minimize
viscosity losses.
There is a need to: Mechanical degradation
-Select the best chemistry, is caused by singular pressure drops.
- Provide the best possible protective package Mechanical degradation through shearing devices
that will protect from the presence of divalent can lead to significant reduction in viscosity.
ions and oxydisers,
-Use specific equipment to avoid shearing and Polyacrylamides are sensitive to shear which
oxygen ingress. degrades the polymer into smaller molecules.
Mobility ratio Lower molecular weight polymers are much less
sensitive to shear.
End-point relative
permeability of water Special attention should be paid to:
oil viscosity - Dissolution and surface injection equipment,
- Velocity of the fluid,
- Injection lines (restriction, chokes),
M=
kw µo - Surface of perforations,
ko µw - Permeability of the reservoir,
- Reduction of the injection surface by plugging
water viscosity
SNF has defined a set of engineering guidelines to
End-point relative minimize shear in the surface equipment.
permeability of oil

Mechanical degradation
Chemical degradation
Thermal degradation Stable fluid
Injection well

Hydrolysis effect

+ gradual effect of
dilution and retention

Reduced hydrodynamic volume

Time
Polymer stability

14
 Chemistry

Temperature hydrolysis : Precipitation with

R+ negative charge increase divalents
Fe2+
O2
R+
O2 Ca2+

R+
H2S
O2
Mg2+

Chemical degradation Thermal degradation

is caused by free radicals. is linked to polymer hydrolysis and precipitation
It is essential to minimize chemical degradation with divalent cations.
by eliminating free radicals, removing oxygen and Polymer microstructure and anionicity should
blanketing dissolution equipment be carefully selected and controlled to minimize
thermal degradation
Free radicals scavenger
SNF sells all its product with a minimal amount of Copolymers acrylamide / acrylic acid are
free radical scavenger. For increased protection, stable up to 75°C. Above 75°C and up to 120°C,
specific packages (F3P) are developed by SNF and polymers containing acrylamide / ATBS or/and
fine-tuned to every case. other thermal resistant monomers can be used
(Flopaam AN 100 & Superpusher SAV series).
Oxygen removal Above 50°C, hydrolysis of the polymer will occur
Oxygen scavengers (ammonium bisulfite for resulting in increased anionicity. When anionicity
example) decrease O2 content below 20 ppb. increases above a critical level (35% to 40%)
The amount of scavenger should be limited to precipitation with divalent ions (Ca2+, Mg2+) will
avoid further degradation in case of oxygen ingress. occur resulting in viscosity loss.
With medium to high temperature reservoirs, low
Nitrogen blanketing anionicity polymers should be the prefered choice.
Dissolution equipment can introduce a large The quality of the manufacturing process of the
amount of oxygen into the injected solution. It is polymer is essential to avoid high polydispersity.
necessary to blanket the dissolution and injection
installation under Nitrogen in order to prevent
oxygen ingress. Negative effect of high temperature

Polymer concentration : 3 000 ppm Brookfield, UL Spindle, 6rpm, 85 C

O2 : 0ppb Brine : 50 000 TDS, no Ca2+, no carbonate
12 12
Viscosity (cps)

Viscosity (cps)

90˚C 110˚C
10 10
100˚C
100˚C 90˚C

8 8

6 6
120˚C

4 4

2 110˚C 2

120˚C
0 0
Time (days) Time (days)
0 10 20 30 40 50 60 0 10 20 30 40 50 60

Temperature limits for sulfonated co-polymers AN-125 New range of polymer for high temperatures
ATBS based copolymer (Flopaam AN 125) w/o O2 NVP addition improves stability at high temperature w/o O2
and divalent cations and divalent cations

15
 Use of surfactants and alkaline
in EOR

Wettability connotes the preference of a given

oil liquid to spread over a solid surface in the

le
presence of a second liquid. It is quantified by the
ng contact angle which represents a drop of liquid
ta
water deposited on a flat surface: the smaller the angle,
ac
nt

the higher the wettability.

co

For example, one can distinguish water-wet

solid reservoirs (with water wetting the grains) and oil-
wet reservoirs (oil wetting the grains).
Exemple of water-wet medium (ϕ<90°)
Factors affecting reservoir wettability
- Oil composition
- Rock mineralogy
- Connate (trapped in rock) water composition
grain
and pH
oil - Reservoir pressure and temperature
water
Interfacial Tension (IFT) It defines the tension
(forces) existing between two immiscible fluids
(oil and water).

Oil is left after a waterflood because it can be:

- Trapped by capillary forces
- Bypassed (because of a bad mobility ratio)

EOR: How to mobilise the oil ?

If bypassed: modification of the mobility ratio by
increasing the viscosity of water :
water-wet reservoir
polymer injection

If trapped by capillary force :

increase capillary number (viscous forces/
capillary forces(IFT))
lower IFT by surfactant injection for instance

Surfactants are compounds that stabilize

mixtures of oil and water by reducing the surface
tension at the interface between the oil and water
molecules. Surfactants are amphiphilic in nature
oil-wet reservoir i.e. they contain 2 distinct structural units:

16
 Chemistry

Tail or hydrophobic group which has little affinity

for water – this group is usually a hydrocarbon
(alkyl) chain.

Head or hydrophilic group which has strong

affinity for water, it can be neutral or charged.

Alkali
Alkaline waterflooding: process where the pH of
injection water is increased by addition of alkali
(sodium carbonate, sodium silicate, sodium
hydroxide, potassium hydroxide). Alkali reacts
with acidic compounds of the crude oil leading
to lower IFT, emulsification of oil in water and
solubilization of rigid interfacial films. Alkali
may react with the rock leading to wettability
alteration

In a nutshell:
Polymer
Increase water viscosity

Surfactants
Lower IFT
Change wettability of the rock
Generate foams or emulsions

Alkalis
React with crude oil to generate soaps
(surfactants)
Increase pH
Alter rock wettability
Alter rock chemistry reducing adsorption of
surfactants

EOR: Other processes

Miscible gas injection
In-situ combustion
Steam injection
Microbial degradation

Final goal: recover as much oil as technically and

physically possible. Necessity to have a good
understanding of the geology, the reservoir, the
Solubilization (microemulsions) fluids…
Surfactant flush
mobilization

Trapped Oil at Residual Saturation

17
 SNF in Enhanced Oil Recovery

Multi-Purpose
Engineering Services
SNF provides dedicated solutions and en-
gineering services to design, build and operate
polymer injection systems.

Frac trailer Expertise : Powder Hydration

FLOQUIP PSU™ is a slicing unit that helps de-
Polymer injection trailer crease the dissolution time of powdered polymer.
Standard PIU 100 and PIUC 100 and PIU 300 MS
Skid based polymer system +Patented technology from SNF
Emulsion inversion, dilution and injection skid +Concentration up to 15 000 ppm
Skid based ASP system +No fish eyes and no need for filtration
Land based polymer / ASP facilities +Nitrogen blanketing
Offshore skids +Subsequent equipment reduced by 3x to 4x
Offshore modular construction
…

Every system is designed per customer require-

ments. Standard injection units also exist for fast
implementation.

1200.0
Viscosity (cps)

FLOPAAM FP 3630 S - 10,000 ppm - 20˚C FLOQUIP PSU™

1000.0

800.0

600.0

Standard Mixing
400.0

200.0

0.0
Dissolution Time (hours)
0 0h05 0h10 0h15 0h20 0h25 0h30 0h35 0h40 0h45 0h50 0h55 1h00

18
 SNF in Enhanced Oil Recovery

1 Magnetic grid
Polymer Unloading system for big bags
2 Dosing screw feeder / Gear Motor
Powder Powder storage silo
3 Flexible connection (weighing)
Nitrogen Mixing unit PSU 100
4 Feeder isolation valve
(Optional) Maturation tank with agitators
5 Wetting funnel 1 Mother solution booster pump
6 Cutting head (rotor / stator) 3 High pressure injection pump
2
7 Electrical Motor / Pulleys / Belt Full E& I Package
4 Electrical control Panel & HMI
System
Primary Water
Fire and gas detection system
5
Polymer Mother
Solution
6 Main Scope
Secondary Detailed Design
Water Procurement & Equipment
7
supply
FAT of the main equipment
FLOQUIP™ PSU – Process Connections Skid Construction
Commissioning, SAT and Start-up
Vendor Data book
E&I package (VSD + MCC)
Blanketing Gas (optional)
E& I Cabling
HOPPER Skid mounted system
Dry
Polymer
Optional
Vent Water run test
Polymer run test
Training
Operation & Supervision

Injection
FLOQUIP PSU
MATURATION APPLICATION
TANK PUMP
PIU 100 Standard Polymer
Water
Injection Unit
FLOQUIP™ PSU – Typical Flowsheet

19
 Projects

Numerous skid-based project

Offshore projects

Large turn key projects

20
 SNF in Enhanced Oil Recovery

Turn-key project - Dissolution

PSU 600 - Brazil PSU 1500 - USA

21
 Notes

22
23
 SNF SAS
ZAC de Milieux
42163 Andrezieux Cedex
FRANCE

tel : + 33(0)4 77 36 86 00
fax : + 33(0)4 77 36 86 96
mail : [email protected]

www.snf-group.com/

Handbook. Edition 2015

While SNF makes reasonable efforts to ensure the information is accurate and up-to-date, SNF makes no warranties or repre-
sentations, express or implied, as to the accuracy, completeness, or any other aspect of the information on this document
and assumes no liability in connection with any use of this information. Nothing herein shall be construed as a recommen-
dation or license to use any information found that conflicts with any patent, trademark or copyright of SNF or others, and
SNF makes no representations or warranties, express or implied that any use of this information will not infringe any such
patent, trademark or copyright.