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www.spe.org/dl
2
Origin and Behaviour of Oil Asphaltenes
Integration of Disciplines

Artur Stankiewicz

Society of Petroleum Engineers

Distinguished Lecturer Program
www.spe.org/dl
Acknowledgments

The data and supporting examples are primarily based on

the research and field application that took place 1998-
2009 at various Shell locations.

Author is grateful to Shell and Schlumberger for

permission of presenting this material to the SPE
audience.

Cooperating service companies, scientific institutions and

all who, over the years, worked with me on the R&D and
implementation of technologies in the area of
asphaltenes.

4
 Outline
Introduction into the World of Asphaltenes
Setting the scene
Basic facts and definitions
Origin of asphaltenes (source and changes in geological time)
Few remarks on asphaltene structure & analytical techniques
Theory of the oils critical range
Fluid properties and live oil behaviour
Stock tank liquid screens
Live oil behaviour and screens
Examples of diversity in the world of asphaltenes and
implications
Field application
Conclusions
5
 Asphaltenes why do we care?

Asphaltenes precipitated in the production system

(reservoir wellbore tubing pipeline topside
facilities) may lead to their deposition =
reduced or shut-in production

Pipes blocked due to asphaltenes

Topside facilities (photo courtesy of Nalco)
 Asphaltenes one of many solid phases
encountered in production systems

16000
Asphaltenes
14000 Waxes
12000 Wax Hydrates
Pressure (psia)

10000
Reservoir Diamondoids
8000
Hydrate Inorganic Scales
Sulfur
6000
Asphaltenes
4000
Asphaltenes when
2000
Flow line unstable typically
0
0 10 38 65 93 121 precipitate at higher T
Temperature (C) and P than other solids
After John Ratulowski 7
 Asphaltenes deposition how?
Composition Changes
Instability due to commingling of incompatible fluids
Carryover & blending with LNG fouls gas side
equipment
Gas lift mandrills foul
Injection gas can cause reservoir impairment,
wellbore deposition, and fouling of pumps

Pressure Changes
Near-perforation reservoir impairment
Deposits in wellbores & flowlines cause excessive
pressure drop & additional plugging
Precipitated solids accumulate in low energy regions
 ASPHALTENES are defined as
the material that precipitates out of crude oil or reservoir
rock extract on the addition of excess light alkanes

5
4 Asphaltenes %
Cn of n-alkane
Asphaltenes 3
in Oil [wt. %] 2
1
0
Pentane Heptane Decane
Precipitant type

IMPLICATIONS:
It is a solubility class = NOT well defined molecule
Various analytical procedures prevent standardization 9
 Asphaltene Content of Unstable Oils

0.9 - 1.9

2-5
4 - 15
0.5 - 5
0.2 ~0.8 0.1 - 4.2

7-9 1-9
0.5-2 0.9 - 3.5

0.3
0.4

Asphaltene problems are localized, <1% of total world production

Some countries have serious challenges (e.g., Venezuela, Kuwait)
10
 Asphaltenes an Engineering Domain,
but Cant we just all get along?
Main Technical Areas:
Prediction (Deposition Potential)
Prevention (Monitoring & Control)
Inhibition (Chemical treatment)
Remediation (Recovery & Removal)

Majority of issues are driven by fluids phase behaviour,

production scenarios, topside separation or the Enhanced
Oil Recovery processes.

Geochemistry brings a fresh view on natures diversity

a global asphaltene molecule does NOT exist
influenced by source rock type and oil
generation/expulsion/migration processes. 11
 Geochemical and Engineering-View on
Asphaltenes
H
N S
OH
S

S
OH S N 0H
H
After Steve Larter & Eugene Frolov
NRG Petroleum Group

Modified from Pelet et al., 1986

Saturate S

Aromatic A
Resin R
Asphaltene A

12
Simple solubility model can explain asphaltene stability
 Natural Processes that can Affect
Asphaltene Stability in Crude Oil

Oil Composition
Asphaltene Content/Stability

Secondary
Source Rock Processes
(in reservoir)

Biodegradation
Kerogen Gas Washing (bacteria)
Composition Thermal Maturity (late gas charge)
(t & T)
Hybridization
(mixing) 13
Where They Come From? Source Rock
Kerogen Types and Origin

Type III Flood Plain Coals

Lacustrine Shales

Type I
Lagoonal shales and coals

Marine deltaic and open

marine settings

Type II
14
 Maturity and its Importance
A rock with sufficient organic matter
of suitable chemical composition to
generate and expel hydrocarbons
at appropriate maturity levels
is called a source rock

Thermal degradation of kerogen

(burial, T )
breakdown and release of hydrocarbons

Maturity = structural simplification

15
Origin and Maturity Affects Structure and
Behaviour (T, from bio- to geomacromolecule)
H0 H0
N N
N N
N 0

N 0 0 0

0 0

0 0

0 0
0
0 0
0
0H

N N
N N V -0
0H N N S
V -0
N N
0H H0
S 0
0H S
N 0 H0 H0
N
H0 S
0 0
H0 H0 HS

HS 0H
0
0 0 0
0 0H
0 H0 0

H0 0 0

H0
0
H0
0

H0
N
N
N
N

S
H0 N
S

HS
S

H0

16
 Asphaltenes General Trends

With maturity (irrespective of their source origin):

Molecular ratios H/C, O/C, N/C and S/C
Molecular weight (size)
Metals (e.g., Ni, V)
Sulfur %

IMPLICATION: Pitch Lake Trinidad

Oils in the specific maturity range show increased

potential for asphaltene precipitation low maturity, heavy
and biodegraded oils, and high maturity condensates
are generally stable 17
 Oil Asphaltene Content and the Oil Gravity
as Indicators of Maturity
11.0
Primary fluids only
10.0 Approx. Region of
West Africa
Fluids with Asphaltene
Oil Asphaltene Content [wt. %]

9.0
Problems Venezuela
8.0 North Sea
Canada
7.0
Middle East
6.0
Italy
5.0 GOM
4.0

3.0

2.0

1.0

0.0
15 20 25 30 35 40 45 50
18
Oil Gravity [API]
 Maturity Controlling Fluid Stability thus
Asphaltene Precipitation Hypothesis
Critical Range

NOTE: Natural processes

and production scenarios
Asphaltene Precipitation
Fluid Instability wrt

can affect asphaltenes

behaviour

Low Maturity High Maturity Fluids

Fluids (Condensates)
(Heavier)

Maturity increase
Maturity indicators: e.g. API increase, Asphaltene % decrease
19
Compositional Asphaltene Stability Screens

Unstable Colloidal instability index

Marginal Critical asphaltene to resin ratio
Stable
SARA plot (shown)
Saturate / Aromatic

Unstable

Stable

Asphaltene / Resin
20
Stankiewicz et al., 2002
 Dead Oil Titration Tests

Discrete or continuous titration

Detection
Visual
Spot test Stable Unstable
Light scattering
FPA Floc Point Analyzer
Does not contain effect of gas
TC
Floc Point
Heptane

P-Value

Transmitted
Power
Computer

Titrator
Volume of Titrant

Neat Oil Oil + 1 ml of 2 mW

Hexadecane P = 1.5 Detector NIR
Laser

Magnetic Stirrer
21
 High p&T System to Evaluate Asphaltene
Behaviour in Live Oil
Neat oil
Oil with asphaltenes

22
DBR Solids Detection System (Light Transmittance)
 Example of Non-problematic Fluid from
Venezuelan Well
Power of Transmitted Light (mW)

Water-like Droplets
Water-like Droplets

Pres

PSAT
~ 1930 psi

0 2000 4000 6000 8000 10000

Pressure (psig)

Non-problematic = no deposition observed

Problematic = deposition in the wellbore observed 23
 Example of Problematic Fluid from
Venezuelan Well
Power of Transmitted Light (mW)

Pres
10mm 10mm

10mm

POAP ~ 3500 psi

10mm
10mm

PSAT ~ 1860 psi

0 2000 4000 6000 8000 10000

Pressure (psig)

Information that can be used to optimize operations 24

 Example of Variation in Molecular
Composition of Asphaltenes
1.6
VEN
1.5 NS
GOM
H/C of Asphaltenes

1.4
World
1.3

1.2
MW~3500
1.1

1.0
MW~2200
0.9 MW~1000
MW based on GPC (SEC)
0.8
0.00 0.01 0.02 0.03 0.04 0.05
S/C 25
 Variations in Flocc Size is Critical
Venezuelan Oil North Sea Oil
(deposition problems) (no deposition observed)
100 100
80 80
60 9000 psi 60 9000 psi
40 40
20 20
0 0

1000 100
800
Particle Count

80
600 5250 psi 60 5000 psi
400 40
200 20
0 0

1000 100
800 80
600 5000 psi 60 4500 psi
400 40
200 20
0 0

1000 100
800 80
600 3500 psi 60 3500 psi
400 40
200 20
0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

0-60 Size [mm] 0-15

26
Depressurization experiments at reservoir T
 Oil/Asphaltene Molecular Composition vs
Activity of Field Chemicals

Venezuelan Oil North Sea Oil

Asphaltenes = 5 % Different Chemical Inhibitors Asphaltene = 1 %
API = 32 API = 38.5
A B C D
Sulfuroil = 1.4 % Sulfuroil = 0.11 %

The same chemical react differently with different asphaltenes 27

 Variations in PVT Behavior

Venezuela type asphaltenes North Sea type asphaltenes

10000 12000

8000 10000
Liquid Phase
Liquid Phase
Pressure (psia)

8000
6000
Asph Stability
6000
L&
4000 L&
L & Asph Phases Asph & L & Asph Phases
Asph &
4000 Wax Bubble point
Wax
Phases
Phases
2000 L & V & Asph Phases
2000
L & V & Asph Phases
Asph Stability
L&V
L&V
0 0
10 38 65 93 121 149 10 38 65 93 121 149
Temperature (C) Temperature (C)

Regions of asphaltenes instability

28
After: Ting et al, Petrophase Trondheim, 2004
 Example of Carbonate Reservoir

30.6
1.8
2
Heavier fluids 6.5

without asphaltene
deposition
29.4
1.78 2
3
28.3
7.9
1.99 29.5
28.7 7.0
3 2.01
28.5 8.8
1.83
6.72
29
426
1.9
7.8 1.81
7.2
2 1.731 1
16000
2.13 5.6
API
13.1 31
S% 1.83
6.0
1 Lighter fluids with
Asphaltene Content asphaltene
Problem ranking
1 Heavy deposition
4 22.2
2.34
28.6
1.73
challenges
11.2 7.8
4 No deposition
3
5000 meters
28.5
1
31.8
1.54
1.72 4.3
N 7.9
3
29
 Conclusions
Molecular composition of asphaltenes varies and depends
on factors such as source rocks and maturity
an average asphaltene structure does not exist.

Knowledge of physical/chemical properties of oil and its

asphaltenes may be successfully used for prediction of their
behavior ahead of production best practices:
Routine measurements of fluid property for each new well or
reservoir
Comprehensive database of fluid properties for each field (existing
and new)
Constant calibration of empirical observations against field
experience
Integrated approach and cooperation of various disciplines
30
 Food for thought

Asphaltene deposition problems to date are confined to

specific areas and relatively light fluids, however:

Increased focus on the EOR/IOR unravels new potential

challenges in the area of precipitation/deposition of
previously stable hydrocarbon fluids.

An integrated approach and cooperation of engineers and

geoscientists (e.g. geochemists) is necessary to
understand oil asphaltene behavior and its influence on
fluid properties.

31