Asphaltene is an old

problem, do we have a
new solution?
27 April 2022
Bahman Tohidi
Institute of GeoEnergy Engineering, Heriot-Watt University
Hydrafact Limited (Hydrate Flow Assurance Consultancy and Technologies)
B.Tohidi@hw.ac.uk, Bahman.Tohidi@hydrafact.com

www.petro-teach.com
Reservoir............ 1
Flow Assurance
• Phase envelope of crude oil and P-T ranges for flow assurance problems
(Modified from Jamaluddin and Kabir 2012).

Dew Point

2
Flow Assurance
• Flow Assurance is ensuring reservoir fluid(s) to end-user
safely and economically by designing/operating a
production system with the aim of:
• Deliverability - achieving production rates (boosting/lifting/sizing)
• Integrity - does not fail (corrosion/erosion)
• Controllability - stable and flexible operation
• Uninterrupted Production (due to hydrates/wax/liquids etc)
• Minimising the effect on the environment
• Maximising the Recovery
• Bridge between subsurface (reservoir) and surface
(production or downstream).

3
Key Areas
• Phase behaviour and fluid properties
• Fluid-related issues:
• Hydrates
• Corrosion
• Wax
• Asphaltenes
• Scale
• Sand (erosion, transport, deposition)
• Other issues, e.g. emulsion, foaming, etc.
• Fluid hydraulics and Heat transfer
• System operational modes (steady state, start-up,
shutdown)

4
Hydrocarbon Classes
Reservoir hydrocarbon fluids

Paraffins Naphthenes Aromatics Polars

• n-paraffins • resins
• iso-paraffins • asphaltenes
Asphaltene
• Are high molecular weight constituents of oil
comprising polycyclic aromatics or naphtheno-
aromatics with hydrocarbon side chains also containing
nitrogen, sulphur, and oxygen compounds.
• The basic units are polyaromatic sheets that are
stacked by molecular association to form asphaltene
particles.
• Reported data on the molecular weight of asphaltenes
ranges from 500 for individual sheets to 500,000 for
aggregates depending on the analytical method
applied.
Asphaltene
• Asphaltenes are insoluble in the low molecular
weight normal paraffin and are classified by the
precipitating solvent since different solvents
precipitate different ranges and hence different
amounts of asphaltenes.
• Asphaltenes are commonly defined as the normal
heptane insoluble fraction of crude oil obtained by
the Test Method IP 143.
• The lighter fractions, which are soluble in normal
heptane but insoluble in ethyl acetate at room
temperature, are known as resins.
• Asphaltene
precipitated from
oil diluted by
different normal
alkanes
Asphaltene Phase Envelope
Variations of Deposited Asphaltene with
Pressure at Constant Temperature
 Phase Envelope
• Accurate prediction of Phase Envelope is very important.
• Need experimental data to tune the model.
• Representative sample Measured
Bubble Point

11 Predictions by HydraFLASH
 Where Should We Get our Sample?
Location Advantages Disadvantages
Reservoir Can capture Very expensive
asphaltene if not
deposited in impossible
the reservoir
Downhole Good Expensive
Tubing No too Is it
expensive homogenous?
Wellhead Relatively Is it
cheap representative?
Separator Cheap, Large Is it
Volume representative?

Reservoir............ 12
Phase Envelope & Flow Assurance

Original slides courtesy of Emile Leporcher, Total

Pressure Drop Near the Welbore

Performance of Flowing Wells 14

Sampling
Location
Reservoir Ideal if the disposition due to drawdown is limited.
How we bring the sample to the surface and how we extract the oil.
Downhole Is it a single phase?
How do we bring it to the surface?
How to condition the sample?
Wellbore / What about asphaltene deposited/re-dissolved from/into the
Tubing oil/wellbore?
Is the GOR correct?
How much time do we need to condition the sample?
Is the resulting sample representative?
Separtor What about asphaltene deposited/re-dissolved in the wellbore?
After mixing with gas, how much time do we need to condition the
sample?
Is the resulting sample representative?
Reservoir............ 15
Oil Formation Volume Factor
above and below bubble point

PVTP by Petroleum Experts (https://www.petex.com/)

Reservoir............ 16
Formation Volume Factor

Reservoir............ 17
Fluid Properties
CII= 1.86
Saturated mass%

Aromatic mass%
15.5
6.4 Resin mass%

49.5
Asphatene mass%

28.6

ASTM D-2007

https://doi.org/10.1016/j.petrol.2017.01.009
SARA Analysis (Saturates, Aromatics, Resins, and
Asphaltenes)

The relationship between SARA fractions and crude oil stability

Siavash Ashoori, Mehdi Sharifi, Mohammad Masoumi, Mehdi Mohammad Salehi
Egyptian Journal of Petroleum, Volume 26, Issue 1, March 2017, Pages 209-213 19
Conditions that Could Result in
Asphaltene
• Depletion
• Acid job
• Gas injection
Can deposit in the reservoir resulting in
• Gas lift wettability alteration and pore blockage
• Miscible or Immiscible Gas Injection EOR
• Mixing two fluids (e.g., Titration)
• Temperature Change (to a lesser extent)
What is common in all these cases

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 Quartz Crystal Micro-Balance
(QCM)

Photo of 1-inch (25.4mm) QCM Crystal

• AT cut quartz crystals (P and S waves, sensitive to density and
viscosity, in addition to mass deposited on its surface).
• It detects 1 nano-gram deposition, hence microbalance (QCM).
• Highly stable compared to the conventional ones.

Reservoir............ 21
Atmospheric QCM Setup

Reservoir............ 22
Atmospheric QCM Setup

Reservoir............ 23
Heptane Titration

Figure 2. Plot showing changes in RF versus ml

of heptane injected per g of stabilised crude
recorded during test with oil sample from FAN-
1 (12.5” Section) 4376.5 mMD. Lines fitted
through raw experimental data. As can be
seen there is a clear change in slope at close to
2.5 ml heptane per g of oil, indicating the
onset of asphaltene deposition. Test
temperature 69.8 °F.

Experimental data by Hydrafact

Heptane Titration

Experimental data by Hydrafact

Reservoir............ 25
 Medium Pressure Setup (300 bar)

• Quartz Crystal Microbalance (QCM) does not need the visual

capability, so safer and cheaper.
• QCM can work at very high pressure (one of our setups can operate
3,000 MPa, 45,000 psi), here the limit is electrical feedthrough.
• Shear forces can be included in the design, as shown above, but the
limit is the mixer
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 High Pressure Setup (700 bar)

• High Pressure and High Temperature (HPHT) Quartz Crystal

Microbalance (QCM) cell with shear and temperature gradient, to
take into account wall cooling.
Why Do We Need to Determine
Wax Phase Boundary?

Experimental data by Hydrafact

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Why Do We Need to Determine
Wax Phase Boundary?
To make sure it is out of the
wax phase boundary.

Reservoir............ 29
Upper and Lower Asphaltene
Onset Points

Experimental data by Hydrafact

Reservoir............ 30
Asphaltene Deposition on QCM
Surfaces

Reservoir............ 31
 Asphaltene Inhibitors Performance
0

-1

-2
Inhibitor
-3 “C”
-4
The reduction in the Resonant Frequency
Inhibitor (DF in the X-axis) is an indication of mass
-5
deposited in QCM.
DF (KHZ)

“B”
-6
Inhibitors “B and C” not only shift AOP
-7 to lower pressure but also reduce the
-8
amount of asphaltene deposited.
Inhibitor
Inhibitor “C” is slightly better.
-9 “A”
The results of some high-pressure tests
-10
on the performance of inhibitors do not
-11 Blank test, agree with titration tests.
-12 no inhibitor
150 200 250P (BAR) 300 350 400

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Micromodel Tests (400 bar)
 QCM for Conditioning the Oil
Monitoring frequency changes during conditions time (69 °C, 6,000 psi) ahead of
AOP measurements test

Experimental data by Hydrafact

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 QCM Results for Blank Oil
2 0.02

Experimental data by Hydrafact

0
0.00

-2

DR (kΩ)
-0.02
DF (kHz)

-4

-0.04

-6

-0.06
-8

Delta F (kHz) Delta R (kOhms)

-10 AOP=300 bar -0.08

200 250 300 350 400

P (bar)
35 Reservoir............ 35
QCM Results for Various Inhibitors
Nucleation

a) Effect of asphaltene inhibitors on AOP changes obtained by QCM; b) ESEM micrograph of

asphaltene deposits onto the QCM gold surface and proposed mechanism of asphaltene
aggregates-gold plate surface interaction

Experimental data by Hydrafact

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 Case Study-Risk of Asphaltene in
the Tubing Simulation of present and future
asphaltene risks in the tubing
Importance of matching the
correct bubble point

Predictions by HydraFLASH
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Case Study: Asphaltene, Wax, and
Hydrate
Experimental AOP

610 Experimental Bubble Point

AOP Line - Tuning 1
AOP Line - Tuning 2
510
AOP Line - Tuning 3
AOP Line - Tuning 4
410
Phase Boundary
P - bara

Hydrate Line
310 Wax Phase Boundary
Phase Envelope - nAlkane

210

110

10
-150 -100 -50 0 50 100 150 200 250 300
T - °C

Predictions by HydraFLASH
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What Are the New Solutions?
• More accurate results using QCM
• Working at high pressures and temperatures
• Better understanding of factors affecting asphaltenes
and inhibitors
• Better conditioning of sample before testing
• Being able to simulate the field process and conditions
• More accurate experimental results
• Better data, means better prediction
A Joint Industry Project (JIP) is running at Heriot-Watt
University. Please contact me at B.Tohidi@hw.acuk, if you
need further information.
Reservoir............ 39
Asphaltene is an old problem, do
we have a new solution?
The main objectives of this 3-day course on Asphaltene (in conjunction with a 2-day course
on Wax) are to give a background on our current understanding of this flow assurance
challenge and offer new experimental equipment and techniques for more accurate
experimental data. The new experimental equipment can generate data on the asphaltene
phase boundary, the effect of shear and the temperature gradient on asphaltene deposition.
The new experimental setups, which are based on Quartz Crystal Microbalance (QCM), in
addition to conventional test equipment, are generating excellent data. More accurate data
will result in more accurate modelling. Some topics that will be covered in this course are:
Asphaltenes and their properties; Conditions that could result in Asphaltene formation and
deposition; Sampling and sample restoration; Generating accurate experimental data, Test
equipment/techniques, (e.g., titration, high-pressure visual setups, viscosity measurement,
QCM; low/high-pressure testing techniques testing facility with/without temperature
gradient/shear); PVT modelling; Asphaltene modelling; Asphaltene inhibitors, dispersant,
solvents; Testing inhibitors in the lab vs field application; The reasons behind the poor
performance of some Inhibitors; Remove asphaltene deposition; Monitoring systems;
Modelling deposition simulation; and finally Case studies
7 – 9 September 2022, Stavanger
9 – 11 November 2022, Online
Register@petro-teach.com
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• Expert on gas hydrates, flow assurance, PVT, phase behavior
and properties of reservoir fluids and H2/H2S/CO2-rich
systems, and production technology.
• Currently, he is the head of the Hydrate, Flow Assurance,
and Phase Equilibria Research Group at the Institute of
GeoEnergy Engineering, Heriot-Watt University.
• He is the Director of the International Centre for Gas
Hydrate Research and the Centre for Flow Assurance
Research (C-FAR) at the Institute of GeoEnergy Engineering
• Hi is a consultant to major oil and service companies.
• Managing Director of “HYDRAFACT LIMITED” a Heriot-Watt
spin-out Company.
• Recipient of “Lifetime Achievement” from the 9th
International Conference on Gas Hydrate, Denver, USA
• His activities played a major role in Heriot-Watt University
winning the Queen’s Anniversary Awards in 2015
• He has more than 450 publications, several book chapters,
and 13 patents
• His research group work was recognized as one of the top
10 UK examples of the role of Chemical Engineering in the
Modern World by the IChemE in 2016.

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World Class Training Solutions
 Introduction to Petro-Teach
• Focus on the Upstream O&G industry

• Providing 150 training course

• About 50 Distinguished Lecturer

• Online, public, and in-house course

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