Development of Asphaltene

Deposition Tool (ADEPT)

Anju Kurup, Walter Chapman
Department of Chemical & Biomolecular Engineering, Rice University

Houston, TX, April 26, 2011

Outline
Introduction / Motivation
Asphaltene deposition simulator structure
Thermodynamic module
Deposition module

Results and discussion

Capillary scale experiments
Field cases Thermodynamic modeling & deposition
simulator predictions

Conclusions
Future work
Acknowledgements

What are asphaltenes?

Heaviest and the most
polarizable components of
the crude oil.
Solubility class of
components of crude oil
Insoluble in low molecular
weight alkanes (e.g. nheptane), Soluble in
aromatic solvents (toluene
or benzene)
Arterial blockage in oil well-bores waxes, gas hydrates and
asphaltenes.
Asphaltenes Special challenge - not well characterized, form
a non-crystalline structure, deposition can occur even at
relatively high temperatures.

Asphaltenes - Flow Assurance Context

http://pubs.acs.org/cen/coverstory/87/8738cover.html

Asphaltenes affect oil production

Deposition in
Reservoirs near well bore
region alter wettability.
Well bore.
Other production facilities
separator, flow lines, etc.
Poison refinery catalysts.

Intervention costs
USD 500,000 for on-shore field
to USD 3,000,000 or more for a
deepwater well along with lost
production that can be more
than USD 1,000,000 per Day*.

*Creek, J. L. Energy & Fuels, 2005

Fast facts about Asphaltenes

Polydisperse mixture.
Deposition mechanism and molecular structure are not completely
understood.
Behavior depends strongly on P, T and {xi} (addition of light gases,
solvents and other oils in commingled operations or changes due to
contamination).

(a) n-C5 asphaltenes

(b) n-C7 asphaltenes

http://baervan.nmt.edu/Petrophysics/group/intro2-asphaltenes.pdf

(a) Condensed aromatic cluster model (Yen et al, 1972),

(b) Bridged aromatic model (Murgich at al., 1991)

Uncertainties in literature
about asphaltenes

Motivation
Predict asphaltene
flow assurance issues

Ability to model
asphaltene phase
behavior as a function of
temperature, pressure,
and composition.

Model mechanisms by which

asphaltenes precipitate,
disperse, and deposit.

Improved operating
practices & risk mgt.

Differentiate between systems

that precipitate and deposit and
those that precipitate and do not
form deposits in well-bores.
Improve deposition prediction.

Literature review
Well bore modeling

Ramirez-Jaramillo et al., 2006, - Molecular diffusion along with shear

removal model to describe deposition (SAFT-VR therm model).
Jamialahmadi et al., 2009, - Mechanistic model - flocculated asphaltene
concentration, surface temperature and flow rates parameters fit to
expt. Soulgani et al., 2009 model of Jamialahmadi et al., with
Hirschberg model (thermodynamic modeling) to predict well shut down
time and compared with field data.
Vargas et al., 2010 Conservation equations with proposal to couple
with PC SAFT (therm model).
Eskin et al., 2010 - Uses particle flux expressions from literature for
particle suspended in turbulent flows to describe diffusion and turbulent
induced particle transport, use population balance model to compute
particle size distribution in the oil phase, Model parameters obtained by
fitting to expt data obtained from Couette flow device.

Reservoir modeling / formation damage modeling

Leontaritis 1997, Nghiem and Coombe 1998, Kohse and Nghiem 2004,
Wang and Civan 1999, 2001, 2005, Almehaideb 2004 - Surface
deposition, pore throat plugging and re-entrainment of deposited solids.
Boek et al., 2008, in press, SRD simulations considering asphaltenes as
spherical molecules.

Need for quantitative & qualitative comparison of deposition profile

Simulator Structure
Experimental
& Field Data

Oil & Asphaltene

Characterization
P&T
Flow rate &
geometry
Precipitation,
Aggregation &
Deposition Rates

Experimental
& Field Data

Translator
Thermodynamic
Modeling Module

Deposition
Simulator

VLXE /
Multiflash

Asphaltene
deposition
profile &
thickness

Thermodynamic modeling
PC SAFT (Perturbed Chain Statistical Associating Fluid Theory)
Chapman et al., 1988, 1990
Molecules modeled as chains of
bonded spherical segments
Gross and Sadowski (2001)
proposed PC SAFT successful in
predicting phase behavior of large
molecular weight fluids
Asphaltene molecules.
Multiflash (Infochem) and VLXE

Parameters required to
characterize each component
of the mixture:
Segment size ( )
Number of segments in a
molecule (m)
Segment-segment interaction
energy ( /k)

e
/k

Thermodynamic modeling
Gonzalez, Ph.D. Dissertation, 2008

10,000
Precipitation
onset

12,000

8,000

Stable region

7,000
6,000
5,000
4,000
3,000
2,000
100

Unstable
region

300

T = 296 F (147 C)

10,000
8,000

Unstable
region

Precipitation
onset

6,000
Bubble point

4,000

Bubble point

VLE
200

Asphaltene precipitation onset

pressure
Stable region

Live oil fluid A

Pressure, psia

Pressure, psia

9,000

14,000

VLE
2,000

400

500

Temperature,
F
Temperature, F

10

15

20

25

30

Added Gas, mole %

P-T diagram: Comparison of

experimental bubble point and
asphaltene onset curves with PC
SAFT predictions

Comparison of experimental
bubble point and asphaltene
onset curves with PC SAFT
predictions for increased
nitrogen gas injection
Oil characterization & PC SAFT parameter estimation:
thermodynamic module
Exp. Data: Jamaluddin et al., SPE 74393 (2001)

Simulator Structure
Experimental
& Field Data

Oil & Asphaltene

Characterization

Translator
Thermodynamic
Modeling Module

VLXE /
Multiflash

P&T
Flow rate &
geometry
Precipitation,
Aggregation &
Deposition Rates

Experimental
& Field Data

Deposition
Simulator

Asphaltene
deposition
profile &
thickness

Wellbore Deposition Simulator

advection

Goal Develop a simulation tool for prediction of occurrence

and magnitude of asphaltene deposition in the well bore.

diffusion

Proposed Model
Mass balance of asphaltene aggregates in a
controlled volume:

Accumulation = Diffusion Convection

Aggregation + Precipitation
Deposition
Asphaltene Precipitation /
Aggregation / Deposition
first order kinetics
Kp, Ka, Kd

PRRC, NMT

Capillary experiments (NMT)

Asphaltene deposition at capillary scale flows
Capillary stainless steel 316

Deposition test-1
Length

3245

cm

T= 70o C

Radius

0.0269

cm

Precipitant= C15

ml/hr

Oil: precipitant= 76:24 v/v

Flow time

63.2

Velocity
0.4888
Oil properties (M1)

hrs

1.50E-07
1.5E-07

cm/s

Saturates

62.9 wt%

Aromatics

21.4

Resins

13.28

Asphaltenes

2.42

(precipitant)

0.74 g/ml

(oil)

0.85 g/ml

(mixture)

0.82 g/ml

(mixture)

3.95 mPa s

Test1 - Sim
Test1 - Expt
Expt

Deposition
(g/cm
Depositionflux
flux,
g/cm2/s)
/s

Flow rate

1.00E-07
1.0E-07

5.00E-08
5.0E-08

0.00E+00
0.0E+00
0 0

0.4 0.6
0.6 0.8
0.8
0.20.2 0.4
Axial
length
(-)(-)
Axial
length

11

Comparison of experimental asphaltene deposition flux with model predictions

Capillary deposition experimental results from NMT (Dr. Jill Buckley)

Capillary experiments
1.50E-07

Test2 - Sim
Test2 - Expt
Expt

Deposition flux, g/cm2/s

22
Deposition
Depositionflux
flux,(g/cm
g/cm /s)
/s

1.5E-07
1.50E-07

1.00E-07
1.0E-07

5.00E-08
5.0E-08

0.00E+00
0.0E+00
00

Test1 - Sim
Test1 - Expt
1.00E-07

5.00E-08

0.00E+00

0.2
0.2

0.4
0.6
0.4
0.6 0.80.8
Axial
Axiallength
length(-)
(-)

1 1

Comparison of experimental asphaltene deposition flux

with model prediction
Deposition test-2
Length

3193

cm

Radius

0.0385

cm

Flow rate

11.68

ml/hr

Flow time

35.9

hrs

0.2

0.4

0.6

0.8

Axial length (-)

Good qualitative and

quantitative agreement
between expt and
simulations.

Some discrepancies exist. Overall trend matched.

Hassi-Messaoud Field case 1

Thermodynamic modeling

PC SAFT

Live oil composition Haskett and Tartera (1965), SARA Minssieux (1997)
Density prediction = 0.8096 g/cm3
Reported = 41.38 = 0.8185 g/cm3

Precipitation envelope

250

4000

2000

5000
4000

200

3000
2000

150

Temperature
Pressure

1000

100

0
0

0
0

100

200

300

400

Pressure (psi)

Temperature ( F)

6000
Pressure (psi)

P-T operating condition

Ponset-SAFT
Psat-SAFT
LowP-SAFT
P-T curve

0.5

Axial length (-)

Temperature ( F)

Ceq variation along the axial length was computed input to simulator.

Hassi-Messaoud Field case 1

Simulator prediction

Simulation parameters
Operating and kinetic parameters

Thickness, in
0

5000
5500
6000

D
e
p
t
h
,
f
e
e
t

335981 cm

11000 ft

5.715 cm

4.5 in dia

VZ, cm/s

179.36

Input from thermodynamic model,

duration 25 days (average of
reported time intervals), thickness
of deposit matched.

6500
7000

Spread of deposit ~ 2000 ft while

reported ~ 1000 ft.

7500
8000
8500

Asphaltene
deposition profile as
reported in (Haskett
and Tarterra, 1965)

1.65 in

9000
9500

Model prediction

Depends on P-T operating curve Changes as production continues.

Paper P-T curve for one well bore
while deposit measurements are
after the asphaltene mitigation
treatment utilized in the paper.

Qualitative and Quantitative

agreement

Kuwait Marrat well Field case 2

Thermodynamic modeling

PC SAFT

Asphaltene precipitation envelope

16000
Psat - Expt*
P-onset - Expt
Psat**
P-T trace **

Pressure (psi)

12000

Psat - SAFT
Ponset - SAFT
LowP - SAFT

API reported* = 36 to 40
PC SAFT = 37. 7

SARA - Kabir and

Jamaluddin, 1999
Live oil composition,
saturation pressure
data from Chevron.

8000

PC SAFT
thermodynamic
characterization.

4000

0
70

140

210

Temperature (oF)
*Kabir et al., SPE 71558, 2001
**Data from Chevron

280

350

Calculated Ceq
variation along the
length of well bore
input to simulator.

Kuwait Marrat well Field case 2

Simulator prediction

Operating parameters
L, cm

457200

15000 ft

R, cm

3.49

2.5 inch ID

VZ, cm/s
Time

240.01
2 months

For 2 months: thickness

matched, 1 and 3 month
kd changes respectively.

P-T curve with axial

length has impact on
precipitation start and end
zone.
*Kabir et al., SPE 71558, 2001

0.6
T
h
i
c
k
n
e
s
s
,i
n

With appropriate choice

of dissolution kinetics and
other kinetics a good
qualitative and
quantitative agreement is
obtained.

0.4

0.2

0
3000

4000

5000

6000

Well depth, ft

7000

8000

Summary
Development of Asphaltene deposition simulator I.
Thermodynamic module.
Deposition module.
Successful application of the simulator to predict
asphaltene deposition in capillary experiments.
Simulator used for deposition prediction in well
bores.
Two field cases studied. Thermodynamic model
of the live oil was developed and coupled with
the deposition module to predict deposition in
well bores.
A good qualitative and quantitative match
between reported field data and simulator
predictions has been obtained.

x
Y
Z

Microsoft Excel interface for ADEPT

Future Activities
Protocol for deposition
prediction
Steps to be followed,
Tests to be conducted,
Parameters to be determined.
Propose set of experiments to
be performed to obtain
kinetic parameters used in
the simulation tool.

Scaling up issues of kinetic

parameters

Obtain more capillary

experiment data and compare
simulator predictions.
Obtain field case data and
compare simulator
predictions.

Model improvement to
address limitations of
the present simulator.
Incorporate effect of
aging

Version I to be used in conjunction with flow simulators

sensitivity analysis of operating parameters
Operating guidelines to reduce deposition probability

Acknowledgments
DeepStar
Chevron ETC
Schlumberger
New Mexico Tech
Infochem
VLXE