1

Nano-Micro Structure of Bitumen and Heavy Oil

Using Viscoelastic Properties

MD. Anwarul Hasan1, Michal Fulem 2,3 , John M Shaw 2

1 Department of Mechanical Engineering, University of Alberta

2Department of Chemical Engineering, University of Alberta

Edmonton, Canada
3 Institute of Physics, Academy of Sciences of the Czech Republic, v. v. i.,

Cukrovarnická 10, CZ-162 53 Prague 6, Czech Republic

In press at energy and fuels

 Introduction 2

• The influence of asphaltenes on the rheological properties of

fluids is typically studied by mixing solvent extracted
asphaltenes with standard solvents or de-asphalted oils.

• The question, how closely the behavior of these mixtures

resembles that arising in the original hydrocarbon resources
remains unanswered in the literature.

• In this work, we report on the rheological properties of nano-

filtered Athabasca bitumen and Maya crude oil samples
obtained by solvent-free nanofiltration
• The purpose of the study is to investigate the nano-micro
structure of bitumen using its viscoelastic behavior.
 Slurry Viscosity 3

Generalized Sudduth’s Equation

• Describes Newtonian & non-Newtonian suspensions alike.

• Encompasses classic equations used for these purposes.

• Parameters appearing in the model are linked directly to

fluid and particle physics theory.

• The intrinsic viscosity [η] for a Newtonian slurry is 2.5; σ

is -1.5 for non interacting hard spheres; 1< k < 2 relates to
particle "crowding“. φ is the solid volume fraction.
 Materials and Sample Preparation 4

Materials:

• Athabasca Bitumen (Alberta) and Maya Crude oil (Mexico).

Sample preparation

• Nanofiltration: 5, 10, 20, 50

nm permeates and retentates.
• Asphaltene wt.%: 0 to 57%

SARA Analysis Nano-filtration Apparatus.

• SARA analysis was performed according to ASTM D2007

and ASTM D33279.
Zhao, B. and Shaw, J.M., Energy & Fuels 2007, 21, (5), 2795-2804.
 Rheological Measurements 5

Rheometer

• A Bohlin Gemini Malvern nano-

rheometer was used.
• Parallel plate geometry used (for
most samples)
• Double gap cylinder used (for very
low viscosity samples, e.g. maltene) Rheometer

Parameters
Parallel Plate
• Frequency (shear rate): 0.1 to 100 Hz.
• Temperature: 25, 30, 50, 75 & 100C. Bohlin Gemini Rheometer.
 Results and Analysis 6

Phase Behavior of AB and Maya Samples

Table 1: Solid Content of Maltenes. Fulem, Becerra, Hasan, Zhao, and Shaw, Fluid

Phase Equilibria 272 (2008) 32-41

Temp, K 149 170 200 230 250 270 290 310 320 325
Maya Maltene 1.00 0.96 0.81 0.59 0.44 0.30 0.17 0.06 0.02 0
AB Maltene 1.00 1.00 1.00 0.8 0.63 0.46 0.28 0.11 0 0
100

Table 2, 3: Solid Asphaltenes (SARA Analysis).

80

ABR1

Total Solid (wt.%)

AB Samples ABP10 ABP20 ABP50 AB ABR200 60
0
Asph.altenes 40
5.3 10.4 13.6 18.6 50.0 57.2
(C5)
20
AB bitumen
Maya crude
Maya 0
Maya Samaples MP5 MP10 MP20 MP50 MR5 150 200 250 300 350
crude Temperature (K)

Asphaltenes (C5) 1.5 6.2 8.1 9.4 15.7 46.7

Fig. Total solid (wt.%) for
Total Solid = Solid from maltene + solid asphaltenes AB and Maya.
 Results and Analysis 7

Complex Viscosity of AB and Maya Samples

(a) (c) 2000

(b)
1

1000
1800

Complex Viscosity (Pa.s)

Complex Viscosity (Pa.s)
Complex Viscosity (Pa.s)

100 1600
0.1

1400
10

298 K 1200
303 K 298 K
1 323 K 303 K
0.01
348 K 323 K
1000 Low shear rate experiment
373 K 348 K
373 K High shear rate experiment
0.1
0.1 1 10 100 800
0.1 1 10 1E-4 1E-3 0.01 0.1 1 10
Frequency (Hz)
Frequency (Hz) Frequency (Hz)

Athabasca Bitumen (AB) Maya Crude oil AB at Low shear rate

•Both Maya crude and Athabasca bitumen exhibit Newtonian plateaus at low shear
rate over the entire temperature interval evaluated.

• For Athabasca bitumen at 298 K the Newtonian plateau is evident only at < 0.01 Hz.
 Results and Analysis 8

Comparison of our data with those in literature

107
• The viscosity values in this study are 106
This work, zero shear rate
Briggs (1978); RBV; γ = (14 to 225) s-1 (Ref. 18, 19)
Briggs (1978); CCV; γ = (12 to 1400) s-1 (Ref. 18, 19)
Camp (1974); n/s ; γ is n/s (Ref. 20)
higher except for values obtained by Ward 105 Charbonnier et al. (1969); n/s ; γ is n/s (Ref. 21)
Dealy (1979); MS; γ = 1 s-1 (Ref. 22)
Ward, Clark (1950), from different locations;
and Clark(Abasand), Charbonnier et al. 104
CapV; γ is n/s (Ref. 23)
Flock, Boogmans (1976); CCV;
γ = (13 to 2300) s-1 (Ref. 24)

(for some locations) and Camp (Abasand). 103

Jackobs (1978); CCV; γ is n/s (Ref. 25)

Viscosity (Pa.s)
Mehrotra, Svrcek (1985); CCV; γ is n/s (Ref. 26)
Svrcek et al. (1979); CCV; γ is n/s (Ref. 27)
Robinson et al. (1983); CapV; γ is n/s
102 Schramm, Kwak (1988); CCV; γ = 460 s-1

•This is because zero shear viscosities are 101

by definition the highest values 100

10-1

10-2
•Also because our bitumen sample is a
10-3
partially processed product from a 300 350 400 450 500
Temperature (K)
naphtha recovery unit at Syncrude. Some
of the more volatile constituents of the Athabasca Bitumen
bitumen have been removed.
 Results and Analysis 9

Complex Viscosity of Permeates

700 (a) Asphaltene concentration 1.50 (b) Asphaltene Concentration

50 nm = 13.6 wt. % 50 nm = 9.4 wt.%
600 20 nm = 10.4 wt. % 20 nm = 8.1 wt.%
10 nm = 5.3 wt. % 1.25 10 nm = 6.2 wt.%
Extrapolated Solid 5 nm = 1.5 wt.%
Complex Viscosity (Pa.s)

Complex Viscosity (Pa.s)

500
Free Maltene = 0 wt. % Extrapolated Solid
1.00 Free Maltene = 0 wt.%
400

0.75
300

200 0.50

100
0.25

0
0.00
0.1 1 10 100 0.1 1 10
Frequency (Hz) Frequency (Hz)

Athabasca Bitumen Permeates Maya Crude oil Permeates

• All permeates exhibit a Newtonian plateau at low frequency.

• Viscosity of Athabasca bitumen samples are about three orders of

magnitude higher compared to Maya crude samples.
 Results and Analysis 10

600000
(a) Asphaltene Concentration
500000 10 nm AB retentate = 57.2 wt.%
200 nm AB retentate = 50 wt.%
5 nm Maya retentate = 46.7 wt.%

Complex viscosity (Pa.s)

400000

Complex viscosity of retentate 300000

samples from viscous modulus

master curve.
200000

100000

0
0.01 0.1 1 10 100
Frequency (Hz)

Complex Viscosity of Retentates

(a)
(b)
1000000 1E9 η0= 8.84 Ε 08 Pa.s
1E8
100000
Viscous Modulus (Pa)

Viscous Modulus (Pa)

1E7

1000000
10000
100000

10000
1000
298 K 298 K, aT = 1
1000
323 K 323 K, aT = 2E-03
348 K 348 K, aT = 1E-05
100 100
373 K 373 K, aT = 6E-07
10
0.01 0.1 1 10 100 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 10 100 1000
Frequency (Hz) ω aT (rad/s)
Viscous modulus of 200 nm retentate Viscous modulus master curve, 298K
 Results and Analysis 11

Relative Viscosity of Permeates

4
8
298 K
298 K
303 K
323 K
323 K
348 K 3 373 K
6 373 K

Relative Viscosity
Relative Viscosity

2
4

1
2

(b)
(a)
0
0 0 5 10 15 20 25
0 5 10 15 20 25 30 35
Total Solid (wt.%)
Total Solid (wt.%)

Athabasca Bitumen Permeates Maya Crude oil Permeates

• Relative viscosity data for all different temperatures fall on a single line
when expressed in terms of total solid content.
 Results and Analysis 12

Relative Viscosity of All Samples

• Generalized Sudduth
Equation with [η] = 2.5; σ = -
1.5; and k = 1.29; fits the
experimental data for the
nanofiltered samples of both
Athabasca bitumen and
Maya crude oil very well.

Zero-shear zero-solid relative

viscosities of all samples.
• The rheological behavior of the nanofiltered samples is consistent with the
behavior of a slurry comprising a Newtonian liquid + non-interacting hard
spheres in the temperature range 298 K to 373 K
 Results and Analysis 13

Zero asphaltene based Relative Viscosity

3
10
(a) 298 K
298 K 303 K
323 K 323 K
8
348 K 373 K
373 K 2

Relative Viscosity
Relative Viscosity

4
1

2
(b)
0
0 0 2 4 6 8 10 12 14 16
0 5 10 15 20
Asphaltene (wt.%)
Asphaltene (wt.%)

Athabasca Bitumen Permeates Maya Crude oil Permeates

• If expressed in terms of asphaltene wt% instead of total solid wt%, apparent

temperature dependence is evident for Athabasca bitumen related samples.
•For Maya crude oil related samples the impact is less pronounced because less of
the maltene is solid.
 Results and Analysis 14

Chemically Separated Maltene based Relative Viscosity

1000
100
298 K (a)
323 K (b)
348 K
373 K
100
Relative Viscosity

Relative Viscosity
10

10

298 K
303 K
323 K
1
0 5 10 15 20 1
0 5 10 15 20
Asphaltene (wt.%)
Asphaltene (wt.%)

Athabasca Bitumen Permeates Maya crude oil permeates

• Again, the apparent temperature dependence is significant.
•These dependences have been wrongly attributed to change of shape of asphaltene
aggregates, asphaltene-maltene interaction, or asphaltene self association. Such
misattributions introduce additional fluid physics and fluid chemistry not needed to
explain the rheological behavior of such fluids.
 Conclusion 15

• Composition and/or phase behavior of maltene plays crucial role in

determining bitumen and heavy oil viscosity.

• Rheological investigations of hydrocarbon resources must account for the

impacts of solid maltenes as well as for asphaltenes in modeling and
analysis.

• Failure to account for solid maltenes in the interpretation of rheological

data for these hydrocarbon resources leads to misattributions related to the
nature and the importance of the role that asphaltenes play in the
determination of hydrocarbon resource viscosity.

• Nanofiltered Maya Crude and Athabasca bitumen exhibit rheological

behaviors consistent with slurries comprising a Newtonian liquid + non-
interacting hard spheres in the temperature range 298 K to 373 K, if all
solids present are accounted for.
 Acknowledgements 16

-Thanks to Mildred Becerra, and Bei Zhao

-This research was supported by the Alberta Energy Research I

nstitute, ConocoPhillips Inc., Imperial Oil Resources, Halliburton, K
ellogg Brown and Root, NEXEN Inc., Shell Canada, Total, Virtual
Materials Group, NSERC, and the Alberta Ingenuity Fund.