Académique Documents
Professionnel Documents
Culture Documents
503-509
Copyright 2004, Institut franais du ptrole
Dossier
Pipeline Transportation of Heavy Oils
coulement des bruts lourds dans les conduits
Rsum Dilution des bruts lourds Les ptroles bruts lourds ne peuvent tre transports par
pipeline sans rduction pralable de leur viscosit. Pour ce faire, la mthode la plus couramment
employe est la dilution par des hydrocarbures lgers. Dans ce cas, la viscosit du mlange dpend
uniquement du taux de dilution et des viscosits et densits respectives de lhuile lourde et du diluant.
Lajout dun solvant polaire une solution dasphaltnes dans du tolune permet dagir sur la structure
collodale des asphaltnes. Ceci conduit une diminution de la viscosit relative de la solution. Des
mesures effectues par diffusion des rayons X aux petits angles indiquent que le rayon de giration des
agrgats dasphaltnes diminue conjointement. De mme, en mlangeant des hydrocarbures avec des
solvants comportant des groupements polaires, il est montr que lefficacit de la dilution des bruts lourds
est amliore. La thorie de Hansen peut tre utilise pour slectionner les solvants les plus efficaces.
taux de dilution constant, une augmentation du paramtre de polarit ou du paramtre reprsentatif des
liaisons hydrogne se traduit par une diminution de la viscosit relative du brut dilu. Nanmoins, les
produits comportant de fortes liaisons hydrogne sont gnralement plus visqueux que les hydrocarbures.
Leffet de leur interaction avec les asphaltnes sen trouve masqu lorsque les rsultats sont exprims en
termes de viscosit absolue. Seuls les solvants polaires donnant peu de liaisons hydrogne permettent
dobtenir une rduction significative de la viscosit du brut dilu.
Abstract Heavy Oil Dilution Heavy crude oils cannot be transported by pipeline without a prior
reduction of their viscosity. This is commonly obtained by blending the oil with light hydrocarbons. In
that case, the resulting viscosity of the mixture depends only on the dilution rate, on the respective
viscosities and densities of the oil, and of the diluent. The addition of a polar solvent to a solution of
asphaltenes in toluene acts on the colloidal structure of the asphaltenes. The relative viscosity of the
solution decreases. Small-angle X-ray scattering (SAXS) measurements show that the radius of gyration
of the aggregates of asphaltenes decreases too. In the same way, by mixing hydrocarbons and solvents
owning polar functional groups in their molecule, it is shown that the efficiency of the dilution of heavy
crude oils is enhanced. Hansens theory can be used to screen the solvent efficiency. At constant dilution
rate, the higher the polarity parameter or the hydrogen bonding parameter of the solvent, the greater the
relative viscosity reduction of the diluted crude oil. Nevertheless, solvent owning high hydrogen bonding
are generally more viscous than hydrocarbons. The influence of their interactions with the asphaltenes is
hidden when the results are expressed in absolute viscosity. Only polar solvents giving few hydrogen
bonding give a significant reduction of the viscosity of the diluted crude oil.
504 Oil & Gas Science and Technology Rev. IFP, Vol. 59 (2004), No. 5
The dilution of the crude oil has been performed using This value agrees well with obtained by fitting the exper-
different organic solvents mixed with nonane (Fluka) or imental values of the viscosity. This is an indication that
naphtha. Naphtha is a petroleum fraction; the composition of hydrocarbons reduce the viscosity of heavy oils in the same
the naphtha used in this study determined by gas way. To increase the efficiency of the dilution, other organic
chromatography is given in Table 2. The samples have been products are probably needed.
homogenized by stirring during 24 h.
1000 80 1.3
100 75 1.25
Radius of gyration ()
10
Viscosity (Pa.s)
0.01 60 1.1
0.001 55 1.05
0.0001
0 20 40 60 80 100 50 1
0 10 20 30 40 50 60
Naphtha concentration (% w/w) Volume fraction of hexanol (%)
Figure 2
Figure 1 Influence of the volume fraction of hexyl alcohol of 3% I5 in
Dilution of Oil A with naphtha. Evolution of the viscosity hexyl alcohol/toluene mixture on the radius of gyration of the
with the dilution rate. asphaltenes at 25C (), the relative viscosity at 3C ().
506 Oil & Gas Science and Technology Rev. IFP, Vol. 59 (2004), No. 5
The obtained values are plotted against the volume The cohesion energy parameters of solvent mixtures can
fraction of hexyl alcohol (Fig. 2). be calculated from the parameters of each solvent using the
The graph shows that there is a minimum for the radius of following equation:
gyration and for the relative viscosity. This minimum is i=n
observed for a hexyl alcohol content of 10% in toluene. This = i Vi (5)
confirms that hexyl alcohol has an effect on the organization i =1
of the asphaltenes in the diluted regime. The decrease of the where is the Hansen parameter of the mixture (dispersion,
relative viscosity and of the radius of gyration can be polar or hydrogen bonding part), i is the Hansen parameter
explained by some disruption of the asphaltene particles. One of the pure solvent i and Vi is the volume fraction of the
can think that hexyl alcohol is able to establish hydrogen solvent i in the mixture.
bonds and polar interactions with the asphaltenes and thus The dispersion component of the Hildebrand parameter
replace some of the asphaltenes/asphaltenes interactions. quantifies the London dispersion forces (or induced dipole-
With 10% of hexyl alcohol, the dissociation phenomenon is induced dipole forces). These forces correspond to weak Van
at its maximum and all linkages between the elementary der Waals interactions and we can think they will not have
particles are broken. An increase of the hexyl alcohol fraction any effect on the asphaltene organization. For the two other
from 10 to 50% in toluene leads to an increase of both the components, we can expect an influence of their value on the
radius of gyration and the relative viscosity. It is known that association of the asphaltenes and therefore on the viscosity
the relative viscosity of asphaltenes in a mixed toluene/ of the diluted crude. To verify this hypothesis, hydrocarbons
heptane tends to increase when the ratio heptane/toluene have been mixed with organic solvents of different p and h
approachs the flocculation point [16]. Hexyl alcohol, like parameters, the resulting parameters of the synthetic mixture
heptane, is a nonsolvent of the asphaltenes. Then, when all being calculated according to Equation (5). The selected
the possible sites able to establish associations between the hydrocarbons are nonane and naphtha. Nonane is a pure
alcohol functions and the asphaltenes are saturated, hexyl alkane for which polar and hydrogen bonding Hansen
alcohol acts as a flocculant, making the gyration radius and parameters are zero. Naphtha is the hydrocarbon mixture
the relative viscosity increase. commonly used to dilute heavy oils. From its composition
(Table 2), one can assume in first approximation that its
Hansen parameters are close from those of ASTM Fuel B i.e.
4 INFLUENCE OF THE SOLVENT ON THE VISCOSITY
d = 15.3, p = 0.4, h = 0.6.
REDUCTION OF THE HEAVY OIL
To compare dilution efficiency of solvents, results are
By varying the concentration of asphaltenes in maltenes, presented using relative viscosity defined as:
Hnaut et al. [17] have found the existence of a critical rel (c,T) = (c,T)/diluent (T)
concentration above which the colloidal particles entangle.
with:
This structural change dramatically increases the viscosity of
(c,T), the viscosity of the diluted crude at a concentration
the heavy crude oils. Limitation of entanglement will likely
c and temperature T (Pas);
reduce the viscosity. This could be enhanced by increasing
interactions between the solvent and the polar compounds of diluent (T), the viscosity of the thinner at the temperature T
the crude oil (mainly the asphaltenes) and breaking the (Pas).
asphaltenes/asphaltenes interactions. From the previous This representation allows to take no account of the
results, polar solvents could assume this function. simple dilution effect and on the contrary to emphasis the
According to the theory of Hildebrand and Scott, the eventual contribution from organization and structural
parameter t is a measure of molecular interactions. The modifications.
solubility parameter is defined by:
4.1 Influence of Polarity
1
E 2
t = LV (3) In order to study the influence of the polar component of the
VM Hildebrand parameter, some organic solvents of different p
with ELV as cohesion energy and VM as molar volume. have been selected, keeping as constant as possible the others
In order to be able to distinguish between dispersion solubility parameters (Table 3).
forces, polar interactions and hydrogen bonding, Hansen [18] The solvents have been mixed with nonane and with
divided this solubility parameter in three parts, i.e. the naphtha at 10 and 50% v/v. This allows to get synthetic
dispersion part d, the polar part p and the hydrogen bonding solvents with polarity parameter varying from 0 to 6.4. Oil A
part h, called cohesion energy parameters: has been diluted with 15% by weight with the synthetic
solvents. Viscosity measurements have been performed
2t = 2d + 2p + h2 (4) at 20C.
P Gateau et al. / Heavy Oil Dilution 507
TABLE 3 polar sites, even the weakest, are associated with solvent
Hansen parameters of nonane and polar cosolvents molecules. This is easier to obtain in naphtha, where the
asphaltenes are relatively well solvated, than in nonane,
d p h
Solvent where they are more compact. The best reduction of viscosity
(MPa1/2) (MPa1/2) (MPa1/2)
is reached in naphtha with butanone, and using an even more
Nonane 15.8 0.0 0.0 polar solvent like butyronitrile does not seem to improve the
Ethyl acetate 15.8 5.3 7.2 efficiency. This is not the case in nonane where, for all the
Butyraldehyde 14.7 5.3 7.0 studied solvents, the higher the value of the polar parameter,
2-Butanone 16.0 9.0 5.1 the better the efficiency.
Butyronitrile 15.3 12.5 5.1
2400 3500
2200
3000
2000
Relative viscosity
Relative viscosity
2500
1800
1600 2000
1400
1500
1200
1000 1000
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
p (MPa1/2) p (MPa1/2)
Figure 3 Figure 4
Evolution of the viscosity of dilute Oil A with the polarity of Evolution of the viscosity of dilute Oil A with the polarity of
the nonane based solvent. the naphtha based solvent.
508 Oil & Gas Science and Technology Rev. IFP, Vol. 59 (2004), No. 5
3500 2
3000 1.5
Relative viscosity
2500
Viscosity (Pa.s)
1
2000
Butyraldehyde (0.1)
Butyraldehyde (0.5)
Ethyle acetate (0.1)
Butyronitrile (0.1)
Butyronitrile (0.5)
Butyric acid (0.1)
2-butanone (0.1)
2-butanone (0.5)
1500
1-hexanol (0.1)
0.5
1-butanol (0.1)
1-octanol (0.1)
Naphtha
1000
0 0.5 1 1.5 2 2.5
0
p (MPa1/2) Solvent (volume fraction in naphtha)
Figure 5
Evolution of the viscosity of dilute Oil A with the hydrogen Figure 6
bonding parameter of the solvent. Nonane based (), naphtha Absolute viscosity of Oil A at 20C diluted with mixtures of
based (). naphtha and polar solvents.
04 Guevara, E., Gonzalez, J., Nuez, G. (1998) Highly Viscous 12 Storm, D.A. et al. (1999) Drag Reduction in Heavy Oil.
Oil Transportation Methods in the Venezuela Industry. Proc. Journal of Energy Resources Technology, 121, 145-148.
15th World Pet. Congress, 495-502. 13 Argillier, J.F., Barr, L., Brucy, F., Dournaux, J.L., Hnaut, I.
05 Meyer, R.F. (1998) World Heavy Crude Oil Resources. Proc. and Bouchard, R. (2001) Influence of Asphaltenes Content
15th World Pet. Congress, 459-471. and Dilution on Heavy Oil Rheology. SPE 69711.
06 Mehrotra, A.K. (1992) A Model of the Viscosity of Bitumen/ 14 Lederer, E.L. (1933) Proc. World Pet. Cong. (Lond.) 2, 526-
Bitumen Fractions - Diluent Blends. J. Can. Pet. Technol., 528.
31, 9, 28-32. 15 Zimm, B.H. (1948) The Scattering of Light and the Radial
07 Gerez, J.M. and Pick, A.R. (1996) Heavy Oil Transportation Distribution Function of High Polymer Solutions. J. Chem.
by Pipeline. Int. Pipeline Conf., 2, 699-710. Phys., 16, 1093-1116.
08 Rahmes, M.H. and Nelson, W.L. (1948) Viscosity Blending 16 Fenistein, D. et al. (1998) Viscosimetric and Neutron
Relationships of Heavy Petroleum Oils. Analytical Chem- Scattering Study of Asphaltene Aggregates in Mixed
istry, 20, 912-915. Toluene/Heptane Solvents. Langmuir, 14, 1013-1020.
09 Shu, W.R. (1984) A Viscosity Correlation for Mixtures of 17 Hnaut, I., Barr, L., Argillier, J.F., Brucy, F. and Bouchard,
Heavy Oil, Bitumen and Petroleum Fractions. SPE 11280. R. (2001) Rheological and Structural Properties of Heavy
Crude Oils in Relation with Their Asphaltenes Content. SPE
10 Anhorn, J.L., Badakhshan, A. (1994) MTBE: A Carrier for 65020.
Heavy Oil Transportation and Viscosity Mixing Rule
Applicability. J. Can. Pet. Technol., 33, 4, 17-21. 18 Barton, A.F.M. (1992) Handbook of Solubility Parameters
and Other Cohesion Parameters, 2nd Ed. CRC Press.
11 Anhorn, J.L. and Badakhshan, A. (1994) Heavy Oil -
Oxygenates Blends and Viscosity Models. Fuel: Guildford,
73, 9, 1499-1503. Final manuscript received in September 2004