Energy Fuels 2011, 25, 539–544 : DOI:10.

1021/ef101074m
Published on Web 02/03/2011

Terpolymers as Flow Improvers for Mexican Crude Oils†

Laura V. Castro,‡ Eugenio A. Flores,§ and Flavio Vazquez*,§
‡
Escuela Superior de Ingenierı´a Quı´mica e Industrial Extractivas, Instituto Polit

ecnico Nacional, Unidad Profesional
“Adolfo L
opez Mateos”, Zacatenco, Delegaci
on Gustavo A. Madero, C.P. 07738, Mexico City, Distrito Federal (DF),
Mexico, and §Programa de Ingenierı´a Molecular, Instituto Mexicano del Petr
oleo, Eje Central Norte
“L
azaro C
ardenas” 152, San Bartolo Atepehuacan, C.P. 07730, Mexico City, Distrito Federal (DF), Mexico

Received August 14, 2010. Revised Manuscript Received January 18, 2011

The rheological behavior of dilute solutions from different terpolymers was investigated over a wide range
of temperatures (20-45 °C) and shear rates (0.1-300 s-1). The investigation focuses on the effect of three
co-monomer contents, their molecular weight, the terpolymer, and the viscosity-temperature relationship
of a Mexican crude oil (MCO). Terpolymers with different contents of styrene (S), n-butylacrylate (BA),
and vinyl acetate (VA) were synthesized through semi-continuous emulsion polymerization. The composi-
tion of the terpolymers was evaluated by nuclear magnetic resonance (NMR) spectroscopy. The average
molecular weight and polydispersity of the polymers were determined through size-exclusion chromatog-
raphy (SEC). Both the untreated crude oil and the one treated with a solution of terpolymer exhibited non-
Newtonian behavior. The results confirm that the viscosity of crude oil is reduced when the terpolymers
have a high percentage of S and small amounts of BA or VA. The molecular weight of terpolymers plays a
fundamental role in their performance as viscosity reducers.

Introduction lubrication, and core-annular flow, thermal cracking, or

blending with lighter distillate fractions (gasoline, kerosene,
A change will be seen in the next few years regarding crude
naphtha, or other solvents) to let them be transported through
oil sources in the global market. Advances in exploration and
pipelines.1,2 Other approaches that have been suggested to
production technologies in the petroleum industry are devel-
reduce viscosity in heavy crude oils include the use of aqueous
oping new major sources, in areas that were previously off
anionic surfactant solutions to form low viscosity in water
limits for geographical, political, and technological reasons.
emulsion;3 such emulsions generally contain a rather high
Some of the new areas in exploitation will have a major
percentage of water, which must be removed.
significance in the U.S. markets, Latin America, mainly
The viscosity of crude oil is affected by the temperature;
Venezuela, Canada, and Mexico.1
increasing the temperature is a common way to reduce
Heavy oil and extra heavy oil are defined as having an
viscosity, resulting in both an expensive and a non-acceptable
American Petroleum Institute (API) gravity below 22° and
procedure for reducing the viscosity of the crude oil to be
10°, respectively. API gravity is an inverse measure of the
carried over a rather long distance in the pipeline. Maintaining
relative densities of oil liquid and water; high-gravity crude
an elevated temperature of crude oil in a pipeline is extremely
oils, such as those, are relatively thin and relatively easy to
difficult.4 An increase in the production of crude oil from
pump.
heavy crude oil reserves in the Sound of Campeche is expected;
Many heavy crude oils contain high levels of sulfur, nitro-
these reserves are intended to produce heavy crudes, with
gen, nickel, and vanadium and are rich in condensed poly-
varying upgrading degrees. With such an increase of heavy
aromatic compounds, reacting readily to form coke. In heavy
crude oil sources in the near future, it looks like a suitable time
crude oils, these types of compounds can lead to various pro-
to exploit new research paths for the reduction of viscosity.
blems in the recovery, transportation, treatment, and refining
A method for decreasing the viscosity of crude oil is
of crude oils.
involved with the fact of injecting crude oil, under high
Reducing the viscosity in the heavy crude is of utmost
pressure, with a gas or a combination of gases, carbon dioxide
importance in the oil industry. Heavy crude production
(CO2) or better, a combination of CO2 and nitrogen (N2).4
increases day after day, and a liable technology to lower crude
Several options are available including methods of electric
oil viscosity has become urgent.
pulses or magnetic fields to reduce the viscosity of crude oil5
Minimizing the viscosity of the heavy crude oil turns into an
and the use of chemical additives, such as flow improvers,6,7
important issue. Highly viscous crude oils, during extraction,
viscosity reducer,8-10 pour point depressants (PPDs),11-14
have to go through some processing, e.g., gas plasticization,
heat dilution, partial field upgrading, water emulsification, (2) Badger, M. W.; Schobert, H. H. Viscosity Reduction in Extra
Heavy Crude Oils, The Laboratory for Hydrocarbon Process Chemistry;
† The Energy Institute: University Park, PA, 1998; Vol. 43-3, pp 461-465.
Presented at the 11th International Conference on Petroleum Phase (3) Flornoy, K. H.; Cardenas, R. L.; Carlin, J. T. U.S. Patent
Behavior and Fouling. 3,943,954, 1976.
*To whom correspondence should be addressed. Telephone: þ52-55- (4) Briggeman, W. H.; Black, J. J. U.S. Patent 6,491,053 B1, 2002.
91-75-7600. Fax: þ52-55-91-75-7969. E-mail: [email protected]. (5) Tao, R.; Xu, X. Energy Fuels 2006, 20 (5), 2046–2051.
(1) Chheda, B. D.; Banavali, R. M.; Mazza, G. U.S. Patent 6,402,934 (6) Rossi, A.; Warren, N. J. U.S. Patent 4,135,887, 1979.
B1, 2002. (7) Botros, M. G. U.S. Patent 5,681,359, 1997.

r 2011 American Chemical Society 539 pubs.acs.org/EF

Energy Fuels 2011, 25, 539–544 : DOI:10.1021/ef101074m Castro et al.

etc. All of the chemical additives are very selective, meaning Table 1. Polymerization Formulation Employed in the Synthesis of
that not all additives are effective enough for every crude oil.15 Emulsion Terpolymers with Different Contents of Transfer Agent
For example, highly waxy crude oils are characterized by a main reactor feeding tank
high pour point, viscosity, and yield stress and exhibit non- substance (g) (g)
Newtonian flow behavior below pour point temperatures.
mixture of monomers 0 100
The process for extracting waxy crude oils from the oil fields is ammonium persulfate solution (4 wt %) 5 20
costly and complex, because the paraffin deposition causes a buffer solution (4 wt %) 25 0
reduction in the production in terms of maintenance and Abex solution (7 wt %) 5 67
removal of deposits already formed. Thus, chemical products Disponil solution (7 wt %) 5 67
CTA 0 0-8
known as flow improvers, crystal modifiers, and pour point
water 103 95-103
reducers need to be used to reduce the apparent viscosity, the
flow limit, and the pour point of oils. co-monomers were selected because of their potential PPD
An efficient polymeric additive for paraffin oils should be a properties and the thermal degradation characteristics; two of
linear polymer or co-polymer with pendant hydrocarbon them were used as polar co-monomers with probable paraffin-
chain groups and/or present hydrocarbon chains in the poly- compatibilizing features. The performance of the prepared
meric backbone. Polymeric compounds, such as polyalkyl additives as viscosity reducers was tested on heavy crude oil
acrylates and methacrylate co-polymers, alkyl esters of styr- samples from Mexican oil fields. The objective of this research
ene-maleic anhydride co-polymers,16 ethylene-vinyl acetate was to observe whether the viscosity of heavy crude oils could
co-polymers, etc., are some of the flow improvers for waxy be reduced by the addition of chemical compounds (polymers)
crude oils.17,18 Other constituents in the crude oil, i.e., asphal- with solvent, which may break down the asphaltene agglom-
tenes, resins, polar aromatics, etc., should also be considered erates and, thus, achieve viscosity reductions.
as important factors while ascertaining the flow behavior of a
crude oil. In addition, it is worth considering that some heavy Experimental Section
Mexican crude oils (MCOs) are characterized by high viscosity, a Materials. The following substances were purchased and
high content of asphaltenes (>8 wt %), a low quantity of paraffin employed without further purification: styrene (S, M1, Aldrich),
components, appreciable amounts of sulfur (>1.9 wt %), and a n-butyl acrylate (BuA, M2, Aldrich), vinyl acetate (VA, M3,
very noticeable content of vanadium and nickel.19 Aldrich), initiator (ammonium persulfate, APS, Fermont), buf-
Flow improvers are quite important for crude oil delivery fer (sodium bicarbonate, J. T. Baker), emulsifiers (Abex 26-S,
through pipelines and for high-quality oil products, with most Rhodia and Disponil AES 13 IS, Cognis), the chain-transfer
of them polymers.20,21 The use of certain fluorochemical com- agent (CTA, 1-dodecanethiol, Aldrich), calibration standard for
pounds having oleophobic and hydrophobic groups is carried nuclear magnetic resonance (NMR) spectroscopy [tetramethyl-
out to reduce the viscosity of asphaltenic crude oils, optionally silane (TMS), Fluka-Aldrich], and deuterochloroform (CDCl3,
Aldrich). Distilled water was used during the experiments.
combined with a low viscosity diluent.9 Novel amine-chelate
Heavy crude oil was obtained from the Gulf of Mexico.
complexes are useful to highly reduce the viscosity of heavy Synthesis. Random terpolymers with various molar ratios of
crude oils.10 For example, some additives that reduce viscosity S, VA, and BuA were synthesized by means of free-radical
and gel strength in a considerable way are poor PPDs. Pre- polymerization in water under a nitrogen atmosphere, using
treatment of heavy MCOs with a viscosity reducer (polymeric ammonium persulfate as the initiator at 70 ( 0.05 °C in a semi-
additives) could be a better choice because of its simplicity and continuous reactor. The polymerization formulation is shown in
economy. Table 1. The CTA is included in latex formulations to regulate
This paper describes the preparation and evaluation of flow (i.e., decrease) the average molecular weight and molecular-
improving additives for MCO and could be regarded as a weight distribution of the latex polymer. Mercaptans are the
continuity of a recent paper.22 Additives were synthesized by most common type of CTA, as well as the most efficient.23 A
semi-continuous emulsion polymerization process was used to
means of free-radical emulsion polymerization using ecologi-
synthesize the additives. All monomers and reagents corre-
cal initiators. A series of different additives of varying com- sponding to the main reactor load (shown in Table 1) were
position and average molecular weights was prepared by semi- introduced into the reactor. At first, the reagents corresponding
continuous polymerization of three different monomers. The to the main reactor were charged at the beginning of the poly-
merization, except the initiator solution. The reactor was heated
at 70 °C for 10 min, and then the initiation solution was added.
(8) Cohrs, C.; Krull, M.; Feustel, M.; Rausch, H. U.S. Patent 20070-
221-539 A1, 2007. After 10 min, the pre-emulsified monomers (feeding tank) were
(9) Karydas, A. U.S. Patent 4,876,018, 1989. added with the aid of a metering pump at q = 6.67  10 -3 g
(10) Pappas, P. G.; Abdul-Malek, A. B. U.S. Patent 4,255,160, 1981. L -1 min -1. The polymerization procedure was followed using
(11) Pober, K. W.; Starks, C. M. U.S. Patent 5,405,916, 1995. an established procedure.22 The reagents were fed under strict
(12) Motz, K. L.; Latham, R. A.; Statz, R. J. U.S. Patent 4,926,582,
1990. starved-feed conditions (with the monomer feed rate being
(13) Baralt, E. J.; Yang, H. U.S. Patent 2007/0095-723 A1, 2007. lower than the polymerization rate) with the aid of a metering
(14) Fischer, J. U.S. Patent 5,256,166, 1993. pump.
(15) Siffeman, R. T. J. Pet. Technol. 1979, 1042–1050. The terpolymers were isolated by means of water evaporation
(16) Al-Sabagh, A. M.; El-Din, M. R.; Morsi, R. E.; Elsabee, M. Z.
J. Pet. Sci. Eng. 2009, 65, 139–146.
and dried at room temperature, showing either yellow viscous
(17) Chanda, D.; Sarmah, A.; Borthakur, A.; Rao, K. V.; Subrahmanyam, liquid or pale yellow wax-like appearances.
B.; Das, H. C. Fuel 1998, 77 (11), 1163–1167. Polymer Characterization. Samples for spectroscopic charac-
(18) Taraneh, J. B.; Rahmatollah, G.; Hassan, A.; Alireza, D. Fuel terization were first precipitated from latex by the addition of a
Process. Technol. 2008, 89, 973–977. solution of 0.1 N HCl. Afterward, the dry polymer was dissolved
(19) Castro, L. V.; Vazquez, F. Energy Fuels 2009, 23 (3), 1603–1609.
(20) Kuzmic, A. E.; Radosevic, M.; Bogdanic, G.; Srica, V.; Vukovic, 3 times in tetrahydrofuran (THF) and subsequently precipitated
R. Fuel 2008, 87 (13-14), 2943–2950.
(21) Soni, H. P.; Kiranbala; Agrawal, K. S.; Nagar, A.; Bharambe,
D. P. Fuel Process. Technol. 2010, 91 (9), 997–1004. (23) Lovell, P. A.; El-Aasser, M. Emulsion Polymerization and Emul-
(22) Castro, L. V.; Vazquez, F. Energy Fuels 2008, 22 (6), 4006–4011. sion Polymers; John Wiley and Sons, Inc.: New York, 1997.
540
Energy Fuels 2011, 25, 539–544 : DOI:10.1021/ef101074m Castro et al.

Table 2. Composition and Molecular-Weight Characterization of

Terpolymers
PC (mol %)
polymer code CTA (%) S BuA VA Mw Mn I

TP1 1.0 87.2 10.0 2.8 45175 21547 2.1

TP2 8.0 57.5 31.7 10.8 7245 2223 3.3
TP3 1.0 87.3 1.7 11.0 18622 6816 2.7
TP4 1.0 7.8 91.0 1.2 39204 20701 1.9
TP5 0.0 63.2 22.9 13.0 557924 139900 2.3
TP6 8.0 49.9 32.4 17.7 3785 2057 1.8 Figure 1. Structural representation of S-BuA-VA terpolymer.

with methanol. The purified samples were finally dried in an have been made to place the radical monomer reaction on a
oven at 150 °C for 24 h. 1H NMR spectra were recorded in Jeol quantitative basis in terms of correlating the structure with
Eclipse-300 equipment using deuterated chloroform with TMS reactivity. The Q-e scheme is the best one considered as an
as an internal standard. The molecular weights and polydisper- empirical approach for placing monomer reactivity on a
sity index (I) of co-polymers were determined using a size- quantitative basis. The average Q and e values of the three
exclusion chromatography Agilent 1100 chromatograph with monomers used in this work are as follows: S (Q = 1.0, and
a 5 μm column of PLgel. THF, at a flow rate of 1 mL min-1 at
30 °C, was used as the mobile phase. A calibration curve was
e = -0.80), BuA (Q = 0.38, and e = 0.85), and VA (Q =
made using the well-defined narrow molecular-weight distribu- 0.026, and e = -0.88);25 therefore, ideal co-polymerization
tion polystyrene standards kit available from Aldrich. occurs between two monomers having similar Q and e
Additive Preparation. Polymer solutions were prepared at values. The tendency toward alternation is highest for mono-
20 wt % of terpolymer in toluene; each solution was stirred mers having the same Q values with high e values of opposite
for 10 min at the doping temperature for homogenization. sign. In summary, the reactivity ratios of the monomers
Terpolymers were mixed in the oil at 1000 ppm. employed in this synthesis are different, modifying in turn
Sample Preparation. To obtain results consistent with accu- the terpolymer structure. Nevertheless, homogeneous terpo-
rate rheological measurements, the memory of the evaluated lymerizations are obtained under monomer-starved condi-
crude oil sample has to be removed by heating at 60 °C while tions in semi-continuous processes independent of reactivity
stirring. Tests were started by heating the preconditioned un-
treated crude oil samples to 60 °C in an ultrasonic bath and then
values.
loading them in a hermetic bottle with an appropriate amount of The free-radical polymerization, employed in many in-
solution preparation; finally, the temperature of the sample in dustrial processes, consists of three stages: initiation, propa-
the ultrasonic bath was maintained at 60 ( 1 °C for 30 min. gation, and termination. The propagation processes can
Rheological Investigation. Rheological investigation was car- proceed on a continuous basis, while some termination pro-
ried out using a Physica MCR301 (Anton Paar) modular cesses take place. There are two different termination man-
rheometer, equipped with a concentric cylinder CC27. The ners: disproportionation and combination. Two radicals
crude oil was examined under a shear rate range of 0.01- react with each other by means of combination (coupling),
300 s-1, and over a temperature range of 20-45 °C. The or when two propagating radicals Pm and Pn meet, they can
mathematical treatment was carried out using the computer transform into two inert polymers, respectively, with m and n
program, Rheoplus, version 3.1, for Windows.
repeating units as a result of disproportionation, in which a
hydrogen radical that is β to one radical center is transferred
Results and Discussion
to another radical center. These termination mechanisms
Molecular Characterization of the Terpolymers. Terpoly- result in the formation of two kinds of polymer molecules: a
mer composition was determined using the method outlined saturated molecule and an unsaturated molecule.25
by Thamizharasi et al.24 The relative peak intensities were The spectroscopical characterization of the synthesized
determined from peak areas calculated by means of electro- terpolymers seems to indicate both different termination
nic integration. Table 2 shows the CTA content, the polymer manners, because after an exhaustive terpolymer purifica-
composition (PC), average molecular weights (Mw and Mn), tion, the signal of the double bond is present in the 1H
polydispersity (I), and degree of polymerization of the spectra. The formation of the double bond at the chain end
S-BuA-VA terpolymers. The chemical structure of the is clear evidence of a termination mechanism by dispropor-
synthesized compounds is shown in Figure 1. It is important tionation. The coexistence of free-radical propagation and
to mention that the conversion of the reported reactions was disproportionation has been reported in the literature, and it
practically 100%; therefore, the compositions of monomer has been remarked that both proceed at constant rates,
mixtures in feed are those of terpolymers. especially in the case when S is employed.26,27 Predominance
The conventional and simplified terpolymerization equa- of a termination mechanism mainly depends upon the M
tions can be used to predict the composition of a terpolymer monomers chemical structure and polymerization tempera-
from the reactivity ratios in the two component systems M1/ ture.28
M2, M1/ M3, and M2/M3.25 For example, in the case of Figure 2 shows the stacked plot of the 1H NMR spectra of
component system M2/M3, the reaction is complicated be- the synthesized S-BuA-VA terpolymers, and the assign-
cause of the large differences in monomer reactivity ratios ments of the different peaks are given in Table 3.
(rVA = 0.08, and rBuA = 7.2) and water solubility (0.291 and
0.006 mol dm-3, respectively, at 20 °C).23 Various attempts (26) Yang, S.; Zhu, S.; Ke, J. Phys. Rev. E: Stat. Phys., Plasmas,
Fluids, Relat. Interdiscip. Top. 2009, 80, No. 031114.
(24) Thamizharasi, S.; Gnanasundaram, P.; Balasubramanian, S. J. (27) Kruse, T. M.; Sang, W. O.; Wong, H.; Khan, S. S.; Broadbelt,
Appl. Polym. Sci. 1999, 74 (5), 1186–1193. L. J. Macromolecules 2002, 35, 7830–7844.
(25) Odian, G. Principles of Polymerization, 3rd ed.; John Wiley and (28) Allcock, H. R.; Lampe, F. W.; Mark, J. E. Contemporary
Sons, Inc.: New York, 1991. Polymer Chemistry; Pearson Education: Upper Saddle River, NJ, 2003.
541
Energy Fuels 2011, 25, 539–544 : DOI:10.1021/ef101074m Castro et al.

Figure 2. 1H NMR for terpolymers.

Table 3. Peak Assignments for Different Functional Groups Table 4. Physical Characterization of Crude Oil19
ppm assignment specification heavy crude oil methods

7.13 aromatic ring proton API density 15.82 ASTM D-287

6.4-6.6 olefinic proton water by distillation (vol %) 0.10 ASTM D-4006-07
4.1 (-OCH-) kinematic viscosity at 2984.97 ASTM D-445
3.9 (-OCH2-) 25 °C (mm2 s-1)
2.0 (-CO-CH3) asphaltene content (wt %) 19.92 ASTM D-2007
1.2-1.8 (-CH2-)
0.9 (-CH3) viscosity” or “apparent shear viscosity”, not necessarily
being contant according to ASTM D4092 and DIN 1342-1.
Rheological Studies. The physical characteristics of crude The viscosity values obtained are apparent and represent one
oil evaluated in this research are given in Table 4. This MCO point if the viscosity function only.29,30 It is clearly seen that,
is heavy, and its asphaltene content is 19.92%, which is at 20 °C, the shear rate against the shear stress curve (flow
mainly responsible for its great viscosity and influences its curve) does not pass through the origin. The apparent
flow behavior strongly. viscosity is not a constant at different values of shear rate
The apparent viscosity of MCO was determined at differ- (viscosity curve). The crude oil viscosities at shear rates
ent additive concentrations and temperatures using a Physi-
ca MCR301 rheometer. A rheogram of MCO is shown in (29) Mezger, T. G. The Rheology Handbook, 2nd ed.; Vincentz Net-
work: Hannover, Germany, 2006.
Figure 3. If the shear stress is not proportional to the shear (30) Malkin, A. Y.; Isayev, A. I. Rheology Concepts, Methods &
rate, then such ratios (τ/γ) are often called the “apparent Applications; ChemTec Publishing: Toronto, Ontario, Canada, 2006.
542
Energy Fuels 2011, 25, 539–544 : DOI:10.1021/ef101074m Castro et al.

Figure 5. Temperature effect on the apparent viscosity of the heavy

crude oil. The crude oil was used as an additive with 1000 ppm of
terpolymer solutions.
Figure 3. Rheogram of the MCO sample at 20 °C.
viscosity, when the shear rate is increased, is more evident at
low temperatures because of the larger polymer molecular
orientation, resulting from larger shear forces acting on the
polymer and the crude oil under these conditions. As men-
tioned in the literature, viscosity of crude oils decreased as
the shear rate increased.32
It was observed that all terpolymers diminish the crude oil
apparent viscosity and reductions strongly depend upon
molecular weight and composition of the terpolymer used
as an additive. The apparent viscosity of the crude oil used as
an additive with polymer solutions depends upon the average
molecular weight (molecular chain length), temperature, and
thermodynamic interaction between polymer chain seg-
ments and crude oil molecules. The performance as the
viscosity reducer of a polymer, with an adequate molecular
weight and composition, mainly depends upon its thermo-
dynamic affinity to the components of crude oil (saturates,
resins, asphaltenes, and aromatics). For example, the poly-
mer samples TP6 and TP5, with very different molecular
weights and almost similar composition, exhibit practically
the same performance as apparent viscosity reducers. How-
Figure 4. Apparent viscosity of heavy crude oil containing 1000 ever, they are not the best rheological modifiers. In a similar
ppm of terpolymer solution as a function of the shear rate at 20 °C. way, terpolymers TP2 and TP4, with different molecular
weights and different product compositions, exhibit the same
between 0.1 and 3 s-1 are not so different. It is obvious that,
flow behavior, after a shear rate of 2 s-1. In contrast, TP3
by increasing the shear rate, the apparent viscosity decreases
and TP1, with a rich S composition, both show the greatest
dramatically (e.g., from 5578 mPa s at 2 s-1 to 3770 mPa s at
falls of apparent viscosity through the range of shear rate.
300 s-1) at 20 °C. This behavior corresponds to that of a
The viscosity curve corresponding to the crude oil used as an
“non-Newtonian” fluid.31
additive with a TP1 solution exhibited the most considerable
Effect of the Molecular Composition and Molecular Weight
reduction of apparent viscosity through the shear rate range,
on Apparent Viscosity. Figure 4 shows representative plots of
and the curve has the same shape as that of the untreated
shear rate (γ) versus apparent viscosity (η) of heavy crude oil
crude oil but at lower viscosity values. An analysis of the
containing 1000 ppm of terpolymer solution at 20 °C.
influence of the terpolymer composition on the rheological
Paraffin crystals have already been formed at this tempera-
behavior of the crude oil used as an additive reveals that, the
ture in the liquid, and the rheological behavior of the crude
higher the content of S, the greater the viscosity reduction,
oil is non-Newtonian. The untreated crude oil and that
independent of the polymer molecular weight. The perfor-
containing polymer solutions are clearly non-Newtonian
mance of a terpolymer as a flow improver may be explained
“pseudo-plastic liquids”, and the flow behavior cannot be
taking into account the following structural effects: (1) S
explained by simple Newtonian behavior. It is important to
allows for better interactions with asphaltenes, resins, and
remark that there was no difference between the curves of the
other compounds because of its aromatic nature, (2) VA,
untreated crude oil and that of the crude oil used as an
conferring polar functionality to the terpolymer backbone,
additive with 1000 ppm of toluene (solvent). The decrease of
lead to the creation of attractive forces between the additive

(31) Nu~nez, S. M. C.; M
endez, M. M. G.; Solorza, F. J. Introducci
on a (32) K€ ok, M.; Letoffe, J. M.; Claudy, P.; Martin, D.; Garcin, M.;
la Reologı´a; Instituto Polit
ecnico Nacional: Mexico City, Mexico, 2001. Volle, J. L. J. Therm. Anal. 1997, 49, 727–736.
543
Energy Fuels 2011, 25, 539–544 : DOI:10.1021/ef101074m Castro et al.

and resins, and (3) BuA units promote interactions between terpolymer added to the crude oil creeps up among the
terpolymers and paraffins in crude oil. hydrogen bonds between asphaltenes and resins, creating
The molecular weight of the polymeric additive plays an spaces and, thus, reducing the apparent viscosity of heavy
important role in the reduction of petroleum viscosity; crude oil.
however, the terpolymer structure, composition, and solu-
bility in crude oil are also very important. It was also
Conclusions
observed that terpolymers with an average molecular weight
in an interval between 22000 and 2000 Da showed best A series of effective terpolymer additives for improving the
performances as flow improvers in petroleum. flow of heavy MCO was synthesized by semi-continuous
Effect of the Temperature on Viscosity. Figure 5 shows the emulsion polymerization. These polymeric additives were
results of both untreated and treated MCO viscosity versus characterized by spectroscopic and size-exclusion chromatog-
temperature, for a TP1, TP2, and TP3, in which the samples raphy (SEC) methods. The terpolymers were added to the
were examined at a shear rate (γ) of 50 s-1 and over a MCO, and their effects on the rheological properties of this
temperature range of 20-45 °C. Also, Figure 5 clearly shows heavy crude oil were investigated. All of the terpolymers
that the addition of terpolymers causes viscosity reduction, satisfied the requirements of flow improvers. The introduction
being more evident between 20 and 30 °C (Figure 5), corre- of a small quantity of polar co-monomer (BuA or VA) in the
sponding to the temperature range of transportation in ducts terpolymer backbone has an effect on the reduction of
for this type of MCO. apparent viscosity in this type of heavy crude oil.35 In contrast,
Figure 5 shows the apparent viscosity behavior of both the addition of a great quantity of S as a component of the
untreated and treated crude oil with terpolymers from 20 to terpolymer shows a conclusive effect on the flow improvement
30 °C. The TP1 terpolymer is the best additive for reducing of petroleum. The importance of choosing an adequate
viscosity, sensibly improving the flow. Indeed, crude oil with molecular weight of the polymer additive was also witnessed.
the TP1 agent presents 23.5% of viscosity reduction at 20 °C Both the untreated crude oil and the treated crude oil with
and 25.1% of viscosity reduction at 30 °C. It is possible to terpolymers show non-Newtonian behavior over a wide range
compare viscosity reductions of the best three terpolymers in of shear rates and temperatures. The apparent viscosity results
the same figure. confirm that the TP1 terpolymer, with an adequate molecular
Mechanism of Viscosity Reduction. Some authors claim weight and a high S content, improves the crude oil flow.
that higher viscosity of crude oils is due to the presence of Consequently, the molecular weight and monomer composi-
hydrogen bonds and the overlapping of aromatic ring planes tion were revealed as key molecular parameters to control the
among resins and asphaltene molecules in it.33,34 In general, performance of a flow improver.
higher amounts of resins and asphaltenes in crude oil in-
crease the apparent viscosity. Thus, to reduce crude oil Acknowledgment. The authors express their deep gratitude to
viscosity, the hydrogen bonds existing between resins and the personnel of Anton Paar de M
exico, especially Ing. Norma
asphaltene molecules have to be broken. The structure of the Cervantes and M. C. Jacquelina Ruiz, for their most valuable
support and help in the rheological measurements.
(33) Soni, H. P.; Bharambe, D. P. Iran. Polym. J. 2006, 15 (12), 943–
954. (35) Torres, E.; Dutta, N.; Choudhury, R.; Matisons, J. Polym. Eng.
(34) Holder, G. A.; Winkler, J. J. Inst. Pet. 1965, 51, 228–234. Sci. 2004, 44 (4), 736–748.

544