SPE-176402-MS

Synthesis and Evaluation of A Macromolecular Viscosity Reducer for

Venezuela Heavy Oil
Ding Bin, Geng Xiangfei, He Lipeng, Peng Baoliang, and Luo Jianhui, Research Institute of Petroleum
Exploration & Development(RIPED), PetroChina

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE/IATMI Asia Pacific Oil & Gas Conference and Exhibition held in Nusa Dua, Bali, Indonesia, 20 –22 October 2015.

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Abstract
Orinoco heavy oil belt in Venezuela is a world-famous heavy oil belt, and difficult to develop due to the
high viscosity of crude oil. In order to reduce the viscosity, a water-soluble macromolecular viscosity
reducer (commercial name: CVR-V) for MPE3 block is designed and prepared. It is synthesized via
copolymerization, and plays an important role as emulsifier in forming O/W emulsion. The experimental
results demonstrate that CVR-V show extremely superior initial viscosity reduction effect and the O/W
emulsion stabilized by CVR-V exhibits excellent static and dynamic stability. The optimum condition for
viscosity reduction is obtained: with the ratio of 10:3 (oil to water), and 0.1 ~ 0.2% of viscosity reducer,
the initial viscosity reduction rate reaches 99.8% approximately and the apparent viscosity is less than 100
mPa·s. Meanwhile, excellent static and dynamic stability are proved, i.e. the apparent viscosity of O/W
emulsion is still less than 500 mPa·s after standing for 60d for static stability tests, and is also less than
200 mPa·s in rotation 7d later by vertical loop for dynamic stability tests. Laboratory experimental results
demonstrate that the fluidity of Venezuela’s ultra heavy oil can be greatly improved by CVR-V, and
CVR-V exhibits strong potential in development of Venezuela heavy oil.
Key words heavy oil · macromolecular viscosity reducer · viscosity reduction evaluation · static and dynamic stability

Introduction
Among all the oil/gas resources in the world, traditional oil only accounts for about 30%, and the rest
belongs to heavy oil, ultra heavy oil and asphalt. In heavy oil reservoirs all over the world, Orinoco heavy
oil belt in Venezuela is the only oil-rich belt with the largest reservations and the lowest level of
development in the world, with about 12 000 billion barrels of heavy oil geological reserves[1]. API
gravity of ultra heavy oil in Venezuela’s MPE3 block is less than 15. The apparent viscosity exceeds 5,000
mPa·s at formation temperature (50°C), and is between 20,000~40,000 mPa·s at 25°C. Therefore, it is of
great urgency and importance to solve the problem of ultra heavy oil fluidity in order to further
development of Venezuela ultra heavy oil. As we know, reducing the apparent viscosity of crude oil is the
best way to improve its fluidity. Currently, there are three major ways to reduce the apparent viscosity of
heavy oil: thermal recovery, dilution by light oil and chemical viscosity reduction using water-soluble or
oil-soluble viscosity reducers[2-3]. Among these methods, the thermal recovery is relatively mature and has
2 SPE-176402-MS

been extensively used, however this method need to consume a lot of energy and the cost is high, besides
this, pollution is another concern due to the generation of waste gas and water. The light oil dilution
method can meet all the requirements for heavy oil recovery at different development phases and has no
effects on the post-treatment of recovered fluid, however, the high cost and the limitation of light oil
resources always inhibit its application[4]. Viscosity reducing by chemicals attracts researchers’ attention
for a long time due to its low cost, simple process and extensive application scope[5-8]. However, current
chemical viscosity reduction methods were limited in real applications. For instance, catalytic viscosity
reduction requires high temperature and elimination of heavy metal in the oil reserves in advance, which
can hardly be extensively applied[9-10]. For oil-soluble viscosity reduction, the molecular design and
synthesis of oil-soluble viscosity reducer were complicated so that the viscosity reduction efficiency is
relative low. So far, there are no reports about reducing the viscosity of the heavy oil with only oil-soluble
viscosity reducer[4]. For emulsification, current emulsifiers are hard to get both excellent static and
dynamic stability for emulsion simultaneously[8,11]. Furthermore, once the O/W phase of the emulsion is
changed, the viscosity of the crude oil will dramatically increase leading to fail to fulfill the practical
requirements for heavy oilfield development such as wellbore lifting, ship and pipeline transportation etc.
In this paper, a water-soluble macromolecular viscosity reducer was synthesized and its properties were
evaluated, it was found that the macromolecular viscosity reducer could reduce the apparent viscosity of
Venezuela heavy oil greatly and the O/W emulsions formed by this viscosity reducer have excellent static
and dynamic stability.
Experimental
Raw materials and instruments
Heavy oil in Venezuela MPE3 block is provided by Petrochina South America Company. The physio-
chemical properties are shown in Table 1.

Table 1—Physiochemical parameters of Venezuela MPE3 heavy oil

Item Value Item Value

Density (20°C) /(g·cm⫺3) 1.0129 Saturation(w), /% 28.14

Kinematic viscosity, 50°C/ (mPa·s) 26,420 Aromatic(w), /% 35.54
Pour point, /°C 26 Asphaltene(w), /% 27.20
Acid(KOH), / mg·g⫺1 6.51 Wax(w), /% 0.44
Residual carbon (w), /% 17.08 Relative molecular value 620

The macromolecular viscosity reducer (CVR-V) was quadripolymer synthesized under the optimum
conditions. The selected monomers were maleic anhydride, unsaturated organic acid ester, unsaturated
alkyl ether and unsaturated benzene derivatives with AIBN (2, 2- azobisisobutyronitrile) serving as
initiator. All the chemicals were chemically pure grade and used without further purification. The water
used was tap water.
Instruments: RS-SST viscometer (BROOKFIELD Co. USA), Vertical loop (laboratory self-made)
Preparation of O/W emulsion of Venezuela’s ultra heavy oil
Certain mass proportions of Venezuela’s ultra heavy oil, CVR-V and water were added to a beaker. Keep
the mixture at 50°C for 30min. Then the mixture was stirred for 1min at the speed of 300 r/min and the
black-brown O/W emulsion was obtained.
Evaluation of apparent viscosity of O/W emulsion
The viscosity of O/W emulsion was measured by RS-SST viscometer. The measurement was carried out
at 50 s⫺1 by vane spindles at 20°C.
SPE-176402-MS 3

Evaluation of static stability of O/W emulsion

The viscosity of O/W emulsion was measured by RS-SST viscometer after standing for different time at
20°C.
Evaluation of dynamic stability of O/W emulsion
The vertical loop was put into the O/W emulsion which was maintained at 20°C and fixed the rotation
speed of loop at 2.38 rpm (50 s⫺1), with pressure collection frequency 300 Hz and temperature collection
frequency 1 Hz. The viscosity and Reynolds number O/W dispersion number can be calculated automat-
ically during the different rotation time.

Results and Discussion

Basic mechanism of dynamic granulation viscosity reduction technology
Common analytical theories of O/W emulsion performance include oriented wedge theory, interface
tension theory, electric effect theory and DLVO theory. Generally speaking, the heavy oil O/W emulsion
viscosity reduction performance is theoretically attributed to steric hindrance of water-oil interface and
interface viscoelasticity effects[12]. When the heavy oil droplets in O/W emulsion collide against each
other, an interface film of mutual collision can be formed between the interfaces of droplets that contact
each other. The formation of interface film not only generates counter-normal deformation and tension,
but also generates deformation of heavy oil droplets and deformation of interface film. The degree of
micro-deformation of emulsion caused by interface film will determine the degree of aggregation among
the heavy oil droplets in O/W emulsion. The addition of viscosity reducer can improve the fluidity of O/W
emulsion. Besides this, viscosity reducer usually has electric property so that the surface of emulsion
droplets has ionic activities, i.e. negative charges will be produced around the droplets. The ions will form
a double electronic layer- stem layer- near liquid droplets, the thicker the stem layer is, the larger the
repulsion force between droplets is, and even more difficult for the droplets to aggregate. Therefore, the
O/W emulsion has good stability and fluidity. Overall, the O/W emulsion is a kind of multi-phase with
relatively high total interface energy whose droplets have the tendency of self-dispersing, self-aggregating
and lowering interface energy. Furthermore, the stability of O/W emulsion is a relative and instable state
in terms of kinetics.
In this paper, the macromolecular viscosity reducer, CVR-V, with strong lipophilic group and weak
hydrophilic group was designed and prepared by copolymerization. It exhibited excellent viscosity
reduction effect and both static and dynamic stability without mixing with surfactants.
Evaluation for initial viscosity reduction effect of O/W emulsion
Influence of the content of CVR-V The effect of CVR-V content on the apparent viscosity of Vene-
zuela O/W emulsion is shown in Figure 1. It is shown that the apparent viscosity of emulsion decreases
dramatically at first, and then goes up with increasing the amount of viscosity reducer. When the mass
ratio of viscosity reducer is relatively low (w⬍0.05%), the O/W emulsion has poor fluidity and the
apparent viscosity is more than 900 mPa·s. As the viscosity reducer amount increases to a certain range
(w⫽0.05%~0.10%), the apparent viscosity of O/W emulsion decreases and reaches the minimum value
which is less than 100 mPa·s at 0.08%. It proves that the viscosity reducer is sufficient and could prevent
O/W droplets aggregations at these conditions. If viscosity reducer consumption is continuously in-
creased, the apparent viscosity of O/W emulsion will raise accordingly, which is probably mainly because
that continuous increment of viscosity reducer could generate smaller and much more O/W droplets and
thus increase the specific surface area of the O/W emulsion significantly. So the O/W droplets need much
more water to form hydrophilic film and maintain low viscosity. However, at this time, the ratio of oil to
water is only 10:3, which means the water content is not enough. So the O/W droplets will be easy to
aggregate in order to achieve lower energy to maintain the equilibrium state, which leads to continuous
increase of apparent viscosity for O/W emulsion.
4 SPE-176402-MS

Figure 1—Viscosity reduction effects on viscosity reducer amount for Venezuela O/W emulsion Emulsification conditions: m(oil):
m(water) ⴝ10:3, Viscosity test temperature: 20 °C

Influence of mass ratio of oil to water According to the optimum conditions obtained from Part 2.2.1,
we fixed the amount of the macromolecular viscosity reducer at 0.08%, and changed the mass ratio of oil
to water from 10:2.5 to 10:6.0. The effect of oil to water ratio on the apparent viscosity of O/W emulsion
is shown in Figure 2.

Figure 2—Visostiy reduction effects on m(oil)⬊m(water) for Venezuela O/W emulsion Emulsification conditions: w (CVR-V)ⴝ0.08%;
Testing temperature:20 °C.

Figure 2 shows that the apparent viscosity of the Venezuela’s O/W emulsion continuously decreases
as the water content increases. This may be attributed to that when there is relatively low water content
(10:3)in the O/W emulsion, it is extremely easy for O/W droplets wrapped by the water film of viscosity
reducer to aggregate, so the emulsion is not stable and the viscosity reduction effect is poor. As the water
content exceeds 10:3, the O/W droplets formed by viscosity reducer can be completely distributed in water
and the apparent viscosity is less than the 100 mPa·s[6,13,14]. Further increasing the water content has little
effect on the apparent viscosity of the Venezula’s O/W emulsion. The possible reason may be that excess
water only increases the distance among the O/W droplets and do not change the size and number for O/W
droplets. Therefore, the viscosity reduction rate maintains at around 99.8% when the mass ratio of oil to
water beyonds 10:3.
SPE-176402-MS 5

Evaluation of stability for O/W emulsion

Evaluation of static stability The effect of the content of the CVR-V on the static stability of O/W
emulsion is shown in Table 2. Obviously, the O/W emulsion is not stable when the content of the
CVR-V is less than 0.08%. It only takes 1d and 8d for the O/W emulsions to aggregate when the
content is 0.06% and 0.08%, respectively, indicating that small quantity of viscosity reducer can not
effectively prevent the O/W droplets from self-aggregation. As the amount of the viscosity reducer
promotes, the static stability of O/W emulsion have been improved significantly. When the amount
of viscosity reducer reaches 0.15%, at which the best static stability effects are obtained, the apparent
viscosity is still less than 500 mPa·s after standing for 60d, suggesting that the O/W droplets do not
to aggregate easily because the amount of viscosity reducer is enough to main the heavy oil and the
water balance for O/W emulsion. Afterwards the effects of static stability become worse and worse
with the amount incensement of initial viscosity reducer content. This is mainly because there are
smaller and much more O/W droplets with larger specific surface area in the initial state as discussed
before. When there is insufficient water content, the O/W droplets are easy to aggregate and adhere
with each other in order to reduce the specific surface area as the static stability time increase, which
leads to continuous increase of apparent viscosity.

Table 2—The effects of viscosity reducer quantity on the static stability for O/W emulsions
Apparent Viscosity (mPa·s) and status

Content (%) Initial 1d 5d 8d 12d 30d 60d

0.06 850 aggregated

0.08 66 120 980 aggregated
0.10 71.1 217 380 480 650 750 1050
0.15 119 154 185 265 350 368 390
0.17 138 251 ⬎3000
0.2 150 289.4 ⬎3000

Emulsification condition: m(oil):m(water) ⫽10:3; testing temperature:20°C

The influence of oil to water ratio on static stability of O/W emulsion is shown in Table 3. It is
clear that when oil to water mass ratio is 10:2.5, the initial viscosity of O/W emulsion is low and can
keep stable less than 4d. This is because that the number of hydrophilic films formed by the viscosity
reducer can not effectively prevent the aggregation of O/W droplets with the constant incensement
of aging time. With the incensement of water content, the static stability of the O/W emulsions
improves significantly. When the mass ratio of oil to water reaches and beyond 10:3, the static
stability of O/W emulsions tend to stable with viscosity is less than 500 mPa·s after standing for 60d.
This trend is consistent with the initial viscosity reducing effect as abovementioned.
6 SPE-176402-MS

Table 3—The effects of ratio of oil to water on the stability for O/W emulsions
Apparent Viscosity(mPa·s)and System Status

m (oil)⬊m(water) Initial 1d 4d 7d 13d 30d 60d

10:2.5 135.6 490 aggregated

10:3.0 73.2 87.0 93.2 220.0 370 425 420
10:3.5 65.2 76.0 86.8 84.0 153 200 123
10:4.0 20.3 20.0 30.1 51.7 124 165 358
10:4.5 15.0 15.0 26.2 34.0 85.0 109 250
10:5.0 ⬍10.0 ⬍10.0 16.3 25.8 54.0 60.0 100
10:6.0 ⬍10.0 ⬍10.0 15.3 22.3 48.7 57.0 110

Emulsification condition: w (CVR-V) ⫽0.15%, testing temperature:20°C

Considering the effects of initial and static stability, application cost, demulsification and dehydration
process for viscosity reducer and water content, it is preferable conditions that the concentration of the
viscosity reducer and oil to water mass ratio should be controlled at 0.15% and 10:3, respectively.
Evaluation of dynamic stability for O/W emulsion Figure 3 shows the diagram and test mechanism of
vertical loop for evaluating the dynamic stability of O/W emulsions. The liquid level difference (h) can
be obtained by the pressure value measured at different positions (A, B and D) and time in the vertical
loop (shown in Figures 4). The rheological properties of O/W emulsions can be determined by the rotation
of vertical loop because the O/W emulsions have different viscosity during the different dynamic aging
time. Thereafter, the dynamic stability of O/W emulsions can be evaluated according to the rheological
parameters measured by means of different equation as follows:

Figure 3—Diagram of the vertical loop

Figure 4 —Pressure curve of the Loop

SPE-176402-MS 7

For Newtonian fluids, the calculation formation for apparent viscosity is[15]:
(1)

Where:
␮: apparent viscosity, Pa·s;
ro: inner diameter of loop, m;
␳: concentration of tested liquid kg/m3;
g: acceleration of gravity, m/s2;
h: height of liquid level at both ends of loop, m;
␻៮ : rotation speed of loop, r/min;
Ro: Rotation radius of loop, m;
␪1: liquid level angel of front liquid section;
␪2: liquid level angel of rear liquid section.
For non-Newtonian fluid, the calculation formation for apparent viscosity is:
(2)

Where, n, the specific index of fluid needs to be fitted according to the following steps:
Tube wall shear stress:
(3)

Where:
Aw: contact area between liquid section and tube wall, m2;
(4)

Where:
␥: shearing rate, s⫺1;
V: Linear speed of loop, m/s;
do: inner diameter of loop, m
For ordinary project, power law model is adopted for non-Newtonian fluid
(5)

Where:
K: consistency coefficient, Pa·s
n: rheological behavior index
Table 4 shows the dynamic stability of the Venezuela O/W emulsions under different dynamic aging
time. It is obviously that under the optimum conditions, the dynamic stability of O/W emulsions are
excellent after 7 days at 20°C. The apparent viscosities of O/W emulsion s do not have obvious change
and are even slightly lower than those under static stability conditions. There are two reasons for the
phenomena, on the one hand, continuous moving of O/W emulsions make it possible that the distribution
of O/W droplets can disperse uniformly and contact harder than static conditions. On the other hand,
during the constant rotation, the macromolecular viscosity reducer can form the O/W emulsion easily
again and again in case the O/W droplets aggregate. Therefore the new hydrophilic films are formed and
the apparent viscosities of O/W emulsion stay lower than those under the static conditions.
8 SPE-176402-MS

Table 4 —The results of dynamic stabilities for the O/W emulsion

Fluid property Time (h) Height difference (m) Apparent viscosity (mPa·s)

0.5 0.20 80.1

1 0.25 125.1
5 0.25 127.6
11 0.24 154.5
27 0.21 139.6
31 0.24 155.8
36 0.23 142.4
52 0.22 135.6
54 0.22 131.3
73 0.18 130.9
102 0.26 164.7
130 0.23 155.3
138 0.23 145.6
153 0.28 181.8

The conditon of vertical loop: d0⫽30 mm, D0⫽1500 mm, ␻⫽2.38 r/min
Emulsification condition: m(oil) : m(water): m (CVR-V) ⫽100:30:0.15%; testing temperature:20°C

Conclusions
The synthetic copolymer macromolecular viscosity reducer can effectively reduce the apparent viscosity
of Venezuela’s ultra heavy oil greatly, improving the fluidity of the Venezuela’s ultra heavy oil
effectively. The optimum viscosity reduction conditions are as follows: the amount of viscosity reducer
is 0.1%~0.2%, the mass ratio of oil to water is 10:3. The initial apparent viscosity of O/W emulsion is less
than 100 mPa·s after standing for 60d and dynamic stability for 7 days, the aging apparent viscosity of
O/W emulsion is still less than 500 mPa·s.
The copolymer macromolecular viscosity reducer for Venezuela’s ultra heavy oil is expected to be
applied in such aspects as ultra heavy oil wellbore lifting, pipeline & ship transportation, and oil
displacement in Venezuela.

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