SPE 144788

A Chemical Agent Enhancing Recovery of the Heavy Oil Reservoir

Fusheng Zhang, SPE, Jian Ouyang, SPE, Xinfang Feng, State Key Laboratory of Oilfield Chemistry, Research
Institute of Petroleum Exploration and Development (RIPED), Petrochina; Liqing Xu, Liaohe Oilfield Company,
Petrochina; Hong Lin, Research Institute of Petroleum Exploration and Development (RIPED), Petrochina

Copyright 2011, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Enhanced Oil Recovery Conference held in Kuala Lumpur, Malaysia, 19–21 July 2011.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
On the basis of analysis of the main reasons for poor oil recovery of heavy oil reservoir by water flooding and according to
the mechanism of the enhancing oil recovery, a chemical agent, which is composed of nonionic surfactants, anionic
surfactants and emulsion stabilizers, can adapt to heavy oil reservoir with high temperature and high salinity. The core
displacement experiments show that displacement system containing chemical agent can enhance oil recovery by over 20%
comparing to water flooding, and the chemical agent contained in produced fluid has no negative effect on demulsification.
Mechanism by which chemical agent enhance oil recovery of heavy oil reservoir are: (1) significantly decreasing viscosity of
heavy oil to improve mobility ratio volumetric and improve sweep efficiency; (2) decreasing oil-water interfacial tension to
increase capillary number and improve oil displacement efficiency; (3) changing wettability of the rock surface from oil-wet
to water-wet to change capillary force from the resistance force to the motive force, and drive the residual oil out of the small
pores and the wall of pores and increase oil displacement efficiency。

Introduction
Heavy oil resource is approximately 70% of the total residual oil resources in the world, the onshore heavy oil reserve is
approximately 20% of the total oil reserve and production of the heavy oil is over 10% of total production of the crude oil in
China [1]. Content of resin and asphaltene higher in heavy oil results in it having high density and high viscosity, so the
development and transportation of heavy oil is more difficult. In the past days, injection steam and injection light oil into oil
well etc. conventional methods were primary methods for production of the heavy oil [2], but above-mentioned methods are
not ideal due to a great need of fuel consumption or light oil, production cost of the heavy oil is higher.
It is economically infeasible to develop the superficial heavy oil reservoir by the thermal method due to excessive thermal
loss,. Recovery percent of water flooding is only 5 to 10% of initial oil-in-place (IOIP) when develop the superficial heavy oil
reservoirs by water flooding [3], the main reasons for poor water flooding effectiveness are follows: (1) high underground
viscosity of heavy oil. The adverse mobility ratio between oil and water results in the serious fingering phenomenon, the
heavy oil is largely bypassed and is trapped in rock pores ; (2) strong reservoir heterogeneity. There are salient permeability
differences between the upper and lower layers, as well as in the same layer. The interaction of the two above-mentioned
factors can result in water flooding fingering phenomenon more prominent and the efficiency of water flooding very poor.
It is a potential method to use viscosity reducer to improve the development efficiency of heavy oil reservoir, and viscosity
reducer played an important role in the development and transportation of the heavy oil [4-5]. But viscosity reducer has strong
pertinency, for its efficiency can be significantly affected by physical properties of heavy oil, formation conditions and water
salinity. Therefore, it is an unresolved challenge to develop new technologies which can adapt to the superficial heavy oil
reservoir, the new technologies will play an important role in improving heavy oil reservoir recovery and reducing the
production cost.
The oil recovery (ER) is defined as the ratio of total oil produced to oil reserves, ER=EV.ED (ER stands for oil recovery; EV
stands for volumetric sweep efficiency; ED stands for oil displacement efficiency). The effective ways of enhancing heavy oil
recovery [6-8], such as: (1) increasing sweep efficiency. Improve the mobility ratio by reduction of the heavy oil viscosity; (2)
increasing oil displacement efficiency. Changing wettability of the rock surface from oil-wet to water-wet, capillary force is
changed from the resistance force to the motive force; Decreasing oil-water interfacial tension to increase capillary number.
2 SPE 144788

Experiment

Measurement of viscosity reduction effect

Prepare the aqueous solution with a certain concentration of chemical agent, then put it into a vessel which already has
heavy oil sample at a certain water/oil mass ratio, stirring to emulsify water and heavy oil into O/W emulsion. Measure the
viscosity (μ) of the O/W emulsion and viscosity (μ0) of the heavy oil at 50℃, the viscosity reduction rate (ф, %) can be
calculated by this formula: ф= (μ-μ0)/ μ0 ×100.

Measurement of water-oil interfacial tension

Measure the dynamic interfacial tension (IFT) between oil and water by the spinning drop interface tensiometer (Model TX-
500C, CNG company, USA), it will cost 2 hours for every samples, until the equilibrium is achieved. Write down the IFT.

Measurement of contact angle

The oil-wet surface is obtained through painting uniformly wax on the surface of glass. The contact angles between the
aqueous solutions containing chemical agent and oil-wet surface are tested by the contact angle machine (Model ODG20P,
Dataphysics company, USA).

Experiment of oil displacement

Measurement of the core porosity

Put core into an inclosed vessel, vacuumize the vessel, go on to vacuumize after injecting formation water, and saturate
core by formation water till there is no bubble. Removal the core and weigh it, then calculate the porosity . Put the core at core
holder and use formation water to displace it, and measure its permeability at 80℃.

Displacement experiment
(1) Saturate core by oil. Put heavy oil sample into a piston-type vessel, inject heavy oil into core at 80℃ ( formation
temperature), don’t stop injecting it until water no longer flow out from the exit of core. Calculate the amount of saturated oil
and initial oil saturation. (2) Displace core by water. Displace core by injecting water at 80℃ ( formation temperature), collect
displaced liquid with a measuring cylinder at the exit of core, keep recording oil volume and water volume. Stop displacing
core when the water cut of displacement liquid reaches 98%, and calculate water flooding recovery. (3) Displace core by
aqueous solutions containing chemical agent. Displace core by aqueous solutions containing chemical agent after water
flooding, collect displaced liquid with a measuring cylinder at the exit of core, keep recording oil volume and water volume at
the same time. Stop the displacement when the water cut of displacement liquid reaches 98%, and calculate flooding recovery
of the aqueous solutions containing chemical agent.

Emulsion demulsification
Prepare aqueous solution containing a certain concentration of chemical agent, then put it into a vessel which already has
heavy oil sample at the water/oil mass ratio of 3:7. Stirring and emulsify water and heavy oil into O/W emulsion.
Demulsification experiment is carried out by Chinese Petroleum and Natural Gas Industry standard SY/T 5281-2000 “Bottle
experiment method for the demulsification performance of crude oil demulsifiers”. 100mg/L of demulsifier Sp169 is added
into O/W emulsion and static settlement time 1 hour at the temperature 60 , record dehydrating amount and calculate
dehydration rate, take sewage water, and oil content in it is measured by Chinese Petroleum and Natural Gas Industry standard
SY/T 0530-1993 “Measurement value of oil in oilfield sewage water by using spectrophotometer”.

Results and Discussion

Compositions of the chemical agent used for enhancing recovery of heavy oil reservoir
To enhancing recovery of the heavy oil reservoir water flooding, chemical agent should have the following functions：(1)it
can emulsify heavy oil and water mixture into O/W system, so viscosity of heavy oil is significantly reduced, mobility ratio is
improved and volumetric sweep efficiency is significantly increased; (2) it can decrease oil-water interfacial tension, so
capillary number can be increased, oil displacement efficiency is significantly increased; (3)it can significantly reduce the
contact angle between displacement liquid and sandstone surface, the oil-wet surface is changed into water-wet surface, so
capillary force is changed from the resistance force to the motive force, oil displacement efficiency is significantly increased.
In order to meet high temperature and high salinity reservoir, the chemical agent should have good performance of the
temperature resistance and the salt resistance. For nonionic surfactants, the salt-resistance is good, but the temperature
resistance is poor; for anionic surfactants, the temperature resistance is very good, but the salt resistance is poor. Considering
the temperature and salinity comprehensively and integrating the advantages of nonionic surfactants and anionic surfactants,
SPE 144788 3

the complex system of nonionic surfactants and anionic surfactants can improve the temperature resistance performance and
the salt resistance performance. So, the chemical agent is composed of nonionic emulsifier, anionic emulsifier and emulsion
stabilizer.

Reduction of heavy oil viscosity to improve mobility ratio and enhance volumetric sweep efficiency [6]
The volumetric sweep efficiency(EV)is defined as the volume ratio of the oil layer by water flooding to the whole oil layer,
which is divided into plane sweep efficiency(EP) and vertical sweep efficiency(EZ), EV=EZ.EP. Expression of plane sweep
efficiency(EP) be expressed as: (1-Ep)/Ep = [a1 ln(M + a2) + a3] fw + a4 ln(M + a5 ) + a6 (EP is plane sweep efficiency; M is
mobility ratio; fw is water cut; a1、a2、a3、a4、a5、a6 are constant according to different oil wells). Expression of thickness
sweep efficiency (EZ) be expressed as: Ez = fw / [0.062 M (1-fw ) + (0.22 H 1.1 + 1) fw] (M is mobility ratio; H is the effective
thickness of oil reservoir; fw is water cut).
Main influencing factors of volumetric sweep efficiency are: mobility ratio, heterogeneity of oil reservoir, gravity and so on.
The above-mentioned formulas show that the volumetric sweep efficiency can be improved by reducing the mobility ratio.
From the expression of volumetric sweep efficiency, volumetric sweep efficiency is inversely proportional to mobility ratio.
The mobility ratio can be defined as the ratio of displacing fluid mobility to displaced fluid (crude oil) mobility, while the
mobility of fluid can be defined as the ratio of effective permeability to viscosity, so the mobility ratio increases with the
viscosity ratio of displaced fluid and displacing fluid. Reducing the viscosity of displaced fluid and increasing the viscosity of
displacing fluid can both decrease mobility ratio, thus the volumetric sweep efficiency is improved.
According to the oil emulsion theory [9], the viscosity of oil emulsion can be expressed as: μ=μ0ekφ (μ: emulsion viscosity,
μ0: external phase viscosity, φ: volume percent of internal phase, k: constant). As can be seen from the formula, for W/O
emulsion, the viscosity of emulsion increases exponentially with water cut (internal phase), so the viscosity of W/O emulsion
is much higher than that of crude oil; for O/W emulsion, the viscosity of water is far less than oil, the viscosity of emulsion
increases exponentially with content of oil (internal phase), so the viscosity of O/W emulsion is far less than that of crude oil.
Therefore, forming O/W emulsion can significantly reduce viscosity of heavy oil, improve mobility ratio and enhance
volumetric sweep efficiency.

Influence of water cut on reduction of viscosity

According to close-packing principle from solid geometry [9], when the water cut of emulsion is lower than 25.98%, stable
emulsion W/O will be formed; when the water cut is between 25.98% and 74.02%, the emulsion is not stable, either W/O
emulsion or O/W emulsion will be formed; when the water cut is higher than 74.02％, stable emulsion O/W will be formed.
Mix injection water with heavy oil from Dagang oilfield, then add chemical agent into mixture of water and heavy oil at
1000mg/L dosage ( in total mass of oil and water), and stir them to form W/O emulsion, measure the viscosity of emulsion at
50 . Influence of water cut to the viscosity is shown in Table 1.
As can be seen from Table 1, when the water cut is 20%, W/O emulsion will be formed, the viscosity
increases significantly; when water cut is 25%, either O/W emulsion or W/O emulsion can be formed, the viscosity reduction
rate is only 75.23%; when water cut is higher than 30%, O/W emulsion is formed, the viscosity reduction rate is higher than
97%. The above-mentioned results show that water cut of emulsion can significantlyaffect the viscosity reducing effect, only
when the water cut is higher than 25%, O/W emulsion can be formed, viscosity can be reduced significantly. By
comprehensively considering economic benefits and viscosity reducing effect, the optimal water cut is not more than 40%.

Influence of the chemical agent dosage on reduction of viscosity

Mix injection water with heavy oil from Dagang oilfield at the mixing ratio of 3:7, then add chemical agent into the mixture
of water and heavy oil, stir to form emulsion, measure viscosity at 50 . Influence of chemical agent dosage on the viscosity is
shown in Table 2.
As can be seen from Table 2, stable O/W emulsion can not be formed until dosage of chemical agent is higher than
1000mg/L, and the viscosity reduction rate is higher than 97%. Viscosity of the emulsion system decreases with the increase
of dosage of chemical agent. It is proved that when the dosage of chemical agent is very low, stable O/W emulsion can not be
formed, only when the dosage of chemical agent is higher than 1000mg/L, stable O/W emulsion can be formed, and the
purpose of reducing viscosity can be achieved. By comprehensively considering both economic benefits and viscosity
reduction effect, the optimal dosage of chemical agent is about 1000 mg/L.

Reduction of oil-water interfacial tension to increase capillary number to mproving oil displacement efficiency [7]
The capillary number is the ratio of oil displacement motive force to resistance force, the relationship between capillary
number and interfacial tension can be expressed as: Nc=v μw /σwo ( Nc is capillary number; v is displacement rate; μw is
viscosity of displacing fluid; σwo is interfacial tension between oil and water). Improving displacement efficiency is often
through increasing capillary number, the larger capillary number is, the smaller residual oil saturation is, so the displacement
efficiency is higher. Especially reducing interfacial tension between oil and water is a primary approach to increase capillary
number.
4 SPE 144788

Interfacial tension between the aqueous solutions containing chemical agent and heavy oil is shown in Table 3.
As can be seen from Table 3, oil-water interfacial tension is decreased to 0.60 mN/m (for the oil-water interfacial tension is
usually between 20 and 30 mN/m), which is to say that capillary number is increased by 30 - 50 times, so the capillary number
is greatly increased and the oil displacement efficiency is improved.

Changing wettability [8]

The capillary force is resistance when non-wetting fluid displaces wetting fluid(crude oil), which can be expressed as: Pc =
2 σ cosθ/r (σ is Water-oil interfacial tension；θ is contact angle water between sandstone surface ； r is capillary radius). If
the surface of rock is water-wet, the capillary force is oil displacement motive force, water flooding could wash down the
crude oil in small pores and on the rock surface, in this case, as a result, the water-wet rock has higher displacement efficiency.
If the surface of rock is oil-wet, the capillary force is oil displacement resistance force, water flooding mainly drives the oil in
the big pores, leaving the oil in small pores and on surface of rock , as a result, the oil-wet rock has lower displacement
efficiency.
Contact angle between the aqueous solutions containing chemical agent and oil-wet surface is shown in Table 4.
As can be seen from Table 4, chemical agent can reduce the contact angle between water and oil-wet surface from 105.7° to
below 60°, the wettability is changed from oil-wet to water-wet.
The oil displacement efficiency is closely related to the wettability of rock, as oil-wet surface leads to lower oil
displacement efficiency and water-wet surface leads to high oil displacement efficiency. The main reasons are: (1) In the oil-
wet rock, the capillary force is oil displacement resistance force, water flooding mainly drives the oil in big pores, the residual
oil is left in the small pores and on the wall of pores; (2) In the water-wet rock pores, water is absorbed on the surface of rock
pores and form water film, but oil can not be absorbed on the surface of rock pores, resulting in the residual oil mainly existing
in the central place of the larger pores in oil droplet form, and capillary force is oil displacement motive force, the residual oil
is expelled from the small pores and the wall of pores.

Oil displacement efficiency of the chemical agent

Heavy oil and water are both from Dagang oilfield, the total salinity of water is 20693.75 mg/L, the concentration of
bivalent cationic ( Ca2+ and Mg2+ ) is 805.38 mg/L. The oil displacement efficiency of the chemical agent is shown in Table 5.
As can be seen from Table 5, water flooding recovery is about 27%. After water flooding, go on displacing using water
containing 0.1% - 0.5% of the chemical agent, the recovery of heavy oil can be enhanced by over 20%.

Influence of the chemical agent on demulsification

When development of the chemical agent, emulsion containing the chemical agent should have proper stability. On the one
hand, if O/W emulsion is not stable, emulsion system will separate quickly and viscosity will increase under static condition,
bringing troubles to restarting wells and even leading to blockage accident of wells. On the other hand, if emulsion is too
stable, it will bring great difficulties to the demulsification.
A lot of chemical agent is adsorbed on sandstone surface, so the concentration of chemical agent in the produced fluid is
much lower than the injection concentration.
Demulsification effect (dehydration rate and oil content in sewage) is shown in Table 6.
According to Table 6, the heavy oil emulsion containing chemical agent can be demulsified easily by the polyether
demulsifier (SP169) used widely in the many oilfields, dehydration rate is over 98% and oil content in sewage is lower than
400 mg/L. It is indicated that this chemical agent does not bring a negative effect on demulsification.

Conclusions
1. Heavy oil viscosity is significantly decreased to blow 100 mPa.s in the case of over 30% of water cut and over 1000mg/L
of chemical agent dosage, mobility ratio is improved and volumetric sweep efficiency is enhanced.
2. Oil-water interfacial tension can be decreased to 0.60 mN/m by chemical agent, capillary number is increased by 30~50
times, the oil displacement efficiency is improved.
3. Contact angle between water and oil-wet surface can be reduced from 105.7° to below 60° by chemical agent and the
wettability is changed from oil-wet to water-wet, then capillary force is changed from the oil displacement resistance
force to the oil displacement motive force and the residual oil is expelled from the small pores and the wall of pores, the
oil displacement efficiency is improved.
4. The core displacement experiments show that displacement system containing chemical agent can enhance oil recovery
by above 20% comparing to water flooding.
5. The chemical agent contained in produced fluid has no negative influence on the demulsification.
SPE 144788 5

References
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59-62.
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Table 1 Influence of the water cut on reduction of viscosity

Water cut /%(W) 0 20 25 30 40 50 60

Viscosity /mPa.s 7510 11500 1860 165 163 152 126
Viscosity reduction rate /% 0 W/O 75.23 97.80 97.83 97.98 98.32

Table 2 Influence of the chemical agent dosage on reduction of viscosity

Chemical agent dosage /mg.L-1 500 800 1000 1500 2000 3000
unstable unstable
Viscosity /mPa.s 165 134 72 60
emulsion emulsion
Viscosity reduction rate /% 97.80 98.22 99.04 99.20

Table 3 Oil-water interfacial tension

Chemical agent dosage / % 0.2 0.4 0.6 0.8

Interfacial tension / mN/m 1.51 1.29 0.98 0.60

Table 4 Contact angle between the chemical aqueous and oil-wet surface

Chemical agent dosage / % 0 0.05 0.1 0.2 0.4 0.8

Contact angle / ° 105.7 85.2 66.8 59.2 58.8 58.6

Table 5 Oil displacement efficiency by the chemical agent

Concentration of Core parameters Recovery

Chemical agent Length Diameter Porosity Permeability Water flooding chemical agent flooding
/% /cm /cm /% /mD /% /%
0.1 10 2.43 27.11 1965 26.38 22.88
0.3 10 2.43 27.14 1570 26.56 26.45
0.5 10 2.43 27.16 1854 28.03 26.70

Table 6 Influence of the chemical agent contained in the produced liquid on demulsification

Concentration of the chemical agent /mg/L 0 100 200 500 1000

Dehydration rate /% 98.4 99.1 98.1 98.2 97.5
Oil content in sewage /mg/L 350 365 375 356 353