Experimental Studies on changes in the

properties of conventional crude oil before and

after CO2 flooding

HARSHAL RAJE (164058)

DEPARTMENT OF CHEMICAL ENGINEERING

THADOMAL SHAHANI ENGINEERING COLLEGE
UNIVERSITY OF MUMBAI

PROJECT GUIDE
DR. ANITA KUMARI
 CERTIFICATE

PROJECT ENTITLED: Experimental Studies on Changes

in the properties of conventional crude oil before and
after CO2 flooding

Submitted by: HARSHAL RAJE (164058)

In partial fulfilment of the degree, Bachelor in Chemical

Engineering for Department of Chemical Engineering has been
approved.

GUIDE EXAMINER (EXTERNAL)

PRINCIPAL HEAD OF DEPARTMENT

 ACKNOWLEDGEMENT

We would like to thank our Principal Prof. Thampi for providing the
various resources as required by us.

We would like to express our sincere gratitude towards our H.O.D

(Chemical Engineering Department) and project guide Dr. Anita
Kumari for invaluable guidance given to us for our work and
providing help in every aspect of it.

We would like to thank the staff of our Chemical Engineering

Department for their indispensable support without which this
project would not be possible.
TABLE OF CONTENTS

1. Abstract
2. Introduction
3. CO2 Flooding
4. Experiment
5. Results and Discussion
6. Conclusion
ABSTRACT
In order to enhance oil recovery of a conventional oil reservoir by
CO2 flooding, the changes in the properties of the crude oil before
and after CO2 flooding are systematically investigated by on-site
sampling and experimental testing. The results show that, after CO2
flooding, the light hydrocarbons of the produced crude oil is
increased and the heavy hydrocarbons of the produced crude oil is
decreased due to the deposition of resins and asphaltenes in the
pores of the formation. In addition, the produced fluid (a mixture of
oil and water) has a high water separation rate, the oil- water
interface has a high tension value, and the crude oil has a high acid
value and a low viscosity. The conclusions can provide certain
guidance for high-efficiency development of a conventional oil
reservoir by CO2 flooding.
INTRODUCTION
Presently, enhancing oil recovery (EOR) has become one of the
major concerns of the petroleum industry. Tertiary oil recovery
technology has played an important role in EOR and further
develops the mature oilfields. It can be said that the process of oil
production has transitioned to the enhancing oil recovery era.
Tertiary oil recovery techniques include chemical flooding, gas
flooding, thermal flooding, and microbial flooding, etc. As an
important part of gas flooding, CO2 flooding has become the most
important EOR method in the United States in 1980s. In the past 10
years, it has also become a major gas flooding for EOR in China.

However, due to the properties of CO2, the properties of the

produced crude oil by CO2 flooding are very different from those by
conventional water flooding. Therefore, it is necessary to study the
difference between CO2 flooding and water flooding (or before and
after CO2 flooding) to recover the crude oil from the produced fluid.
As it is well-known, the amount of CO2 dissolved in crude oil can
lead to the asphaltenes precipitation. And then, the properties of
the crude oil can be changed. It has been studied that the chemical
and physical properties of heavy oil change before and after CO2
treatment. It was found that CO2 treatment lead to an increase in
the viscosity of the heavy oil a decrease in the conductivity of the
heavy oil. However, due to high concentrations of resins and
asphaltenes, heavy oil is different from the conventional crude oil.
Therefore, it is necessary to systematically study the influence of
CO2 flooding on the properties of the conventional crude oil.
CO2 FLOODING
Carbon dioxide (CO2) flooding is a process whereby carbon
dioxide is injected into an oil reservoir in order to increase output
when extracting oil.

Figure 1. Carbon dioxide pressure-temperature phase diagram

When a reservoir’s pressure is depleted through primary and
secondary production, carbon dioxide flooding can be an
ideal tertiary recovery method. It is particularly effective in
reservoirs deeper than 2,500 ft., where CO2 will be in
a supercritical state, with API oil gravity greater than 22–25° and
remaining oil saturation greater than 20%. Carbon dioxide flooding
is not affected by the lithology of the reservoir area, but simply by
the reservoir porosity and permeability, so that it is viable in both
sandstone and carbonate reservoirs. By injecting CO2 into the
reservoir, the viscosity of any hydrocarbon will be reduced and
hence will be easier to sweep to the production well.
As an oil field matures and production rates decline, there is
growing incentive to intervene and attempt to increase oil output
utilizing tertiary recovery techniques (also termed improved
or enhanced oil recovery). Petroleum engineers assess available
options for increasing well productivity, options that include
chemical injection, thermal/steam injection, and CO2 injection.
Based on data-gathering and computer simulations, the most
optimal enhanced oil-recovery technique to maximize well-
productivity is determined. To increase the rate of oil production,
the pressure within the reservoir must be increased.
In CO2 flooding, the first step is injection of water into the reservoir,
which will cause the reservoir pressure to increase. Once the
reservoir has sufficient pressure, the next step is to pump the
CO2 down through the same injection wells. The CO2 gas is forced
into the reservoir to come into contact with the oil. This creates
a miscible zone that can be moved more easily to the production
well. Normally the CO2 injection is alternated with water injection
and the water acts to sweep the oil towards the production zone.
CO2 flooding is the second most common tertiary recovery
technique and is used in facilities around the world. In connection
with greenhouse gas emissions and global warming,
CO2 flooding sequesters CO2 underground and therefore offsets
CO2 emissions elsewhere.
EXPERIMENT

INTRODUCTION OF A PILOT SITE BY CO2 FLOODING

IAs a conventional oil reservoir, Pucheng oildom of Zhongyuan

oilfield in China is taken as a research object for CO2 flooding. The
oildom is developed in a five-point well pattern with a well space of
220 m. The average temperature of the oil reservoir is 95 C and the
average depth of the oil reservoir is 3400 m. The density of the
crude oil is 0.8685 g/cm3 and the original pressure of the oil
reservoir is 29 MPa. The oildom is converted to CO2 flooding when
it is in a high water cut stage by water flooding. The injection
pressure of CO2 is 30 MPa and the pressure at the bottom of the
corresponding well is 20 MPa. The purity of CO2 used for
displacement is 99.6%.

EXPERIMENTAL MATERIALS AND EQUIPMENT

The used crude oil and water in the experiment are the produced
oil and water after separation and treatment from the produced
fluid of the sampling oil well. Methylbenzene, ethanol, petroleum
ether, and n-heptane used for separation of resins and asphaltenes
in the crude oil are all analytically pure and are obtained from
Beijing Chemical Reagents Company. Potassium hydroxide solution
(KOH) is obtained from Sinopharm Group in China. The main
instruments include a DV-III Brookfield viscometer, a centrifuge, an
Agilent 1260 Infinity II liquid chromatograph, and a high
temperature and high pressure interface tension meter.
EXPERIMENTAL PROCEDURE
Testing the compositions of the crude oil before and after CO2
flooding
The compositions of the crude oil are tested by liquid
chromatography before and after CO2 flooding. By using of
methylbenzene, ethanol, petroleum ether, and n-heptane, the resins
and asphaltenes of the crude oil can be separated and their mass
concentration (w %) can be measured.
Testing the water separation rate of the emulsion before and
after CO2 flooding
The produced fluids are on-site sampled from the target oil well in
Pucheng oildom of Zhongyuan oilfield before and after CO2 flooding,
respectively. Thus, the volume of water and crude oil in the fluids
are recorded at fixed intervals.
Testing the acid values and viscosities of the crude oil before
and after CO2 flooding
The acid values of the crude oil before and after CO2 flooding can be
measured by the acid-base titration method with KOH. The
viscosities of the crude oil before and after CO2 flooding are
measured by viscometer at the shear rate of 7.34 s-1 at 40 ̊–80 C
̊ .
Testing the interfacial tension of water and crude oil before
and after CO2 flooding
The interfacial tensions of the water and crude oil before and after
CO2 flooding are measured by an interfacial tensiometer with an
autoclave at the temperature of 95 C. The experimental procedures
are as follows: (1) The formation water is added to the hanging
drop chamber and then be pressurized to a design pressure (10
MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa, 35 MPa, 40 MPa);
(2) The crude oil is pushed to the hanging drop chamber by a
sample pump. When the pressure is stable, the oil drop is formed
at the probe head in the hanging drop chamber.
(3) After the oil droplet is stable, the magnification camera system
is applied to acquire the outer contour of the oil droplet.
(4) The obtained contours of the oil droplet can be processed by
using a computer image and the interfacial tension can be
calculated.

RESULTS AND DISCUSSION

Changes in the compositions of oil crude

The compositions of the oil crude before and after CO2 flooding are
shown in Figure 1, which is obtained by the chromatographic
analysis. Due to the extraction effect of CO2, the light hydrocarbons
(C6–C21) of the produced crude oil are increased after CO2 flooding.
During oil displacement, the oil crude can be mixed with CO2, and
then the gas molecules can be dispersed and penetrated into the
aggregates of organic molecules. The interaction between CO2 and
the light hydrocarbons are stronger than the cohesive energy of CO2
itself, so that the light hydrocarbons are wrapped with CO2
molecules. Next, when the gas is released, the light hydrocarbons
can be escaped with the flow of the gas molecules, which can make
the mass of the light hydrocarbon in the produced crude oil
increase. With the extraction of the light hydrocarbons, the heavy
hydrocarbons (C22–C44) are deposited in the pores of the formation,
which leads to the decrease of the heavy hydrocarbons of the crude
oil.

After separation of four components of the oil crude, the mass

concentration of resins and asphaltenes before and after CO2
flooding are 6.28%, 1.72%, 5.13%, and 1.32%, respectively, which
are shown in Figure 2. This is mainly because the extraction effect
of CO2 is counteracted the negative charge of the asphaltenes
particles and reduces the stabilizing effect of the resins on the
asphaltenes particles, which leads to the reduction of the solubility
of the resins and the asphaltenes. Thus, the asphaltenes are
aggregated and deposited in the pores of the formication to reduce
the content of resins and asphaltenes of the crude oil.

Change of water separation rate of the produced fluid

The produced fluid on the ground is a mixture of oil and water with
the existence form of an emulsion after degassing, which is an
unstable thermodynamic system. Changes of water separation rate
of the produced fluid with time before and after CO2 flooding are
shown in Figure 3. The water separation rate of the produced oil-
water emulsion after CO2 flooding is lower than that before CO2
flooding. The stability of emulsion is primarily affected by the
oil/water inter-facial film. During CO2 flooding, the properties of
water and crude oil are both changed due to the CO2 dissolution in
water and the extraction effect of CO2 on the crude oil. Acidic water
is adverse to the stability of the emulsion. During the formation of
the emulsion, the resins and asphaltenes have a certain interfacial
activity and easily form a spatial network structure, which can
greatly promote the formation and stability of the emulsion. After
CO2 flooding, the content of resins and asphaltenes in the produced
fluids is reduced, which results in a lower emulsification of the
produced fluids after CO2 flooding.
Change of the acid value of the crude oil
According to acid-base titration experiments, the acid value of the
crude oil after CO2 flooding is 9.28 mg(KOH)/g, and that before CO2
flooding is 8.22 mg (KOH)/g. The high acid value reflects the high
content of naphthenic acids, fatty acids, phenols, and other acidic
oxides in the crude oil. CO2 is dissolved in water to form the
carbonic acid, which can react with calcium carbonate of rock to
produce the bicarbonates. After the decrease of the pressure on the
ground, the bicarbonates can re-decomposed into carbonate, which
can plug the pipelines and equipment due to the scaling on the wall
surfaces. In addition, too high acid value has a great influence on
the properties of the produced fluids. Impurities such as clay and
corrosion products in the formation caused by the acid can affect
the thickness of the oil/ water interface film. Asphaltenes
precipitation resulting from the weak acid value and the
precipitated rock particles are both affect the emulsification of the
produced fluids. The acidity can increase the conductivity of the
produced fluids, but the operation of the electric dehydration is
affected, which cause the frequent tripping of the electric
dehydrator.
CaCO3∘MgCO3 + CO2 + H2O → CaCO3 + MgCO3 + CO2 + H2O
Changes of the viscosity of crude oil

The change in the viscosity of crude oil before and after CO2
flooding is shown in Figure 4. After CO2 flooding, the viscosity of the
crude oil has a small amplitude decrement than that before CO2
flooding. This shows that CO2 flooding can leads to the deposition of
the heavy components of the crude oil, which can influence the
characteristics of viscosity and temperature of the crude oil.
Changes of the interfacial tension of crude oil
The change of the oil-water interfacial tension before and after CO2
flooding under different pressures is shown in Figure 5. The
interfacial tensions of the two both have a decrease with the
increase of the pressure, but the interfacial tension of the water and
crude oil after CO2 flooding is always higher than before CO2
flooding. This shows that CO2 has a greater influence on the
interfacial tension of the system of water and crude oil. The higher
the pressure, the greater the influence there is. Before CO2 flooding,
due to the polar groups (such as asphaltenes, the asphaltenes
molecules) of the asphaltenes of the crude, the asphaltenes can
move toward the interface and be adsorbed at the interface, which
can stabilize the interfacial film to reduce the interfacial tension
and enhance the emulsification. After CO2 flooding, the content of
asphaltenes is decreased and the interfacial tension is increased.
CONCLUSION
1. After CO2 flooding, the light components are increased and the
heavy components are decreased. Meanwhile, the viscosity of the
crude oil is decreased.
2. Due to the effect of the acidity of CO2, the acid value of the crude
oil is high after CO2 flooding.
3. Due to the impact of CO2 flooding on the reduction of
asphaltenes, the interfacial tension of water – crude oil is high.