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PROJECT REPORT

IN
POLYMERS IN ENHANCED OIL RECOVERY
A Project Report submitted to the
Pune University
For the Degree of
B.E (Polymer Engineering)
by
Nikhil Shrikisan Chandak
Valay Jagdish Khobragade

Advisor : Prof. (Dr.) Hemant V. Joshi
Co-Advisor : Dr. Jayant Gadgil, Polymer Consultant, Pune


Polymer Engineering Department
MAEERs Maharashtra Institute of Technology (MIT)
Pune 411 038




2013-14




i




MAEERs
Maharashtra Institute of Technology, Pune


CERTIFICATE

This is to certify that the project report entitled
Polymers in Enhanced Oil Recovery
has been successfully completed under my/our guidance by,

Chandak Nikhil Shrikisan
Khobragade Valay Jagdish

towards partial fulfillment of the requirement for Fourth Year Degree in Polymer Engineering
as prescribed by University of Pune for the academic year--2013-2014.


Dr. Jayant Gadgil Prof. (Dr.) Hemant V. Joshi
Co-Advisor Advisor
Polymer Consultant, Associate Professor,
Pune Polymer Engineering Dept
MIT, Pune


Prof. (Dr.) Pramod S. Joshi
Head
, Polymer Engineering Dept,
MIT, Pune
ii




ABSTRACT

Polymers are used extensively in the various phases of drilling, operating and maintaining oil and
gas wells. Polymer flooding has been applied for petroleum oil recovery and the main results of
these methods are the effective increase in oil production and reduction of water circulation.
Application of polymers in enhanced oil recovery processes prolongs the economic life time of
oil fields.

The aim of the project is to find out the best possible polymer composition which is effective in
every aspect of enhanced oil recovery. The experimental work will based on studies on partially
hydrolysed polyacrylamide (PHPA), the system currently used, and effectiveness of self-
associating polymeric systems for the same purpose. The reason for the use of partially
hydrolysed polyacrylamide is that, it has very good physical properties such as adsorption, shear
stability and thermal stability with a good degree of hydrolysis.

In our experimental work, effect of solution concentration and temperature on the viscosity of
PHPA solution has been studied using Brookfield viscometer. The viscosity of freshly prepared
PHPA solution is tested on day 1 and consequently after 6 days was found out using Brookfield
viscometer. Additionally, the effects of additives on the viscosity of PHPA solution will be
studied.

A self associating copolymer of methyl methacrylate acrylic acid is prepared and the effect of
varying concentration and temperature on viscosity of this copolymer was carried out and the
results were interpreted.













iii




ACKNOWLEDGEMENT

We owe many thanks to who helped and supported us during the writing of this report.
Our deepest thanks to Prof. (Dr.) Hemant V. Joshi our project guide for giving us this
opportunity of collecting such a handful and healthy experience. His timely suggestions made it
possible for us to complete this project report.
We would also like to thank to Prof. A.D. Kulkarni and Mr More of Petroleum Engineering
Department for providing their valuable time and support without whom we where not able to
complete the experimental work.
We also like to thank Mr Shivaji Ghule for their kind support in the preparation of different
solution for our experimental work.
































iv



TABLE OF CONTENTS

CONTENTS PAGE NO.
TITLE PAGE I
CERTIFICATE II
ACKNOWLEDGEMENT III
ABSTRACT IV
TABLE OF CONTENTS V
LIST OF TABLES IX
LIST OF FIGURES XI
CHAPTERS
1. INTRODUCTION 1
2. OVERLOOK OF EOR PROCESSES 2
2.1 Various primary and secondary EOR processes 3
3. CLASSIFICATION OF EOR PROCESSES 4
3.1 Chemical EOR Processes 4
3.1.1 Micellar Polymer Process 4
3.1.2 Alkaline Process 4
3.1.3 Problems in applying Chemical EOR Processes 4
3.2 Miscible Process 5
3.2.1 Problems in applying Miscible Processes 6
3.3 Thermal EOR Process 7
3.3.1 Steam flooding 7
3.3.2 Problems in applying Thermal EOR Processes 8
4. SCREENING CRITERIA FOR CHEMICAL
EOR PROCESSES 9
4.1 Critical parameters for Chemical EOR process 9
(i) Formation 9
(ii) Oil composition and Oil viscosity 9
v



(iii) Formation water salinity and divalent 9
(iv) Reservoir Temperature 9
(v) Formation Permeability 10
5. POLYMER FLOODING 11
5.1 Introduction 11
5.2 Several benefits of Polymer flooding 13
6. SCREENING CRITERIA FOR POLYMER
FLOODING 14
6.1 Screening Procedure 14
6.1.1 Crude Oil 14
6.1.2 Reservoir Temperature 14
6.1.3 Reservoir Brine 14
6.1.4 Reservoir Factor 15
6.1.5 Reservoir Permeability 15
6.1.6 Oil Saturation 15
7. LABORATORY TESTING OF EOR POLYMERS 16
7.1 Polymer Mixing 16
7.2 Stability testing 16
(i) Filterability of Polymer solution 16
(ii) Determination of pH 16
(iii) Rheological Behaviour 17
(iv) Mechanical degradation 17
(v) Determination of Concentration 17
(vi) Polymer reservoir interaction 17
8. CHARACTERISTICS OF EOR POLYMERS 18
8.1 Factors on which EOR Processes depends 18
8.2 Characteristics of EOR polymer materials 18
(i) Degree of hydrolysis 18
(ii) Water content 18
vi


(iii) Thermal stability 18
(iv) Molar mass 18
(v) Molecular size of the polymer 18
(vi) Sweep efficiency 19
8.3 Design of Polymer solutions 20
9. POLYMERS USED IN EOR PROCESS 21
9.1 Synthetic Polymers 21
9.1.1 Polyacrylamide 21
9.2 Other synthetic Polymers 22
9.3 Polysaccharides 22
9.3.1 Xanthan 22
9.3.2 Hydroxyethyl cellulose 23
10. EXPERIMENTAL WORK 24
10.1 Preparation of PHPA polymer solution 24
10.2 Experiments based on PHPA solution 25
10.2.1 Effect of thiourea concentration on PHPA stability 25
10.2.2 Effect of different shear rates with thiourea on
PHPA stability 27
10.2.3 Effect of sodium carbonate concentration on PHPA\
Stability 29
10.2.4 Effect of different shear rates with sodium carbonate
on PHPA stability 31
10.3 Preparation of MMA-Acrylic acid Copolymer 33
10.4 Variation in viscosity of Copolymer at different
temperature with aging time 33
10.5 Variation in shear rate of Copolymer at different
temperature with aging time 35
10.6.1 Effect of Thiourea concentration on Copolymer
stability 35

vii



10.6.2 Effect of different shear rate with thiourea on
Copolymer stability 38
10.6.3 Effect of sodium caronate concentration on
Copolymer stability 40
10.6.4 Effect of different shear rate with sodium carbonate
on Copolymer stability 42
11. OBSERVATION AND CONCLUSION 44
11.1 Effects of additives on PHPA solution 44
(i) Effect of thiourea 44
(ii) Effect of sodium carbonate 44
11.2 Effect of additives on Copolymer 45
11.3 Conclusion 45
REFERENCES 46

















viii



LIST OF TABLES

Table No. Particulars Page No.
4.1 Criteria for different Chemical EOR processes 10
10.1 Effect of thiourea concentration on PHPA
stability at 27
0
C.
25
10.2 Effect of thiourea concentration on PHPA
stability at 70
0
C.
25
10.3 Effect of different shear rate on PHPA stability
with thiourea at 27
0
C.
27
10.4 Effect of different shear rate on PHPA stability
with thiourea at 70
0
C.
27
10.5 Effect of sodium carbonate concentration on
stability of PHPA at 27
0
C.
29
10.6 Effect of sodium carbonate concentration on
stability of PHPa at 70
0
C.
29
10.7 Effect of different shear rate on PHPA stability
with sodium carbonate at 27
0
C.
31
10.8 Effect of different shear rate on PHPA stability
with sodium carbonate at 70
0
C.
31
10.9 Variation in viscosity of Copolymer at different
temperatures with aging time
34
10.10 Variation in shear rates of the Copolymer at
different temperatures with aging time
35
10.11 Effect of thiourea concentration on stability of
Copolymer at 27
0
C.
36
10.12 Effect of thiourea concentration on Copolymer
stability at 70
0
C.
36
10.13 Effect of different shear rate on Copolymer
stability with thiourea at 27
0
C.
38
10.14 Effect of different shear rat on Copolymer
stability with thiourea at 70
0
C.
38
ix



x

LIST OF TABLES

Table No. Particulars Page No.
10.15 Effect of sodium carbonate concentration Of
Copolymer stability at 27
0
C.
40
10.16 Effect of sodium carbonate concentration on
Copolymer stability at 70
0
C.
40
10.17 Effect of different shear rate on Copolymer
stability with sodium carbonate at 27
0
C.
42
10.18 Effect of different shear rate on Copolymer
stability with sodium carbonate at 70
0
C.
42
10.4.1 Observation was seen while preparing the
Copolymer of MMA-Acrylic acid
34
























LIST OF FIGURES

Sr. No. Particulars Page No.
Fig 1.1 OPEC chart for crude oil reserves in year
2012
1
Fig 3.1 Chemical EOR process 5
Fig 3.2 Miscible EOR process 7
Fig 3.3 Thermal EOR process 8
Fig 5.1 Influence of mobility ration on areal
sweep efficiency
11
Fig 8.2.6 Sweep efficiency of polymer in EOR 19
Fig 9.1.1 Structure of Polyacrylamide 22
Fig 9.3.1 Structure of Xanthan 23
Fig 9.3.2 Structure of Hydroxyethyl cellulose 23
Fig 10.1 Effect of thiourea concentration on PHPA
stability at 27
0
C.
26
Fig 10.2 Effect of thiourea concentration on PHPA
stability at 70
0
C.
26
Fig 10.3 Effect of different shear rates on PHPA
stability with thiourea at 27
0
C.
28
Fig 10.4 Effect of different shear rate on PHPA
stability with thiourea at 70
0
C.
28
Fig 10.5 Effect of sodium carbonate concentration
on PHPA stability at 27
0
C.
30







xi




LIST OF FIGURES

Sr. No. Particulars Page No.
Fig 10.6 Effect of Na2CO3 concentration on PHPA
stability at 70
0
C.
30
Fig 10.7 Effect of different shear rates on stability
of PHPA with Na2CO3 at 27
0
C.
32
Fig 10.8 Effect of different shear rate on PHPA
stability with Na2CO3 at 70
0
C.
32
Fig 10.9 Variation in viscosity of Copolymer at
different temperatures with aging time
35
Fig 10.10 Variation in shear rates of Copolymer at
different temperatures with aging time
37
Fig 10.11 Effect of thiourea concentration on
Copolymer stability at 27
0
C.
37
Fig 10.12 Effect of thiourea concentration on
Copolymer stability at 70
0
C.
37
Fig 10.13 Effect of different shear rate on the
Copolymer stability with thiourea at 27
0

C.
39
Fig 10.14 Effect of different shear rate on the
Copolymer stability with thiourea at 70
0

C.
39
Fig 10.15 Effect of Na2CO3 concentration on
Copolymer stability at 27
0
C.
41
Fig 10.16 Effect of Na2CO3 concentration on
Copolymer stability at 70
0
C.
41
Fig 10.17 Effect of different shear rate on
Copolymer stability with Na2CO3 at 27
0

C.
43
Fig 10.18 Effect of different shear rate on stability
of Copolymer with Na2CO3 at 70
0
C.
43
xii



CHAPTER:- 1
INTRODUCTION
In spite of efforts in searching alternate sources of energy and growing environmental
concern, petroleum continues to be the largest source of energy of the world. Statistical analysis
shows that the oil volume discovered and not recovered is larger than the entire oil already
produced. The demand for new petroleum may not only be met by more efforts in exploration but
also by improving the production of known reservoirs. However, through enhanced oil recovery
it is possible to increase or maintain the present level of production.

` Fig 1.1 :- OPEC chart for crude oil reserves in year 2012
Organization of the Petroleum Exporting Countries (OPEC) is an international
organization and economic cartel whose mission is to co-ordinate the policies of the oil-
producing countries.
According, to the current estimates more than 81% worlds oil reserves are located in
OPEC member countries with the bulk of OPEC oil reserves in the middle east, amounting to
66% of the OPEC total. Presently India ranks 23
rd
in the total oil production of the world. It
accounts to 1.04% of the total world share, which is about 987,000 bbl/day.
1



Polyacrylamide, a water soluble polymer which has become more and more important
in the last years for the improvement of oil recovery using a process called polymer flooding. The
main objective of polymer flooding is to remedy the problem with water flood because of high
molecular weight or because of heterogeneity. Almost all this early work was carried out with the
synthetic polymer, polyacrylamide (PAM), usually in its partially hydrolysed form (HPAM).
The production history of a petroleum reservoir may be divided into different phases.
The first, where oil is flowing freely from the reservoir to the production well, in the best known,
but in most cases also the shortest. Very early in the life of the reservoir, energy must usually be
supplied to the porous medium which bears the crude oil, so that it continues to flow to the
producing wells. This energy is brought into the reservoir by injection of water or gas. With these
secondary methods about 30 to 40 percent of the original oil in place may be recovered, while the
rest must be left in the earth. In order to recover some of this oil as well, tertiary methods have
been developed which are still the subject of research.
The forces that hold back oil in the porous body of the reservoir are the interfacial
tension between the different phases of oil, water and gas flowing in the porous medium and the
viscosity of the crude oil. The interfacial tension may be overcome by injection of surface active
agents (surfactants) or by injection of a gas that is miscible with the crude oil (miscible flooding
using CO2 at high pressure). The viscosity of the oil may be reduced by applying heat to the
reservoir, or the viscosity of the displacing phase may be adapted to the viscosity of the crude oil,
which is accomplished by adding a water soluble polymer to the floodwater.
The instrument used for testing the different samples of PHPA (with or without
additives) was Brook field DV-II+Pro viscometer which measures the fluid viscosity at the given
shear rate. The DV-II+Pro offers exceptional versatility in modes of controlling and automation.





2



CHAPTER :-2
OVERLOOK OF EOR PROCESS
EOR entails the injection of fluids of some types into a reservoir. The injected fluids
and injection processes act as supplement to the natural energy present in the reservoir to displace
oil into a producing well. Also, the injected fluids interact with the reservoir rock/oil system to
create condition favorable for oil recovery. These interactions includes lowering the interfacial
tension, swelling of oil,, viscosity reduction, wettability modifications or favorable phase
behavior. The interaction are attributable to physical and chemical mechanism and to injection or
production of thermal energy.
1.1 EOR refers to the recovery of oil after the primary and secondary recovery processes.
In primary recovery processes, the natural pressure at the depth is responsible for flow of
oil through the rocks towards the production well, where it is lifted to the surface. Recovery is
usually between 10-15% of original oil.
In secondary recovery process, a process of water flooding is used, in which the large
amount of water under high pressure is induced to sweep out the oil from the reservoir via wells.
This is also an insufficiently not convenient process, almost 10-20 % of oil is recovered of the
original oil content.
The tertiary process can be referred to as the EOR process by using a polymer flooding
technique. This process is obtained after secondary recovery which uses miscible gases,
chemicals and/or thermal recovery to displace additional oil after the secondary recovery process
become uneconomical.
In classifying recovery processes care should be taken because many reservoir
production operations are not conducted into the specified manner as describe above. If the crude
oil is sufficiently viscous, it may not flow at economic rates under natural energy devices, so
primary production would be neglected. Water flooding is also not useful thus, the use of thermal
energy might be the way to recover a significant amount of oil. In other words, a supported
tertiary process becomes first stage. This can also be applied where secondary recovery process is
skipped.
3



CHAPTER :- 3
CLASSIFICATION OF EOR TECHNIQUES
There are three categories of EOR which includes namely:
(1) Chemical EOR process
(2) Miscible EOR process
(3) Thermal EOR process
3.1 Chemical Process : Chemical flooding relies on the addition of one or more chemical
compound to an injected fluid either to reduce the interfacial tension between the reservoir oil
and the injected fluid or to improve the sweep efficiency of the injected fluid.
There are three general methods in chemical flooding technology. The first is polymer flooding,
in which a large macromolecule is used to increase the displacing fluid viscosity, this leads to
improve sweep efficiency in the reservoir. We deal with polymer flooding in detail in the next
Chapter. The second and third methods, Micellar polymer and alkaline flooding make use of
chemicals that reduces the interfacial tension between an oil and displacing liquid.
3.1.1 : Micellar-Polymer Processes:- The micellar-polymer processes uses a surfactant to
lower the interfacial tension between the injected fluid and the reservoir oil. A surfactant is a
surface active agent that contains a hydrophobic part to the molecule and a hydrophilic part. The
surfactant migrates to the interface between the oil and the water phases and helps make the two
phases more miscible. Soaps and detergents used in the cleaning industry are surfactants. The
same principle is involved in washing greasy hands. As the interfacial tension between an oil
phase and a water phase is reduced, the capacity of the aqueous to displace the trapped oil from
the pores of the rocks increases.
3.1.2 : Alkaline Processes:- When an alkaline solution is mixed with certain crude oils
surfactant molecules are formed. When the formation of surfactant molecules occurs in situ, the
interfacial tension between the brine and oil faces could be reduced. The reduction of interfacial
tension causes the microscopic displacement efficiency to increase which thereby increases oil
recovery.

4



3.1.3 Problems in Applying Chemical Processes :
The main technical problems associated with chemical processes include the following: (1)
screening chemicals to optimize the microscopic displacement efficiency, (2) making contact
with the oil in the reservoir, and (3) maintaining good mobility in order to lessen the effects of
viscous fingering. The requirements for screening of chemicals vary with the type of process.
Obviously, as the number of components increases, the more complicated the screening
procedure becomes. The chemicals must also be able to tolerate the environment they are placed
in. High temperature and salinity may limit the chemicals that could be used.
The major problem experienced in the field to date in chemical flooding processes has been the
inability to make contact with residual oil. Laboratory screening procedure shave developed
micellarpolymer systems that have displacement efficiencies approaching 100% when sand
packs or uniform consolidated sandstones are used as the porous medium. When the same
micellar polymer system is applied in a natural reservoir rock sample ,however, the efficiencies
are usually lowered significantly. This is due to the heterogeneities in the reservoir samples.
When the process is applied to the reservoir, the efficiencies become even worse.

Fig 3.1: Chemical EOR process
3.2 Miscible Process : Miscible process is one in which interfacial tension is zero i.e the
displacing fluid and residual oil mix to form one phase. If the interfacial tension is zero than the
capillary number becomes infinite and microscopic displacement efficiency is maximized.


5



In miscible process fluid A is injected and it mixes with crude oil which forms an oil bank.
Mixing zone develops between fluid A and oil bank and it grows due to dispersion. Fluid A is
followed by fluid B which is miscible with fluid A but not generally miscible with the oil and it is
much cheaper than fluid A. Mixing zone will also be created at the fluid A fluid B interface. It is
important that the amount of fluid A that is injected be large enough that the two mixing zones do
not come in contact if the front of the fluid A fluid B mixing zone reaches the rear of fluid A oil
mixing zone, viscous fingering of fluid B through the oil could occur.
There are, in general, two types of miscible processes .One is referred to as the single-contact
miscible process and involves such injection fluids as liquefied petroleum gases (LPGs) and
alcohols. The injected fluids are miscible with residual oil immediately on contact. The second
type is the multiple contact, or dynamic, miscible process. The injected fluids in this case are
usually methane, inert fluids, or an enriched methane gas supplemented with a C 2 C6 fraction.
The injected fluid and oil are usually not miscible on first contact but rely on a process of
chemical exchange between phases to achieve miscibility.

3.2.1 Problems in Applying the Miscible Process :
Because of differences in density and viscosity between the injected fluid and the reservoir
fluid(s), the miscible process often suffers from poor mobility. Viscous fingering and gravity
override frequently occur. The simultaneous injection of a miscible agent and a brine was
suggested in order to take advantage of the high microscopic displacement efficiency of the
miscible process and the high macroscopic displacement efficiency of a water flood. The
improvement was not as good as hoped for since the miscible agent and brine tended to separate
due to density differences, with the miscible agent flowing along the top of the porous medium
and the brine along the bottom. Several variation so the simultaneous injection scheme have been
suggested and researched. They typically involve the injection of a miscible agent followed by
brine or the alternating of miscible agentbrine injection. The latter variation has been named the
WAG (water alternate gas) process and has become the most popular. A balance between
amounts of injected water and gas must be achieved. Too much gas will lead to viscous fingering
and gravity override of the gas, whereas too much water could lead to the trapping of reservoir oil
by the water. The addition of foam-generating substances to the brine phase has been suggested
as a way to aid in reducing the mobility of the gas phase. Research is continuing in this area.


6



Operational problems involving miscible processes include transportation of the miscible
flooding agent, corrosion of equipment and tubing, and separation and recycling of the miscible
flooding agent

Fig 3.2 : Miscible EOR process
3.3 Thermal Process :Thermal methods accounts foe about 70% of the overall enhanced oil
recovery into the globe. This process involve the steam floods or surface mining operations. This
is consider to be the best or ideal EOR technique due to following advantages:-
(1) It utilizes the two cheapest and most plentiful of all EOR injectants : Air and water
(2) For fuel, it burns about 10% of the least desirable filtration of the oil, and upgrade the rest.
(3) It works over a wide range of the field conditions than steam flooding, especially in the deep
reservoir.
3.3.1 Steam Flooding : Steam stimulation process also known as, steam huff and puff or
steam soak, or cyclic steam injection have the following mechanism of oil recovery:
(1) Reduction of flow resistance near the well bore by reducing the crude oil viscosity.
(2) Enhancement of solution gas drive mechanism by decreasing the gas solubility with an oil as
temperature increases.
The oil recovery obtained by this process are much smaller than the oil recoveries that could be
obtained from a steam drive. However, it should be apparent that the steam simulation process
is much less expensive to operate.





7



.
Fig 3.3 : Thermal EOR process

3.3.2 Problems in Applying Thermal Processes :
The main technical problems associated with thermal techniques are poor sweep efficiencies,
loss of heat energy to unproductive zones underground, and poor injectivity of steam or air. Poor
sweep efficiencies are due to the density differences between the injected fluids and the reservoir
crude oils. The lighter steam or air tends to rise to the top of the formation and bypass large
portions of crude oil. Data have been reported from field projects in which coring operations
have revealed significant differences in residual oil saturations in the top and bottom parts of the
swept formation. Research is being conducted on methods of reducing the tendency for the
injected fluids to override the reservoir oil. Techniques involving foams are being employed.
Large heat losses continue to be associated with thermal processes. The wet combustion process
has lowered these losses for the higher-temperature combustion techniques, but the losses are
severe enough in many applications to prohibit the combustion process.










8



CHAPTER :- 4
SCREENING CRITERIA FOR CHEMICAL EOR PROCESSES

4.1 CRITICAL PARAMETERS FOR CHEMICAL EOR PROCESSES:-

(1) Formation : Almost all EOR application have been in sandstone reservoirs, except a few
stimulation projects. Clays causes high surfactants and polymer adsorption and high alkaline
comsumption. Therfore, clay must be low for a chemical EOR application to be effective.

(2) Oil Composition and Oil Viscosity : Oil composition is very important to alkaline-
surfactant because different surfactanats must be selected for different oils, but it is not critical to
polymer flooding. Oil viscosity should be less than 35 mPa.s for A/S projects. For polymer
flooding, oil viscosity could be 10 to 150 mPa.s.

(3) Formation Water Salinity and divalent : Formukation water salinity and divalent are
critical to chemical EOR processes for both surfactants and polymers. Although chemical
suppliers claim their products can be tolerate to high salinity, most of the chemical EOR
processes have been applied in low-salinity reservoir. The formulation water salinity in below
10,000 ppm, and fresh water is injected. It must be emphasized that the salinity and divalent
depends on the type of polymer used. Biopolymer xanthan has much more salinity or hardness
tolerant than HPAM.

(4) Reservoir Temperature : The reservoir temperature should be lower than 93
0
C for A/S
projects, but the avearge temperature for the actual A/S filed project reportedwas 49
0
C. Some
chemical suppliers state that polymer can be applied up to 120
0
C.

(5) Formation Permeability : High permeability is favourable to chemical flooding, and is
critical for polymer flooding. Low permeability formulation will have injectivity and excess
retention problems.




9




Table 4.1 The table shows criteria for different Chemical EOR processes


Process


Oil gravity
(API
0
)

Formation type


Oil
viscosity
(cP)


Depth
(ft)

Temperature
(
0
C)

Avg
permeability
(mD)
Chemical
Processes


>25

Sandstone
preferred


5-125

<9000


<200


>20

Polymer

Alkaline

13-35
Sansdstone
preferred


<200

<9000

<200

>20

Surfactant

>15

Sandstone
preferred

20-30

<9000

<200

>20



















10



CHAPTER :- 5
POLYMER FLOODING

5.1 Introduction :.
Polymer flooding consists in mixing long chain polymer molecules with the injected water in
order to increase the water viscosity. This method improves the vertical and areal sweep
efficiency as a consequence of improving the water/oil Mobility ratio. In addition, the polymer
reduces the contrasts in permeability by preferentially plugging the high permeability zones
flooded by polymers. This forces the water to flood the lower permeability zones and increases
the sweep efficiency.

Flooding petroleum reservoir with water soluble polymers may be regarded as the most
economic tertiary oil recovery method, though by definition of reservoir rock; the remaining
volume of oil in the porous media is assumed to be the same after a polymer flood as after a
water flood. Thus the physical laws derived for water flooding may be applied to the injection
polymer solutions. The two phases flow of the crude oil and polymer solution may be described
by using the relative permeability concept. For the displacement of oil by a polymer solution the
fractional flow equation derived by BUCKLEY and LEVERETT (1942) may be used. (1954),
the mobility ratio is,

M = =

influences the areal sweep efficiency as shown in fig.

Fig 5.1 : Influence of mobility ratio on areal sweep efficiency.

11



Surfactants may be used in conjunction with polymers; They decrease the surface tension
between the oil and water. This reduces the residual oil saturation and improves the microscopic
efficiency of the process.

Primary surfactants usually have Co-surfactants, activity boosters, Co-solvents added to them to
improve stability of the formulation.

Caustic flooding is the addition of sodium hydroxide to injection water. It does this by lowering
the surface tension, reversing the rock wettability, emulsification of the oil, mobilization of the
oil and helps in drawing the oil out of the rock.

Oil and water are immiscible fluids. As a result neither can completely displace the other from
an oil reservoir. This is reflected in the irreducible water and residual oil saturation (ROS) on a
relative permeability curve regardless of the amount of water cycled to the system the oil
saturation will not be reduced below the ROS. In polymer flooding, water soluble polymer is
added to the flood water. This increases the viscosity of water. Depending on the type of the
polymer used, effective permeability to water can be reduced in the swept zones. Polymer
flooding does not reduce the ROS, but is rather a way to reach the ROS more quickly or to allow
it to be reached economically.
There are three potential ways in which polymer flood can make the oil recovery process more
effective:
(1) Through the effect of polymers on fractional flow.
(2) By decreasing the water/oil mobility ratio.
(3) By diverting injected water from zones that have been swept.
The oil produced by primary depletion results in drop in reservoir pressure, in order to maintain
the reservoir pressure and to sweep out oil in more efficient manner water flooding was used, but
the inefficiency of the water flood oil displacement mechanism is its unfavorable mobility ratio,
thus this overcome by use in polymer. To mobilise residual oil the capillary number (Nc) must be
increase by several order i.e. only achieved by lowering interfacial tension.
Capillary number (Nc) = vu/z
Where, v- fluid velocity, u- Viscosity, z- Interfacial tension.
12



Particular emphasis is placed on the structure-property co-relation and the synthetic methods of
polymers. In addition the influence of external parameters like pH, salt, temperature etc. on the
rheological behavior of polymer is examined.
Polymer flooding comes forward as a sustainable method for petroleum recovery. The principle is
based on the injection of a bank of polymeric solution in the injection well, which travels through
the reservoir towards the production wells. These results are consequences of the physio-
chemicals interactions of the polymer solution the reservoir-rock system and the fluids.
During the whole operation it is important that the viscosity of the polymer solution should be
close to displaced phase so as to improve the sweeping efficiency and consequently the amount
of oil efficient recovery.
In our literature research we basically dealt with the only polymer named Partially hydrolysed
PolyAcrylamide (PHPA). And all further details of polymer is about PHPA.
5.2 Several benefits of polymer flooding :
- Improve oil recovery.
- Increase swept efficiency.
- Significantly less water required when compared with typical water flooding and steam
injection.
- Superior EOR technology with heavy poil formation/reservoirs with low viscosity and where
steam assisted gravity drainage (SAGD) is not suitable.










13



CHAPTER:- 6
SCREENING CRITERIA FOR POLYMER FLOODING
6.1 Screening Procedures:
Because polymer flooding is not always suitable for every reservoir, in this chapter the most
important criteris are outlined. Before a polymer project may be planned in detail a screening of
the reservoir parameters may give a first indication as whether a polymer flood is at all
possible; which polymeris most likely to be successful, and if the project might prove
successful with respect to technical performance and profitability.
6.1.1 Crude Oil :-
The properties of the crude oil to be recovered essentially determine the EOR process to be
applied . Low oil viscosities and thus low mobility ratios often only allow small
improvements by polymer flooding as compared to water flooding, except for the case
when polymer flooding is favorable because of high permeability variations. At high oil
viscosities the reduction in mobility for polymer flooding may be considerable. Oil viscosities
between 5 and 50 mPa.s are regarded as advantegeous.
6.1.2 Reservoir Depth and Temperature:-
Reservior depth is important in relation to the injection pressure. injection pressure is
significantly higher in polymer flooding than in water flooding. The limit for injection pressure
is given by that pressure attained when the reservoir is fractured. Hence low depth may be a
restriction for polymer flooding.
The temperature of the reservoir is related to the depth. Reservoir temperature in polymer
flooding should not be too high. Though many manufacurers gives values of up to 120
degrees and more for the thermal stability of their products. The upper limit should be
nevertheless seen at 70 degrees in order to avoid the problems. A low temperature also
has adverse effects on polymer flooding because the activities of bacteria are generally higher
at such temp.
6.1.3 Reservoir Brine:-
The brine that saturates the pores of a reservoir, besides the oil itself is one of the most
important parameter for the selection of a suitable polymer. If the reservoir water is of high
salinity the polymer should be salt stable or the reservoir must be preconditioned by preflush of
fresh water.


14



6.1.4 Resistance Factor:-
The measure of the resistance to the flow of polymer solution is expressed as Resistance
Factor which is defined as the ratio of the mobility of water to the mobility of a polymer
solution.


At low velocities the resistance factor is constant, which reflects the newtonian flow behaviour.
At higher velocities shear thinning starts, where the RF decrease and at much higher velocities
the RF increases due to the elastic behavior of polymer. This behavior depends upon the
polymer type used and its MW.
6.1.5 Reservoir Permeability:-
Polymer flooding has lower mobility than water or brine, so low permeability formation to be
avoided. Two problem could be arise while injecting solution in low permeability
formation:-
Reducing the injection rate would prolong the life of project beyond the economic limit and the
high shear around the injection well bore could cause shear degradation.
6.1.6 Oil Saturation:-
Oil saturation may be mentioned that the polymer flood is a modified water flood, which does
not have any effect on wettability or interfacial water flood tension in reservoir rock fluid
systems. Hence, this process is not capable of lowering residual of saturation below the limit
water flood is capable of bringing. Therefore, for a successful application of polymer flood
adequate quantity of oil saturation is must.










15



CHAPTER:- 7
LABORATORY TESTING OF EOR POLYMERS
At the beginning of a polymer flood, extensive laboratory work is neccesary. The task id to find
a polymer product suitable to the condition in a particular oilfield with respect to salinity
tolerances, temperature stability, quality of mixing water, and economic condition. The
consumption of chemicals, that is not only polymer, but also other chemicals such as
surfactants that are needed to mixed emulsion polymers, oxygen scavengers, boicides that
reduces adsortion that determines mainly the efficiency of polymer flood.
7.1 Polymer Mixing :-
The assumption made previously was that the polymer solution is a homogeneous solution of
single macromolecule in water. The size of the particles in that solutions should not vary too
much and should be small enough to pass through the pores of reservoir rock.This means that
proper mixing of the polymers is neccesary for any application in the field. For this purpose
adequate mixing methods must be developed.

7.2 Stability Testing:-
As chemical flood projects last from of five to ten years, the chemicals used should be stable
throughout this long periods. Polymer should not lose there viscosity, they should not floculate
or change their behavior in any way that could plug the reservoir. The stability criteria that
should be applied to the polymers are solution stability, thermal stability and long term
stability. This means that the polymer should not crosslinked or precipitate or lose its
viscosity and thus plug the reservoir.
(1) Filterability of polymer solution : The homogeneity of all polymer solutions made is
verified by this method. In this process, the solution samples are submitted to filtered in a
10 m steel filter with a controlled flow rate and monitored pressure. The increase in the
pressure indicates that the presence of hetero genetics, known as Fish eyes in the
solution. When an increasing in pressure was observed the solution was discarded and new
solution was prepared according to the standard. This is most important procedure before
polymer- reservoir interaction.
(2) Determination of pH : Using a pH analyser the pH of the polymer solution is
calculated.


16




(3) Rheological behaviour : The curves of concentration vs viscosity for all polymer
samples is carried out to know different rheological behaviour of the polymer solution
under different temperature condition such as checking of shear rate which should be
compatible to shear rate of the fluid in the reservoir by using brook field viscometer.
(4) Mechanical Degradation : Shearing test for all polymer solution is done by passing
each solution under higher pressure through a different velocities. The shear rates is than
calculated as a function of velocities, capillary diameter and a flow rates.
For this we can calculate the rate of decreasing shear rate as

Shear rate = 4( flow rate )/ ( capillary radius )
2

(5) Determination of concentration : This is used to calculate the concentration of the
polymeric solution by using a turbidimeter method.
(6) Polymer-reservoir interaction : This interaction made by static adsorption, which
was performed with the original reservoir rock to preserve the rheological characteristics
even though it is a disaggregated form. The disaggregation of the rock was made using a
special mill that separates the grains, maintaining their integrity. After disaggregation a
granulo-meteric separation was made to remove the small material, named silt which is a
consequence of the disaggregation of natural cement that joints the grains and may harm the
analysis. Then, the disaggregated rock was dried and sample were put in contact with the
polymer solution. After the equilibrium time, the final concentration of the solution was
measured and compared with initial one. The physical- chemical adsorption was calculated
as the ratio between the difference of initial and final concentration and the total mass of the
rock. The procedure is repeated for different concentrations to make an adsorption curve as
a function of concentration.








17



CHAPTER :- 8
CHARACTERISTICS OF THE POLYMERS IN EOR
8.1 The enhanced oil recovery depends on the following two important factors
which are as follows:
(1) The characteristics of the polymer to be used.
(2) The design of the polymeric solution to be used.

8.2 Characteristics of the polymer material should have :
(1) Degree of hydrolysis : This is one of the most important factor; the polymer must posses
a good degree of hydrolysis.
(2) Water content : This is been calculated by using liofilization process. The amount of
water present is calculated based on the weighed determine before and after treating.
(3) Thermal stability : The thermal stability of the polymers is much important in oil
recovery as the process is associated with high temperature. The polymer should be
thermally stable to sustain to such high tempearture
(4) Molar mass : The higher the viscosity of the polymer solution the more viscous will be
the mass of it obtained. It is calculated by using intrinsic viscosity.
intrinsic = sp/C
Where, sp- specific viscosity of polymer
C- concentration mole
(5) Molecular size of polymers : It is related with the viscosity of the polymers. The
higher the viscosity of polymer; the larger the molecular size associated with polymer
solution.
Related to viscosity there are many other quantities associated with it such as inherent
viscosity, specific viscosity, relative viscosity, reduced viscosity, intrinsic viscosity.The
relation between intrinsic viscosity and molecular weight is given by,
Mark-Houwink equation,

Where, K and a are constants and there values are given in the literature.



18



Important of using the polymer flooding over water flooding is that using polymer flooding
process through which the mobility between the viscous- to- capillary action is reduced by
polymer flooding.
This is the drawback of water flooding as there is a large mobility between the viscous and
capillary action forces due to the lesser viscosity of water.

The mobility ratio M is given by,
M = o/ko/ w/kw = mobility of dispersed phase/mobility of displaced phase

Where, k and are permeability and viscosity related to oil and water.
(6) Sweep efficiency : A measure of the effectiveness of an enhanced oil recovery process
that depends on the volume of the reservoir contacted by the injected fluid. The volumetric
sweep efficiency is an overall result that depends on the injection pattern selected, off-pattern
wells, fractures in the reservoir, position of gas-oil and oil/water contacts, reservoir
thickness, permeability and areal and vertical heterogeneity, mobility ratio, density
difference between the displacing and the displaced fluid, and flow rate.


Fig 8.2.6 : Sweep efficiency of the polymer in oil recovery



19



8.3 Design of Polymer Solutions :
- Preparation of polymer aqueous dispersion :
In preparation of polymer aqueous dispersion care must be taken in the amount and intensity
of mixing that is applied in making up to the original solution in order to avoid uncontrolled
mechanical degradation of the polymer molecules in the solution.
Therefore, in preparing biopolymer solution it is quite common to use blender such as waring
and/or silveson machines in order to disperse the polymer. It should be taken into account up
to a certain limit of time otherwise, degradation of polymer can takes place.
While for a hydrolysed polymer dispersion solution can be made by using a less vigorous
method of dispersion such as vortex mixing followed by the longer time of smooth stirring.

























20



CHAPTER:-9
POLYMERS USED IN EOR
The overall objective is to established the chemical structure of various
polymer molecules and their molecular conformation in solution the two most commonly used
polymer in EOR applications are Polyacrylamide in its partially hydrolysed form (HPAM)
and the biopolymer Xanthan. The chemical structure of xanthan and polyacrylamide are
considered separately as each material represents a different class of polymer not only in its
origin but also in the details of its structural type in solution. HPAM has a flexible coil
structure in aqueous solution whereas xanthan shows the characteristics of a more rigid
molecule. These structural differences relate to the method of synthesis and in turn they
strongly effect the solution properties of two polymers.
9.1 Synthetic Polymers:-
9.1.1 Polyacrylamide
Polyacrylamide in its partially hydrolised form is most widely polymer for EOR application.
It is most frequently used than xanthan biopolymer. For given polymer has concentration
or viscosity level, HPAM solution have provided significantly greater oil recovery as it
has greater viscosity level, HPAM solutions have provided significanlty greater oil recovery
as it has greater viscoelasticity than xanthan. HPAM is a synthetic straight- chain polymer of
acrylamide the degree of hydrolysis is important in certain physical properties such as polymer
adsorption, shear stability and thermal stability. HPAM is a polyelectrolyte and as such it will
interact quite stronglywith ions in solutions. However, since the polyacrylamide chains is
flexible it may respond much more to the iconic strength of the aqueous solvent, and its
solution properties are much more sensitive to salt hardness than are those of xanthan.
Polyacrylamide adsorbs strongly on mineral surfaces. Thus the polymer is partially hydrolysed
to reduce adsorption by reacting polyacrylamide with a base such as sodium or potasium
hydroxide or sodium carbonate. Hydrolysis convert some of the amide groups to carboxyl
groups. Degree of hydrolysis is the mole fraction of amide groups that are converted by
hydrolysis. It ranges from 15% to 30% in commercial products. Hydrolysis introduces
negative charges on the backbone of polymer chains that have a large effect on the rheological
properties of the polymer solution. At low salinities, the negative charges on the polymer
backbone repel each other and caue the polymer chains to stretch, when an electrolyte such as
Nacl is added the stretch is reduced.

21



Unhydrolised polyacrylamide also is used in some applications even unhydrolised PAM will
have small percent of hydrolised groups.The MW of HPAM used in EOR proesses are upto
higher than 20 million daltons.


Fig 9.1.1:- Structure of Polyacrylamide
9.2 Other Synthetic Polymers :-
Some efforts has been made to overcome the disadvantages of polyacrylamide i.e they cannot
used in waters of high salinity, especiallyat raised temperature. These polymers e.g
vinysulfonate/vinylamide co-polymers as described by HILLE. They where originally
developed for drilling fluids in high temperature wells.
9.3 Polysaccharides:-
9.3.1 Xanthan
The backbone of Xanthan consist of glucosidic linkage and the pendant side chains which are
attached to every second glucose unit in the backbone structure. Some amount of pyruvic acid
is also present in Xanthan structure.
Xanthan is another widely used polymer for EOR application. Xanthan is a biopolymer. It acts
like a semi-rigid rod and is resistant to mechanical degradation. MW of xanthan biopolmer used
in EOR process range from 1 million to 15 million. It is supplied as dry powders
polyacrylamide copolymers are much more viscous than polysaccharide biopolymer at
equivalent concentration in fresh water ,but these copolymers are much more sensitive to
saline water than the biopolymers. The viscosity of copolymers is lower than that of
biopolymers in saline water. Some permanent shear loss of viscosity could occur for
polyacrylamide, but not for polysaccharide at the wellbore. however, the residual
permeability reduction factor of polysaccharide polymers is low. Other potential EOR
biopolymers are scleroglucan, simusan, AGBP etc.

22




Fig 9.3.1 :- Structure of xanthan

9.3.2 Hydroxyethyl cellulose (HEC) :-
The basic component of the structure is cellulose.Within the glucose ring the smallest unit in
the molecule there are three positions where an addition or reaction with other chemicals can be
possible without destroying the character of the molecule. These positions are the two OH
groups and CH2OH group. The structure is shown in fig:-


Fig 9.3.2 :- Structure of Hydroxyethyl Cellulose







23



CHAPTER :- 10
EXPERIMENTAL WORK
Partially hydrolysed polyacrylamide used for EOR is known to be sensitive to
temperature and divalent ions. The amide group present in this polymer will hydrolysed in
aqueous solution to extent that depends on the temperature and pH. The resultant hydrolysed
polyacrylamide has more degree of hydrolysis sufficient to cause precipitation in presence of
multivalent ions present in reservoir or injection water used.
As the polymer used was sensitive to temperature, until recently they were only used in
shallow and low temperature reservoir, because above 70
0
C polymer starts precipitating losing
its viscosity and this loss in viscosity was a major constraint in the success of polymer flooding.
Thus our objective in this experimental work is to overcome to these barriers. For that
we initially studied the chemical effect to retain the polymer solution viscosity at higher
temperature with different additives and with different concentrations, for 14 days aging time.
The objective of this project is to study the effect of various factors on viscosity and thermal
stability of high molecular weight commercially available PHPA. In our experimental work, we
have studied the effect of two additives namely Thiourea and Sodium Carbonate with different
concentrations and at two different temperatures on freshly prepared PHPA solution.
The experimental work on associating co-polymer of Methylmethacrylate and Acrylic
acid was earned in similar manner as with PHPA with two different additives at different
concentration and temperature, for 14 days aging time. At last, the comparison between these
two solutions is shown with the help of a graphs.
10.1 Preparation of Polymer solution :-
The following is the procedure used for the preparation of PHPA solution:-
(1) In a clean beaker 300 ml of distilled water was taken in to which 9.64 gm of NaCl was
added.
(2) This brine solution was then kept in the laboratory reactor at the room temperature of 30
0
C
under constant stirring of 90-100 rpm and external heating medium.
(3) A vortex extending 2/3
rd
of the beaker and reaching at the bottom of the solution is created
with stirrer.
(4) Then 0.3 gm of polymer powder was added in the vortex slowly.
(5) After 1 minute stirrer speed was reduced to 60-80 rpm and kept constant till the dissolution
was completed.
(6) The reactor is covered with aluminium foil and the solution was kept standstill overnight.
24



10.2 Experiment based on PHPA solution:-
10.2.1 Effect of Thiourea on the stability of PHPA solution:-
Readings are taken at 27
0
C and 70
0
C using Brookfield LVDV- II viscometer and 20 rpm is
selected as a standard for experimental purpose. For testing the polymer solution viscosity with
additive on Brookfield viscometer, separate 3 samples of solution each of 20 ml were taken in
which .02 gm of thiourea is added to prepare 1000 ppm solution.
Similarly, for 2000 ppm and 3000 ppm solution, .04 and .06 gms of thiourea was added
respectively. For testing, of Viscosity and Shear rate of PHPA we have used spindle number
S00.

Table 10.1: Effect of Thiourea concentration on PHPA stability at 27
0
C.

Aging time
(days)
Viscosity (cP)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 8.16 7.59 7.50 7.69
2 8.16 7.63 7.41 7.81
7 8.20 7.73 7.56 8.00
14 9.00 7.61 7.57 8.11
*All reading are strictly taken at 20 rpm.


Table 10.2: Effect of Thiourea concentration on PHPA stability at 70
0
C.

Aging time
(days)
Viscosity (cP)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 6.63 6.60 6.57 6.75
2 6.57 6.51 6.38 6.83
7 6.45 6.38 6.46 6.97
14 6.21 6.21 6.06 6.98
*All reading are strictly taken at 20 rpm.



25





Fig 10.1: Effect of Thiourea concentration on PHPA stability at 27
0
C..





Fig 10.2: Effect of Thiourea concentration on PHPA stability at 70
0
C.





26
6
6.5
7
7.5
8
8.5
9
9.5
10
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)


Aging time (days)

Effect of Thiourea on PHPA stability

0 ppm 1000 ppm 2000 ppm 3000 ppm
5.6
6.1
6.6
7.1
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging time (days)
Effect of Thiourea concentration on PHPA stability

0 ppm 1000 ppm 2000 ppm 3000 ppm



10.2.2 Effect of Shear rate on stability of PHPA solution with Thiourea:
The effect of different Shear rate on the polymer solution viscosity is studied using Brookfield
LVDV-II viscometer at 27
0
C and 70
0
C temperature.

Table 10.3: Effect of different Shear rates on PHPA stability with Thiourea at 27
0
C.

Aging time
(days)
Shear rate (sec-1)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 27.2 25.3 25.0 25.6
2 27.2 26.4 25.9 27.3
7 29.1 28.1 26.1 27.6
14 28.2 29.3 26.3 30.2
*All reading are strictly taken at 20 rpm.

Table 10.4: Effect of different Shear rates on PHPA stability with Thiourea at 70
0
C.

Aging time
(days)
Shear rate (sec-1)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 22.1 22.0 21.7 23.5
2 24.3 20.3 22.8 20.3
7 26.2 19.1 21.9 18.7
14 28.3 16.8 18.3 17.3
*All reading are strictly taken at 20 rpm.










27





Fig 10.3: Effect of different Shear rates on PHPA stability with Thiourea at 27
0
C.





Fig 10.4: Effect of different Shear rates on PHPA stability with Thiourea at 70
0
C.




28
24
26
28
30
32
1 2 7 14
S
h
e
a
r

r
a
t
e

(
s
e
c
-
1
)

Aging time (days)
Stability of PHPA solution with thiourea at different
shear rates

0 ppm 1000 ppm 2000 ppm 3000 ppm
15
17
19
21
23
25
27
29
1 2 7 14
S
h
a
e
r

r
a
t
e

(
s
e
c
-
1
)

Aginig time (days)

Stability of PHPA solution with thiourea at different
shear rates
0 ppm 1000 ppm 2000 ppm 3000 ppm




10.2.3 Effects of Sodium carbonate on stability on PHPA :
Readings are taken at 27
0
C and 70
0
C using Brookfield LVDV- II viscometer and 20 rpm is
selected as a standard for experimental purpose. For testing the polymer solution with additive
on Brookfield viscometer, separate 3 samples of solution each of 20 ml were taken in which .02
gm of sodium carbonate is added to prepare 1000 ppm solution.
Similarly, for 2000 ppm and 3000 ppm solution, .04 and .06 gms of sodium carbonate was
added respectively. For testing, of Viscosity and Shear rate of the PHPA we used spindle
number S00.

Table 10.5: Effect of Sodium Carbonate concentration on PHPA stability at 27
0
C.

Aging time
(days)
Viscosity (cP)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 8.16 7.32 7.61 7.81
2 8.16 7.09 7.28 7.69
7 8.20 6.96 7.02 7.86
14 9.00 7.61 7.45 8.11
*All reading are strictly taken at 20 rpm.


Table 10.6: Effect of Sodium Carbonate concentration on PHPA stability at 70
0
C.

Aging time
(days)
Viscosity (cP)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 6.63 5.32 5.21 5.29
2 6.57 5.16 5.01 4.89
7 6.45 5.14 4.74 4.98
14 6.21 4.76 4.98 5.49
*All reading are strictly taken at 20 rpm.
-


29





Fig 10.5: Effect of Sodium Carbonate concentration on PHPA stability at 27
0
C.





Fig 10.6: Effect of Sodium Carbonate concentration on PHPA stability at 70
0
C.





30
6
6.5
7
7.5
8
8.5
9
9.5
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging Time(days)
Effect of Sodium Carbonate conc. on PHPA
stability
0 ppm 1000 ppm 2000 ppm 3000 ppm
4
4.5
5
5.5
6
6.5
7
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging time (days)
Effect of Sodium Carbonate conc. on PHPA stability
0 ppm 1000 ppm 2000 ppm 3000 ppm



10.2.4 Effects of different Shear rates on the stability of PHPA solution with
Sodium Carbonate:
The effect of different Shear rate on the polymer solution viscosity is studied using Brookfield
LVDV-II viscometer at 27
0
C and 70
0
C temperature.

Table 10.7: Effect of different Shear rates on PHPA stability with Sodium Carbonate at
27
0
C.

Aging time
(days)
Shear rate (sec-1)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 27.2 38.2 39.6 46.3
2 27.2 39.1 38.2 45.6
7 29.1 41.8 32.1 46.7
14 28.2 48.8 40.1 49.9
*All reading are strictly taken at 20 rpm


Table 10.8: Effect of different Shear rates on PHPA stability with Sodium Carbonate at
70
0
C.

Aging time
(days)
Shear rate (sec-1)
0 ppm 1000 ppm 2000 ppm 3000 ppm
1 22.1 31.2 21.7 23.5
2 24.3 29.3 22.8 20.3
7 26.2 29.1 21.9 18.7
14 28.3 23.2 18.3 17.3
*All reading are strictly taken at 20 rpm






31






Fig 10.7: Effect of different Shear rates on PHPA stability with Sodium Carbonate at 27
0
C.






Fig 10.8: Effect of different Shear rates on PHPA stability with Sodium Carbonate at 70
0
C.



32
20
25
30
35
40
45
50
55
60
1 2 7 14
S
h
e
a
r

r
a
t
e

(
s
e
c
-
1
)

Aging time (days)
Stability of PHPA solution with sodium carbonate
at different shear rates

0 ppm 1000 ppm 2000 ppm 3000 ppm
20
25
30
35
40
45
50
1 2 7 14
S
h
e
a
r

r
a
t
e

(
s
e
c
-
1
)

Aging time (days)
Stability of PHPA solution with sodium carbonate
at different shear rates
0 ppm 1000 ppm 2000 ppm 3000 ppm



10.3 Preparation of Methylmethacrylate Acrylic acid Co-Polymer:
A 10:90 composition of MMA-Acrylic acid co-polymer is Prepared as follows:
(1) Inhibitor free MMA was obtained by washing with NaOH pellets and then with water.
(2) About 935 gm of water was taken into a reaction vessel with 31.3 gm of NaCl iwas added to
it to prepare brine solution.
(3) The reaction vessel was then kept in a reactor having an electric agitator used for constant
stirring.
(4) 324 gm of acrylic acid with 50 gm of MMA and 15 gm of potassium per sulphate is weighed
on electronic balance.
(5) A vortex of about 2/3
rd
of the solution was created and MMA, acrylic acid and potassium per
sulphate are added slowly in to the solution.
(6) An external heating medium was provided to heat the reactor for the quick dissolution of the
reactants.
(7) At 80
0
C a white viscous liquid (copolymer) is obtained. The heating was stopped and
stirring was continued till the temperature reaches 55
0
C.
(8) After the completion of reaction, the copolymer is divided into 7 equivalent samples for
viscosity testing with and without additives.
10.4 Variation in the Copolymer viscosity with the aging time:
There is a drastic change in the viscosity of the freshly prepared copolymer solution with aging
time. We have taken reading of viscosity at different rpms using Brookfield LVDV-II
viscometer but readings at 10 rpm are considered as standard due to the following two reasons:
(1) There is formation of agglomerates within the solution with the aging time.
(2) There is a formation of hydrogen bonding between the constituents in the solution which
leads to the saturation of the solution which results in very high viscosity.
.









33



Table 10.4.1 Observation was seen while preparing the Copolymer of MMA-Acrylic acid
Reaction
Time
(min)

Temperature
(
0
C)
Colour
of the
solution

Viscosity
(cP)
Initial
reaction
time

30

Transparent

Normal as of
water
After
15-20
Minutes

50-52

Whitish
transparent

Higher than
previous
solution
After
30-35
Minutes

60-62

Lime
yellowish

Much higher
than previous
solution
After
45- 50
Minutes

78-80

White turbid

Much higher
than previously
observed
solutions.

After completion of the reaction heating is stopped and the stirring is continued till the
temperature lowers down to 55 degrees and rpm is reduced. Viscosity of finally obtained
copolymer is similar to that of Fevicol
R
.
Table 10.9: Variation in viscosity of copolymer at different temperatures.

Aging time
(days)
Viscosity (cP)
At 27
0
C. At 70
0
C.
1 119.6 64.3
2 129.2 112.7
7 159.2 127.8
14 384.5 331.7


34





Fig 10.9: Variation in viscosity of copolymer at different temperatures.
10.5 Variation in Shear rate with the aging time of Copolymer:
The readings for shear rates are also taken at different rpm but 10 rpm is considered as the
standard one for testing due to the same reasons explained in the above section.

Table 10.10: Variation in Shear rates of copolymer at different temperature.

Aging time
(days)

Shear rate (sec-1)

At 27
0
C.

At 70
0
C.
1 14.0 10.7
2 15.7 11.7
7 40.3 27.5
14 64.2 55.3

10.6.1 Effect of Thiourea on the stability of copolymer:
Reading of viscosity of the copolymer is taken at 27
0
C and 70
0
C temperatures using Brookfield
LVDV-II viscometer, 20 rpm is taken as the standard for the experimental purpose. Additive
testing of copolymer was done by taking three samples of 200 ml each to determine the change
in viscosity at different concentration. For, 1000 ppm concentration solution, 0.2 gm of thiourea
was added to the freshly prepared copolymer solution.

35
0
50
100
150
200
250
300
350
400
450
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging time (days)
Change in Viscosity of Copolymer at different
temperatures with aging time

0 ppm at 27 degrees 0 ppm at 70 degrees



Similarly, for 2000 ppm and 3000 ppm solutions, 0.4 and 0.6 gms of thiourea was added
respectively. For testing, of Viscosity and Shear rate of the Copolymer with and without
additives we used spindle number S63

Table 10.11: Effect of Thiourea concentration on Copolymer stability at 27
0
C..
Aging time
(days)
Viscosity (cP)
1000 ppm 2000 ppm 3000 ppm
1 96.3 77.7 63.7
2 108.3 110.4 97.4
7 157.4 173.9 156.9
14 191.4 226.5 220.6
*All reading are taken strictly at 20 rpm.



Table 10.12: Effect of Thiourea concentration on Copolymer stability at 70
0
C.

Aging time
(days)
Viscosity (cP)
1000 ppm 2000 ppm 3000 ppm
1 67.8 63.7 50.3
2 87.0 90.0 69.2
7 121.3 131.7 120.7
14 147.3 141.0 152.3
*All reading are taken strictly at 20 rpm.










36




Fig 10.10: Variation in Shear rates of copolymer at different temperatures.


Fig 10.11: Effect of Thiourea concentration on Copolymer stability at 27
0
C.


Fig 10.12: Effect of Thiourea concentration on Copolymer stability at 70
0
C.
37
0
10
20
30
40
50
60
1 2 7 14
S
h
e
a
r

r
a
t
e

(
s
e
c
-
1
)

Aging time (days)
Variation in shear rates of the Copolymer at
different temperature with the aging time

0 ppm at 27 degrees 0 ppm at 70 degrees
50
100
150
200
250
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging Time (days)
Effect of Thiourea Conc. on Copolymer
Stability
1000 ppm 2000 ppm 3000 ppm
40
70
100
130
160
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging Time (days)
Effect of Thiourea Conc. on Copolymer
Stability
1000 ppm 2000 ppm 3000 ppm



10.6.2 Effect of Shear rate on the stability of Copolymer with Thiourea:
The effect of different Shear rate on the copolymer solution viscosity is studied using
Brookfield LVDV-II viscometer at 27
0
C and 70
0
C temperature.
Table 10.13: Effect of different Shear rates on Copolymer stability with Thiourea at 27
0
C.

Aging time
(days)
Shear rate (sec-1)
1000 ppm 2000 ppm 3000 ppm
1 32.1 25.9 19.7
2 36.1 36.8 29.2
7 50.3 55.9 50.7
14 63.8 75.5 73.3
*All reading are strictly taken at 20 rpm.

Table 10.14: Effect of different Shear rates on Copolymer stability with Thiourea at 70
0
C.

Aging time
(days)
Shear rate (sec-1)
1000 ppm 2000 ppm 3000 ppm
1 22.6 17.3 10.7
2 29.0 30.0 23.1
7 33.4 37.6 39.2
14 49.1 49.0 52.7
*All reading are strictly taken at 20 rpm.











38





Fig 10.13: Effect of different Shear rates on Copolymer stability with Thiourea at 27
0
C.



Fig 10.14: Effect of different Shear rates on Copolymer stability with Thiourea at 70
0
C.







39
10
20
30
40
50
60
70
80
90
100
1 2 7 14
S
h
e
a
r

R
a
t
e

(
s
e
c
-
1
)

Aging Time (days)
Stability of Copolymer with Thiourea at
different Shear rate
1000 ppm 2000 ppm 3000 ppm
0
10
20
30
40
50
60
1 2 7 14
S
h
e
a
r

R
a
t
e

(
s
e
c
-
1
)

Aging Time (days)
Stability of Copolymer with Thiourea at
different Shear rates
1000 ppm 2000 ppm 3000 ppm



10.6.3 Effect of Sodium Carbonate concentration on stability of Copolymer:
Additive testing of copolymer was done by taking three samples of 200 ml each to determine the
change in viscosity at different concentration. For, 1000 ppm concentration solution, 0.2 gm of
sodium carbonate was added to the freshly prepared copolymer solution.
Similarly, for 2000 ppm and 3000 ppm solutions, 0.4 and 0.6 gms of sodium carbonate was
added respectively. For testing, of Viscosity and Shear rate of Copolymer with and without
additives we have used spindle number S63.

Table 10.15: Effect of Sodium Carbonate concentration on Copolymer stability at 27
0
C.

Aging time
(days)
Viscosity (cP)
1000 ppm 2000 ppm 3000 ppm
1 96 68.9 66.7
2 117.3 97.5 101.7
7 172.6 144.0 133.8
14 223.7 198.0 184.9
*All reading are taken strictly at 20 rpm.

Table 10.16: Effect of Sodium Carbonate concentration on Copolymer stability at 70
0
C.

Aging time
(days)
Viscosity (cP)
1000 ppm 2000 ppm 3000 ppm
1 69.9 58.4 53.4
2 83.2 85.4 85.0
7 132.0 113.1 111.9
14 159.8 149.8 141.7
*All reading are taken strictly at 20 rpm.






40





Fig 10.15: Effect of Sodium Carbonate concentration on Copolymer stability at 27
0
C.





Fig 10.16: Effect of Sodium Carbonate concentration on Copolymer stability at 70
0
C.





41
50
100
150
200
250
300
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging Time (days)
Effect of Sodium Carbonate Conc. on Copolymer
Stability
1000 ppm 2000 ppm 3000 ppm
40
80
120
160
200
1 2 7 14
V
i
s
c
o
s
i
t
y

(
c
P
)

Aging Time (days)
Effect of Sodium Carbonate Conc. on Copolymer
Stability
1000 ppm 1000 ppm 2000 ppm 3000 ppm



10.6.4 Effect of Shear rate on the stability of Copolymer with Sodium
Carbonate:
The effect of different Shear rate on the copolymer solution viscosity is studied using
Brookfield LVDV-II viscometer at 27
0
C and 70
0
C temperature.

Table 10.17: Effect of Sodium Carbonate concentration on Copolymer stability at 27
0
C.

Aging time
(days)
Shear rate (sec-1)
1000 ppm 2000 ppm 3000 ppm
1 32.0 22.3 17.4
2 29.1 32.5 28.2
7 57.3 48.0 42.3
14 72.9 69.7 62.9
*All readings are taken strictly at 20 rpm.



Table 10.18 : Effect of Sodium Carbonate concentration on Copolymer stability at 70
0
C.

Aging time
(days)
Shear rate (sec-1)
1000 ppm 2000 ppm 3000 ppm
1 23.3 19.8 16.0
2 27.4 23.9 21.3
7 44.0 37.7 33.4
14 57.9 51.7 50.7
*All readings are taken strictly at 20 rpm.







42





Fig 10.17: Effect of Sodium Carbonate concentration on Copolymer stability at 27
0
C.





Fig 10.18 : Effect of Sodium Carbonate concentration on Copolymer stability at 70
0
C..





43
10
20
30
40
50
60
70
80
90
100
1 2 7 14
S
h
e
a
r

R
a
t
e

(
s
e
c
-
1
)

Aging Time (days)
Stability of Copolymer with Sodium Carbonate
at different Shear rates
1000 ppm 1000 ppm 2000 ppm 3000 ppm
10
25
40
55
70
85
1 2 7 14
S
h
e
a
r

r
a
t
e

(
s
e
c
-
1
)

Aging time (days)
Stability of Copolymer with Sodium Carbonate
at different Shear rates
1000 ppm 2000 ppm 3000 ppm



CHAPTER :- 11
OBSERVATION AND CONCLUSION
As a part of the project we performed different experimental work on Partially Hydrolysed
Polyacrylamide and MMA- Acrylic acid Copolymer to see the effect of various factors on
viscosity and thermal stability of high molecular weight commercially available PHPA
Flowpam 3630. Experiment were carried out to see effect of concentration, thiourea and
sodium carbonate on PHPA and Copolymer solution viscosity for about 14 days of time.
Sensitivity of PHPA and Copolymer to different additives such as thiourea and sodium
carbonate were determine at about 28 and 70 degrees temperature.
Because it is sensitive to high shear, temperature and salinity it looses its initial viscosity before
and after injecting into the reservoir. To enhance the PHPA and Copolymer viscosity in al
above conditions we designed the experiment to improve the viscosity and effect of different
chemicals on PHPA and Copolymer solution viscosity such as thiourea and sodium carbonate
and room and elevated temperature.
The following are the observations where found out during our experimental work :
11.1 Effects of additives on PHPA solution :
- 1. Effect of Thiourea on PHPA solution :
(1) At room temperature it has been found that there is negligible increase in viscosity of
PHPA solution with respect to aging time, but with addition of thiourea the viscosity change is
appreciable and it increases with increase in concentration.
(2) At the room temperature it has been found that the shear rate is initially increasing
but it decreases with aging time, but opposite is true for thiourea
(3) At higher temperature the viscosity of both PHPA and thiourea additive decreases
but shear rate at this temperature for PHPA constantly increases while thiourea additive it
decreases constantly for all concentrations.
- 2. Effect of Sodium Carbonate on PHPA solution :
(1) Viscosity of PHPA solution with sodium carbonate as an additive increases for all
concentrations at both room and higher temperature.
(2) While Shear Rate for sodium carbonate additive for room temperature first decreases
and then increases rapidly, and for higher temperature it shows constant decrease in Shear Rate.




44



11.2 Effects of additives on Copolymer solutions:
(1) The viscosity of thiourea additive increases rapidly with aging time but the viscosity
increase is less at higher temperature.
(2) The Shear Rate while increases in both cases but the increase is higher at higher
temperature.
The following are the conclusions we made after the completion of our experimental work:
11.3 CONCLUSION:
(1) The change in viscosity of PHPA with compare to the copolymer is negligible i.e the
increase in viscosity of the copolymer is very rapid.
(2) The viscosity change with sodium carbonate additive is greater than thiourea additive in
PHPA solution.
(3) While for copolymer solution the viscosity change with thiourea is greater than sodium
carbonate.
(4) Large number of agglomerates where found in the copolymer solution with respect to aging
time.
(5) Practically the copolymer tested cannot be used for the actual field work because of its
higher viscosity and because of the agglomerates developed within the solution with aging
time.















45



REFERENCES
1. Littmann W., Development in petroleum science- Polymer flooding, Vol. 24,
Elesevier science Publisher, B.V, 1988.
2. Sorbie Kenneth S., Polymer Improved Oil Recovery, 1
st
edition, Blackie and
sons ltd, New York, 1991.
3. Ronald E. Terry, Brigham Young University, Enhanced Oil Recovery, In
Encyclopedia of Physical Science and Technology, 3
rd
Edition, Vol. 18, Robert
A. Mayers Ed., Academic press (2001) pp 503-518.
4. Lake Larry W., Enhanced Oil Recovery, University of Texas at Austin,
Prentice Hall Publications.
5. F.R Wassmuth Alberta Research Council, W. Arnold Pen growth Corporation, K.
Green Alberta Research Council, N. Cameron Pen growth Corporation Polymer
Flood Application In Heavy Oil Recovery At East Bodo, Paper 2007-184.
6. R.L Jewett, SPE-AIME, The Dow Chemical Corporation and G.F Schum, SPE-
AMIE, The Dow Chemical Corporation Polymer Flooding A current
Appraisal, Paper June 1970-2545.
7. Jain Adarsh Kumar, Dr. A.K Dhawan, SPE and Misra T.R, ONGC India SPE
153667,ASP flood pilot in Jhalora (K-IV) A case study, SPE Oil and Gas India
Conference and Exhibition held in Mumbai, India, 28-30 March 2012.
8. Improving Oil Recovery (IOR) with Polymer Flooding in A Heavy-Oil River Channel
Sandstone Reservoir by Von der Fakultt fr Geowissenschaften, Geotechnikund
Bergbau der Technischen Universitt Bergakademie Freiberg Genehmigte.
9.BROOKFIELD DV-II+ Pro Programmable Viscometer operating instructions
and manual.
10. www.wikipedia.com/wiki/Enhanced_oil_recovery
11. www.onepetro.org/polymer flooding
12. www.polymerflooding.com/polymer_flooding


46



13. www.sciencedirect.com/science/article/pii/S0079670011000682
14. www.webdoc.sub.gwdg.de/ebook/serien/aa/Freiberger_Diss_Online/183.pdf
15. www.opec.org/opec_web/en/data_graphs/330.html
16. www.wikipedia.org/wiki/oil_reserves
17. www.ify.valuewalk.com/wp-content/uploads/2012/03/31.bmp
























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