S

SPE 1556
653

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D
Developmment of New
N Polym
mers withh Better P
Performance unde
er Condittions
o
of High Temperatuure and High
H Salin
nity
Y
Yongfu Wu, SP
PE; Amir Mahm
moudkhani, SPE
E; Philip Watso
on, SPE; Thom as Fenderson, SPE; Mohan Nair, SPE; Kemira

C
Copyright 2012, Society
y of Petroleum Enginee
ers

T
This paper was prepare
ed for presentation at the SPE EOR Conferen
nce at Oil and Gas We
est Asia held in Muscatt, Oman, 16–18 April 2
2012.

T
This paper was selected for presentation by an a SPE program comm mittee following review of information containned in an abstract submmitted by the author(s)). Contents of the papeer have not been
re
eviewed by the Society y of Petroleum Engine eers and are subject to o correction by the autthor(s). The material ddoes not necessarily reeflect any position of the Society of Petroleu
um Engineers, its
officers, or members. Electronic
E reproductionn, distribution, or stora
age of any part of thiss paper without the wrritten consent of the S Society of Petroleum E Engineers is prohibite
ed. Permission to
re
eproduce in print is res
stricted to an abstract of
o not more than 300 words;
w illustrations mayy not be copied. The abbstract must contain co
onspicuous acknowled dgment of SPE copyrig ght.

A
Abstract
IIt is estimated that
t about 7,00 00 billion barreels of oil will remain
r in reserrvoirs after prooduction by connventional metthods. This
vvalue is the taarget for Enhaanced Oil Reccovery (EOR) techniques. T The purpose off the water-sooluble polymerrs in EOR
aapplication is to enhance th he rheologicall properties off the displacinng fluids. These polymers have been suuccessfully
immplemented in n China’s oilfiields. Given thhe harsh condiitions present iin most oil resservoirs, new pproblems and challenges
aarise with the use of such polymers. Currrently partiallly hydrolyzed polyacrylamiides (HPAMs)) are the majoor class of
ppolymers used for chemical EOR applicatiion. However, due to the hiigh flexibility of HPAM chaain in aqueouss solutions,
pparticularly at high
h temperatuure (HT) and ata high salinity (HS), the mollecular chains begin to fold iirreversibly ressulting in a
ssignificant losss in viscosity. In this paper, we are reportiing a bench-sccale developm ment of new PA AM-based polyymers with
immproved perfo ormance in HS SHT conditionss. The new pollymers were evvaluated condiitions for their viscosity perfo formance at
vvarious temperratures and sallinities. The polymers
p weree dissolved at different conccentrations in brines with T TDS (Total
DDissolved Solid ds) of 34,655 ppm
p and 180,00 00 ppm. Visco osity measured at room tempeerature is in thee range of 30 too 120 cP at
thhe shear rate of
o 6 RPM. Aftter aging at 90 0 °C and 120 °C ° for six monnths under ultraalow oxygen llevel (< 5 ppb)), viscosity
rremains relativvely stable forr some polymeers while show w a decline fo
for others. Com mpared with tthe conventionnal HPAM
ppolymers, thesee new polymerrs have much better stability at a HTHS condiitions.

Introduction
PPolymer floodiing is the technnology wherein n high molecullar weight, waater-soluble pollymers are addded to the injecction water
inn order to incrrease the visco water and the ccrude oil to be displaced.
osity and to reeduce the mobility ratio of thhe injection w
CCompared with h secondary water
w flooding, polymer flooding has beenn found to signnificantly acceelerate the process of oil
rrecovery and immprove econom mic efficiency of chemical fllooding. In adddition, equipmeent is relativelyy simple and aavailable at
loower cost. To date, various polymers
p are used for floodin
ng. They includde synthetic poolymers, modiffied natural pollymers and
bbiological polyymers. Due to low thermal stability of th he modified naatural polymerrs and the higgh cost of the biological
ppolymers, theirr applications in
i large scale have
h been limiited. Hydrolyzeed polyacrylam mides (HPAMss) are syntheticc polymers
thhat are widely used for chemmical flooding.

PPolymers main nly used for flo

ooding are partiially hydrolyzeed polyacrylam mide (HPAM) and their derivvatives. HPAM M possesses
thhe following properties:
p stro
ongly hydroph hilic, easy to form
f hydrogenn bonds with w water moleculles and therefofore readily
ssoluble in wateer, large hydroodynamic volu ume in water that
t greatly enh
nhances its visccosity; the chaarges introduceed into the
mmolecules increease the electriical repulsion between
b the molecular
m chainns that causes m
molecular chaiin stretching. A
As a result,
eeven a greater hydrodynamicc volume in water can be ob btained. Due too the high flexxibility of the H
HPAM chain in aqueous
ssolution at highh temperature and high salin nity, there will be random/cooil conformatioon of the moleecules, which rresults in a
ssignificant loss in the viscositty. In recent yeears, much globbal research haas been focuseed on the devellopment of new w polymers
wwith high perfoormance in high a high saliniity, and some pprogress has beeen made.[1-10]
h temperature and
2 SPE 155653

Once a polymer solution is injected into the reservoir, it will impact the reservoir in two ways: (1) Increasing the viscosity of
water phase; (2) Increasing polymer retention in the oil strata caused by the reduced permeability. These are accomplished by
two mechanisms: one is the control of water-phase flow in the water injected section, by which the water-oil mobility ratio
and the actual flooding efficiency can be improved; the other is the reduction of water penetration into the flooded section of
the total fluid layer. Water-line movement speed is much lower in the oil layer segment with low permeability than the layer
with high permeability. Adjusting the water injection profile can increase the actual sweep efficiency. A higher viscosity in
the water phase will cause a greater residual resistance coefficient, a lower movement speed of the water phase (driving
phase) and a lower mobility ratio between water (driving phase) and oil phase (driven phase). All these allow higher oil

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recovery from both the larger reservoir volume swept and higher displacement efficiency of oil with polymer fluids.
Basically, flooding polymers should have the following features:
1) Water solubility: This is the first requirement polymers need to meet for flooding application. Water solubility is
achieved through the formation of hydrogen bonds between the polymer side groups and the polar water molecules.
For most oilfield applications, the dry polymers have to be dissolved in water or brine solution on site. Therefore
any superamolecular association, microgel formations and insoluble contents during the dissolution process can
reduce the injection performance and cause formation damage.
2) Molecular weight: Polymers for flooding should have a molecular weight in the range of 10 – 25 million Daltons.
3) Chain distribution: The polymers should have different chains with various molecular weights. They usually are
mixtures of homologous polymers with different molecular weights.
4) Geometry diversification: The polymers should have various molecular geometries. They include linear, branched
and body types.
5) Viscoelasticity: The polymer solution should have viscoelasticity when it is injected and transported through porous
media. The polymer molecular chains can stretch out to touch the unswept oil and bring back the residual oil when
the molecular chains contract to the original size. In this way, the displacement efficiency can be further improved.
6) Viscosity build-up efficiency: The polymers should be highly effective on viscosity build-up. That means even at
very low concentration, the polymer can quickly dissolve in water or brine solution and produce high enough
viscosity, specially, in high salinity brine.
7) Chemical and mechanical stability: Polymer solution will penetrate, migrate and propagate in the porous media
under reservoirs conditions, and eventually come out of the ground with the produced water; therefore polymers
should also have excellent properties such as viscoelasticity, filtration, chemical and mechanical stability. Since the
polymer flooding needs a relatively long time for response and pay back, typically about six months or longer, it is
required that the polymer solutions remain effective and stable for a long period of time. They should be compatible
with formation water, reservoir rocks and clay minerals, and be stable to shear, chemical additives, high temperature
and biological activity.
8) Environmental protection: The polymers should be non-toxic and meet all local/regional environmental regulations.

Design New Polymer Molecules for Flooding at High Temperature and High Salinity
HPAM solutions rapidly lose their viscosity at high temperatures and high salinity which limits their application for polymer
flooding. Therefore new polymer products with enhanced performance must be developed to meet the requirements for harsh
reservoir conditions.[11-17]

In general, there are two major reasons for loss of polymer solution viscosity under reservoir conditions:
1) Polyacrylamide can lose molecular weight through hydrolysis and mechanical degradation during pumping and
injection.
2) Interactions with various ions in formation water result in a change of macromolecular conformation. Solubility of
water-soluble polymer under HTHS conditions depends on their molecular nature. For non-ionic polymers, the
salinity has little effect on their water solubility, but for ionic polymers, solubility is very sensitive to the ionic
strength of the aqueous phase. At high salt concentrations, solubility of ionic polymers decreases rapidly, and phase
separation may take place. Many water-soluble polymer products are commercially available with different salt
tolerance and temperature resistance. But only a few products can satisfy requirements of HTHS conditions.

The following approaches may be tried to make new polymers with better stability under HTHS conditions:

Introduction of Ring Structure

The main chain or backbone of a polymer plays a key role in thermal stability. From the perspective of molecular design,
increasing molecular rigidity by introducing a rigid ring to the structure can effectively improve the thermal stability of
polymers.[18-23]
SPE 155653 3

Introduction of Large Side Group or Rigid Side Group

Polymers with large side groups demonstrate high thermal stability and can maintain a high viscosity at high temperatures.
Even during the aging process where the polymer suffers from breakage of molecular chains, the solution viscosity may
decrease very little. This is due to the steric effect of the rigid groups in the molecules that prevents molecules from
coiling/folding. Many monomers can provide large side groups or rigid side groups, e.g. styrene sulfonic acid, n-alkyl
maleimide, acrylamide-based long-chain alkyl acid, 3- acrylamide- 3- methyl butyric acid and more.[24-29]

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Introduction of Salt-tolerant Group
The carboxyl group in HPAMs can easily react with Ca2+, Mg2+ ions in solution and to form precipitate, resulting in a phase
separation or formation damage. If -SO3H groups can be introduced to acrylamide, the copolymer will exhibit both good
thermal stability and higher tolerance with divalent and multivalent metal ions. There are also many monomers containing
sulfonic acid group, e.g. vinyl sulfonic acid, allyl sulfonic acid, 2- acrylamido-2-methyl propane sulfonic acid (AMPS), etc.,
of which AMPS has been used most widely. The large side-chain group in AMPS molecules can increase the steric hindrance
and reduce hydrolysis significantly. In addition, -SO3H group is a strong polar group and its strong hydrophilic interaction
and electrostatic repulsion increase water solubility of the copolymers and the fluid volume of the molecular chain.

McCormick and Salazar synthesized a type of MPS/AM copolymer with high molecular weight and high linear regularity.[30]
It was determined that copolymer has good performance in viscosity build-up and excellent resistance to high salinity.
However, due to hydrolysis of amide group at elevated temperatures, this MPS/AM copolymer is only stable at temperatures
up to 93 °C. Song and co-workers synthesized copolymers of AM-N,N-dimethyl acrylamide (DMAM)-AMPS and
experimental results indicated that this type copolymer may have good heat resistance and anti-aging performance.[31]

Introduction of Hydrolysis-resistant Group

The reason for viscosity decrease of HPAM in saline water is partially due to the dissociation of its carboxylic acid group
being suppressed at high ionic strength. If a group with strong dissociative ability in salt solutions can be introduced to the
polymer molecule, dynamic properties of polymer can be improved. The new water-soluble copolymers with excellent
performance of temperature and salt resistance can be synthesized by the use of AM monomers and other monomers which
resist hydrolysis.[32-34] Currently, 2-acrylamido-2-methyl propane sulfonic acid (AMPBS) and AM have been used for
synthesis of high molecular weight copolymer with excellent performance under HSHT conditions. Several industrial
applications have been reported for this new polymer.

Introduction of the Groups that can Inhibit Hydrolysis of Amide

Usually hydrolysis of the amide group on the molecular chain is one of the reasons for lower polymer stability at high
temperatures. Thermal stability of the HPAM polymers may be improved by introduction of the groups that can inhibit
hydrolysis of amide. It has been reported that N-vinyl-2-pyrrolidone (NVP) can inhibit hydrolysis of amide in aqueous
solutions and thus improve polymer thermal stability. The stability can be further improved by incorporating AMPS into the
monomers.[35-37]

Introduction of Hydrophobic Groups

Another effective way to improve polymer salt tolerance and thermal stability is by increasing polymer hydrophobic
interaction by introducing hydrophobic groups into the molecular chains. Polymers with hydrophobic groups exhibit similar
viscosities in fresh and saline waters. Available hydrophobic monomers are acrylic acid dodecyl ester, N-alkyl (C6 or more
alkyl) acrylamide, styrene, etc.

Experimental Procedures

Polymer Samples
More than 10 different polymer samples were tested in this study. Results from representative polymers are presented here.
All the polymers were synthesized in laboratory scale by polymerization of acrylamide with one or more monomers such as
sodium 2-acrylamido-2-ethyl sulfonate(Na-AMPS), N-vinyl pyrrolidone(N-VP), sodium 3-acrylamide 3-methyl butyrate
(Na-AMB), N-vinyl amide (N-VAM).

Brines
The low salt brine has a total dissolved solids (TDS) of 34,655 mg/L and relative high hardness. The high salinity brine has a
TDS of 180,000 mg/L, with relatively high hardness of 14,558 mg/L Ca2+ and 3,253 mg/L of Mg2+. Recipes for the brines in
the test program are given below in Tables 1-3.
4 S
SPE 155653

TThermal Stabiliity Test

TThermal stabiliity test was con
nducted at 90 ºC
º and 120 ºC.. An importantt part of the exxperimental proocedure is to exclude any
ddissolved oxyg
gen. A glove box b was used forf handling thhe solutions in an oxygen free atmosphere. Great care was taken to
olutions be lesss than 5 ppb ((parts per billiion). After preeparing the
hhave the dissollved oxygen leevels in the teest polymer so
ppolymer solutio
ons, they were dispensed intoo 20-25 glass am
mpoules and seealed as shownn in Figure 1.

TThe sealed amp poules were weeighed using an n analytical baalance to 0.000 1 grams, and th then were placeed in an oven aand aged at

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thhe given temperature. The focus
f has been on testing at 90 9 ºC, but we hhave conducteed thermal aginng tests successsfully with
ssome samples at a 120 ºC with no significantt leakage or breakage problem ms. [4] After sppecified aging ttimes, each am
mpoule was
taaken out of thee oven and coool to room tem mperature. Thiss ampoule wass reweighed to confirm there has been no leeakage and
ssolvent escape. If the weight loss
l was aboutt 0.001 grams or o more, there was possible leakage and thee ampoule wass discarded.
IIn that case anoother ampoulee would be useed for a post-ag ging viscosity measurement. If there was no leakage, thhe ampoule
wwas transferredd to the glove box
b purged and d filled with nittrogen gas. Insside the glove bbox, an ampouule was broken open at its
toop and the tipp of the Chemeet® chemical teesting tube waas immersed inn its polymer solution. Wheen the tube tipp is broken
oopen, it takes up
u some polym mer sample. Th he change in co olor of the indiicator solutionn in the tube prrovides a measuurement of
thhe dissolved oxxygen level. Typically
T the dissolved oxygeen level is show wn to be 5 ppbb or less for aboout 90% of thee ampoules.
FFor those casess where the diissolved oxygeen was greaterr than 20 ppb, the results shhow a net reduuction in viscoosity. More
ccertainly for tho
ose cases wherre the dissolved d oxygen is 30 0 ppb or higherr, this has an addverse reactionn on the polymmer solution
vviscosity for the products usedd in this evaluaation and viscoosity results weere not to be taaken.

TThe solution th
hen was taken from
f the glovee box and the viscosity
v was mmeasured at 25 ºC with the Brrookfield viscoometer at 3
oor more shear rates.
r The visccosity at 6 and 30 RPM were used as the ba sis of comparisson before andd after thermal aging. The
innitial concentrration of the poolymer solutions were selectted such that thhey would inittially generate a solution visccosity near
220 cp at 90 ºC at
a 6 RPM rotattion with a #18 8 spindle on thee Brookfield viiscometer.

Figure 1. Manifold
M to purge dissolved O2 in polymer brine so
olution.

SScreen Factor Test

T
SScreen factor (S SF) measurem ments are widelyy used in the petroleum
p induustry to charactterize polymer solution.[38] SF
F measures
thhe elongationaal viscosity of a polymer sollution, which is i related to a transition in tthe conformatiion of a flexible polymer
mmolecule, such h as PAM, from m a coiled to a stretched staate. It is generrally agreed thhat SF is muchh more sensitivve than the
inntrinsic viscossity to a differeence in molecu
ular weight, M,
M and molecullar weight disttribution (MW WD). A screen viscometer
wwas used for SF F measurementt as shown in Figure
F 2.
S
SPE 155653 5

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Figure 2. Scre
een viscometer to
o measure polym
mer solution scre
een factor.

FFilterability Teest
TThis test metho od is recommended by API (American
( Petrroleum Institutte) RP 63.[39] A 600 mL presssurized cell annd a 5 μ m
mmembrane filteer are used to measure
m variatiions in solution
n filterability ddue to non-disssolved solids aas shown in Figgure 3. The
ffilterability will be evaluated by the filter raatio (FR):

(1)

w ms of the solutiion, respectively.

where, t100 , t2000 , t400 and t500 , are the time reequired to filter 100, 200, 4000 and 500 gram

Figure 3. Filterability test method recomm

mended by API R
RP 63.
6 S
SPE 155653

Table 1. Compositions
C s and Recipe for Low Salt Brine

Salt M.W.
M mg/L Ions mg
g/L
+
NaCl 58.5
5 24,000 Total Na 10,7
736
2+
KCl 74.5
7 740 Ca 414
2+
Na2SO4 14
42.0 4,010 Mg 1,303
+
CaCl2⋅2H2O 47.0
14 1,520 K 38
87

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2-
MgCl2⋅6H2O 20
03.3 10,900 SO4 2,711
-
Total Cl 19,1
105
pH Adjusted to 7.0 TDS 34,6
655

Table 2. Compositions
s and Recipe for High Saltt Brine

Salt M.W.
M mg/L Ions mg
g/L
+
NaCl 58.5
5 126,500 Total Na 49,8
848
2+
KCl 74.5
7 0 Ca 14,5
558
2+
Na2SO4 14
42.0 350 Mg 3,253
+
CaCl2⋅2H2O 14
47.0 53,500 K 0
2-
MgCl2⋅6H2O 20
03.3 27,200 SO4 23
37
-
Total Cl 112,104
pH Adjusted to 7.0 TDS 180,000

Table
T 3. Expe
erimental Con
nditions for the
e New HTHS Polymers
Brine Salinity
Temperature
Low Salt Brine Low Sallt Brine
25 °C √ √
90 °C √ √
120 °C √ √

MMechanical Deegradation Test

TTo test effect of
o mechanical degradation on n a polymer so olution that maay be caused
bby pumping an nd handling th he solutions inn laboratory an nd oilfield. Thhe apparatus
rrecommended by b API is shown in Figure 4. 4 [40] In our laaboratory test, mechanical
ddegradation off the new poly ymers has been n determined by b measuring the solution
vviscosity and the
t screen facttor before and after the sheaar degradationn at different
sshear rate, whicch can be calcu
ulated by the eq
quation below::

4
(2)

wwhere, Q = flo ow rate, cm3/secc; R = inside raadius of capillaary, cm. It shoould be

nnoted that this calculation
c assumes a fluid density of 1.0 grram/cm3. For m most
ppurpose, e. g., brine
b with low salinity, this approximation
a is
i acceptable.

Fiigure 4. Mechan nical degradation

n test by
capillaryy shear method.
S
SPE 155653 7

R
Results and Discussion
D

PPolymer Therm mal Stability att 90 ºC and 12 20 ºC: Figures 5-8 show the detailed plotss of the polymer viscosity veersus aging
tiime at 90 ºC and
a for some caases also at 12 20 ºC and in loow salt and higgh brines. Recall that the proocedure is to mmeasure the
vviscosity of theese samples at 6 and 30 RPM M at 25 ºC. Th hese viscosity measurementss were perform med for polymeer solutions
wwhen made up initially and th hen measured again
a for sealeed ampoule sammples as they w were removed after their aginng times at
thhe test temperaature. Samplees were allowed d to cool beforre measuring thhe solution visscosity again aat 25 ºC. A bettter thermal
sstability is indiicated by a staable viscosity for
f a longer peeriod of aging time. As an exxample, Figuree 5 shows thatt the initial

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vviscosity of Po olymer A in lo i 116 cp at 6 rpm shear raate, after agingg at 90 °C forr 180 days, the viscosity
ow salt brine is
ddecreases sligh htly to 105 cp. The initial viscosities
v are retained moree than 90%. T This shows in some cases thhe solution
vviscosity remaiins fairly constant, even with an extended period of aging at 90 ºC.

Figure 5. Visc
cosity in low salt brine vs. aging tiime (90 °C) Figure
e 6. Viscosity in low salt brine vss. aging time (120
0 °C)

Figure 7. Visco
osity in high salt brine vs. aging time
t (90 °C) Figure 8. Viscosity in h
high salt brine vs. aging time (120
0 °C)

FFor further investigation of th

he thermal stab bility of the po
olymers, experriments were cconducted at 1220 ºC, and the results are
sshown in Figs. 6 and 8. In loww salt brine, alll the polymer show
s fairly stab
able behavior, aalso exhibit thee same trends aas in 90 ºC.
BBut the viscosity is much lowwer. Figure 8 shows that therrmal stability oof the polymerss in high salt bbrine at 120 °C C. It can be
ffound that visco
osity of the polymers decreasses rapidly oveer a period of 660 days except for Polymer D D. However, it always has
a lowest viscossity in differentt brine. It meanns that Polymeer D has good stability in higgh temperaturee and high salinnity, but its
pperformance off increasing briine viscosity iss poor.

AAs expected, thhe viscosity an

nd thermal stab bility are muchh better in the low salt brinee than that for high salt brinee. In some
ccases there is observed
o a whiite precipitate or
o gel at the bo ampoules. One explanation foor the observattions could
ottom of the am
bbe, for example, that a calciu
um-polymer prrecipitate form ms and therebyy reduces soluttion viscosity bby reducing thhe apparent
ppolymer concen ntration. There could be also o another compplementary meechanism of fuurther hydrolysis of amide grooups in the
ppolymer chain to carboxylatee functionalitiees that is accelerated by tem mperature. Ann increase in caarboxylate grooups would
inncrease the prrobability of the
t formation of a calcium-polymer preciipitate. These mechanisms cconcern the reeduction in
8 S
SPE 155653

ssolution viscosity due to the reduction

r in thhe total polymeer concentratioon remaining inn the brine soluution. Of courrse another
eexpected mech hanism for losss of solution viscosity is the longer polym mer chains splittting apart andd effectively reeducing the
aaverage molecu ular weight off the polymer. That is, one long polymer chain that deggrades into several smaller ppieces will
eexhibit a reduceed solution viscosity, even iff none of the po
olymer pieces aare removed frrom solution.

FFilterability Reesults: Filterability curves an

nd the calculateed filter ratio (F
FR) for the 4 ppolymers are sshown in Fig 9 and listed
inn Table 4. Filltration ratio of the polymer samples is bettween 1.0 and 2.0, indicatingg the insolublee contents of thhe polymer
aare fairly low and
a filtration peerformance is acceptable
a to oilfield
o applicaation, which wiill not cause foormation damaage. For the

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ffour samples, Polymer
P C has best performaance in the filtrration test bec ause its filtratiion ratio is 1.00, while Polym
mer A has a
ffiltration ratio close
c to 2 and it
i took much loonger time than n other polymeers to get 500 ggrams of fluid tthrough the filtter.

Figure 9.
9 Filtration curv
ves of the polyme
ers through 5 µm
m filter and underr pressure of 20 p
psi.

Table 4. Filterability
F Re
esults of New
w Polymer Sam
mples

Polymer Sam
mple t5000 (min) t 400(min) t 2000(min) t 100(min) FR
R500
Polymer A 91.5
9 72.5
7 37.0 17.6 1
1.0
Polymer B 101.5 77.0
7 38.5 23.2 1
1.6
Polymer C 126.0 94.5
9 4
45.0 23.2 1
1.4
Polymer D 154.5 108.0 4
49.5 25.5 1
1.9

MMechanical Deegradation Ressults: As descrribed in previo ous part of thiss paper, mechaanical degradattion of the new w polymers
hhas been determmined by visco osity and screeen factor of thee solutions beffore and after tthe shear degraadation at diffferent shear
rrate. A decreasee of the viscosity and screen factor indicatees a degradationn of the polym
mer molecules ccaused by the m mechanical
eeffect. The resu
ults for the fourr polymers are listed in Tablee 5 and shown in Figure 10.

Figure 10. Viscosity

V retention of the polymerr solutions after sshear degradatio
on at different she
ear rate.
SPE 155653 9

Table 5. Experimental Results of Shear Degradation for the New Polymers

Solution Collected Final Solution Properties

Polymer Pressure Flow Rate Shear Rate
-1
Sample (psi) (g/sec) (sec )
Viscosity Screen
gram sec
(cP) Factor

0 (initial) ‒ ‒ ‒ ‒ 116 52.4

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50 32.43 6.50 4.99 24820 104 48.6
Polymer A
100 37.90 5.28 7.17 35703 89 46.4
150 54.57 6.45 8.46 42080 75 42.2
200 47.69 4.88 9.77 48609 57 39.8
0 (initial) ‒ ‒ ‒ ‒ 95 48.6
50 38.65 7.55 5.12 25467 86 45.4
Polymer B
100 44.28 5.96 7.43 36957 74 41.7
150 56.47 6.51 8.67 43124 64 39.4
200 55.86 5.35 10.45 51978 46 35.9
0 (initial) ‒ ‒ ‒ ‒ 65 51.7
50 45.62 6.77 6.87 34171 60 42.3
Polymer C
100 54.45 6.44 8.46 42080 53 38.6
150 61.28 5.85 10.47 52078 47 36.9
200 62.48 4.95 12.61 62722 42 33.4
0 (initial) ‒ ‒ ‒ ‒ 38 57.5
50 46.74 5.32 8.78 43671 33 41.0
Polymer D
100 58.85 5.57 10.56 52525 25 34.5
150 75.79 5.91 12.83 53868 20 25.8
200 81.48 5.20 15.66 77893 15 19.4

In Figure 10, it can be found that the polyacrylamide based polymers are sensitive to mechanical degradation. The effect of
shear degradation on the polymer performance can be evaluated by the viscosity retention percentage (η /η0×100%) after
degradation at different shear rates. At shear rate of 50,000 sec-1, Polymers A and B can only maintain about 48% of their
initial viscosity (η0); Polymer C can maintain 76% of the initial viscosity; Polymer D can maintain about 70% of the initial
viscosity. Even at very high shear rate 80,000 sec-1, Polymer D can still maintain about 40% of its initial viscosity. However,
viscosity of Polymer D solution is generally lower than the others as listed in Table 6.

Conclusions:
1) There are several different approaches to design and synthesize new polymers for better performance at higher
temperature and in high salinity brines. A successful design of new water-soluble polymers or modification of PAM-
based polymers for application under these conditions requires multidisciplinary approach. Therefore, knowledge of
polymer molecular structure must be conceptually linked to the desired product performance requirements.
2) For the four new polymers developed for EOR application under the HTHS conditions, Polymers A and B show better
performance of thermal stability than Polymers C and D at 90 °C and in low salt brine. But at 120 °C and in high salt
brine, Polymer D is the most stable sample. As to filtration and shear degradation test results, Polymer C and D are better
than Polymer A and B. Particularly Polymer D has very good performance of filtration and shear degradation. But its
viscosity is the lowest compared with the other polymer samples.
3) The effect of external parameters such as temperature, salinity, pressure, shear rate on polymer rheological behavior
must be correlated with a comprehensive understanding of the relationship between the chemical structure and
architecture of the polymer and the rheological behavior. A comprehensive study of new polymers for EOR application
should include the effect of temperature, salinity, pressure and mechanical degradation on their rheological properties.
The other parameters like screen factor and filtration ratio should be also determined.
10 SPE 155653

4) There are many different water-soluble polymers capable of increasing the solution viscosity, it is important to be aware
of their differences and similarities. For example, on a molecular level the fundamental is indeed quite general: the
presence of relatively weak inter-molecular interactions, e. g. hydrophobic association and hydrogen bonding, will
increase the molecular weight of the polymer chains. As a result, the solution viscosity will increase. However, an
excessively strong interaction might compromise solubility of the system by leading to gel formation.

Acknowledgements

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The authors are grateful to the management of Kemira Chemicals Inc. for permission to publish this work.

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