Chapter 2 Literature Review -...

Chapter 2 Literature Review

5

CHAPTER 2

LITERATURE REVIEW

The challenges associated with matured oilfields as well as different polymer gel systems

are reviewed with particular emphasis on their application to improve sweep efficiency

through profile modification during enhanced oil recovery processes The cross-linked

polymer gels have great potential for the use in permeability reduction fluid control and

profile modification This review includes gel formation and gelation mechanism models

for rheological and gelation behavior for polymer gel systems development of different gel

systems using different cross-linkers selection criteria of wells for gel treatment and

designing of job for oil field application

21 CHALLENGES ASSOCIATED WITH MATURED OIL FIELDS AND THEIR

CONTROL

The enhanced oil recovery processes like water flooding polymer flooding (Needham and

Doe 1987 Sohn et al 1990 El-Hadidi et al 1997 Norris et al 2013) foam flooding

(Miller et al 1994) alkaline-surfactant-polymer and alkali flooding etc are used for the

mature oil fields (Baojun et al 2004 Ma et al 2007 Benson et al 2007 Thorne et al

2010) In these processes some kind of fluid is injected to push the oil from the injection

well toward the producer Water and gases are the most commonly used displacing fluids in

this process Water flood is the most common practice of secondary oil recovery techniques

(Dalrymple et al 1994 Zheng et al 2002 Tang et al 2004) Injection of carbon dioxide

or other gases is also a common practice to improve oil recovery efficiency (Sydansk and

Reichman 1996) Regardless of the type of the fluid used to displace the oil the displacing

fluid could bypass the oil and early breakthrough could occur In the case of water flood

the water oil ratio could become so high that the process ceases to be economical any more

(Jordan et al 1982) For injection of CO2 or other gases the high gasoil ratio renders the

process uneconomical (Modesto et al 2009)


6

The major problem associated with matured oil fields during enhanced oil oil recovery

process is channelling of injected fluid (gas and water) through high permeability zones

fractures and fracture network in the reservoir In this situation injected fluid starts to move

towards producing well and oil along with injected fluid or sometimes only injected fluid is

produced (Albonico et al 1994 Glenat et al 1996 Chauveteau et al 1997 Al-Anazi et

al 2011 Elsharafi and Bai 2012) This causes pressure energy of injected fluid being

wasted without producing the oil in the permeability zones (Krilov et al 1998 Larson et

al 1999) The breakthrough of injected fluid and production of injected fluid in the

producer well makes the enhanced oil recovery process uneconomical (Scott et al 1987

Bryant et al 1997 Thomas et al 1998 Seright et al 2001 Parez et al 2001 Sakissian et

al 2005 Ye et al 2005 2010 Chung et al 2011 Elsharafi and Bai 2012)

The above problem will be remedied if the already swept high permeable zones andor

layers could be somehow plugged so that the injected fluid is forced to re-direct itself into

the unswept regions andor unswept layers causing additional oil recovery and improving

volumetric sweep efficiency (Stavland et al 1996 Krishnan et al 2000 Pritchett et al

2003 Sydansk and Seright 2007 Liu et al 2010 Shi et al 2011 Yu et al 2011 Zhao et

al 2011)

There are several methods to control the excessive water production problems associated

with enhanced oil recovery methods (Kabir 2001 Alqam et al 2001) These include

mechanical and chemical methods

211 Mechanical methods

There are different types of mechanical methods for controlling the excessive water

production (Mohammad et al 2007) These methods works on the mechanism of coning

control via draw down reduction co-production and downhole separation simultaneous

water and oil production for coning mitigation and downhole separation and disposal Most

common and current excessive water production methods include


7

Bridge plugs

Straddle packers

Tubing patches

Cement

Sand plugs

Expandable tubular

212 Chemical methods

The chemical methods are most suitable for reservoir related problems (Kabir 2001)

Chemical means can be applied without a rig on location making them more convenient

for the operator and less expensive (Mennella et al 2001) Unlike cement and bridge

plugs chemicals including gelling polymers can be placed deep into the formation They

form a gel that acts as a physical barrier that hinders the flow of water for a long period of

time The length of this period depends on the characteristics of the reservoir the gel and

water movement in the treated reservoir The examples include

Micro matrix cements

Polymers

Micro particle blends

Foamed systems

Resinsparticulate chemical blend

Gelsgelant

Profile modification is one of the latest techniques considered to increase the oil recovery

during EOR process (Seright 1988 Mahto et al 2009) The profile modification is process

of reducing the permeability of high permeability zones by placing the injected fluid in the

porous media making the injected fluid to flow through the low permeability zones (Gao et


8

al 1993 Xiang 1995 Alqam et al 2001) The method comprises emplacement of a

gelant slug into the highly permeable flooded out layers of the formation close to well bore

(Chang et al 1988 1985 Ali and Barrufet 1994) The gel is designed to reduce the flow

profile and diverting injected fluid into zones of greater residual oil content (Krumrine and

Boyce 1985 Mahto 2009 Yadav and Mahto 2010)

Today polymer gel treatment is the most useful chemical method to reduce the water

production (Cai and Huang 2001) Some kind of polymer solution is injected into the

reservoir and is allowed to gel under certain conditions The gel viscosity being much

higher than the displacing fluid could impede the flow of displacing fluid through the

already flooded regions thus the displacing fluid finds new paths which means additional

oil can be displaced (Ghosh et al 2011) Polymer gel systems are typically composed of a

water soluble polymer and a cross-linking agent which are dissolved in water (Zaitoun et

al 1991) This solution is considered as a gelant solution After allowing sufficient time

the gelant sets into a semisolid mass and behaves as a flow diverting or blocking agent

(Bryant et al 1996)

Selection of a gel polymer system strongly depends on the reservoir conditions such as

temperature salinity hardness and pH of water used for the preparation of the gelant Other

parameters for the proper selection of a given gel polymer system include salinity of the

formation water permeability of the target zone and the lithology of the formation (Yan et

al 1999 He et al 2009 Urbissinova et al 2010 Ponnapati et al 2011)


9

22 GEL PROPERTIES AND GELATION MECHANISMGEL CHEMISTRY

221 Gel properties

Gels are classified as semi-solids The water-based gels that are of interest here are highly

elastic with high water content 98 to 99 trapped in the three-dimensional polymer

structure of the gel Many systems have been developed which form gels in beaker tests

under conditions anticipated in petroleum reservoirs Through extensive testing it is

possible to determine conditions such as ranges of composition pH and temperature that

the gels are stable over long periods of time (Mahto and Maurya 2007) Stability of the gel

under reservoir conditions is one of the most important properties of the gel Some of the

important pertinent properties of the gels to their application in the profile modification are

the following (Mahto et al 2011)

2211 Rheological properties

Gels are highly elastic and their rheological properties are significantly different than those

of polymer solutions that they are made from (Al-Muntasheri et al 2007) Gels formed at

low shear rates were more viscous than gels formed at high shear rates However the

structure of these gels was susceptible to shear degradation Kharrat amp Vossoughi 1992

studied rheological behavior of four different gel systems and concluded that each gel

system is unique in their rheological behavior and generalization of their rheological

characterization does not seem to be warranted

2212 Gelation time

In-depth gel treatment requires gelation systems with long gelation times Gelation time is

not a limitation where near-wellbore treatments are desired but is of concern where it is

desired to have in-depth treatment to reduce cross-flow between layers (Al-Muntasheri et

al 2006 Mahto 2010) Gelation time is controlled differently for different gel systems


10

For example the chromium redox gelling system can be used to promote long gelation time

by controlling the rate that Cr (VI) is reduced to Cr (III) In high temperature reservoirs in

situ gelation rate can be controlled using low molecular weight polyacrylamide with a low

degree of hydrolysis 1 by the rate that amide groups are auto-hydrolyzed to carboxyl

groups These groups subsequently react with chromium introduced as chromium acetate to

form gels which are stable in synthetic sea water to temperatures Gelation time is a

function of temperature and it follows the Arrhenius-type plot That is a semi-log plot of

gelation time vs inverse of absolute temperature produces a straight line In their study of

viscometric behavior of chromium (III)polyacrylamide gels Aslam et al 1984 observed

that gelation time decreased with increasing polymer concentration and also with

increasing initial sodium dichromate concentration It was also observed that gelation rate

was affected by shear rate and shear rate history Implication from the latter observation is

that extrapolation of gel time measurements obtained from viscometry to In-situ gelation

should be done at comparable shear rates More importantly shear rate dependence means

that in situ gelation may be influenced by the shear rate history which a gelling solution

experiences as it flows from mixing equipment through surface and subsurface equipment

into the reservoir Shear rate also varies in the reservoir as the gelling solution flows from

the wellbore into the formation

Figure 21 Stages of gel formation


11

2213 Selective injectivity

It is desired for the gelling solution to enter the zone of high permeability with minimum or

no flow into the zones of low permeability Most operators prefer not to isolate zones when

injecting a gel solution into a well where several intervals may take the gel solution

Selective injectivity with the majority of the gel solution going into the high permeability

zone Simple models of polymer injection indicate that selective injection occurs only in

parallel linear displacement tests and is absent when polymer is injected into a layered

reservoir in radial flow Todd et al 1990 show that selective injection is possible for a

chromium-redox gelling system injected into a well containing three layers with different

permeabilities However the tight zones had significant permeability reduction in the

immediate vicinity of the wellbore and this would have to be removed before water could

subsequently be injected into the zones Hoefner et al 1992 presented laboratory core

flood data for parallel linear cores which showed selective penetration of chromium

xanthan gels Selective flow behavior was found to be a function of process variables such

as permeability and injection rates and was observed only over a limited range of

conditions Hoefner et al 1992 acknowledge that selective gels are not completely

excluded from the lower permeability media

2214 Syneresis

Gels normally undergo syneresis with time This causes shrinkage in gel volume and

consequently water is expelled from the gel structure It is believed that syneresis is the

result of increasing the cross-link density with time It seems that syneresis is a function of

brine salinity pH temperature and gel composition (Albonico et al 1997 Al-Muntasheri

et al 2006) Although syneresis could become a hindrance for the long-term effectiveness

of the gel placement in the fracture in pore scale it does not have significant effect


12

2215 Dehydration

Gels dehydrate when exposed to a high pressure gradient Dehydration causes shrinkage in

gel volume and loss of water

222 Gelation mechanism of most useful polymer gel systems used for profile

modification jobs

2221 Gelation mechanism of partially hydrolysed polyacrylamide and chromium

(III) gel system

Chromium (III) forms a complex ion in solution and reacts by a ligand-exchange reaction

with the carboxylate or hydrolysed group on the polymer molecules to form crosslinks

resulting in a network or gel In this gelation mechanism where one Cr (III) interacts two

carboxylic groups (Jain et al 2005)

C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P

Partially Hydrolyzed Polyacrlamide + Cr (III)


13

2222 Gelation mechanism of polyacrylamide tert-butyl acrylate (PAtBA) copolymer

with polyethyleneimine (PEI)

There is two gelation mechanism involve for polyacrylamide tert-butyl acrylate (PAtBA)

copolymer with polyethyleneimine (PEI)

First is the formation of covalent bonds between the carbonyl carbon at the ester group and

an imine nitrogen from PEI

Figure 22 Cross-linking reaction with PEI through ester carbonyl carbon

(Hardy et al 1999 Al-Muntasheri et al 2007)


14

Second is the PEI nitrogens form covalent bonds with the carbonyl carbons at the amide

group of PAtBA through a transamidation reaction

Figure 23 Cross-linking reaction with PEI through transamidation of the amide

group (Reddy et al 2003 Al-Muntasheri et al 2007)


15

2223 Gelation mechanism of partially hydrolysed polyacrylamide-hexamine-

hydroquinone gel system (Yadav and Mahto 2013)

The hexamine on hydrolysis yields formaldehyde which then combines with hydroquinone

and form 2 3 5 6 tetramethylol hydroquinone Further partially hydrolyzed

polyacrylamide reacts with 2 3 5 6 tetramethylol hydroquinone and forms three

dimensional networks of polymer gel the different steps of which are as follows

Step I

In the initial step hexamine hydrolyses to yield formaldehyde

N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II

Formaldehyde produced in step-I then react with hydroquinone to form a condensed

structure known as 2 3 5 6-tetramethylolhydroquinone

+

O

C

H H

OH

OH

OH

OHHO

HO

Hydroquinone Formaldehyde 2 3 5 6-Tetramethylol Hydroquinone

OH

OH

4


16

Step III

The condensed molecule formed in step-II then reacts with PHPA to form the 3-

dimensional gel structure which helps in profile modification jobs

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide

Partially Hydrolized Polyacrylamide (PHPA)

Amide

O-

Na+

+

OH

OH

OH

OHHO

HO

2 3 5 6-Tetramethylol Hydroquinone

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water

Crosslinking 3-D gel structure


17


pyrocatechol gel system (Yadav and Mahto 2012)

The hexamine on hydrolysis yields formaldehyde which then combines with pyrocatechol

and form 3 4 5 6-tetramethylol pyrocatechol Further partially hydrolyzed

polyacrylamide reacts with 3 4 5 6-tetramethylol pyrocatechol and forms three


Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II

Formaldehyde produced in step-I then react with pyrocatechol to form a condensed

structure known as 3 4 5 6-tetramethylol pyrocatechol

+

O

C

H H

OH

OH

OH

OHHO

HO

Pyrocatechol Formaldehyde 3 4 5 6 Tetramethylol Pyrocatechol

OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO

3 4 5 6 Tetramethylol Pyrocatechol


19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water

Crosslinking 3-D gel structure 3-D Structure of polymer gel

23 MATHEMATICAL FLOW MODELS FOR THE RHEOLOGICAL BEHAVIOR

OF POLYMER GEL SYSTEMS

Several rheological models are reported in literature for the determination of rheological

behavior of polymer gel solutions (Kelessidis and Maglione 2006 Park and Song 2010)

The Bingham model is expressed as

τ = τ + kγ

Fluids that exhibit Bingham plastic behavior are characterized by a yield point (τ0) and a

plastic viscosity (μp) that is independent of the shear rate

There are several rheological models that involve three or more adjustable parameters It is

necessary to include a third parameter to describe the flow of the fluids in the upper or

lower Newtonian region as well as the Power law region The Herschel-Bulkley model


20

corrects this deficiency by replacing the plastic viscosity term in the Bingham model with a

Power law expression as follows

τ = τ + kγ

τ ndash Shear stress Pa

τ0 ndash Yield point Pa

K ndash Consistency index Pasn

γ ndash Shear rate s-1

n ndash Flow behavior index

The parameters K and n are similar to those of power law model For fluids having a yield

stress however the calculated values of n and K will be different from those calculated

using power law model The parameter τ0 is the fluidrsquos yield stress at zero shear rate In

theory this yield stress is identical to the Bingham plastic yield point (YP) though its

calculated value is different The model is reduce to the Bingham plastic model when n=1

and reduces to the power law rheological model when τ0=0

In a general way the rheological model proposed by Mizrahi-Berk may be gives a good fit

with most of the rheograms of polymer gel systems

τ = τ + kγ

While the power index of the shear rate (n) is generally less than 1 to show a shear-thinning

behavior neither the consistency index nor yield stress from the models shows any pattern

with the solids content

A nonlinear relation exits between the shear stress and the shear rate above the yield stress

There are a number of rheological models used to describe this behavior RobertsonndashStiff

(Ohen and Bick 2011) proposed a three-parameter yield-pseudo-plastic model for relating

the shear stress to the shear rate may be used in determination of rheological behavior of

polymer gel system as follows


21

τ = k (γ + C)

Where k C and n are model parameters The RobertsonndashStiff model includes the

Newtonian Bingham plastic and power law models as special cases

24 DEVELOPMENT OF POLYMER GEL SYSTEMS USING DIFFERENT

CROSS-LINKERS

Cross-linked polymers have been widely used for profile modification jobs over the last

decades (Mahto and Sharma 2010)

241 Polymers used for profile modification jobs

The most commonly used polymers are the following

2411 PolyacrylamidePartially hydrolyzed polyacrylamides

These are water soluble polymer whose monomeric unit is the acrylamide molecule The

polyacrylamide has undergoes partially hydrolysis which causes anionic carboxyl group to

be scattered along the backbone chain (Wever et al 2011) The polymers are called

partially hydrolyzed polyacrylamide is between 1x106 to 8x106 The size of the molecules

about 01 to 03 micro meters By hydrolysis in a caustic water solution some of the

CONH2 group react to form carbyl group (COOH)


22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide Amide

O-

Na+

Figure 24 Chemical structure of partially hydrolyzed polyacrylamides

2412 Xanthan gum

Xanthan gum is a polysaccharide with a a-D-glucose backbone like cellulose but every

second glucose unit is attached to a triaccharide consisting of mannose glucuronic acid

and mannose The mannose closest to the backbone has an acetic acid ester on carbon 6

and the mannose at the end of the triaccharide is linked through carbons 6 and 4 to the

second carbon of pyruvic acid Xanthan gum is produced by the bacterium Xanthomonas

campestris which is found on crucifereous vegetables such as cabbage and cauliflower

The negatively charged carboxyl group on the side chains because the molecules to form

very viscous fluids when mixed with water (Chatterji and Borchardt 1981 Taylor and

Nasr-El-Din 1998)


23

Figure 25 Chemical structure of xanthan gum (Song et al 2006)

2413 Copolymers

The main copolymers used in profile modification jobs are copolymer of acrylamide ter

polymer with N-vinyle pyrrolidone and 2-acrylamide-2-methyl-1-propanesulfonic acid

(PAAm-VP-AMPS) amphoteric copolymer polyacrylonitrile and lignin sulphonate

Table 21 Properties of polyacrylamide and xanthan gum polymers

Sl

No

Property Polyacrylamide Xanthan Gum

1 Transition Metal

Cations

Easily crosslinked Easily crosslinked

2 Shear stability Undergoes irreversible

shear degradation

Reversible shear thining


24

3 Thermal stability Maximum use upto 225-

250 (degF)

Maximum use 160-170 (degF)

4 Hydrolytic

stability

Hydrolysis promoted by

acid or base Partially

hydrolyzed product more

sensitive to Ca+2 Mg+2

Hydrolytic de-

polymerization promoted by

acid or base especially at

high temperature

5 Oxidative

stability

Susceptible Particularly susceptible

especially at high

temperature

6 Brine tolerance Very limited especially to

Ca+2 Mg+2

Good tolerance to mono and

divalent captions

7 Microbial

degradation

Susceptible to attack by

yeast fungi bacteria

Very susceptible in aerobic

conditions

242 Cross linkers used for profile modification jobs

Crosslinkers are the chemical compound which formed stable three dimensional structures

with high molecular weight polymers like polyacrylamide and xanthan gum

The cross-linkers used in cross-linking of the high molecular weight polymers are the

following

2421 Metallic crosslinkers

The most common metallic crosslinkers are Al+3 Cr+6 Cr+3 zirconium titanium boron etc

2422 Organic crosslinkers

Two classes of organic cross-linkers namely phenolic and aldehydes are used for profile

modification jobs The different cross-linkers in the phenolic group are phenol

hydroquinone resorcinol phenyl acetate salicylic alcohol furfuryl alcohol etc In the


25

aldehyde group main crosslinkers are formaldehyde paraformaldehyde hexamethylene

tetra mine etc

243 Emerging developments of cross linked polymer gel systems

Polymer gel systems have emerged as one of the most effective conformance solution for

controlling of excessive water production worldwide The different cross-linked polymer

gel systems are the following (Moradi 2000 Mahto and Sharma 2010)

2431 Polyacrylamide-chromium (III) gel system

The short gelation time of Cr(III)-acetatepolymer composition at elevated temperature

limit their application to reservoirs that are at relatively at lower temperatures (Sydansk and

Southwell 2000) The existing gelation characteristics of these systems have limited

control over the gelation time of the polymer solutions at elevated temperature For the

delay in gelation time at elevated temperature chromium (IV) or formaldehyde are used but

their use in the field is complicated by significant health and environmental issues At

present many organic ligands are used for their delaying power with Cr(III)polymer and

Cr(OAc)3 polymer solutions and provides outstanding control over the gelation time over

60-135degC With the use of this gelation time spanning the range from several hours to one

month or more at temperature up to 120degC The most interesting features of the ligands like

glycolate malonate and salicylate are their gelation delaying power and cost which

provides gelation delays of 12 to 33 times longer than acetate The other ligands include

oxalate citrate maleate and EDTA which are characteristic by their extremely strong Cr

(III) binding capacity and are found to block gelation entirely (Lane 1998 Jain et al

2004)


26

2432 Polyacrylamide-chromium (IV)-thiourea gel system

The chromium (VI)-Thiourea-polyacrylamide gels form as the result of two chemical

reactions First chromium (VI) is reduced to chromium (III) by thiourea Second the

produced chromium (III) reacts with carboxylate groups on the partially hydrolyzed

polyacrylamide to form a crosslinked gel The pH range for the reduction of chromium (VI)

to chromium (III) by thiourea is in the range of 40 to 50 Gel times on the order of days to

weeks can be achieved which is desirable to allow proper placement of the gel system in

the formation Another option is to use chromium (III) ligands like acetate lactate or

manolate

2433 Xanthan-Cr(III) gel system

The chromium (III)-xanthan gel systems have been widely recommended for matrix

treatment because they are shear thinning inject easily and have been claimed to reheal

after shearing (Chang et al 1985 1988 Kolnes et al 1991 Liang et al 1992 Nagra et

al 1996) The initial gelation rate of xanthan-chromium gel system is inversely

proportional to the hydrogen ion concentration and is strongly affected by pH in the porous

matrix (Storm et al 1991)

2434 Acrylamide-polymerchromium (III)-carboxylate gel system

The aqous acrylamide-polymercarboxylate gels are formed by crosslinking water soluble

acrylamide polymers with a Cr(III) carboxylate complex crosslinking agent (Sydansk

1990) The water soluble acrylamide polymer can be polyacrylamide partially hydrolyzed

polyacrylamide or tert-polymer containing acrylamide Acrylamide-polymerCr(III)

carboxylate gels can be used for near wellbore total shutoff treatments where matrix rock is

to be treated These are stable at elevated temperatures and they are stable and rigid at

225degF at elevated temperature These new matrix of gels are functional in the presence of

high salinity water at elevated temperatures (Sydansk 1988)


27

2435 Polyacrylamide-aluminum citrate gel system

The aluminum citrate solution form gels with anionic polyacrylamide under certain

conditions Cationic polymers do not form gels with aluminum under similar conditions

The low pH aluminum system begins crosslinking with polymer solution immediately

even before it can be injected This prevents in depth penetration of the plugging solution

Because aluminum is known to be amphoteric in aqueous solution they can crosslink at

high pH environment

2436 Polyacrylamide-polyethyleneimine gel system

These gels are rigid and non-flowing at polyacrylamide concentration of 7 and 9 These

are thermally stable at 100degC and a permeability reduction of more than 94 was realized

indicating the possibility of using this system in profile modification jobs or water shutoff

2437 KUSP1-monoethylphthalate systemKUSP1-boric acid gel system

KUSP1 is a biopolymer that is extracted from a medium after the growth of the bacterium

cellumonasflavigena It is nontoxic and exhibit viscosities on the order of 2-3 cP at 25degC

KUSP1 is soluble in alkali but forms a gel with monoethylphthalate ester and permeability

reduction by treatment with the KUSP1-MEP system is stable to brine flow for periods of

up to six months Alkaline KUSP1 can also form gel with boric acid and the gelation time

of the KUSP1-boric acid system could be regulated up to several days by selection of pH

and boric acid concentrations (Vossoughi and Buller 1991)

2438 Polyacrylamide and tert-butyl acrylate copolymer-polyethylene-imine gel

system

Polyacrylamide and tert-butyl acrylate copolymer-polyethylene-imine system at acidic

conditions the gelation time was short and the gel did not last for a longer period of time


28

High viscosity is obtained at high initial values This system can be used where formation

brine contains high concentration of divalent cations (ranges from 10000 to 15000 mgl)

Iron (III) can react with the polymer and accelerated the gelation process and produce a gel

that breaks over a short periods of time (Al-Muntasheri 2007) Hence it should not be used

after acid treatment jobs especially in sandstone reservoirs as the possibility of iron

concentration is high in the well bore area which can cause premature setting of gel This

system can be used at a temperature less than 140degC (Al-Muntasheri 2007 2006 2008)

2439 Polyacrylamide-phenol-formaldehyde gel systemspolyacrylamide-resorcinol

formaldehyde gel system

Phenol-Formaldehyde polymer gels system is an attractive tool fluid shutoff or profile

modification in high temperature formations By selecting between different polymer

compositions reasonable flexibility in the gelation time can be achieved over the

temperature range from 60degC to at least 140degC (Bryant et al 1997 Mahto et al 2009

2010) Choice of polymer composition permits the control of the gelation time and the

gelants display good injectivity even when the residence time approaches the gelation time

(Zhuang et al 2000 Banerjee et al 2006) Cross-linking occurs over a wide range of pH

and is insensitive to lithology (Seright and Martin 1993 Dovan et al 1997)

24310 Polyacrylamide-hydroquinone-hexamine gel system

Hexamethylenetetramine (HMTA) undergoes hydrolysis to produce methyldiol and

ammonia Methyldiol compound is very much unstable Hence it looses water molecules to

produce formaldehyde Thus formed formaldehyde is then reacting with hydroquinone

Hydroquinone undergoes electrophilic substitution reaction to produce 2356

tetramethylol hydroquinone (intermediate) Then intermediate react with partially

hydrolyzed polyacrylamide (PHPA) polymer Hence form a large viscous molecule Hence

OHmacr in methylol group of intermediate and H+ from amide group of polymer are leaving as


29

a water molecule while producing N-C crosslinker (Dovan et al 1997 Gwaish et al 2008

Mahto and Sheikh 2009)

Table 22 Summary of thermally stable gels

Sl

No

Polymers Crosslinkers Comments

1 Polyacrylamide low mol wt

(Bryant et al 1996)

Cr(III) Acetate 5 or more polymer

needed

2 Polyacrylamide high mol wt

(Lockhart and Albonico 1994)

Cr(III) Molonate Slower gelation rate

than with Cr(III)

Acetate


(Bryant et al 1997 1997)

Phenol and

Formaldehyde

Ligands such as

citrate oxalate

lactate stabilized the

gel


(Gawish et al 2008)

Hydroquinone amp

Hexamethylenetetramine

2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde

dihydroxynaphthalene

HMTA etc

Stable gel

6 Acrylamide based thermally

stable polymer (Moradi 2000)

Phenol formaldehyde Stable gel


stable polymer

(Moradi 2000)

Phenyl acetate phenyl

salicylate etc with

HMTA

Stable gel lower

toxicity than phenol

amp formaldehyde gel

8 Acrylic esteracrylic acid Polyethyleneimine Stable gel required


30

copolymer

(Moradi 2000)

larger concentration

amp cooling at below

93degC

9 Resorcinol

(Mahto et al 2009)

Formaldehyde Water like viscosity

of gelant is plus

toxicity is a problem

10 Scleroglucan

(Moradi 2000)

Cr(III) Stable gel the

polymer is very

expensive

11 Lignosulfate

(Moradi 2000)

Cr(III) Expensive gel due to

high chromium

required

12 Alcaligenes biopolymer PVA

(Moradi 2000)

Na+ phenol amp aldehyde Stable gel in pH

range of 7-8 higher

concentration of

polymer and

crosslinkers needed

13 PVA-polyvinylamide copolymer

(Hoskin and Shu 1989)

Dialdehydes or

polyaldehydes

Not widely used

14 Copolymer tert butyle acylate

(Al-Muntasheri et al 2006

2007)

Polyethyleneimine

15 Partially hydrolysed

polyacrylamide (Jia et al 2010

2011)

Polyethyleneimine


31

25 SELECTION CRITERIA OF WELLS FOR GEL TREATMENT

Polymer gels can be applied to both injection and production wells (Al-Muntasheri et al

2010 Canbolat and Parlaktuna 2012) The objective of treating injection well is to

improve vertical injection profile resulting in more efficient distribution of injected water

(avery et al 1987) The production well treatment is to improve areal efficiency and to

reduce water oil ratio by reducing water channeling in the near wellbore region

(Giangiacomo 2001 Larson et al 1999 Ghafoori et al 2008) The following criterions

for candidate selection of injection and production wells are reported in the literature

(Maghsood and Bringham 1984 Sharma et al 2009)

251 Selection criteria for injection wells

The selection criteria for the injection wells candidates are the following

(a) Low secondary oil recovery due to poor sweep efficiency that is high degree of

reservoir heterogeneity

(b) Pre-matured water breakthrough of producing wells

(c) Evidence of direct injector to producer channeling through fractures bugs or high

matrix permeability rock

(d) High injection rate associated with low well head pressure

252 Selection criteria for production wells


(a) Recovery calculations indicate that considerable mobile oil remains that could be

recovered most cost effectively if a blocking agent could be realistically placed in the

proper location

(b) High water oil ratio (WOR) values are observed

(c) The source of excess water production is identified (ie using profiles logs or

tracers)


32

(d) The candidate well exhibits high productivity

26 DESIGNING GEL JOB FOR OIL FIELD APPLICATION

Gel volume is to be designed for both injection and production wells

261 Injection well

When cross flow occurs between thief zone and low permeability oil bearing zone a large

volume of gel is to be injected so that gel penetrates significant distance into the thief zone

(Romero et al 2003) In case where there is no cross flow ie thief zone is separated by an

impermeable barrierlayer from oil bearing zone a small volume of gel is placed near the

wellbore (Glenat et al 1996) Gel volume can be designed in two ways one is based on

filling a portion of channel volume from injector to producer and another is based on

distance from the injection well up to which the gel is to be placed (Parez et al 2001

Sarkissian et al 2005)

262 Production well

There are no definite design criteria available for bulk volume for producing well

treatment Gels with higher polymer concentrations are used in producing well (vs

injection well) treatment because the gel has to withstand high differential pressure in the

direction of producing wellbore (Glenat et al 1996 Giangiacomo 2001) Based on field

experience the following guidelines have been given

(a) Gel volume is equivalent to the volume of fluid that the well can produce in 24 hours

in a pumped-off condition

(b) Gel volume is based on 50 feet radius and thief zone thickness 0

(c) Gel volume is based on 50-200 barrels of gel per perforated foot


33

26 CONCLUSIONS

The conclusion of the study provided strong evidence that stable gels can be produced

under harsh environmental conditions with organic and inorganic crosslinkers which may

be used for the profile modification jobs in the oil fields These crosslinkers typically

produced gels at temperature ranges from 40 degC to 140 degC and salinity up to 60000 ppm

They are generally less toxic then chromium acetate phenol and formaldehyde croslinkers

The majority of the crosslinkers are readily available at prices not much higher than the

toxic crosslinkers

5

CHAPTER 2

LITERATURE REVIEW

The challenges associated with matured oilfields as well as different polymer gel systems

are reviewed with particular emphasis on their application to improve sweep efficiency

through profile modification during enhanced oil recovery processes The cross-linked

polymer gels have great potential for the use in permeability reduction fluid control and

profile modification This review includes gel formation and gelation mechanism models

for rheological and gelation behavior for polymer gel systems development of different gel

systems using different cross-linkers selection criteria of wells for gel treatment and

designing of job for oil field application

21 CHALLENGES ASSOCIATED WITH MATURED OIL FIELDS AND THEIR

CONTROL

The enhanced oil recovery processes like water flooding polymer flooding (Needham and

Doe 1987 Sohn et al 1990 El-Hadidi et al 1997 Norris et al 2013) foam flooding

(Miller et al 1994) alkaline-surfactant-polymer and alkali flooding etc are used for the

mature oil fields (Baojun et al 2004 Ma et al 2007 Benson et al 2007 Thorne et al

2010) In these processes some kind of fluid is injected to push the oil from the injection

well toward the producer Water and gases are the most commonly used displacing fluids in

this process Water flood is the most common practice of secondary oil recovery techniques

(Dalrymple et al 1994 Zheng et al 2002 Tang et al 2004) Injection of carbon dioxide

or other gases is also a common practice to improve oil recovery efficiency (Sydansk and

Reichman 1996) Regardless of the type of the fluid used to displace the oil the displacing

fluid could bypass the oil and early breakthrough could occur In the case of water flood

the water oil ratio could become so high that the process ceases to be economical any more

(Jordan et al 1982) For injection of CO2 or other gases the high gasoil ratio renders the

process uneconomical (Modesto et al 2009)


6

















al 2011)











7

Bridge plugs

Straddle packers

Tubing patches

Cement

Sand plugs

Expandable tubular










Polymers


Foamed systems


Gelsgelant






8















(Bryant et al 1996)







9


221 Gel properties


















2212 Gelation time






10





















11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


6

















al 2011)











7

Bridge plugs

Straddle packers

Tubing patches

Cement

Sand plugs

Expandable tubular










Polymers


Foamed systems


Gelsgelant






8















(Bryant et al 1996)







9


221 Gel properties


















2212 Gelation time






10





















11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


7

Bridge plugs

Straddle packers

Tubing patches

Cement

Sand plugs

Expandable tubular










Polymers


Foamed systems


Gelsgelant






8















(Bryant et al 1996)







9


221 Gel properties


















2212 Gelation time






10





















11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


8















(Bryant et al 1996)







9


221 Gel properties


















2212 Gelation time






10





















11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


9


221 Gel properties


















2212 Gelation time






10





















11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


10





















11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


11


















2214 Syneresis








12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


12

2215 Dehydration




modification jobs


(III) gel system





C

CH

CH2

CH

C

O

CrOO

P

P

NH2

O

O C

CH

CH2

CHCH

O

P

NH2

P



13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


13










14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


14






15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


15







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

OH

4


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


16

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO


R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water



17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


17







Step I


N

N N+ H2O CH2 OH +

O

C

H H

Formaldehyde

Hexamine

N

6 OH 4 NH3

_ H2O


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


18

Step II



+

O

C

H H

OH

OH

OH

OHHO

HO


OH

4OH

Step III



C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO

Carboxylate Amide


Amide

O-

Na+

+

OH

OH

OH

OHHO

HO



19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


19

R

R

o N

H

H

OH

OH

OH

OH

OH

HO

Water







τ = τ + kγ







20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


20



τ = τ + kγ














τ = τ + kγ










21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


21

τ = k (γ + C)




CROSS-LINKERS













22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


22

C C C C C C

C H C H C H

H H H H H H

ONH2 NH2 OO


O-

Na+


2412 Xanthan gum









Nasr-El-Din 1998)


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


23


2413 Copolymers





Sl

No


1 Transition Metal

Cations



shear degradation



24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


24


250 (degF)


4 Hydrolytic

stability





Hydrolytic de-



high temperature

5 Oxidative

stability


especially at high

temperature


Ca+2 Mg+2


divalent captions

7 Microbial

degradation




conditions





following








25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


25


tetra mine etc




















2004)


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


26









manolate


















27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


27







high pH environment














system




28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


28



























29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


29




Sl

No



(Bryant et al 1996)


needed




than with Cr(III)

Acetate



Phenol and

Formaldehyde

Ligands such as

citrate oxalate


gel


(Gawish et al 2008)

Hydroquinone amp


2 sodium

carbonate needed

for softening and

stability


(Moradi 2000)

Terephthaladehyde


HMTA etc

Stable gel





stable polymer

(Moradi 2000)


salicylate etc with

HMTA

Stable gel lower





30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


30

copolymer

(Moradi 2000)



93degC

9 Resorcinol

(Mahto et al 2009)


of gelant is plus


10 Scleroglucan

(Moradi 2000)


polymer is very

expensive

11 Lignosulfate

(Moradi 2000)


high chromium

required


(Moradi 2000)


range of 7-8 higher

concentration of

polymer and

crosslinkers needed



Dialdehydes or

polyaldehydes

Not widely used



2007)

Polyethyleneimine



2011)

Polyethyleneimine


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


31






















proper location



tracers)


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


32




261 Injection well









262 Production well











33

26 CONCLUSIONS







toxic crosslinkers


33

26 CONCLUSIONS







toxic crosslinkers

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Chapter 2 Literature Review -...

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