Polyacrylamide and its derivatives for oil recovery

LIST OF ILLUSTRATIONS 
SECTION Page 
Figure 1.1. Oil production in different stages ......................................................................1
Figure 1.2. Illustration of a typical chemical flooding .........................................................2
Figure 1.3. Timeline for the Development of Polyacrylamides for Enhanced Oil
Recovery ............................................................................................................5
PAPER I 
Figure 1. Key issues to be resolved to maximize oil recovery. .........................................11
Figure 2. Timeline for the development of Polyacrylamides for Enhanced Oil 
Recovery. ...........................................................................................................14
Figure 3. Structure of monomer B in KYPAM..................................................................26
Figure 4. Structure of monomer in KYPAM. ....................................................................28
Figure 5. Schematic of AMVPPS copolymer conformations in aqueous NaCl
solution ...............................................................................................................32
Figure 6. Structure model of the gelation of polyacrylamide / nanoclay gelant
solution ...............................................................................................................35
Figure 7. Schematic illustration of force acting on a pair clay layers during
interaction. .........................................................................................................36
Figure 8. The sketch of a cross-linked network formation by ionic bonds using
the multivalent ion Cr (III) as example. .............................................................39
Figure 9. Sketch of a cross-linked network structure formed by covalent bonds
using formaldehyde as example. ........................................................................40
Figure 10. Mechanism of cross-linked network formation by the
copolymerization of PAM with

,

-poly (ethylene glycol) diacrylate
as example. .......................................................................................................41

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Figure 11. The Reaction Mechanism Between PAM and PEI ...........................................47
Figure 12. Mechanism of KYPAM-PEI crosslinking gelation reaction ............................49
Figure 13. Illustration of the fundamental difference between macro-gels and
micro-gels. .......................................................................................................52
Figure 14. Proposed swelling mechanism of an expandable polymer particle. .................52
Figure 15. The surfactant of inverse-emulsion polymerization of acrylamide
in ScCO
2
...........................................................................................................55
PAPER II 
Fig. 1. Synthesis of N-alkylacrylamide............................................................................117
Fig. 2. Phase diagram: stable suspension of surfactant and monomer.............................123
Fig. 3. Schematic representation of the copolymerization mechanism in the
water-free S/O system ..........................................................................................124
Fig. 4. The SEM picture of crude poly-(acrylamide-co-octadecylacrylamide) ...............125
Fig. 5. Foruirer transfer infrad (FTIR) spectra of octadecylacrylamide,
acrylamide and poly-(acrylamide-
co
- octadecylacrylamide) ...............................127
Fig. 6. (a) 
1
H NMR of ocadecylacrylamide (b) 
1
H NMR and (c)
13
C NMR
spectra of poly-(acrylamide-
co
-octadecylacrylamide). .......................................128
Fig. 7. Thermogravimetric (TG) curves of the hydrophobically modified
copolymer. ...........................................................................................................130
Fig. 8. Apparent viscosity of aqueous solution as a function of copolymer 
concentration.. ......................................................................................................131
PAPER III 
Figure 1. Schematic diagram of the pore occlusion filtration test apparatus. ..................146
Figure 2. FTIR spectrum of polyacrylamide crosslinked microspheres. .........................148

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Figure 3. Thermogravimetric curve of the PAM micro-gel dry spheres .........................149
Figure 4. a). SEM of polyacrylamide dry particles; b). Microscopic image
of swelled polyacrylamide microgels. ...............................................................151
Figure 5. Swelling kinetic and diameter change of crosslinked microgels in
DI water under 40 º
C and 80 º
C. ......................................................................152
Figure 6. Proposed swelling mechanism of the crosslinked microgels in
DI water at 40 º
C and 80 º
C. ..............................................................................153
Figure 7. Nuclear-pore modeling of pore occlusion performance ...................................156
Figure 8. Schematic diagrams of pore occlusion mechanisms ........................................159
Figure 9. SEM Picture of membranes after pore occlusion testing. ................................160
PAPER IV 
Fig. 1 (a). The first network: polyacrylamide with N, N-methylene bisacrylamide
as crosslinker; (b). The second network: poly (vinyl alcohol) –
glutaraldehyde; (c). The representation of interpenetrating network of 
PAM/PVA. .............................................................................................................173
Fig. 2 FTIR of (a) Pure PAM;(b) PVA-2%/PAM IPN; (c) PVA-10%/PAM IPN;
(d) PVA-15%/PAM IPN; (e) Pure PVA. ...............................................................174
Fig. 3 Scanning electron micrographs of PAM hydrogel and PAM/PVA IPN 
hydrogel. ................................................................................................................175
Fig. 4 Elastic (G') and viscous (G") moduli vs. oscillation in the stress sweep
test. .........................................................................................................................176
Fig. 5 Influence of frequency on the elastic modulus (G’) and viscous modulus
(G’’) of PAM hydrogel and PAM/PVA IPNs........................................................178
Fig. 6 (a). Strain-stress curves of PAM hydrogel and PAM/PVA IPNs;
(b).Expanded strain-stress curves of PAM hydrogel .............................................179
Fig. 7 The swelling behavior of the PAM/PVA hydrogels. .............................................181

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Fig. 8 Dependence of the effective crosslinking density (
v
e
) on the
concentration of PVA. ...........................................................................................186
Fig. 9 Dependence of the complex modulus on the concentration of PVA. ....................187 

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