Chemical Modification of Guar by Different Synthetic Vinyl Monomers for Enhancing Oil

Recovery under Severe Sandstone Reservoir Conditions

a, *
Samah A. M. Abou-alfitooh , F.I. El-Hosiny b, M.Ramzi a, E. M. Mansour a, Osama M. Elnaggar a,
A.N.El-hoshoudy a

a
Production Department, Egyptian Petroleum Research Institute (EPRI), Naser City, Cairo, Egypt.
b
Chemistry department, Faculty of Science, Ain Shams University, Abassia, Cairo, Egypt.

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 Figure S1: Molecular Structure of Guar Gum.

Figure S2: Mobility ratio effect on sweeping efficiency.

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 K+
-
O

O S O

O
Initiation /600C
2 KSO4
.
O
(1)

O S O

O-
K+ CH2OH

O
OH H H
CH2

SO
. HC CH2
C
H
OH H
4 H2N O

O
+ + H OH
CH2
O O H H
O
H O H
OH OH
OH OH
H
O O
n
H H
CH2OH

CH2 O

O
 H
  OH H
CH2
HC CH2 
OH H
C
Propagation H O
H2N
H OH
CH2
(2) O O O H H
O
H O H
OH OH
OH OH
H
NH2 O O
n
H H
H3C C O CH2OH

CH2C HCH2C O
l m
C O CH2

OCH3 O
OH H H

OH H
Termination H O

(3) H OH
CH2 H H
O
H O H
OH OH
OH OH
H
O O n
H H
CH2OH

methyl 5-amino-4-((((2R,3R,4S,5R,6S)-6-(((2R,3S,4R,5S,6S)-6-(((2R,3S,4R,5S,6S)-4,5-dihydroxy-2-(hydroxymethyl)-6-
methyltetrahydro-2H-pyran-3-yl)oxy)-4,5-dihydroxy-3-methoxytetrahydro-2H-pyran-2-yl)methoxy)-3,4,5-
trihydroxytetrahydro-2H-pyran-2-yl)methoxy)methyl)-2,2-dimethyl-5-oxopentanoate

GG-g-AM& MMA (3D- structure)

Figure
FigureS3:
S1:Grafting
GraftingGuar
Guarwith
withacrylamide and
acrylamide methyl
and methacrylate
methyl methacrylate

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 K+
-
O

O S O

O
Initiation /600C .
2 KSO4
O
(1)

O S O

O-
K+ CH2OH

O
OH H H
CH2
. HC CH2
C O
H
OH H
SO4 H2N O
Si
+ + O
+ H OH
CH2
O O O O H H
O
H O H
OH OH
OH OH
H
O O
n
H H
CH2OH

CH2 O

 H2C O
  OH H H
CH2
HC CH2 
CH 
C O OH H
Propagation H O
H2N Si
O H OH
O O O O CH2
(2) H H
O
H O H
OH OH
OH OH
H
O O O
NH2
O n
H H
Si CH2OH
H3C C O
O

HCH2C CH2C HCH2C O

k l m
C O CH2

OCH3 O
OH H H

OH H
Termination H O

(3) H OH
CH2 H H
O
H O H
OH OH
OH OH
H
O O n
H H
CH2OH

methyl 5-amino-4-((((2R,3R,4S,5R,6S)-6-(((2R,3S,4R,5S,6S)-6-(((2R,3S,4R,5S,6S)-4,5-dihydroxy-2-(hydroxymethyl)-6-
methyltetrahydro-2H-pyran-3-yl)oxy)-4,5-dihydroxy-3-methoxytetrahydro-2H-pyran-2-yl)methoxy)-3,4,5-trihydroxytetrahydro-2H-
pyran-2-yl)methoxy)methyl)-2-methyl-5-oxo-2-(2-(triethoxysilyl)propyl)pentanoate

GG-g-AM, MMA&TEVS (3D- structure)

Figure S2: Grafting Guar with acrylamide, methyl methacrylate and Triethoxy vinyl silane.
Figure S4: Grafting Guar with acrylamide, methyl methacrylate, and triethoxyvinyl silane.

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* Mechanism of reaction

Based on OH groups of guar gum that serve as active sites, the grafting copolymerization

reaction occurred. There are different odds for grafting of vinyl monomers with guar gum as

shown in Scheme S1. Firstly, K2S2O8 dissociates to give (SO4–*) which reacts with water to give

(*OH). Both (SO4–*) and (*OH) attack the guar to form a free radical site on it. ( *OH) also acts

with vinyl monomers to produce free radicals. The activated monomer molecules associate with

the biopolymer's free-radical sites, and the copolymerization takes place. The reaction further

propagates where swollen sodium dodecyl sulfate (SDS) micelles serve as a meeting place for

monomers and the initiator. However, the reaction is stopped either by a reaction between *OH

and the free radical of the backbone or by a reaction between two activated chains[1, 2].

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Where, M* = monomer free radical; R-O* = Backbone free radical of biopolymer (guar)

Scheme S1. Copolymerization mechanism of guar gum with different vinyl monomers

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Figure S5: 1H-NMR of guar gum and its two modifications.

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The 1H-NMR spectrum of native guar gum shows chemical shifts at δ (ppm) = 4.65 (s) for

anomeric protons and broad chemical shifts at δ (ppm) = 3.5– 4 (m) due to sugar protons. The
1
H-NMR spectrum of GG-g-AM& MMA displays additional chemical shifts at δ (ppm) = 7.06

(s, 2H, -CONH2); 3.38 (s, 3H, terminal -CH3 group in COOCH 3); 1.24 (s, 6H, terminal -CH3

groups in -C(CH3)2-) chemical shifts at δ (ppm) = 2.1- 4.9 correspond to (-OH & -CH2) groups

of anhydro mannose units of guar. The 1H-NMR spectrum of GG-g-AM, MMA&TEVS

displays chemical shifts at δ (ppm) = 3.82 (d, 2H, -OCH 2CH3) that present in

triethoxyvinylsilane; 3.73 (s, 3H, terminal -CH3 group in COOCH 3). The chemical shift at δ

(ppm) = 7.1 related to (-CH=CH2) indicates the reaction of a complete monomer.

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 (a)

(b)

(c)

Figure S6: GPC of (a)-guar gum, (b)- GG-g-AM& MMA, and (c)- GG-g-AM, MMA&TEVS.

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Table S1: Ionic composition of synthetic brine solution.

Dissolved ions Concentration, ppm

Na+ 49409
K+ 1991
Ca2+ 2075
Mg2+ 5687
SO4-2 2206
- 18632
HCO3
Total Dissolved Salts (TDS) 80000

Table S2: Physical properties of crude oil

Physical properties Value

Average molecular weight, g/mol 186.69

Density at 60 0F, g/cc 0.8236

API gravity at 60 0F 40.13

Kinematic viscosity, CSt at 120 0F 2.44

at 180 0F 1.74

Dynamic viscosity, CP at 120 0F 1.96

at 120 0F 1.43

Flash point, 0C 3.0

Pour point, 0C 30.0

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Table S3: Conditions of polymer flooding.
Parameters Value

Pore volume (PV), cc 360

Bulk volume (VB), cc 1368

Porosity (%) 26.3

Injected oil volume, cc 270

Initial water saturation (SWi), % 25

Residual oil saturation (Sor), % 25

Initial oil saturation (Soi), % 75

Displacement temperature, 0C 90

Brine salinity, ppm 80000

Displacement Pressure, psi 1500.0

Brine injection rate, cc/h 10.0

Oil phase injection rate, cc/h 5.0

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Table S4: Permeability and mobility ratio of native guar and its two modifications.

Water Water permeability Water permeability

Oil
Parameters permeability (GG-g-AM& (GG-g-AM,
permeability
(Native guar) MMA) MMA&TEVS)

Vol, cc 7 4.5 4.3 3.27

Time, s 180 180 180 180

q, cc/s 0.03888 0.025 0.02388 0.01816

Water vis,
11 17 20 1.97
cp

L, cm 32.5 32.5 32.5 32.5

A, cm2 14.687 14.687 14.687 14.687

(ΔP), bar 13.8 14.5 18.5 10

Kr 68.59451658 64.859141 57.1484536 7.91939

M 1.551212162 0.949066751 0.710802546

References

[1] H. Naguib, Journal of Polymer Research. 9 (2002) 207-211.

[2] T. Yoshida, K. Hattori, Y. Sawada, Y. Choi, T. Uryu, Journal of Polymer Science Part A:

Polymer Chemistry 34 (1996) 3053-3060.

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