Research and development of new Autor

Larry Eoff
chemical systems for the control of water
and gas for naturally fractured reservoirs

Villahermosa, Tabasco 13 y 14 de Noviembre de 2014

 Contents

Introduction

Foamed Gels

High Molecular Weight Sealant

Thixotropic Sealant

Improved Hydrocarbon Based Cement

2
 Introduction

• Pemex’s naturally fractured formations offer

unique problems
• Ease of water to move up from below,
gas from above
• High temperature
• Depleted zones
• Difficulty in isolating oil/water zones

• Gel and hydrocarbon based cement

treatments have become common for water
and gas shutoff, although improvements
can be made

3
 Foamed Gels

• Improves placement in depleted, naturally

fractured or fissured carbonate reservoirs.
• Improves the ability to fill fractures and
displace reservoir fluids.
• Reduces hydrostatic pressure
• Enhances ability to shut off upper
portions of offending zones
• Provides diverting fluid properties for
optimum coverage when targeting long intervals.

4
 Foamed Gel Components

• Standard Gel Components

• Base Polymer
• Crosslinker
• Viscosifying Agent
• Unique Polysaccharide with high low-shear
viscosity
• Foaming Agent

5
 Foamed Gel Properties

• Capable of generating a foam of up to 70% Foam quality

(% volume of nitrogen, ~2.4 ppg)
• Stability at High Temperature, up to 350°F
• Thixotropic (shear thinning)
• Same controllable gel times as non-foamed Gel
• Similar Permeability reduction properties

6
 Foamed Gel Rheology
Foam Viscosity vs RPM

14000.00

12000.00
11665.50

10000.00
Viscosity (cp)

8000.00

6664.00
6000.00

4600.00
4000.00

2000.00
1060.00 700.00 450.00 435.00
0.00
0 20 40 60 80 100 120 140 160 180 200
RPM

7
 Foamed Gel Stability

Bottle Tests at Various Temperatures

8
 Foamed Gel Stability
• Pressurized Foam Loop
• 65% Foam Quality
(1/sec) (kg/m³) (cP)
800 1000

500

800
600
400

Shear Rate (1/sec)

Density kg/m3
Viscosity (cp)

600
300
400

400
200

200
100 200

Uniform Texture
0 0 0
-20 0 20 40 60 80 100 120 140 160 180 200
Time (sec)

9
 Foamed Gel Flow Tests

Brine Permeability Reduction

50% Foam Quality, 190 °F

Porous Media 20/40 Sand Crushed Field Core

Initial Water 42 170

Permeability, Darcy
Percent Permeability 99.9 99.2
Reduction

10
 Foamed Gel Flow Tests

Calcium Carbonate Packs, 221 °F

Foam Quality Initial Permeability, mD % Permeability Reduction

50 7910 99.8
60 8610 99.9
70 7490 99.9

11
 High Molecular Weight Sealant

Applications Based on Polymer Molecular Weight

Type of
Molecular Where to Depth of Well to be
Weight Apply Applications Penetration Treated
(millions)

<1 Matrix Water/gas shutoff, Near Injector

coning, channels Wellbore and
behind pipe Producer
>5 High Improved sweep Intermediate Injector
permeability efficiency, water/gas to deep and
and fractures fracture shut off Producer

12
 High Molecular Weight Sealant

High-Molecular Weight Polymer Low-Molecular Weight Polymer

(organic crosslinker) (organic crosslinker)

(increased gel Strength

with time)

• Lipping gels • Stronger Ringing Gels

• Higher Precrosslinked viscosity • Lower Precrosslinked Viscosity
• Lower Polymer Concentration • Higher Polymer Concentration

13
 High Molecular Weight Sealant

High-Molecular Weight Polymer

(metal crosslinker)

X
(increased gel Strength
with time)

• Lipping gel • Stronger Ringing Gel

14
 High Molecular Weight Sealant
Components
Base polymer: High molecular weight, partially hydrolyzed
polyacrylamide (HMW HPAM), 50% active invert oil emulsion, 14-15
million Dalton
Organic Crosslinker: Low molecular weight, organic
Inverting Surfactant: for faster hydration of base polymer

7500 ppm polymer, 2% KCl @ 75°F

15
High Molecular Weight Sealant

1400
Base Polymer
1200 4300 ppm crosslinker
8250 ppm crosslinker
1000
12500 ppm crosslinker
Viscosity (cp)

800

600

400

200

0
0 50 100 150 200 250 300
Shear Rate (1/sec)

7500 ppm base polymer in 2% KCl @ 75°F

16
High Molecular Weight Sealant

5.0wt.% LMW vs. 0.75wt% HMW Polymer

17
High Molecular Weight Sealant

7500 ppm base polymer in 2% KCl @ 225 °F

16 mesh calcium carbonate
Initial Permeability = 126 Darcy 18
 Thixotropic Sealant

OPEN HOLE GRAVEL PACK or Slotted Liner

ANNULUS (or fracture)
COILED TUBING
PLUGS

OIL ZONE
THIXOTROPIC
Sealant
WATER ZONE

19
 Thixotropic Sealant

Static Slump Tests

No Thixotropic Additives Thixotropic Additives

20
 Thixotropic Sealant

Static Slump Tests

No Thixotropic Additives Thixotropic Additives

21
Thixotropic Sealant

Rheological Tests

175 F 175F
Time 0 Time 60 minutes

N θ N θ
(rpm) (reading) (rpm) (reading)
1 32 1 52
2.0 35 2.0 58
3.0 38.00 3.0 63.00
30.0 54.00 30.0 104.00
60.0 72.00 60.0 127.00
100.0 94.00 100.0 152.00
200.0 143.00 200.0 202.00
300.0 185.00 300.0 243.00
600.0 294.00 600.0 300.00

22
 Hydrocarbon Based Cement

 Hydrocarbon-based cement
slurry that activates upon
contact with water

23
 Hydrocarbon Based Cement

Initial appearance of the system after mixing (upper left), after contamination
with water (upper right) and after setting (lower left) 24
 Hydrocarbon Based Cement

• Improved Surfactant Package

• More environmentally acceptable surfactant
• Higher and more rapid compressive strength
development
• Improved static setting properties

25
 Hydrocarbon Based Cement

• Improved static
setting properties

26
 Conclusions

• Highly Fractured Formations offer unique

problems in respect to water/gas shut off
• New developments offer improved solutions to
these problems
• Foamed Sealants
• High Molecular Weight Sealants
• Thixotropic Sealants
• Improved Hydrocarbon Based Cement

27
 Gracias

Villahermosa, Tabasco 13 y 14 de Noviembre de 2014