Polymer Rheology/Transport Reseach

Role of Polymers in Chemical EOR Processes Do Hoon Kim Gary A. Pope, Chun Huh Seungjun Lee, David Levitt, Will Slaughter

Chemical EOR Research Program Annual Workshop The University of Texas at Austin April 23-24, 2009

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Topics of Presentation

Rheology of EOR polymers - Structure-property relationship - Effects of different salinity with hardness Role of EOR polymers in chemical floods: Case Studies. - ASP/SP/Polymer Flood - Different reservoir conditions - Different salinity with hardness Motivation for development of comprehensive polymer rheology database

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Rheological Study of EOR Polymers

Provide polymer-solution bulk viscosity in terms of polymer concn, M.W., degree of hydrolysis, salinity, pH and shear rate Convert the bulk viscosity to apparent viscosity in reservoir rock, for both shear-thinning and shearthickening regimes More efficient polymer screening for chemical EOR applications to particular reservoirs

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Rheological Characterization of Polymers

Polymer MW Degree of Hydrolysis
||* **

p, m****

Description

Floppam 3630S

20M

25-30%

2046

0.063

0.58

HPAM HPAM, Posthydrolyzed

Hengfloc 63026

26M

30-40%

2115

0.07

Hengfloc 63020

20M

30-40%

1859

0.043

0.56

HPAM, Posthydrolyzed AMPS/ Acrylamide AMPS/ Acrylamide

AN-125

8M

20-30%***

1913

0.059

0.42

AN-125 VLM

2M

20-30%***

* Synthetic brine at 30 C ** 2000ppm polymer in Synthetic brine at 30 C *** Mole % of AMPS

****

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Steady Shear Viscosity of EOR Polymers

10
5

5000 ppm Polymer at 0.1% NaCl (25C)

4

10

FP 3630S (20M) AN125 (8M) FP 3230S (5M) AN125 VLM (2M)

10

10

10

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10-3

10-2

10-1

100

101

102

103

Effect of Divalent Ions on Steady shear Viscosity

2000 ppm polymer in Synthetic brine at 30 oC Viscosity (cP @ 10 s-1)

FP 3630S
(20 MM, = 25-30%)

Hengfloc 63020
(20 MM, =30-40%)

Hengfloc 63026
(26 MM, =30-40%)

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Oil and Reservoir data

# Oil viscosity [cP] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1.5 1.78 3.4 4 5 7.8 8.6 9 11 30 82 100 100 5000 Brine Salinity [TDS,ppm] 1,100 35,000 2800 200 200,000 65000 20,000 11,000 60,000 6000 60,000 5,000 38000 20,000 Hardness [ppm] Ca++ 330 60 16,000 2700 80 1200 300 640 1700 Mg++ 7 5 2000 1000 40 200 260 570 50~500 1000 5000 ~ 10000 2000 500~1000 500~1000 2000 5000 5~ 10 50~ 300 500~1000 Reservoir Perm. [mD] 2000 Temp [oC] 85 120 85 100 69 28 85 54 36 62 30.6 46 55 < 25 ASP SP ASP/ AS SP ASP ASP SP ASP SP/ASP ASP ASP ASP EOR

ASP

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Oil and Reservoir data

# Oil viscosity [cP] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1.5 1.78 3.4 4 5 7.8 8.6 9 11 30 82 100 100 5000 Brine Salinity [TDS,ppm] 1,100 35,000 2800 200 200,000 65000 20,000 11,000 60,000 6000 60,000 5,000 38000 20,000 Hardness [ppm] Ca++ 330 60 16,000 2700 80 1200 300 640 1700 570 200 260 50~500 1000 5000 ~ 10000 2000 500~1000 500~1000 Mg++ 7 5 2000 1000 40 5~ 10 50~ 300 500~1000 2000 Reservoir Perm. [mD] 2000 Temp [oC] 85 120 85 100 69 28 85 54 36 62 30.6 46 55 <25 ASP SP ASP/ AS SP ASP ASP SP ASP SP/ASP ASP ASP ASP EOR

ASP

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Polymer Selection Criteria for Chemical Flood

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Viscosity of polymer solutions Salinity tolerance Chemical and thermal stability at reservoir temperature Transport characteristics in reservoir Sorption and retention characteristics Availability and cost Compatibility with surfactant

Case #1. ASP flood

100 cP Oil, 1500 mD, 46 oC Same surfactant formulation with good solubilization ratio Selection of adequate polymer viscosity improve the oil recovery
100%

Oil Cut or Cumulative Oil Recovered (%)

90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

0.0 0.2

Oil cut

Polymer = 85 cP

Polymer = 46 cP

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Pore Volumes

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Comparison of Injection & Effluent Polymer viscosity in ASP flood

Adequate viscosity with good filterability of Polymer greatly improves oil recovery and transport in the porous media.
1000

Injected Polymer

Viscosity, cP

100

Effluent (2.02 PV)

10

2700 ppm FP 3630S 1.2 um Filter F.R. = 1.11 (15psi)

1 0.1 1 10 100 1000

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Shear Rate, s-1

Case #2. High MW Polymer in Low Permeability Rock

8 MM M.W. polymer causes plugging in very low permeability rock (5~ 10 mD).

14 12 10 8 6

K brine = 3.1 mD Polymer = 4.76 cP @ 500 s-1 Whole Inlet 1500 ppm AN-125 1.96 ft/D, 69 oC

Pressure Drop (psi)

4 2 0 0 1

Outlet
2 PV 3 4

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Case #2. Low MW Polymer in Low Permeability Rock

2 MM M.W. polymer can be transported through very low permeability rock ( 5 ~ 10 mD).
10 9 8 7 6 5 4 3 2 1 0 0.0 0.5 1.0 1.5 2.0 Pore volume 2.5 3.0 3.5 4.0

K brine = 3.1 mD Polymer = 3.73 cP @ 500 s-1 2500 ppm AN-125 VLM 1.96 ft/D, 69 oC Whole

Pressure Drop (psi)

Inlet Outlet

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M.W. measurements by GPC does not show any significant degradation/chromatograph separation

Injected

Effluent

M.W.

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Case #3. Apparent Viscosity from Core Flood

High M.W. polymer (20 M) need to propagate into high permeability sand (~ 6.6 D).
K brine = 6.6 D Polymer = 60 cP @ 10 s-1 3000 ppm FP 3630S 1,2,4,8 ft/D, 30 oC

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Apparent viscosity can be predicted from bulk viscosity

Apparent shear rate:

Carreau-Model :

=(o ) 1+( )

2 (n1)/2

Calculated from core flood

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Summary

Selection of adequate polymer viscosity improve the oil recovery in chemical flood. Low M.W. polymer can be transported through very low permeability rock (3mD). Apparent viscosity can be predicted from bulk viscosity in both shear-thinning and shearthickening regimes.

For a wide range of reservoir conditions, optimum polymer can be selected from rheology data and corefloods.

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For a wide range of reservoir conditions, optimum polymer can be selected from rheology data and corefloods

Salinity (TDS, ppm) : 200 ~ 200,000 ppm Hardness (Ca++, ppm) : 0 ~ 16,000 ppm Temperature (oC) : 25 ~ 120 oC Oil viscosity (cP) : 3 ~ 100 cP, 5000 ~ Million cP for Heavy oil Reservoir type: unconsolidated sandstone, Dolomite, High-k sand Permeability (mD) : few mD ~ thousands mD

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Motivation for Development of Polymer Rheology Database

Comprehensive rheology database for currently employed polymers is not available. Database for comprehensive rheology model parameters for process simulations are needed. Comprehensive bulk Rheology database

Limited Corefloods for Rheology correlation in porous media (eff ,

Reservoir simulation input (UTCHEM)

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Variables Studied for Database Development

Rheological properties Various EOR polymers Viscosity Relaxation time Planned : up to 10%

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