method for the determination of residual carbon dioxide saturation

Method for the Determination of Residual Carbon Dioxide Saturation Using Reactive Ester Tracers

M. Myers, L. Stalker, K.B. Ho, A. Ross and C. DytSenior Researcher with CSIRO and CO2CRCTCCS-6 Trondheim (June 2011)

CSIRO. Determination of Residual Saturation Using Reactive Ester Tracers

Outline

• Why use tracers?• How tracers have been previously applied to CCS sites

• Case studies from Frio and Otway• Inert tracer behaviour• Reactive tracer behaviour• Proposed tracers and hydrolysis• Laboratory determination of partition coefficients• Computational modelling of reactive tracers vs. inert tracers for

residual gas saturation• Conclusions and ongoing work

• Single well residual saturation testOtway Stage 2B (CO2CRC)

Otway


Why use tracers?

• Tracers can….

• Verify the presence of injected CO2

• Confirm arrival at monitoring wells/demonstrate breakthrough

• Show differences in behaviour in different sections of a formation

• Assurance monitoring• overlying aquifers• soil gas• atmosphere

• Potentially give information on storage capacity and saturation levels

Residuallytrapped CO2

Rockgrains Water

Flow of CO2

CO2

Tracer ATracer B

Flow direction


Case study – Frio Stage 1

-0.2

0

0.2

0.4

0.6

0.8

1

10/10/2004 10/11/2004 10/12/2004 10/13/2004

Nor

mal

ised

ratio

SF6KryptonPFT

2nd TracerBreakthrough

3rd TracerBreakthrough

• Injection well to monitoring well

• 30 m distance• 1500 m depth• Arrival 51 hours• Tracers used

• Sulphur hexafluoride• Krypton• Perfluorocarbons

perfluoromethylcyclohexane(PMCH)perfluorotrimethylcyclohexane(PTCH)perfluoromethylcyclobutane(PMCB)perfluorodimethylcyclohexane(PDCH)

From Freifeld et al., 2005


Case Study – Otway

• Injection well to monitoring well

• 300 m distance• 2000 m depth• Arrival 101-121 days• Tracers used

• Sulphur hexafluoride• Krypton• Perdeuterated methane• 1,1,1,2-tetrafluoroethane

0

0.5

1.0

1.5

2.0

2.5

-100 -50 0 50 100 150 200 250 300 350 400 450 500 550 600 650Days

SF6/K

r

0

10000

20000

30000

40000

50000

60000

70000

tonn

es in

ject

ed

Pre-

inje

ctio

n

U1U2U3tonnes gas

Bre

akth

roug

h

Inje

ctio

nst

ops

Data from Boreham et al., 2011


Single well test – Inert vs reactive tracers

= residual CO2Caprock

Storage formation

1. Tracer is injected with water and pushed out of the wellbore into the formation.

2. There it can partition between the water phase (where it is mobile) and the supercritical carbon dioxide phase (where it is stationary).

3. The velocity of the tracer in the formation is therefore dictated by the partition coefficient and the amount of residual CO2saturation.

Inert Reactive


= Tracer 1: With higher partitioning coefficient into water (PCH2O)

= Tracer 2: With higher partitioning coefficient into CO2 (PCCO2)

= Parent tracer compound

Inert Reactive


= Tracer 1: PCH2O

= Tracer 2: PCCO2


Reactive


Reactive tracers require a “soak” time to hydrolyse. Some parent tracer will convert to multiple daughter products.

The daughter products have different functionality to the parent so have different partitioning properties.

= Daughter hydrolysis compound(s)


Inert Reactive

CSIRO. Determination of Residual Saturation Using Reactive Ester TracersTime

Con

cent

ratio

n0

0 Time

Con

cent

ratio

n0

0

= Tracer 1: PCH2O

= Tracer 2: PCCO2 = Daughter hydrolysis compound(s)


Reactive


Con

cent

ratio

n0

0

= Daughter hydrolysis compound(s)


Inert Reactive


Con

cent

ratio

n0

0 Time

Con

cent

ratio

n0

0

= Tracer 1: PCH2O



Single well test – Inert vs reactive tracers


Con

cent

ratio

n0

0

REACTIVE

Time

Con

cent

ratio

n0

0

INERT = Tracer 1: PCH2O




Single well residual saturation test – Otway Stage 2B (CO2CRC)


Rockgrains Water Flow of CO2





1. Reactive tracer injected and pushed into formation with CO2/water.

2. Soak period to allow hydrolysis reaction.

3. Back production and recovery of parent tracer and daughter products.

CO2

Parent tracerDaughter product(s)

Parent Compound Triacetin Tripropionin Propylene glycol diacetate

Structure

Formula C9H14O6 C12H20O6 C7H12O4

Breakdown/daughter products

GlycerolPartially hydrolysed triacetinAcetic acid

GlycerolPartially hydrolysed tripropioninPropionic acid

Propylene glycolPartially hydrolysed propylene glycol diacetateAcetic acid

Partitioning coefficient

~10 ~50 ~4

Cost per Kg $3 $8 $10

OHSE on parent and daughter compounds

Parent compounds are commonly used as food flavourings and cosmetic additives. The corresponding acids and alcohols (hydrolysis daughter products) are also food and cosmetic additives.

Amounts required* Solubility = 72g/L Solubility = 2.6g/L Solubility = 100g/L


Tracers Proposed

Summary of what we expect to see

0

0,001

0,002

0,003

0,004

0,005

0,006

0,007

0 100 200 300 400

Non-reactive no drift PC 5

Non-reactive no drift PC 0.2


Hours

Rel

ativ

e ab

unda

nce

No drift

Tracers injected Tracers produced

= With higher partitioning coefficient into CO2

= With higher partitioning coefficient into H2O

CO2 saturation = 0.2 CO2 saturation = 0.2


0

0,001

0,002

0,003

0,004

0,005

0,006

0,007

0 100 200 300 400

Non-reactive drift PC 5

Non-reactive drift PC 0.2


= With higher partitioning coefficient into CO2

= With higher partitioning coefficient into H2O

CO2 saturation = 0.2 CO2 saturation = 0.2

Tracers injected Tracers produced

Rel

ativ

e ab

unda

nce

Hours

Drift


0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

168.00 188.00 208.00 228.00 248.00 268.00 288.00 308.00 328.00

Sc = 0.05

Sc = 0.30

Sc = 0.30

Sc = 0.05Inert tracersno drift velocity

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0.0035

0.004

0.0045

168.00 188.00 208.00 228.00 248.00 268.00 288.00 308.00 328.00

Sc = 0.30

Sc = 0.05

Sc = 0.30Sc = 0.05

Inert tracers1.08 m/day drift velocity

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

168.00 188.00 208.00 228.00 248.00 268.00 288.00 308.00 328.00

Sc = 0.05

Sc = 0.30

Sc = 0.05 Sc = 0.30 Reactive tracers1.08 m/day drift velocity

Inert tracersNo drift velocity

Inert tracers1.08 m/d drift velocity

Reactive tracers1.08 m/d drift velocity


PC 5PC 0.2

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0.0035

0.004

0.0045

168.00 188.00 208.00 228.00 248.00 268.00 288.00 308.00 328.00

Sc = 0.05

Sc = 0.30

Sc = 0.05

Sc = 0.30

Reactive tracersno drift velocity

Reactive tracersNo drift velocity

• Conclusions• Reactive tracers are potentially more accurate and robust systems

for determining residual saturation (including drift) compared to inert tracers

• Choice of reactive tracer is dictated by • Residual saturation estimation• Temperature (reaction kinetics)• pH & salinity• Rock matrix (adsorption effects)• Toxicity

• Ongoing work• Field trials at CO2CRC Otway Residual Saturation Test• Analytical method development • Laboratory experiments to develop a package of partition

coefficients and core flood experiments


Conclusions & Ongoing work

Contact UsPhone: 1300 363 400 or +61 3 9545 2176

Email: [email protected] Web: www.csiro.au

Thank you

CESREMatt MyersPostdoc

Phone: 08 6436 8708Email: [email protected]: www.csiro.au

CESRELinda StalkerSenior Researcher

Phone: 08 6436 8909Email: [email protected]: www.csiro.au/people/Linda.Stalker.html


method for the determination of residual carbon dioxide saturation

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