Safety and Security for CO 2 Geological Storage while CO 2 /H 2 O/Rock Reaction

Safety and Security for CO2 Geological Storage while CO2/H2O/Rock Reaction

Bo Peng Enhanced Oil Recovery Research Center, China University

of Petroleum, Beijing, China

Sep.23, 2009 Canberra,Australia

Content

1. Background 2. CO2 and Salt Solution Reaction 3. CO2 and Rocks Reaction 4. Wettability of the Rock 5. Permeability of the Rock 6. Safety and Security for CO2 Storage 7. Conclusion

1.Background1.Reduction of Green House Gas Emission---A topic which

concerned around the world nowadays. Carbon Capture and Storage(CCS) is one of the most important technology.

①

②②

2-3℃

1.Background

Biggest Emitters 2000-2025

24%

15%

12%6%4%

4%

35%USAChinaWest EuropeRussiaIndiaJ apanOther

Top six = 66%

Cumulative CO2 Emissions 2000-2025, EIA, IEA 2002

2. Chinese Government Concerns Greatly about Reduction of CO2 Emission and Utilization of It as Resources

Chairman Hu Jintao

Primer Wen Jiabao

“973”, “863” Reseach

Projects….

Petrochina,HuanengPil

ot Test….

1.Background3. CO2 Storage and EOR in China

Oil&Gas Reservoir,

Subsurface Salaquifer, coal

bed, ideal Place for CO2

Storage

923 billion tons of CO2 can

be storaged in reservoir,

which is 45% of global

cumulative emission in

2050.

1. Background4. Safety and Security for CCS have attracted more and mor

e attention.

1. Background

CO2/H2O/Rock Reaction

Wettability Permeability

EOR and CO2 storage EOR and CO2 Storage

NaCl

Salt Solution(Aqueous Solution)

Na2SO4

MgCl2

CaCl2

CaCO3

Ca(HCO3)2

Daqing Formation Water

The Effect Factors

Pressure

Tempreture

2. CO2 and Salt Solution Reaction

CC

1

3

5

7

8

4

6

2

1. CO2 ； 5.Higher Pressure Vessel ； 8. pHS － 3C Meter

pH Measurement System in Higher Pressure


0.0 0.5 1.0 1.5 2.0 2.53.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

pH

压力 / MPa

去离子水 0.1% 0.5% 1.0%

0.0 0.5 1.0 1.5 2.0 2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

pH

压力 / MPa

去离子水 50 mg/L 300 mg/L 800 mg/L 1000 mg/L

NaCl Solution Na2SO4 Solution


Effect on pH by Pressure on Aqueous SystemsEffect on pH by Pressure on Aqueous Systems (25℃)

pH≈3.0

CO2:H2CO3in Water,

0.0 0.5 1.0 1.5 2.0 2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

pH

压力 / MPa


0.0 0.5 1.0 1.5 2.0 2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

pH

压力 / MPa


CaCl2 SolutionMgCl2 Solution



≈

pH≈3.0

CO2:H2CO3in Water,

0.0 0.5 1.0 1.5 2.0 2.5

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

pH

压力 / MPa

去离子水 50 mg/L 300 mg/L 500 mg/L 1000mg/L

0.0 0.5 1.0 1.5 2.0 2.5

3.54.04.55.05.56.06.57.07.58.08.59.09.5

10.010.511.0

pH

压力 / MPa




Na2CO3 Solution NaHCO3 Solution

pH≥3.0

CO2:HCO3－ in Wa

ter,

NaCl NaHCO3 Na2CO3 Na2SO4 CaCl2 MgCl2·6H2O

1987.8 3013.11 170.38 1.00 1.99 6.97

0.0 0.5 1.0 1.5 2.0 2.5

5

6

7

8

9

10

pH

压力 / MPa

Daqing Formation Water （ mg/L ）

2. CO2 and Salt Solution ReactionpH≥3.5

CO2:HCO3－ in Wa

ter,

0.0 0.5 1.0 1.5 2.0 2.52.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

pH

压力 / MPa

25℃ 40℃ 60℃

0.0 0.5 1.0 1.5 2.0 2.5

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

pH

压力 / MPa

25℃ 40℃ 60℃

10% CaCl2

10% MgCl2

Effect on pH by Temperture on Aqueous SystemsEffect on pH by Temperture on Aqueous Systems

2. CO2 and Salt Solution ReactionpH decrease while T goes up. H2CO3 give more H+

Calcite PiecesCalcite PiecesHH22O + COO + CO22

Rock Surface TopograRock Surface Topographic Imagephic Image

Formation of the Solution Formation of the Solution

Calcite PowdersHH22O + COO + CO22

Permeability of Sand PipePermeability of Sand Pipe

SEMSEM

Ions Spectrum Ions Spectrum

Permeability Measurement Unit

3. CO2 and Rocks Reaction


Rock Surface TopograRock Surface Topographic Imagephic Image


Permeability of Sand PipePermeability of Sand Pipe

取样1

2

3

4

P2

P1

1.CO2 ； 3.Reaction Vessel ； 4.Heating System ；

Reaction Unit in High Pressure Reaction Unit in High Pressure


Rock CharacteristicRock Characteristic

Calcite:97.8%Calcite:97.8% ；； Dolomite:2.2%Dolomite:2.2%

d=9.

3611

d=3.

8503

d=3.

1185

d=3.

0295

d=2.

4913

d=2.

2801

d=2.

0911

d=1.

9236

d=1.

9077

d=1.

8711

d=1.

6009

d=1.

5224

d=1.

5141

d=1.

5037

d=1.

4179

10 20 30 40 50 60 70

2-Theta(°

x10 3̂

25

50

75

Inte

nsity

(CP

S)

[PYL3.ASC]


Before Reaction

Rock Surface Topographic ImageRock Surface Topographic Image

Pressure ： 2 MPa ； Temperature ： 25 ℃； Reaction Time ： 20days


After Reaction

Before Reaction




After Reaction

Ion

TimeK+ Na+ Ca2+ Mg2+

Before Reaction

1.5 3.0 12.6 1.4

After Reaction

2.7 3.26 108 6.5

Ion in the solution before/after CO2 and Rock Reaction （ mg/L ）

CaCO3 + H2O + CO2 Ca2+ + 2HCO3-




0 2 4 6 8 10 120

10

20

30

40

50

阳离

子浓

度 /

mg/

L

反应时间 / d

K+

Na+

Ca2+

Mg2+

0 2 4 6 8 10 12-200

0

200

400

600

800

1000

1200

1400

1600

HC

O3-

浓度

/ m

g/L

反应时间 / d

Ions in Formation Water Ions in Formation Water


Pressure ： 2 MPa ； Temperature ： 25 ℃；

Ca2+,HCO3-↑. 8 days Stably



Pressure ： 2 MPa ； Temperature ： 60℃；

0 2 4 6 8 10 12

0

100

200

300

400

500

600

700

800

阳离

子浓

度 /

mg/

L

反应时间 / d

K+

Na+

Ca2+

Mg2+

0 2 4 6 8 10 12

0

500

1000

1500

2000

HC

O3-

浓度

/ m

g/L

反应时间 / d



Pressure ： 2 MPa ； Temperature ： 90℃；

0 2 4 6 8 10

0

50

100

150

200

250

阳离

子浓

度 /

mg/

L

反应时间 / d

K+

Na+

Ca2+

Mg2+

0 2 4 6 8-200

0

200

400

600

800

1000

1200

1400

1600

HC

O3-

浓度

/ m

g/L

反应时间 / d

CO2↑

Sand Core + Daqing Formation WaterCO2

Permeability of Sand Core

Rock Pieces +

Non-ion water

Daqing Formation Water

Dilute Daqing Formation Water

NaCl

CaCl2

CO2Contact Angle

CO2Contact Angle

CO2

Contact Angle

4. Wettability of the Rock

d=4.

2569

d=4.

0331

d=3.

3446

d=3.

2465

d=3.

1918

d=2.

8833

d=2.

4584

d=2.

2828

d=2.

2371

d=2.

1291

d=1.

9808

d=1.

8189

d=1.

6724

d=1.

6593

d=1.

5424

d=1.

3827

d=1.

3727

10 20 30 40 50 60

2-Theta(°

x10 3̂

10

20

30

40

50

60

70

Inte

nsity

(CP

S)

[PYL1.ASC] <2T(0)=-0.16>

Silica Sand:97.7% ； Potash feldspar:0.6% ； Calcite:0.1% Dolomite:0.6% others:1% ；


Non-ions Non-ions

Contact Angle: Rock Pieces + Non-ions + CO2

Time（ d ） θa0 θa θa0 -θa

2 120.59° 120.52° 0.07°

4 119.57° 119.09° 0.48°

6 120.14° 118.08° 2.06°

8 120.65° 120.61° 0.04°

时间（ d ）

0 2 4 6

θa1 121.14° 120.30° 120.94° 120.94°

PressurePressure ：： 1MPa1MPaTempretureTempreture ：： 25 25 ℃

θa0 –No-CO2 ； θ a – CO2 ； θa1 – Water Treatment


Daqing Formation WatDaqing Formation Water er

Contact Angle: Rock Pieces + Non-ions + CO2

PressurePressure ：： 1MPa1MPaTempretureTempreture ：： 25 25 ℃

θa0 –No-CO2 ； θ a – CO2 ； θa1 – Water Treatment


时间（ d ） θa0 θa θa0 -θa

2 120.78° 61.61° 59.17°

4 117.35° 43.55° 73.80°

6 119.49° 51.63° 67.86°

8 118.39° 42.31° 76.09°

时间（ d ） 0 2 4 6

θa1 122.93° 106.23° 107.06° 111.88°

Contact angle ↓ 。

NO CO2, NO Contact Angle Change.

Pressure ： 1 MPa Tempture ： 25 ℃

Effect of Ions on Contact Angle Effect of Ions on Contact Angle

2 3 4 5 6 7 8

0

10

20

30

40

50

60

70

80

90

100

110

120

接触

角变

化 /

°

反应时间 / d

100% 去离子水 25% 大庆模拟水 +75% 去离子水 50% 大庆模拟水 +50% 去离子水 75% 大庆模拟水 +25% 去离子水100 % 大庆模拟水


More Daqing Water, More change on contact angle

Pressure ： 1 MPa Tempture ： 25 ℃

Effect of Ions on Contact Angle Effect of Ions on Contact Angle


2 3 4 5 6 7 8

0

10

20

30

40

50

60

70

80

90

100

接触

角变

化 /

°

反应时间 / d

去离子水 0.01mol/kg 0.1mol/kg 0.5mol/kg

2 3 4 5 6 7 8

0

20

40

60

80

100

接触

角变

化 /

°

反应时间 / d

去离子水 0.01mol/kg 0.1mol/kg 0.5mol/kg

NaCl CaCl2

5. Permeability of the Rock

1.N2 2.CO2 3. 5.Sand Filling Model 6. Pumper

d=4.

2529

d=3.

3421

d=2.

4558

d=2.

2812

d=2.

2355

d=2.

1272

d=1.

9787

d=1.

8175

d=1.

6715

d=1.

6585

d=1.

5413

d=1.

3818

d=1.

3715

10 20 30 40 50 60 70

2-Theta(°

x10 3̂

25

50

75

Inte

nsity

(CP

S)

[PYL6.ASC]

Silica Sand:98.1.7% ； Potash feldspar:0.3% ； Calcite:0.3% Dolomite:1.2% others:0.1% ；


Time(CO2)（ d ）

P （ kPa ） Permeability（ mD ）

Changement （％）

0 5.5 111.3 －2 5.0 122.5 10

7 4.0 153.1 37.6

Time(CO2)（ d ）

P （ kPa ） Permeability（ mD ）

Changement （％）

0 5.0 125.8 －

7 4.0 157.3 25

14 3.0 209.7 66.7

Effect of CO2 on permeability of Sand CoreEffect of CO2 on permeability of Sand Core

L ： 50. 24 mm ； D: 25 .00 mm ； S ： 25.57% ； T ： 30℃

L ： 51.60mm ； D ： 25 mm ； S ： 31.23% ； T ： 30℃


CO2 Increase the permeability 。

-2 0 2 4 6 8 10 12 14 16200

400

600

800

1000

1200

1400

反应时间 / d

渗透

率 /

mD

放置

通入 CO2

0 5 10 15 20100

150

200

250

300

350

400

渗透

率 /

mD

反应时间 /d

放置

通入 N2

通入 CO2

P:2MPa ； Reaction T: 65℃； Test T ： 25 ℃

Silica sand: Calcit=1 ： 1


Effect of CO2 on Permeability of Sand Filling Model Effect of CO2 on Permeability of Sand Filling Model

6.Safety and Security for CO2 Storage

6.Safety and Security for CO2 Storage

6.Conclusion1. After carbon dioxide injection, pH of single brine, Daqing modeled

water dropped and then gradually decreased to a steady value. Magnesium chloride and calcium chloride solution (wt%=10%) pH decreased with temperature increase.

2. The SEM study shows that dissolution occurs on calcite surface. The Ca2+ and HCO3- concentration increased with reaction time to steady values. The time reach to steady is shorter with temperature increase.

3. The permeability of sand pipe filled with calcite and quartz increased with reaction time.

4. When inject into CO2, contact angle of cores slice in Daqing modeled water decreased and the proportion of Daqing modeled water is bigger, the change of contact angle is bigger.

5. The Safety and Security for CO2 Storage is correlated to the CO2/H2O/Rocks Reactions

Thanks for your attention!

Documents

Safety and Security for CO 2 Geological Storage while CO 2 /H 2 O/Rock Reaction