Carbon Dioxide Sequestration

in Concrete
for Performance Enhancement and
Emissions Reduction
Yixin Shao,
Shao Andrew Boyd,
Boyd Sean Monkman and Sam Wang
McGill University
Gilles Bernardin
St Lawrence Cement

Carbonation curing at early age:

A CO2 consuming process

Early carbonation mechanism (Young, 1974)

CxSHy+(n-x)CaCO3

CO2 uptake (Steinour, 1956)

CnS+(n-x)CO2+yH2O

%CO2 = 0.78 CaO + 1.1 MgO + 1.4 Na2O + 0.9 K2O

Technical advantages:

Accelerated hydration and early age strength

Eliminated [Ca(OH)2]
Reduced atmospheric carbonation in service
Reduced efflorescence in service
Decreased permeability

Objectives

To quantify carbon uptake by precast

concrete products (blocks, pavers,
cement boards and fiber boards)
To evaluate performance of carbonated
products at different ages
To determine the potential for emissions
reduction
d ti

Processing parameters

Carbonation parameters:

For flue
F
fl gas (14% CO2),
) P
P=5
5b
bar, ti
time=2-8hr
2 8h
For recovered CO2 (99% CO2), P=1.5 bar,
time=2hr

Materials (dimension=75x100xt mm):

Block: c=10%, w/c=0.26, compact=10 MPa

Paver: c=20%, w/c=0.26, compact=10 MPa
Mesh bead board: c=60%, w/c=0.3 , cast, dried
Fiber board: c=52%, w/c=0.2-0.26,
compact=0.7MPa, dried

Setup for Carbonation Curing

Heater
CO2 Meter

Thermocouple
Pressure Transducer
Samples

System 5000
Water Tank

Scale

Pressure
V
Vessel
l

Flue
gas

Pure
CO2

Collection of cement kiln flue gas

20

Detected at stack

18
16

CO2 contentt, %

14
12

CO2 content in cylinders = 13.8%

CO2
t t

10
8
6
4
2
0
9:36

10:48

12:00

13:12

14:24

Ti
Time,
hour:min
h
i

15:36

16:48

18:00

Pressure and temperature curves

0.55

45
44

Fiberboard, flue gas

43

0 50
0.50

42
41
40
39
38

0.40

37
36
0.35

35
34
33

0.30

32
0.25

31

Pressure for FG-FRC#6

30

Temperature for FG-FRC#6

29
0.20

28
0

50

100

150

200

250

Time (min)

Pseudo-dynamic
Pseudo
dynamic process
for flue gas

300

Temperrature (oC)

Pressu
ure (MPa)

0.45

Statics process for

recovered
d CO2

Quantification of CO2 uptake

Uptake due to direct mass gain:

( Mass ) aft ,CO 2 ( Mass ) bef ,CO 2 + ( Mass ) lost water

mCO 2
% Mass gain =
=
mcement
mcement

Uptake
p
from mass curve
140
Cellulose fiberboard

2 hours in pure gas

120

Mass (g)

100
80
60
5 hours in flue gas
40
20
0
0

50

100

150

200

Time (Min)

250

300

350

Carbonated concrete block

CO2 uptake (%) & compressive strength (MPa):
Case(withrecovered
CO2)

Uptake,
%

2/4/6/8hr
fc
fc

1,Permaconproduct
2,hydrationreference

24hr
fc

14.2
12.8
10.4
14.6
14.6

6 4hr steam+2hr CO2

6,4hrsteam+2hrCO2

0
7.7
8.8
0
13 7
13.7

2.1(2hr)
7.4(2hr)
8.4(8hr)
( h)
5.2(6hr)
10 8 (8hr)
10.8(8hr)

15 2
15.2

7,4hrCO2

11.0

7.6(4hr)

10.3

3,2hrCO2
4 2h CO2 4 h
4,2hrCO2+4hrsteam
5,4hrsteam

28daysin
plastic
plastic
bag,fc

28daysin
water,
fc

16.1
22.8
21.4
22.4

23.5
25.5
23.7
24.0

23.3
w/spray

23.2

SEM of carbonated block (99%CO2)

Average CO2 uptake=9.8%

SEM of carbonated block (14%CO2)

Average
g 5-hr strength=8.3
g
MPa
Average CO2 uptake=6.4%

14.0
Hydrated

pH
H of Curing Water

13.0

pH of carbonated
p
cement

12 0
12.0
11.0
Carbonated (2 hour)
10.0
9.0
8.0

After 2 hours, uptake=13%

7.0
0

12
16
Curing Time(day)

20

24

28

After 24 hours in sealed bag

1: calcite
2: C3S
3: C2S

Type 30 cement,
after 2-hour carbonation
(2hr) and subsequent
7-day hydration (2hr+7d)

2,3
2,3
2

2,3
1
C30, 2hr+7d, core

After 28 days in sealed bag

2,3

C30, 2hr+7d, surface

C30, 2hr, core
C30, 2hr, surface
10

20

30

40

2 Theta

50

60

Eliminated Ca(OH)2

Carbonated fiberboard
Comparison of uptake and strength by flue gas & pure gas:

Batch Product
B1
B2
B3
B4

Paste
CFB
Paste
CFB

Mass
Gain %
Gain,%
6.8
7.0
13 5
13.5
18.9

Water
Loss %
Loss,%
13.5
14.7
55 5
55.5
59.5

Carbonation
Strength (MPa)
2hr/5hr
28day
7.4(5h)
11.0
10.2(5h) 15.7
8 1(2h)
8.1(2h)
84
8.4
10.5(2h) 12.0

B1 & B2: flue gas carbonation (99% CO2);

B3 & B4: pure gas carbonation (14% CO2).

Hydration
strength (MPa)
5-hr
28day
0.4
10.2
3.1
15.6
04
0.4
10 2
10.2
3.1
15.6

SEM of carbonated
cellulose
ll l
fiberboard
fib b
d
Hydrated

Carbonated in flue gas

Carbonated in pure gas

Effect of subsequent
h d ti on pH
hydration
H

Immediately after 2hr carbonation

Phenolphthalein tests

After 28 days in moisture room

Potential of carbon uptake by precast

products in US and Canada
CMU

Paver

Mesh
board

Fiberboard

4.3109
units

74106
m2

75106 m2

9.1108 m2

5.9

2.6

0.595

4.8

%Uptake with 99% CO2

9.8%

9.8%

12.2%

18.9%

Total uptake from 99% CO2

(Mt)

0.578

0.255

0.073

0.907

%Uptake with flue gas CO2

6.3%

6.3%

4.4%

8.1%

Total uptake from flue gas

(Mt)

0.372

0.164

0.026

0.389

Annual production in US
and Canada
Cement used (Mt)

Energy consumption and CO2 penalty

On site
Step
Recovery

Compression

Transport
Total

Off site

Aspect

Unit

US

CAN

US

CAN

Energy

(kWh/t)

198

198

198

198

CO2e

(kg/t)

119.8

43.6

119.8

43.6

Pressure

(MPa)

(kWh/t)

92.5

92.5

92.5

92.5

CO2e

(kg/t)

56.0

20.4

56.0

20.4

distance

(km)

150

150

CO2e

(kg/t)

16 4
16.4

16 4
16.4

CO2e

(kg/t)

177.4

64.5

193.8

80.9

Net Efficiency

(%)

82.3

93.5

80.6

91.9

Energy
Required

Assuming: 605 gCO2/kWh in the US, 220 gCO2/kWh in

Canada.

Energy comparison
Energyfor1500 Energyperm3
concrete
concrete
blocks(GJ)
( )
((GJ))
Steamcuring
I:atmosphericsteamcuringinordinarykiln

5.242

0.463

II:highpressuresteamcuring(autoclaving)

7.976

0.705

III:atmosphericsteamcuringinEPSinsulation
kiln
1.540

0.136

IV:atmosphericsteamcuringusingautoclave
chamber

2.366

0.209

MEAmethod(290kWh/tCO2=1.04GJ/tCO2)at 0.213
9.8%uptakerateand10%cementcontent

0.019

C b di id
Carbondioxidecuring
i

Conclusions

The annual CO2 sequestration in concrete

building products can reach 1
1.8
8 Mt (1
(1.44
44 net
Mt) with recovered CO2 and 0.9 Mt (0.72 net
Mt) with flue gas in US and Canada .
Assuming cement production in US and
C
Canada
d iis about
b t 100Mt/
100Mt/y and
d itits CO2
emissions is 70%, 1.44Mt net CO2 uptake
can reduce
d
emissions
i i
b
by 2
2.1%.
1%

Conclusions

Flue gas carbonation can have sufficient

early strength and subsequent hydration
hydration.
Early carbonation has no detrimental effect
on late
l t hydration
h d ti strength.
t
th
pH of early carbonated concrete can be
maintained above 11.5, while Ca(OH)2 is
eliminated.
Carbonation consumes much less energy
p
than steam process.

The future

Cement plant could produce two

commodities: cement and CO2.
A carbon credit system has to be established
t provide
to
id iincentives
ti
ffor producers.
d
More researches are needed to help
enhance the uptake capacity, identify the
limits and introduce more niche products that
are in favor of carbonation.

Acknowledgment

Natural Science and Engineering Research

Council (NSERC) of Canada
St Lawrence Cement
CJS Technology