Академический Документы
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Культура Документы
(NETL, 2011)
q MEA Challenges
Water-Gas
Shi-:
CO
+
H2O
!"
H2
+
CO2
MO + CO2 MCO3
MO + CO M + CO2
MCO3 MO + CO2
M + H2O MO + H2
CO2 Utilization
Challenges and Opportunities
(NETL, 2011)
U8liza8on
Capture
Storage
q Ocean storage
q Biological fixation
q Geologic storage
q Mineral carbonation
Graphic
courtesy
of
BP
(Geo3mes,
2003)
Research Objectives
Develop transformative approaches towards sustainable
energy with integrated carbon capture, utilization, and storage
Availability
silicate minerals >> industrial wastes
Crystallinity
industrial wastes < minerals
Reactivity
industrial wastes > minerals
Pre-processing requirements
(e.g., mining, crushing etc.,)
industrial wastes < minerals
Carbon Mineralization
Source: Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier
q Develop technologies to integrate carbonation of industrial wastes at the site of CO2 generation
q Determine the fate of hazardous components such as Cr, Ni during carbonation
q Use CO2 to treat hazardous Asbestos Containing Materials (ACM)
9
Worldwide Availability of
Ca and Mg-bearing Alkaline Materials for CCUS
Mineral Carbonation of
Peridotite
10
In-Situ CO2
Storage
Relatively
homogenous
mineralogy
Heterogeneous
mineralogy
40
Not limited by
reactor size; Use of
geothermal gradient
20
Possible production
of value-added
products
Multiple CO2
trapping
mechanisms
No monitoring
required
Relatively
economical at this
time
80
E x te n t
of
C a rb on a tion
(% )
Ex-situ CO2
Storage
1 hr
4 hr
0
Magnetite
A northite
B as alt
T alc
A ugite
L izardite
Alumino-silicates
Abundance of less reactive
minerals vs. limited availability
of highly reactive minerals
A ntigorite
F ayalite
Silicates
Carbonation efficiency defines
whether mineral is utilized for
ex-situ or in-situ storage
11
Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier
12
Ca-bearing Silicates
Mg-Carbonate
Phases
Geothite
(a-FeO(OH))
(CaSiO3)
Silica
(SiO2)
Ca-Carbonate
Phases
Nesquehonite
(MgCO3.3H2O)
Vaterite
30 m
Hydromagnesite
(Mg5(CO3)4(OH)24H2O)
1 m
500 nm
1 m
Aragonite
30 m
1 m
Magnesite
(MgCO3)
30 m
Calcite
1 m
13
16
Ea = 52.9 kJ/mol
Ea = 31 kJ/mol
( 0.1
2042
)
T (K )
+ 0.5
(H )
+ 0.003 10
2
+ 0.46
Hanchens rate law: r
e
Mg ,dis 2 (mol / cm .s ) = 0.0854 ( H )
Magnesite
Precipitation Rate:
(Saldi et al., 2012)
( 2.5
6362.76
T (K )
KCO3 KOH
KOH aCO 2 + KCO3 KOH + KCO3 aOH
3
2042
)
T (K )
) M (1 MMg )
17
-
-
-
-
-
Brucite: Mg(OH)2
Lansfordite: MgCO35H2O
Nesquehonite: MgCO33H2O
Hydromagnesite: Mg5(CO3)4(OH)24H2O
Magnesite: MgCO3
19
" IAP %
= log $
'
# K SP &
!
20
Magnesite:
MgCO3
Hydromagnesite: Mg5(CO3)4(OH)24H2O
Nesquehonite:
MgCO33H2O
21
At 150 C
Make Hydromagnesite
At 200 C
Make Magnesite
22
Mg(OH)2
Al2O3
MgCO3
Starting materials
Swanson et al., PCCP 2014
23
25
10
-2
10
-2
10
-3
80
100
120
140
160
o
T e m p e ra
ture
( C )
180
200
1 2 5
C
o
1 5 0
C
o
1 8 5 C
9 0
C
o
1 2 5 C
8 -4
10
1 5 0
C
o
1 8 5 C
6 1
10
P ore
D ia m e te r
(nm )
100
0
1
10
100
1000
9 0 C
10
P a rtic le D ia m e te r ( m )
-4
10
T G A
T C A
A R C
[1
h r]
-3
E x te n t of C a rbona tion (% )
100
10
10
P ore
D ia m e te r
(nm )
100
26
Olivine
(b)
(b)
Magnesite
(II)
(II)
185 C
o
y
ti
s
n
e
t
n
I
e
v
it
a
l
e
R
150 C
CC
(I)(I)
o
125 C
10 m
(b)
(b)
90 C
40
50
60
70
80
30
Mg
Mg
(II)
(II)
U nre a cte d
20
OO
(a)
(a)
0 .10 .1
CC
Magnesite
Magnesite
(I)(I)
SiSi
OO
Mg
Mg
Si-rich
Si-rich
Phase
Phase
10 m
0 .10 .1
1 1
1 01 0
keke
VV
27
(a)
80
80
60
60
40
40
T G
GA
A
T
T CC A
A
T
A SS U
[1
h
U
[1
hr]
A
r]
0.5
0.5
1.0
1 .0
1.5
1.5
2.0
2 .0
2.5
2.5
10
- 3
10
- 4
10
- 5
10
- 6
(b)
Mg -e qu ilibrium
C arb ona te
-
equ ilib rium
0 .0
0 .5
[N
[NaaHHCC O
O 3 ]
(M)
]
( M)
(c)
4
4
2
2
0
0
1
1
10
100
1000
P a rtic10
le
D ia m e10
te0r
( m ) 1 0 00
P a rtic le
D ia m e ter
( m )
oC,
10
2.0
10
(d)
- 2
-3
10
10
10
-2
U nre a c te d
D .I.W a te r
Un re ac te d
0.32
M
D .I .W a ter
0.48
M
0. 32
M
0.64
M
0. 48
M
1.00
M
0. 64
M
2.00
M
1. 00
M
2. 00
M
V o lum e ( % )
V olum e (% )
10
1 .5
P ore
V m
olum
(m
C uCmum
u laula
tiv etiv
Peore
V olu
e
( mel/g
) l/g )
10
1.0
[N a H C O 3 ] ( M)
- 3
-4
10
- 4
10
10
U nrea c ted
D
.I.Wac
a ter
Unre
ted
0.32
M
D .I .W a ter
0.48
M
0.3 2
M
0.64
M
0.4 8
M
1.00
M
0.6 4
M
1.0 0
M
2.00
M
2.0 0
M
100
100
00
0.0
0 .0
10
- 2
20
20
10
- 1
100
1 00
C on c e ntra tio n
(m ol /k g )
E x ten t of C a rb o na tio n ( % )
E x te nt of C a rbona tion (% )
P ore D i a m e te r ( n m )
28
(a)(a)
(b) (b)
O
Mg Mg
(2) (2)
10 m
Magnesite
Magnesite
O
Si
Si
Mg Mg
Si-rich
Phase
Si-rich
Phase
0.1 0.1
0.1
11
10
10
10
k eV k eV
keV
(b)
Ratetime Vtime
=
Ratetime=0 Vtime=0
30
(1) (1)
125 oC 150 oC
(Medium) (High)
90 oC
(Low)
R ela tiv e
In
ten s ity
Relative
Intensity
(a)
(b)
Our work
T (oC)
rMg,dis1, t = 0
(mol/m2.s)
90
2.1 x 10-12
125
6.5 x 10-12
150
1.3 x 10-11
(c)
(d)
Hanchen et al.,
T (oC)
rMg,dis2, t = 0
(mol/m2.s)
90
1.4 x 10-11
125
6.7 x 10-11
150
1.7 x 10-10
31
pH of fluid
+
pH<5
+
pH>7
Pressure
Temperature
+
Mineral reactivity
+
+ +
+
+
Mineral dissolution
Mineral carbonation
Reactive
surface area
+
+
Porosity
+
Permeability
+
Formation of microfractures
32
Research Objectives
Develop transformative approaches towards sustainable
energy with integrated carbon capture, utilization, and storage
Deeper formations
Lack of water
34
of clay matrix
q Before CO2 injection
36
Non-calcite
Carbonaceous
(wt%)
58.6
21.4
5.1
1.6
0.2
0.3
4.1
1.1
0.1
0.03
0.05
0.03
7.2
1.26
0.74
0.52
Shale
Calcite-bearing
Argillaceous
(wt%)
55.7
17.5
6.6
2.3
3.6
0.2
4.2
0.8
0.1
0.04
0.04
0.04
8.0
1.62
0.67
0.95
Oil-rich
Bituminous
(wt%)
40.3
9.5
4.1
1.7
19.4
0.8
2.1
0.5
0.2
0.05
0.03
0.02
19.4
6.49
2.48
4.01
37
Research Questions
What is the effect of dry vs. wet scCO2?
What are the effects of variable chemical compositions of shale?
Can CO2 be used as an alternative for acid-induced fracking?
38
40
Acid fracking
Typical shale deposit
Are there are any alternative benign chemicals that can be used
to induce chemical changes?
44
Reacted
0.1 M Na-citrate,
PCO2 = 150 atm
Unreacted
Calcite-rich
Calcite-rich
Non-calcite
Non-calcite
Oil-rich
Oil-rich
Reacted
45
Research Objectives
Develop transformative approaches towards sustainable
energy with integrated carbon capture, utilization, and storage
Summary
Combination of multi-scale experimental and modeling studies
are needed to develop CCUS technologies
Investigation of coupled physical and chemical phenomena is
essential for predicting the fate of CO2 above and below the
ground
Accurate kinetic and mechanistic data are needed to predict
multi-scale and multi-temporal interactions of CO2 with different
materials
Identification of all processes that emit CO2 and determination of
methods to limit these emissions are needed to close the carbon
balance
47
Acknowledgements
Advisors and Collaborators
Prof. Alissa Park (Columbia)
Prof. Peter Kelemen (Columbia)
Prof. Juerg Matter (Southampton)
Dr. Pat Brady (Sandia)
Prof. Venkat Venkatasubramanian (Columbia)
Dr. Babji Srinivasan (IIT)
Dr. Claudio Natali (IGR, Italy)
Dr. Chiara Boschi (IGR, Italy)
48