Green Methanol from the Hydrogenation of Carbon Dioxide
Claudio J. A. Mota1,2
cmota@iq.ufrj.br
1Federal
University of Rio de Janeiro – Institute and School of Chemistry, Brazil
2INCT
Energy & Environment, UFRJ, Brazil
Chemistry and Fuels
Wood
Until 1700
Coal
1700-1900
Petroleum
1900 - today
CO2 Concentration in the Atmosphere
CO2 Net Emissions in 2011:
16.1 Billions Mton
[CO2 atmosphere
concentration]:
400 ppm
(2013)
~ 40%
increase
1 Pg = 1 Petagram = 1x1015g = 1 Billion metric tons = 1 Gigaton
278 ppm
1 Kg Carbon (C) = 3.67 Kg Carbon Dioxide (CO2)
(1785) – Industrial Revolution
starts
Source:
Global
Carbon Project 2014
CO2 Concentration in the Atmosphere
Glycerol
C&EN 2009, vol 87, number 22, pages16-17
Glycerol
O
OH
HO
"H+"
OH +
O
O
+ H2O
OH
C. X. da Silva, V. L. C. Gonçalves, C. J. A Mota Green Chem. 2009, 11, 38-41
6
2.5
4
3
Gasoline A
Gasoline C
2
1
Octane number increment
Gum (mg/mL)
5
2.0
Gasoline A
Gasoline C
1.5
1.0
0.5
0.0
0
0
1
2
3
4
Ketal (%)
5
6
0
1
2
3
4
5
Ketal (%)
Mota, C. J. A., Silva, C. X. A.; Rosenbach, N.; Costa, J. Silva, F.. Energy Fuels 2010, 24, 2733
Glycerol
OH
OH
HO
OH +
HO
EtOH
O
"H+"
+
O
HO
OH
+ H2O
OH
O
O
O
+
HO
O
Flow Properties ASTM – D 97
SAMPLE
Cloud (°C)
Freezing (°C)
Pour (°C)
B 100 (PALM)
18
15
18
B100 + 0.1 % ETHERS
15
12
15
B100 + 0.5 % ETHERS
14
11
14
B100 + 1 % ETHERS
14
11
14
Biodiesel
O
O
R1
R1
O
OCH3
OH
O
R2
O
O
+ 3 CH3OH
HO
KOH
R2
OCH3
O
OH
+
B7 - 2014
glycerol
O
R3
O
vegetable oil
R3
OCH3
Biodiesel
A. L. Lima, A. Mbengue, M. Guarnier, R. A. Sangil, C. M. Ronconi, Claudio J. A. Mota. Catal. Today 2014, 226, 210-216.
Biodiesel
RCO2H
RCO2CH3
+
+
H
+
H
H
OH-
-
OH
Triglyceride
-
OH
H+
H+
3 RCO2CH3
H+
Concept of CO2 Utilization
http://co2chem.co.uk/
“Anthropogenic Chemical Carbon Cycle" , George A. Olah et al, JACS 2011,133,12881
Industrial Initiatives of CO2 Hydrogenation to Methanol
Mitsui Chemicals | Osaka, Japan
Pilot Plant - 100 tonnes MeOH/yr
 Cu/ZnO promoted catalyst
 Packed bed (25 kg catalyst)
 CO2 as feedstock
 H2 from Water Photolysis
 Catalyst life: 4,500 h

Source: Mitsui Chemicals – Information Brochure
Carbon Recycling International | Iceland




Commercial Plant since 2011
5 MM Liters/yr of methanol
CO2 Reclaim: 4.5 MM Tonn/yr
H2 from water electrolysis using
geothermal energy
Source: Carbon Recycling International
Importance of Methanol
 Production of biodiesel
 Production of formaldehyde
 Production of acetic acid
 Production of dimethyl ether (DME)
World production around
50 millions tonnes per year
Fonte: Methanol Institute
 Production of resins and plastics
 MTH  olefins and hydrocarbons (fuels)
World Methanol Industry  US$ 36 billions/year with 100 thousand jobs
Fonte: Methanol Institute
Thermodynamics Considerations
Methanol formation:
CO + 2H2
CH3-OH
ΔHO50Bar,298K = - 90.6 kJ/mol
CO2 + 3H2
ΔHO50Bar,298K = - 49.4 kJ/mol
CH3-OH + H2O
Reverse WGS as a side reaction:
CO2 + 3H2
CO + H2O
ΔHO50Bar,298K = + 41.1 kJ/mol
 Methanol synthesis is exothermic
 Reduction of molecularity (3:1 for CO/H2; 4:2 for CO2/H2)
 Thermodynamics:
Low temperature and high pressure favor the methanol synthesis
Green Methanol Plant in Brazil  Bioethanol Economy
C6H12O6
yeast
2 C2H5OH + 2 CO2
Methanol forma on:
CO2 + 3H2
CH3-OH + H2O
Initial studies
ΔHO50Bar,298K = - 49.43 kJ/mol
Cu/Zn/Al
50/40/10 molar ratio
Weight: 500 mg
Reverse WGS as a side reac on:
Catalyst Activation:
3-steps reduction: 10%H2/N2
(1) 140oC for 5 h;
(2) Raised to 270oC in 2 h
(3) 270oC for 2 h
Reaction Conditions:
Temperature: 230, 250, 270oC
Pressure: 15, 30, 50 bar
WHSV: 10 h-1
CO2/H2: 1/3 molar ratio
TOS: 20 h
CO2 + H2
CO + H2O
ΔHO50Bar,298K = + 41.12 kJ/mol
Initial Studies
Cu/Zn/Al (50/40/10 mol%) WHSV = 10 h-1 ; TOS = 20 h ; H2:CO2 = 3:1
20
100
18
90
70 bar
16
80
50 bar
14
70
Selectivity (%)
CO2 Conversion (%)
270 oC
12
10
8
6
30 bar
60
50
40
30
4
20
2
10
0
70
50
Pressure (bar)
30
0
CH3OH
CO
Products
CH4
Cu/Zn/Al (50/40/10 mol%) WHSV = 10 h-1 ; TOS = 20 h ; H2:CO2 = 3:1
MeOH Yield (gCH3OH/kg.h)
1000
50 bar CuZnAl
900
30 bar CuZnAl
800
15 bar CuZnAl
700
Mitsui
600
500
400
300
50 bar
200
30 bar
100
15 bar
0
220
230
240
250
260
270
280
290
Temperature (oC)
R. S. Monteiro and C. J. A. Mota Quím. Nova 2013, 36, 1483-1490
300
Standard Catalyst Preparation  Effect of Promotors
1. Metal salts water solution
Cu, Zn, Al, Ce, Mg and Zr Nitrates
2. One-single pot solution
pH ~ 3; heating
1000 rpm
3. Co-precipitation (pH = 6-7)
1M NaOH; dropwise
T = 60- 70oC; aged 60 min
pH = 3
4. Filtration/Washing
5. Drying
T = 160oC; 10oC/min
18 hrs.
6. Calcination
T = 600oC; 10oC/min
2h
7. Crushing and Sieving
Cu/Zn/Promotors (50/40/10 mol%)
pH = 5
pH = 7-8
CO2 Hydrogenation over Standard-Prepared Catalysts
Methanol Yield (gMeOH/kgcat.h)
800
700
600
Equilibrium Yield (250oC, 50 bar)
CuZn based catalysts – Promotion Effect
500
400
300
200
100
0
Al
Zr
ZrAl
CeAl
230oC
CeZr
250oC
MgAl
MgZr
ZrAlGaSi
CO2 Hydrogenation over Standard-Prepared Catalysts
CO2 + 3H2
CH3-OH + H2O
CO2 + H2
ΔHO50Bar,298K = - 49.4 kJ/mol
CO + H2O
ΔHO50Bar,298K = + 41.1 kJ/mol
CuZn based catalysts
CO2 Conversion (mol.%)
25
100
40
90
20
CO Selectivity (mol.%)
CH3OH Selectivity (mol.%)
35
80
30
70
15
25
60
50
10
20
40
15
30
10
5
20
5
10
0
0
230oC
ZrAl
250oC
ZrAlGaSi
0
230oC
ZrAl
250oC
ZrAlGaSi
230oC
250oC
ZrAl
ZrAlGaSi
Activity/Structure Correlation  BET Area
CuZn based catalysts
700
ZrAlGaSi
600
ZrAl
MeoH Yield
500
CeAl
400
CeZr
MgAl
300
Zr
MgZr
200
R² = 0.894
100
0
0
10
20
30
40
BET Surface Area (m2.g-1)
50
60
Activity/Structure Correlation  TPR Profile
CuZn based catalysts
300oC
416oC
ZrAlGaSi
• Catalyst activation: 270oC
ZrAl
• CuO  Cuo (> 300oC)
• CuO surface reduction under
CeAl
reaction conditons.
• Better MeOH yield on catalysts
Al
with lower temperature of
reduction
CuO
100
150
200
250
300
350
400
Temperature (oC)
450
500
550
600
• Promoters allow CuO reduction
at lower temperatures
Activity/Structure Correlation  DRX
CuZn based catalysts
ZnO
(100)
CuO
(111)
ZnO
(101)
ZnO
(002)
CuO
(111)
Amorphous phase
or tiny particles??
ZrAlGaSi
ZrAl
SnAl
CeAl
MgAl
Al
30
31
32
33
34
35
36
2 Theta (O)
37
38
39
40
Improved Catalyst Preparation
1. Metal salts water solution
Cu, Zn, Al, Ce and Zr Nitrates
Reaction Conditions: 250oC; 50 bar; 10 h-1
2. One-single pot solution
pH ~ 3; heating
Cu/Zn/Zr/Al
1000 rpm
IMP
3. Co-precipitation (pH = 6-7)
1M Na2CO3; dropwise
T = 60- 70oC; aged 60 min
4. Filtration/Washing
STD
5. Drying
T=
160oC;
10oC/min
18 hrs.
6. Calcination
T=
600oC;
10oC/min
(STD)
T = 380 oC; 10oC/min (IMP)
MeOH Yields – Cu/Zn/Zr/Al:
7. Crushing and Sieving
IMP: > 700 gMeOH/Kgcat.h
STD: > 500 gMeOH/Kgcat.h
Improved Catalyst Preparation
Methanol Selectivity
Methanol Yield
Cu/Zn/Zr/Al
Cu/Zn/Zr/Al
Improved Catalyst Preparation
CO Selectivity
Catalyst
BET Area (m2/g)
CuZnZrAl_IMP
78
CuZnZrAlGaSi
54
CuZnAl_STD
31
Cu/Zn/Zr/Al
Summary of the Results
T = 2500C, P = 50 bar, 10 h-1, TOS 8 h
Composition
Methanol Yield
(gMeOH.kgcat-1.h-1)
% Equilibrium Yield
Mitsui Reference*
721
100
Cu/Zn/Zr/Al_IMP
720
100
Cu/Zn/Zr/Al_STD
510
70
Cu/Zn/Ce/Al_STD
480
67
Cu/Zn/Mg/Al_STD
370
51
Cu/Zn/Ce/Zr_STD
350
48
Cu/Zn/Zr_STD
320
44
Cu/Zn/Mg/Zr_STD
280
39
Cu/Zn/Al_STD
180
25
* K. Ushikoshi, K. Mori. T. Kubota. T. Watanabe and M. Saito, Appl. Organometal. Chem 2000, 14, 819
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Thermodynamic limitations
1600
70 bar Equilibrium
MeOH Yield (gCH3OH/kg.h)
1400
50 bar Equilibrium
1200
30 bar Equilibrium
15 bar Equilibrium
1000
800
600
400
200
0
200
210
220
230
240
250
260
Temperature (oC)
270
280
290
300
W.-J. Sien, K.-W. Ju, H.-S. Choi, K.-W. Lee, Korean J Chem Eng 2000,17, 210-216 ()
Mechanistic Studies
Lowest-energy pathway:
CO2* → HCOO* → HCOOH* → CH3O2* → CH2O* → CH3O* → CH3OH*
L. C. Grabow and M. Mavrikakis, ACS Catalysis 1 (2011) 365