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Transcript of Green Methanol from the Hydrogenation of Carbon Dioxide Claudio J. A. Mota 1,2 [email protected] 1...
Green Methanol from the Hydrogenation of Carbon Dioxide
Claudio J. A. Mota1,2
1Federal University of Rio de Janeiro – Institute and School of Chemistry, Brazil
2INCT Energy & Environment, UFRJ, Brazil
Chemistry and Fuels
Petroleum
Until 1700
1700-1900
1900 - today
Coal
Wood
CO2 Concentration in the Atmosphere
Source: Global Carbon Project 2014
[CO2 atmosphere concentration]:
400 ppm (2013)
~ 40% increase
278 ppm (1785) – Industrial Revolution starts
CO2 Net Emissions in 2011:
16.1 Billions Mton
1 Pg = 1 Petagram = 1x1015g = 1 Billion metric tons = 1 Gigaton
1 Kg Carbon (C) = 3.67 Kg Carbon Dioxide (CO2)
CO2 Concentration in the Atmosphere
Glycerol
C&EN 2009, vol 87, number 22, pages16-17
Glycerol
HO OH
OH
+
OO
O
OH
+ H2O "H+"
C. X. da Silva, V. L. C. Gonçalves, C. J. A Mota Green Chem. 2009, 11, 38-41
0 1 2 3 4 5
0.0
0.5
1.0
1.5
2.0
2.5
Oct
an
e n
um
be
r in
cre
me
nt
Ketal (%)
Gasoline A Gasoline C
0 1 2 3 4 5 60
1
2
3
4
5
6
Gasoline AGasoline C
Ketal (%)
Gu
m (
mg/
mL
)
Mota, C. J. A., Silva, C. X. A.; Rosenbach, N.; Costa, J. Silva, F.. Energy Fuels 2010, 24, 2733
Glycerol
OH
OHHO + EtOH
OH
OHO
OH
O
"H+"
O
OHHO
O
OHO
+
O+
+ H2O
Flow Properties ASTM – D 97SAMPLE 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
B7 - 2014
R1 OCH3
O
O
O
O
R1
O
R2
O
R3O
+ 3 CH3OH KOHR2 OCH3
O
R3 OCH3
O
+HO OH
OH
vegetable oilBiodiesel
glycerol
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
H+ H+H+
H+ H+ H+
OH- OH-
OH-
RCO2H RCO2CH3
Triglyceride 3 RCO2CH3
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
Source: Mitsui Chemicals – Information Brochure
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
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)
Production of resins and plastics
MTH olefins and hydrocarbons (fuels)
World production around 50 millions tonnes per year
Fonte: Methanol Institute
World Methanol Industry US$ 36 billions/year with 100 thousand jobs
Fonte: Methanol Institute
Thermodynamics Considerations
Methanol formation:CO + 2H2 CH3-OH ΔHO
50Bar,298K = - 90.6 kJ/mol
CO2 + 3H2 CH3-OH + H2O ΔHO50Bar,298K = - 49.4 kJ/mol
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
C6H12O6 yeast 2 C2H5OH + 2 CO2
Green Methanol Plant in Brazil Bioethanol Economy
Initial studies
Cu/Zn/Al50/40/10 molar ratioWeight: 500 mg
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, 270oCPressure: 15, 30, 50 barWHSV: 10 h-1
CO2/H2: 1/3 molar ratioTOS: 20 h
Initial Studies
70 50 300
2
4
6
8
10
12
14
16
18
20
Pressure (bar)
CO2
Conv
ersio
n (%
)
CH3OH CO CH40
10
20
30
40
50
60
70
80
90
100
70 bar
50 bar
30 bar
Products
Sele
ctivi
ty (%
)
Cu/Zn/Al (50/40/10 mol%) WHSV = 10 h-1 ; TOS = 20 h ; H2:CO2 = 3:1
270 oC
Cha
lleng
e fo
r C
atal
yst
Opt
imiz
atio
n
R. S. Monteiro and C. J. A. Mota Quím. Nova 2013, 36, 1483-1490
50 bar
30 bar
15 bar
Cu/Zn/Al (50/40/10 mol%) WHSV = 10 h-1 ; TOS = 20 h ; H2:CO2 = 3:1
Standard Catalyst Preparation Effect of Promotors
pH = 3 pH = 5 pH = 7-8
7. Crushing and Sieving
6. CalcinationT = 600oC; 10oC/min 2h
5. DryingT = 160oC; 10oC/min 18 hrs.
4. Filtration/Washing
3. Co-precipitation (pH = 6-7)1M NaOH; dropwise T = 60- 70oC; aged 60 min
2. One-single pot solutionpH ~ 3; heating 1000 rpm
1. Metal salts water solutionCu, Zn, Al, Ce, Mg and Zr Nitrates
Cu/Zn/Promotors (50/40/10 mol%)
CO2 Hydrogenation over Standard-Prepared Catalysts
Al Zr ZrAl CeAl CeZr MgAl MgZr ZrAlGaSi0
100
200
300
400
500
600
700
800
Methanol Yield (gMeOH/kgcat.h)
230oC 250oC
Equilibrium Yield (250oC, 50 bar)
CuZn based catalysts – Promotion Effect
230oC 250oC0
5
10
15
20
25
CO2 Conversion (mol.%)
ZrAl ZrAlGaSi
230oC 250oC0
10
20
30
40
50
60
70
80
90
100
CH3OH Selectivity (mol.%)
ZrAl ZrAlGaSi
230oC 250oC0
5
10
15
20
25
30
35
40
CO Selectivity (mol.%)
ZrAl ZrAlGaSi
CO2 + 3H2 CH3-OH + H2O
ΔHO50Bar,298K = - 49.4 kJ/mol
CO2 + H2 CO + H2O
ΔHO50Bar,298K = + 41.1 kJ/mol
CO2 Hydrogenation over Standard-Prepared Catalysts
CuZn based catalysts
Activity/Structure Correlation BET Area
0 10 20 30 40 50 600
100
200
300
400
500
600
700
R² = 0.89395151246559
BET Surface Area (m2.g-1)
Meo
H Y
ield
ZrAlGaSi
ZrAl
CeAl
MgAl
Zr
CeZr
MgZr
CuZn based catalysts
• Catalyst activation: 270oC
• CuO Cuo (> 300oC)
• CuO surface reduction under
reaction conditons.
• Better MeOH yield on catalysts
with lower temperature of
reduction
• Promoters allow CuO reduction
at lower temperatures
CuO
Al
CeAl
ZrAl
ZrAlGaSi
300oC416oC
Temperature (oC)
CuZn based catalysts
Activity/Structure Correlation TPR Profile
Activity/Structure Correlation DRX
ZnO(100)
ZnO(002)
CuO(111)
ZnO(101)
CuO(111)
Al
MgAl
CeAl
SnAl
ZrAl
ZrAlGaSi
2 Theta (O)
Amorphous phase or tiny particles??
CuZn based catalysts
Improved Catalyst Preparation
7. Crushing and Sieving
6. CalcinationT = 600oC; 10oC/min (STD) T = 380 oC; 10oC/min (IMP)
5. DryingT = 160oC; 10oC/min 18 hrs.
4. Filtration/Washing
3. Co-precipitation (pH = 6-7)1M Na2CO3; dropwise T = 60- 70oC; aged 60 min
2. One-single pot solutionpH ~ 3; heating 1000 rpm
1. Metal salts water solutionCu, Zn, Al, Ce and Zr Nitrates Reaction Conditions: 250oC; 50 bar; 10 h-1
MeOH Yields – Cu/Zn/Zr/Al:
IMP: > 700 gMeOH/Kgcat.h
STD: > 500 gMeOH/Kgcat.h
Cu/Zn/Zr/Al
IMP
STD
Improved Catalyst Preparation
Cu/Zn/Zr/Al
Methanol Yield
Cu/Zn/Zr/Al
Methanol Selectivity
Improved Catalyst Preparation
CO Selectivity
Cu/Zn/Zr/Al
Catalyst BET Area (m2/g)
CuZnZrAl_IMP 78
CuZnZrAlGaSi 54
CuZnAl_STD 31
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
T = 2500C, P = 50 bar, 10 h-1, TOS 8 h
* K. Ushikoshi, K. Mori. T. Kubota. T. Watanabe and M. Saito, Appl. Organometal. Chem 2000, 14, 819
Summary of the Results
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Thermodynamic limitations
200 210 220 230 240 250 260 270 280 290 3000
200
400
600
800
1000
1200
1400
1600
70 bar Equilibrium
50 bar Equilibrium
30 bar Equilibrium
15 bar Equilibrium
Temperature (oC)
MeO
H Y
ield
(gC
H3O
H/k
g.h
)
W.-J. Sien, K.-W. Ju, H.-S. Choi, K.-W. Lee, Korean J Chem Eng 2000,17, 210-216 ()
Mechanistic Studies
L. C. Grabow and M. Mavrikakis, ACS Catalysis 1 (2011) 365
Lowest-energy pathway:CO2* → HCOO* → HCOOH* → CH3O2* → CH2O* → CH3O* → CH3OH*