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

2. Chemistry and Fuels Wood Coal Petroleum Until 1700 1700-1900
today

3. CO2 Concentration in the Atmosphere
CO2 Net Emissions in 2011:
16.1 Billions Mton
[CO2 atmosphere concentration]:
400 ppm
(2013)
~ 40%
increase
278 ppm
(1785) – Industrial Revolution starts
1 Pg = 1 Petagram = 1x1015g = 1 Billion metric tons = 1 Gigaton
1 Kg Carbon (C) = 3.67 Kg Carbon Dioxide (CO2)
Source: Global
Carbon Project 2014

4. CO2 Concentration in the Atmosphere

5. Glycerol
C&EN 2009, vol 87, number 22, pages16-17

6. Glycerol
C. X. da Silva, V. L. C. Gonçalves, C. J. A Mota Green Chem. 2009, 11, 38-41
Mota, C. J. A., Silva, C. X. A.; Rosenbach, N.; Costa, J. Silva, F.. Energy Fuels 2010, 24, 2733

7. Flow Properties ASTM – D 97
Glycerol
Flow Properties ASTM – D 97
SAMPLE
Cloud (°C)
Freezing (°C)
Pour (°C)
B 100 (PALM) 18 15
B % ETHERS 12
B % ETHERS 14 11
B % ETHERS

8. Biodiesel B
A. L. Lima, A. Mbengue, M. Guarnier, R. A. Sangil, C. M. Ronconi, Claudio J. A. Mota. Catal. Today 2014, 226,

9. Biodiesel
RCO2H
RCO2CH3
Triglyceride
3 RCO2CH3

10. Concept of CO2 Utilization

11. “Anthropogenic Chemical Carbon Cycle" , George A
“Anthropogenic Chemical Carbon Cycle" , George A. Olah et al, JACS 2011,133,12881

12. Industrial Initiatives of CO2 Hydrogenation to Methanol
Mitsui Chemicals | Osaka, Japan
Carbon Recycling International | Iceland
Pilot Plant tonnes MeOH/yr
Cu/ZnO promoted catalyst
Packed bed (25 kg catalyst)
CO2 as feedstock
H2 from Water Photolysis
Catalyst life: 4,500 h
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
Source: Mitsui Chemicals – Information Brochure

13. World Methanol Industry  US$ 36 billions/year with 100 thousand jobs
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

14. Thermodynamics Considerations
Methanol formation:
CO + 2H CH3-OH ΔHO50Bar,298K = kJ/mol
CO2 + 3H CH3-OH + H2O ΔHO50Bar,298K = kJ/mol
Reverse WGS as a side reaction:
CO2 + 3H CO + H2O ΔHO50Bar,298K = 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

15. Green Methanol Plant in Brazil  Bioethanol Economy
C6H12O yeast C2H5OH + 2 CO2

16. Initial studies Cu/Zn/Al 50/40/10 molar ratio Weight: 500 mg
Catalyst Activation:
3-steps reduction: 10%H2/N2
140oC for 5 h;
Raised to 270oC in 2 h
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

17. Initial Studies
Cu/Zn/Al (50/40/10 mol%) WHSV = 10 h-1 ; TOS = 20 h ; H2:CO2 = 3:1
270 oC

18. Cu/Zn/Al (50/40/10 mol%) WHSV = 10 h-1 ; TOS = 20 h ; H2:CO2 = 3:1
Challenge for Catalyst
Optimization
50 bar
30 bar
15 bar
R. S. Monteiro and C. J. A. Mota Quím. Nova 2013, 36,

19. 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 = oC; aged 60 min
4. Filtration/Washing
5. Drying
T = 160oC; 10oC/min
18 hrs.
6. Calcination
T = 600oC; 10oC/min 2h
7. Crushing and Sieving
pH = 3
pH = 5
pH = 7-8
Cu/Zn/Promotors (50/40/10 mol%)

20. CO2 Hydrogenation over Standard-Prepared Catalysts
Equilibrium Yield (250oC, 50 bar)
CuZn based catalysts – Promotion Effect

21. CO2 Hydrogenation over Standard-Prepared Catalysts
CO2 + 3H CH3-OH + H2O
ΔHO50Bar,298K = kJ/mol
CO2 + H CO + H2O
ΔHO50Bar,298K = kJ/mol
CuZn based catalysts

22. Activity/Structure Correlation  BET Area
CuZn based catalysts
ZrAlGaSi
ZrAl
CeAl
MgAl Zr
CeZr
MgZr

23. Activity/Structure Correlation  TPR Profile CuZn based catalysts
CuO Al
CeAl
ZrAl
ZrAlGaSi
300oC
416oC
Temperature (oC)
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

24. Activity/Structure Correlation  DRX
CuZn based catalysts
ZnO
(100)
(002)
CuO
(111)
(101) Al
MgAl
CeAl
SnAl
ZrAl
ZrAlGaSi
2 Theta (O)
Amorphous phase or tiny particles??

25. Improved Catalyst Preparation
1. Metal salts water solution
Cu, Zn, Al, Ce and Zr Nitrates
2. One-single pot solution
pH ~ 3; heating
1000 rpm
3. Co-precipitation (pH = 6-7)
1M Na2CO3; dropwise
T = oC; aged 60 min
4. Filtration/Washing
5. Drying
T = 160oC; 10oC/min
18 hrs.
6. Calcination
T = 600oC; 10oC/min (STD)
T = 380 oC; 10oC/min (IMP)
7. Crushing and Sieving
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

26. Improved Catalyst Preparation
Methanol Selectivity
Methanol Yield
Cu/Zn/Zr/Al
Cu/Zn/Zr/Al

27. Improved Catalyst Preparation
CO Selectivity
Catalyst
BET Area (m2/g)
CuZnZrAl_IMP 78
CuZnZrAlGaSi 54
CuZnAl_STD 31
Cu/Zn/Zr/Al

28. 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
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

29. People

30. Financing

31. Give Nature a Chance

32. Forthcoming events in Rio
2016  International Zeolite Conference (IZC)
2017  Acid Base Catalysis (ABC)
2017  IUPAC Congress (São Paulo)
2018  ICCDU - XVI

34. Thermodynamic limitations
W.-J. Sien, K.-W. Ju, H.-S. Choi, K.-W. Lee, Korean J Chem Eng 2000,17, ()

35. CO2* → HCOO* → HCOOH* → CH3O2* → CH2O* → CH3O* → CH3OH*
Mechanistic Studies
Lowest-energy pathway:
CO2* → HCOO* → HCOOH* → CH3O2* → CH2O* → CH3O* → CH3OH*
L. C. Grabow and M. Mavrikakis, ACS Catalysis 1 (2011) 365