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

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*