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Trondheim CCS Conference 14th June 2017 – Trondheim (Norway)
Techno-Economic and Environmental Assessment of the Conversion of CO2 into Methanol
Nicolas MEUNIER, Remi CHAUVY, Diane THOMAS and Guy DE WEIRELD
University of Mons (Belgium)
Faculty of Engineering
Thermodynamics Department
University of Mons
1. Selection of CO2 Conversion Pathway • CO2 Conversion Activities
• Multi-criteria Assesment
2. CO2 Conversion into Methanol • Thermodynamics & Kinetics
• CO2 Conversion Process
• Economic Considerations (CAPEX & OPEX)
• Environmental Assesment (LCA Analysis)
3. Conclusion & Perspectives
Presentation Plan
2 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
University of Mons
Examples • Carbon Recycling International (Iceland) Methanol
• Calera (USA) Calcium carbonate
• Lanzathech (USA) Ethanol
• Covestro (Bayer Material Science) (DE) Polyols
CO2 Conversion Activities
3
CO2 Reuse Activities throughout the world [1]
• 25 Research Centers • 202 Projects • 60 Start-ups Large number of processes Different levels of maturity Different performances Over 30 routes identified
Final CO2-based products
Technologies of conversion
MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
[1] Technische Universität Berlin – Centre for Entrepreneurship: http://www.entrepreneurship.tu-berlin.de/CCU
University of Mons 4 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Identification of the CO2 conversion routes
STEP 1: Pre-selection Reduction of the panel of CO2 conversion routes A. Timeframe to deployment B. Level of maturity (TRL) C. Size of CO2 utilization
STEP 2: Selection based on criteria and indicators Semi-quantitative selection 1. Environmental, health and safety performance 2. Maturity of the process 3. Economic potential 4. CO2 reduction potential 5. Energetic performance and operating conditions Evaluation via scoring and weighting factors: Double-weighted matrix
Simulation of the process
Are the selected routes validated?
No
Yes
Selection of CO2 Conversion Pathways
University of Mons 5
Selecting CO2 conversion pathways Multi-criteria assessment
Ranking of CO2 conversion options for the cement industry
MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Applications
Energy
• Automotive & Marine fuels
• Biodiesel
• Dimethyl ether (LPG), …
Chemicals
• Formaldehyde
• Acetic acid
• Dimethyl ether (adhesives)
• Solvents, …
Waste Water Treatments
University of Mons
Thermodynamics & Kinetics
6
𝐶𝑂2 + 3𝐻2 ⟺ 𝐶𝐻3𝑂𝐻 + 𝐻2𝑂𝐶𝑂 + 2𝐻2 ⇔ 𝐶𝐻3𝑂𝐻 + 𝐻2𝑂𝐶𝑂2 + 𝐻2 ⇔ 𝐶𝑂 + 𝐻2𝑂
𝑟𝐶𝐻3𝑂𝐻,𝐴3′ =
𝑘𝑝𝑠,𝐴3′ 𝐾𝐶𝑂 𝑓𝐶𝑂 𝑓𝐻2
3/2− 𝑓𝐶𝐻3𝑂𝐻/ 𝑓𝐻2
1/2𝐾𝑝10
1 + 𝐾𝐶𝑂 𝑓𝐶𝑂+ 𝐾𝐶𝑂2 𝑓𝐶𝑂2 𝑓𝐻21/2
+ 𝐾𝐻2𝑂/𝐾𝐻21/2
𝑓𝐻2𝑂
𝑟𝐻2𝑂,𝐵2′ =
𝑘𝑝𝑠,𝐵2′ 𝐾𝐶𝑂2 𝑓𝐶𝑂2 𝑓𝐻2 − 𝑓𝐻2𝑂 𝑓𝐶𝑂/𝐾𝑝2
0
1 + 𝐾𝐶𝑂 𝑓𝐶𝑂+ 𝐾𝐶𝑂2 𝑓𝐶𝑂2 𝑓𝐻21/2
+ 𝐾𝐻2𝑂/𝐾𝐻21/2
𝑓𝐻2𝑂
𝑟𝐶𝐻3𝑂𝐻,𝐶3′ =
𝑘𝑝𝑠,𝐶3′ 𝐾𝐶𝑂2 𝑓𝐶𝑂2 𝑓𝐻2
3/2− 𝑓𝐶𝐻3𝑂𝐻𝑓𝐻2𝑂/ 𝑓𝐻2
3/2 𝐾𝑝3
0
1 + 𝐾𝐶𝑂 𝑓𝐶𝑂+ 𝐾𝐶𝑂2 𝑓𝐶𝑂2 𝑓𝐻21/2
+ 𝐾𝐻2𝑂/𝐾𝐻21/2
𝑓𝐻2𝑂
Reactions Kinetics[1]
MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
[1] Graaf et al., « Intra-particle diffusion limitations in low-pressure methanol synthesis », Chemical Engineering Science Journal, p. 773-783, 1990
CuO/ZnO/Al2O3 catalyst
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20 40 60 80 100 120
Met
han
ol y
ield
(m
ol%
)
Pressure (bar)
At 230°C
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120 170 220 270 320
Met
han
ol y
ield
(m
ol%
)
Temperature (°C)
At 80 bar
University of Mons
Inspired from US 5.631.302 Patent
• Conversion of synthesis gas
• 2 catalytic reactors
• 1 distillation column
• 2 internal heat exchangers
Conversion of pure CO2 !
OPTIMIZATION
Energetic factors
• Electrical consumption
• Heat integration
Economic factors
• CAPEX & OPEX
Methanol Conversion Process
7 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Catalytic Block
Separation Block
CO2 + CO + H2
University of Mons
Methanol Conversion Process
8 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Catalytic Block
Separation Block
Thermal Loop
CO2 + H2
Adiabatic first reactor
Isotherm second reactor
Purge
CH3OH > 99 w%
H2O > 99.99 wt%
Flare
Simulations with Aspen Plus &
Economics v8.8.
Upgraded Methanol Conversion Process
𝜼 ≅ 𝟏𝟓% 𝜼 ≥ 𝟗𝟗%
80 bar – 230°C 80 bar – 230°C
1 bar 𝑻𝒓𝒆𝒃 ≅ 𝟗𝟗°𝑪
19 000 Nm³/h CO2
H2/CO2 ratio of 3
University of Mons
Streams
• Inlet 19 000 Nm³/h CO2 57 000 Nm³/h H2 (Ratio 3:1)
• Outlet 580 ton/day CH3OH 935 ton/day H2O
Sizing
• Compressors 2 compressors
Power : 1 and 1.6 MWe
• Reactors 2 reactors
Adiabatic, L = 12 m, D = 5 m 11 tons catalyst
Isotherm, L = 12 m, D = 10 m 41 tons catalyst
• Distill. Column Isobare, 24 stages, D = 3m
Reboiler Duty : 5.6 MW
• Heat Exchangers 5 exchangers
Heat duties : 1 – 21 MW
Total heat exchange : 38 MW
Methanol Conversion Process
9 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
University of Mons
CAPEX estimations • 35% of the CO2 emissions coming from a 3 000
tpd clinker cement plant (19 000 Nm³/h CO2)
• Global CAPEX of 19 000 k€
Reduction of the CAPEX by 13% !
OPEX estimations • Estimated to reach 10 €/ton CO2 converted
(i.e. 14 €/ton CH3OH produced)
Reduction of the OPEX by 70% !
CAPEX and OPEX Estimations
10 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
k€/year €/ton CO2
€/ton CH3OH
Elec
tric
ity 1st
Compr. 1025
5.0 7.6 2nd
Compr. 570
Hea
t
Steam 1391 4.4 5.6
De
pre
c.
Catalyst 225 0.7 1.1
OPEX estimations
CAPEX estimations (equipment)
Heat Exch. 51%
Compressors 40%
Reactors 36%
Distil. Column
18%
Others 7%
Simulations with Aspen Plus & Economics v8.8.
University of Mons 11
System Boundaries
Environmental assessment
Methanol
synthesis Cement plant
Production of
hydrogen
CO2 capture
&
purification
CO2 H2
Flue gas
Emissions Water / air /
solid wastes
Clinker Methanol
Energy
Raw
materials
Product
conversion
Fuel
consumption Recycle Disposal
Emissions Water / air /
solid wastes
Energy
Raw
materials
Emissions Water / air /
solid wastes
Energy
Raw
materials
Emissions Water / air /
solid wastes
Energy
Raw
materials
Emissions Water / air /
solid wastes
Energy
Raw
materials
USE DISPOSAL
PRODUCTION
MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Life Cycle Analysis based on
ISO 14040 & 14044
GATE – TO – GATE
University of Mons 12
Initial assumptions
• Transport neglected (CO2 recovery and H2O electrolysis plants close)
Impact assessment method
• ReCiPe Midpoint Europe (H) V1.13
Inventory data
• Primary data: process simulation (Aspen Plus)
• Secondary data: EcoInvent v3.3
Software: SimaPro 8.3.0.0
MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Environmental assessment
Included sub-systems Excluded sub-systems
• Infrastructure • Equipment • Life time: 30 years
• Decommissioning of infrastructures and equipment
• Catalysts • Maintenance of capital goods
University of Mons 13 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
0 200 400 600 800 1000 1200 1400 1600 1800 2000
This study(water electolysis, wind energy)
Water electrolysis: wind energy
Water electrolysis:solar energy
Amalgam (alkaline) electrolysis,NaCl / NaOH
Diaphragm (alkaline) electrolysis,NaCl / NaOH
Membrane (alkaline) electrolysis,NaCl / NaOH
Coal gasification
Steam methane reforming
Emitted 𝑘𝑔𝐶𝑂2, 𝑒𝑞. / Converted 𝑡𝐶𝑂2,𝑒𝑞.
Environmental benefits
Environmental assessment
Influence of the hydrogen production on Global Warming
H2 produced through water electrolysis coupled with wind electricity
University of Mons 14 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
149 kg H2
150 kg CO2 eq.
79.4 kWh Electricity
19.9 kg CO2 eq.
Conversion unit
170 kg CO2 eq.
297.2 kg Steam
55 kg CO2 eq.
Distillation unit
225 kg CO2 eq.
Construction phase
1.42 kg CO2 eq.
Methanol synthesis unit
226.4 kg CO2 eq.
1000 kg CO2
Environmental assessment
Global warming Network (kg CO2 eq. per ton CO2 converted)
• Construction phase negligible • 66 % due to H2 production • 25 % due to steam production
227 kg CO2 eq. for the conversion of 1000 kg CO2
330 𝑘𝑔𝐶𝑂2, 𝑒𝑞. / ton methanol
Benchmark [1]
520 𝑘𝑔𝐶𝑂2, 𝑒𝑞. / ton methanol
[1] Methanol from steam reforming of natural gas : Swiss Centre for Life Cycle Inventories: EcoInvent v3.3 (2016)
University of Mons
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Rel
ativ
e co
ntr
ibuti
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%)
Electricity
Construction phase
Hydrogen
Steam
15
Impact assesment for the conversion of 1 ton CO2
Relative contribution on the selected impacts categories
Environmental assessment
MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
University of Mons
A methodological multi-criteria method of selection has been developed to propose defined CO2 reuse possibilities to specific industries
Methanol has been chosen as one the most promising compounds for CO2 reuse
A CO2-methanol conversion process has been developped :
• Check and Update of the kinetic data related to catalysts
• Optimization of the methanol conversion process (CAPEX & OPEX)
Life Cycle Analysis (LCA) of the methanol conversion process presenting the positive impacts of the proposed CO2-methanol process in comparison the classical way of production
Investigation of other pertinent CO2 reuse processes
Propose environmentally friendly, integrated and optimized CO2 conversion processes applied to the industrial sector !
Conclusions & Perspectives
16 MEUNIER N. | Trondheim CCS Conference – 14th June 2017 – Trondheim, Norway.
Thank you for your attention
Acknowledgements to the Belgian National Fund for Scientific Research (F.R.S.-FNRS)
and the European Cement Research Academy (ECRA) for their technical and financial supports.
University of Mons (Belgium)
Faculty of Engineering
Thermodynamics Department
