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Operation of a Movable Modular Plant on CO2 Hydrogenation to CH4 coupled with Renewables
C. Bassano1, P. Deiana1, Carlo Visconti 2, Luca Lietti 2
ENEA1
Italian National Agency for New Technologies, Energy and Sustainable Economic Development Via Anguillarese 301, 00123 Rome, ITALY
Politecnico Di Milano2 Dipartimento di Energia, Milano, 20156, Italy Berlin, 5 June 2018
• Introduction
• Pilot Plant Description
• Experimental Activities
• First Results and Ongoing Activities
• Conclusions
2
Summary
ENEA activities are targeted to research, innovation technology and advanced services in the fields of energy.
ENEA performs research activities and provides agency services in support to public administrations, public and private enterprises, and citizens.
ENEA is the Italian National Agency for New Technologies, Energy and Sustainable Economic Development
HR: 2863 permanent staff
71 temporary staff
Headquarters in Rome
9 Research Centers
5 Research Laboratories
12 Local Officies
Brussel Liason Office
ENEA - The Italian National Agency for …
4
Introduction
RES Increase
Renewables are steadily growing becoming a significant part of the global energy mix, in particular in the power sector.
Energy Union Strategy
EU's energy and climate goals for 2030 introduce a new renewable energy target of at least 27% of final energy consumption in the EU by 2030
Energy Storage Technologies
Energy Storage Technologies can contribute in renewable energy peak shaving avoiding temporal fluctuation that can cause shortage or surplus in energy supply.
R&I are required to reduce technology and non-technology costs, improve performances and promote technology deployment to market
CO2 from Energy Intensive Industry
Syngas from gasification
Biogas
Geothermic fields
Soil gas and gas wells
Methanation
E elettrica
Electrolizer
CH4
H2O
H2
Mobility
Heat supply
Storage
Seasonal Energy Storage: Power To Gas
Natural gas grid
CO2 source
Variable Renewable Energy sources (vRESs)
Final users
PtG Technology Platform: advantages
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SNG has good market opportunities (refuelling stations, heating, …) SNG produced from renewables can be used either :
locally in the case of area not supplied by natural gas injected into the natural gas grid
SNG partially alleviate the energy dependency on foreign gas, enhance energy security, ensure energy sources differentiation. CCUS: CO2 is recycled to a new product, CO2 as waste material derived from fossil fuel is reused, allowing to decarbonize industrial processes Goal of the activity is to enhance the economic competitiveness of gas from Renewables compared to competitors (Natural Gas and LPG)
1. Experimental tests of commercials catalysts on laboratory scale
2. Pilot-scale testing of systems and components
3. System modeling and economic assessment
4. Coordination and projects, collaborations with Universities
5. Technology transfer, patents, support to administration and policy makers
PtMethane: R&D Activities at ENEA
Increase of the temperature in the reactor
Optimal use of reaction heat
CO2 + 4H2 CH4 + 2H2O DH°298 = - 165 kJ/mol Highly Exothermic
Reaction
R&D key topics • Development of different process schemes • Development of different reactors design • Development of new catalysts • Test of full chain process at pilot scale • Dynamic test
PtMethane: R&D Challenges, experimental test
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Movable Modular skidable plant description 1/2
Methane flow 0.2 ÷ 1.5 Nm3/h
Pilot scale experimental facility dedicated to study and to test methanation process
Feed gas mixing Multitubular fixed bed reactor Cooler and condenser (shell and plate) Back pressure valve Ancillaries units : heater, fan, torch Temperatures, pressures, flows and gas composition online monitoring Data acquisition and control system
Movable Modular skidable plant description 2/2
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Experimental activities
Experimental tests First experimental activities carried out to assess the process performance
Catalysts Ru/Al2O3 - Ni/Al2O3 Pressure 0 - 5 barg Temperature 250 - 350 °C
The section was feed with different gas mixtures N2 /CO/H2 /CO2/CH4
Different GHSV
Experimental activities: operative conditions
Catalysts Ni 25% wt. Ru 0.5% wt.
Support Al2O3 pellets Al2O3 pellets
Temperature range 250-350 °C 250-350 °C
Pressure range 1-5 bar 1-5 bar
Feed gas mix T in 250 °C 250°C
GHSV Ncm3/(g*h) 8000 3000-17000
Reactor Isothermal singletube
Isothermal /adiabatic multitube
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Experimental activities: CO/H2 feed & 25 % wt. Ni/Al2O3
Catalysts 25 %wt. Ni/Al2O3 Pressure: 5 bar Isothermal reactor Single tube T internal : 250 °C GHSV 8000 Ncm3/(h*g)
RX-02
in RX-01 % vol.
H2 80 CO 20 CO2 0 CH4 0
RX-01 RX-03
in RX-02 % vol.
H2 57 CO 5 CO2 4 CH4 34
in RX-03 % vol.
H2 41 CO 3 CO2 3.5 CH4 51.5
out RX-03 % vol.
H2 36 CO 1.5 CO2 3.5 CH4 58
RX-04
out RX-04 % vol.
H2 28 CO 1 CO2 3 CH4 67
0
10
20
30
40
50
60
70
80
% vol.
time
H2 CH4 CO CO2
0
10
20
30
40
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60
70
80
% vol.
time
H2 CH4 CO CO2
0
10
20
30
40
50
60
70
80
% vol.
time
H2 CH4 CO CO2
0
10
20
30
40
50
60
70
80
% vol.
time
H2 CH4 CO CO2
RX-01 out RX-02 out
RX-03 out RX-04 out
Experimental activities: CO/H2 feed & 25 % wt. Ni/Al2O3
Experimental activities: CO2/H2 feed & 0.5 %wt.Ru/Al2O3
0.00.10.20.30.40.50.60.70.80.91.0
0 1 2 3 4 5
SCH4
p (barg)
Thermodynamic selectivity in function of pressure
Catalysts 0.5 %wt. Ru/Al2O3
Pressure: 5 bar
Multitube Isothermal reactor
T in gas 250°C
GHSV 8000 -11000 Ncm3/(h*g)
1. Effect of pressure
Flowin 1.11 Nm3/h
H2/CO2 4.3
p 5 bar
T internal medium value 280 °C
CH4 conversion 0.9 0
1000
2000
3000
4000
5000
6000
7000
8000
0
10
20
30
40
50
60
70
80
90
100
Ncm3
h*g
% vol.
hh:mm
% CH4
% H2
% CO2
GHSV Ncm3/(h*g)
Flowin 1.45 Nm3/h
H2/CO2 4.3
p 5 bar
T internal medium value 350 °C
CH4 conversion 0.87 0
2000
4000
6000
8000
10000
12000
0
20
40
60
80
100
Ncm3
h*g
% vol.
hh:mm
% CH4 % H2 % CO2 GHSV Ncm3/(h*g)
2. Effect of different GHSV
Experimental activities: CO2/H2 feed & 0.5 %wt.Ru/Al2O3
0
1000
2000
3000
4000
5000
6000
7000
8000
0
10
20
30
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60
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Ncm3
h*g
% vol.
hh:mm
% CH4
% H2
% CO2
GHSV Ncm3/(h*g)
Flowin 1 Nm3/h H2/CO2 4.3 p 5 bar T internal medium value 290 °C
CH4 conversion 0.92
0
50
100
150
200
250
300
350
400
450
500
°C
hh:mm
TC tube 1
TC tube 2
TC tube 3
TC tube 4
TC tube 5
TC tube 6
TC tube 7
TC out products
2. Effect of different GHSV
Experimental activities: CO2/H2 feed & 0.5 %wt.Ru/Al2O3
Isothermal reactor Temperature trend inside 7 tube
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
0
10
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Ncm3
h*g
% vol.
hh:mm
% CH4
% H2
% CO2
GHSV Ncm3/(h*g)
Flowin 1.27 Nm3/h
H2/CO2 4.3
p 5 bar
T internal 250 °C - 390°C
CH4 conversion 0.86
Reactor condition adiabatic
0
50
100
150
200
250
300
350
400
450
500
°C
hh:mm
TC tube 1
TC tube 2
TC tube 3
TC tube 4
TC tube 5
TC tube 6
TC tube 7
TC out products
3. Adiabatic condition
Experimental activities: CO2/H2 feed & 0.5 %wt.Ru/Al2O3
0
2000
4000
6000
8000
10000
12000
0
20
40
60
80
100
Ncm3
h*g
% vol.
hh:mm
% CH4 % H2 % CO2 GHSV Ncm3/(h*g)
Flowin 1.81 Nm3/h
H2/CO2 4.5
p 5 bar
T internal medium value 330 °C
CH4 conversion 0.85
in RX % vol.
H2 38 CO2 8 CH4 54
Experimental activities: CO2/H2 feed & 0.5 %wt.Ru/Al2O3
4. Effect of CH4 in the feed
0
5000
10000
15000
20000
0
20
40
60
80
100
Ncm3
h*g
% vol.
hh:mm
% CH4 % H2 % CO2 GHSV Ncm3/(h*g)
Flowin 3.09 Nm3/h
H2/CO2 4.5
p 5 bar
T internal medium value 330 °C
CH4 conversion 0.89
in RX % vol.
H2 22 CO2 5 CH4 73
4. Effect of CH4 in the feed
Experimental activities: CO2/H2 feed & 0.5 %wt.Ru/Al2O3
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Ongoing Activities
The work of the ENEA is progressing:
1. New experimental tests on different composition feed gas.
Future developments include:
1. Design of a second reactor.
2. This complete moveable plant will be test “on site” condition in Energy Intensive Industry (EII) environment fed by already captured CO2 and electrolytic hydrogen coming from Renewables
3. The Facility is now open to future research projects and program in the CCUS field but also could be replicated dealing with patenting and commercial activities
Conclusions
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1. A new Moveable Modular Plant dedicated to CO2 Hydrogenation to CH4 has been designed and built at Enea research Center.
2. The experimental activity was carried out in order to check the operability of all components and to improve the knowledge on methanation in the different phase of start-up, run and shut down.
3. A first characterization of the process was performed and the modalities and key parameters to achieve standard operating conditions were identified.
4. The declared objective of testing the system behavior and assessing different configuration/catalysts performance was successfully achieved
5. After the first experimental sessions, different ongoing activities are running and many future developments are in progress.
Thank you for kind attention
www.enea.it
