ENEA
Rome, Italy

CAPTURE

UTILISATION

ZECOMIX (IT3.1)

Zero Emission of Carbon with Mixed technologies

The purpose of the ZECOMIX (Zero Emission of Carbon with Mixed technologies) pilot plant is twofold. One is the production of hydrogen from conventional fuels (e.g methane and coal) by means of the Calcium Looping (CaL) process that is an high temperature gas solid reaction. The Ca based material used in ZECOMIX is low cost (<10 €/t) and has no impact to the environment and the human being. The other objective of the ZECOMIX is the study of the CaL process as thermochemical storage of heat. The main aim of the project is to demonstrate, through a series of modelling and experimental activities, the feasibility of an this innovative process for storage not only the solar energy but also the waste heat produce in high energy demand industries (e.g. steel making process and cement production).

The plant which has a TRL 6/7 (see figure1) was presented in international research frameworks (e.g. CSLF, ZEP and EERA) as one of the advanced technological initiatives of the European and worldwide scientific community. One of the key advantages of this option which makes it a valuable route for gas decarbonisation or the heat storage is the low cost and wide availability of the feed material (a naturally occurring sorbent such as limestone or dolomite) and its high reactivity with CO2. In the CaL process, CaO is converted into CaCO3 by reacting with gaseous CO2, then the spent solid sorbent is regenerated in a calcination step (heat storage) at a temperature range from 800 to 850 °C leading to the release of the captured CO2 in a pure stream that can be sent to final storage. The heat is released during the successive reaction between CO2 and CaO (carbonation step) at 650 °C.

ZECOMIX is also composed of a 500 kWth steam/oxygen blown bubbling fluidised bed coal gasifier. The coal feed system was designed for a nominal load of 1.4 t/d of coal. The system includes a 2 m3 unit for coal storage, which allows the stationary operation of the gasifier for up to 36 hours, and two screws driven by an engine connected to an inverter. Finally, the clean syngas generated by the coal gasifier will fed a 100 kW micro turbine.

Areas of research

nd

State of the Art, uniqueness & specific advantages

The novelty of ZECOMIX is the combination of well-known industrial processes (e.g. calcination for the clinker production, gasification and reforming of conventional fuels) for the production of H2 as energy carrier and the storage of solar power and industrial heat waste. The Ca based material used in ZECOMIX is low cost (<10 €/t) and has no impact to the environment and the human being.

Scientific Environment

Carbon valorisation via plasma assisted catalysis (PAC) processes.
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In particular, innovative CO2 valorisation processes based on the use of intermittent electrical energy sources are being studied, developing technological processes of CO2 treatment based on the activation of plasma catalysts and rapid thermal cycles. In the first class of processes we are developing technological systems where the catalyst is immersed in a plasma volume, in the second the catalysts are heated by magnetic induction. In ZECOMIX research infrastructure we are studying:
1) catalysts, also in the form of nano-particles.
2) the catalyst supports, optimizing the dielectric, thermochemical and thermal characteristics.
3) The systems and the reactors, taking into account the possible scale-up of the same, giving emphasis to the time constants typical of electricity from renewable sources.

Synthesis of high regenerable material for O2 carrying capacity and/or CO2 capture.
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Alternatively to modifying naturally occurring minerals to improve their properties there is also the option to develop completely new synthetic sorbents with tailored properties. ENEA is investigating the use of synthetic long life sorbent CaO/Ca12Al14O33 synthesised our laboratories which has been used for 1000 CO2 uptake / regeneration cycles under industrially relevant conditions. This material could be used as a support of O2 carrying phase (e.g. CuO);

Process intensification: integration of CaL technology with cement production process
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In the field of process intensification a potential common area of interest is the integration of cement production process with a fluidised bed of CO2 acceptor to decarbonise flue gases leaving a rotary kiln. In the facility of ENEA is currently investigating the effect of CO2 presence during the calcination of limestone;

Developing of particle models for the study of simultaneous diffusion and reaction process in gas solid reaction
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ENEA is active in developing a grain model which can be integrated in commercially relevant software tool for the simulation of CO2 capture systems (e.g. bubbling fluidised bed reactors).

ZECOMIX is supported by a set of analytical apparata composed of:
• Micromeritics ASAP 2020N
Automatic physiosorption analyser for the evaluation of specific surface area and distribution of the pore in porous solid material
• Micromeritics Autochem HP micro-reactor
It is an automated high-pressure catalyst and sorbent characterization system that is capable of preparing and analyzing samples at elevated pressures up to 68 atm and at temperatures up to 1100 °C. The instrument can perform a variety of experiments including pulse chemisorption, temperature-programmed reduction (TPR), desorption (TPD), oxidation (TPO). This micro-reactor, combined with a FTIR or gas chromatograph GC, can also be used to determine product yields and catalytic and sorbent activity under industrial conditions;

• Mettler Toledo GC-200 thermo-gravimetric analyser, differential scanning calorimetry TGA-DSC
TGA-DSC records the change in weight of a solid sample when it is heated, cooled or dwelled at constant programmed temperature. Heat exchanged with the environment is also recorded during the analysis. The apparatus can be connected online to a FTIR spectrometer or gas chromatograph GC. Analysis of the decomposition products yields additional information about the investigated solid sample;

• Varian 640-IR Fourier Transfer Infrared (FTIR) Analyzer
FTIR spectroscopy provides quantitative determination of a wide range of species. This enables us to interpret measurement curves collected from micro-reactor and TGA-DSC with greater accuracy;

• Agilent 6850 Gas Chromatograph (GC)
Agilent GC is available for H2, N2, CH4, CO, CO2, H2S and equipped with an Electron Capture Detector (ECD).

Operating by

ENEA

Italian National Agency for New Technologies, Energy and Sustainable Economic Development
Italy
CAPTURE technologies:
Sorbents, Membranes
UTILISATION technologies:
Thermochemical Conversion and Hydrogenation of CO2, PLASMA ASSISTED CATALYSIS FOR CO2 CONVERSION, CO2 Conversion to Solid Carbonates
Research Fields:
Fluid dynamics, Chemistry/Geochemistry, Material science, Modelling, Engineering, Thermodynamics

Location & Contacts

Location
Rome, Italy
Contacts
Stefano Stendardo
RICC Contacts - Secondary contact
Cinzia De Vittor

Facility Availability

Availability per year (in UA)
12 weeks
Duration of a typical access (average) and number of external users expected for that access
1 week

Quality Control / Quality Assurance (QA)

Activities / tests / data are:
State of Quality: Data collection and analysis methods are chosen to match the particular evaluation in terms of its key questions and resources available. Probability sampling allows for ‘statistical generalization’ in which a certain margin of error risk is set (typically, 5 to 10 per cent) that defines the level of acceptable risk.
Link to your institution QA webpages if available:
http://energia.enea.it/wp-content/uploads/2019/01/I-ZECOMIX.pdf

Operational or other constraints

Specific risks:
Potential risks are associated with a forklift or material elevators including hazards relating to its mobility, its electrical, hydraulic and mechanical power sources, its moving parts, its load-carrying capacity and operator protection.
Legal issues:
A code of practice is a guide to achieve the standards of health, safety and welfare required under the Italian Work Health and Safety Act (D.Lgs. 81/08).

CCUS Projects

EU-Funded CCUS Projects
EC DG RESEARCH - FP6 & 7
ASCENT - Advanced Solids Cycles with Efficient Novel Technologies (ASCENT)
EC DG RESEARCH - FP6 & 7
UNIQUE gasifier for hydrogen Production (UNIfHY)
Other CCUS Projects
National Fund
2019-2021
Italian Research Programme “Piano Triennale della Ricerca di Sistema Elettrico 2019-2021”

Selected Publications

Energy 03/2016; 103, DOI: 10.1016/j.energy.2016.03.011 (2016)
High quality syngas production via steam-oxygen blown bubbling fluidised bed gasifier
Stefano Stendardo, Pier Ugo Foscolo, Mirko Nobili, Silvera Scaccia
Energy 06/2008; 33(6)., DOI:10.1016/j.energy.2008.01.004 (2008)
Possible optimal configurations for the ZECOMIX high efficiency zero emission hydrogen and power plant
Antonio Calabro, Paolo Deiana, Paolo Fiorini, Giuseppe Girardi, Stefano Stendardo
Journal of CO2 Utilization 05/2018; 25:14-21., DOI:10.1016/j.jcou.2018.03.002 (2018)
Integration of a calcium looping process (CaL) to molten carbonate fuel cells (MCFCs), as carbon concentration system: First findings
M. Della Pietra, M. Santarelli, S. Stendardo, S. McPhail, Juan Pedro Perez-Trujillo, Francisco Elizalde-Blancas
Fuel Processing Technology 09/2015; 139:204-215., DOI:10.1016/j.fuproc.2015.07.011 (2015)
Characterization and density separation of coal gasification residues generated from the ZECOMIX research infrastructure
Milena Morone, Giulia Costa, Stefano Stendardo, Renato Baciocchi
11/2016;, DOI:10.1007/s12649-016-9781-0 (2016)
Granulation–Carbonation Treatment of Alkali Activated Steel Slag for Secondary Aggregates Production
Milena Morone, Giulia Costa, Evangelos Georgakopoulos, Vasilije Manovic, Stefano Stendardo, Renato Baciocchi

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