GTL4CCU

The GTL4CCU is an infrastructure facility dedicated to the development of innovative catalytic systems for an efficient conversion of CO2 into e-fuels, in a continuous feedback between kinetic studies and thermodynamics predictions. A large variety of experimental equipment is available for: a) design and preparation of powdered and structured materials with tailored properties; b) advanced bulk and surface characterization of catalytic systems under relevant conditions; c) lab-scale test rigs equipped with fixed-bed and stirred reactors to study and validate catalytic behaviour, performances and stability of catalytic materials during CO2 hydrogenation to e-fuels, like methane, methanol, dimethyl ether or higher hydrocarbons. 

Founded on a consolidated experience by researchers working in the field of preparation of solid catalysts both by conventional synthesis and innovative techniques, the facility takes advantage from a core installation represented by a customized robocasting machine, as a state-of-art technology of 3D printing being penetrating into the market of smart materials with catalytic applications. The additive manufacturing performed via layered micro-extrusion of catalytic pastes really ensures a superior control on the tunability of the solid features, joined to an uniform dispersion of the active phases over unconventional architectures wherein a punctual internal network of matrix-like structures is designed to facilitate fluid mixing as well as to address heat transfer and/or pressure drop issues, so overcoming some typical barriers related to conventional catalytic reactors. 

The facility is equipped to perform an advanced physico-chemical characterization of CCU materials through in situ/operando investigations by spectroscopic techniques (i.e., InfraRed spectroscopy and Mass Spectroscopy) as well as X-Ray Diffraction equipped with dedicated environmental chambers able to work under real reaction conditions. The powerful capacity of operando techniques is fundamental for qualitative and quantitative determination of surface active sites along with the assessment of mechanistic pathways prompted by peculiar catalyst surfaces or interface features in presence of gaseous mixtures simulating the catalytic reaction environment. Specifically, the combination of in situ/operando IR/DRIFT measurements, for identification of surface intermediates, spectator/transient species and nature of active sites, with real-time analysis of gas phase components by mass spectroscopy allows establishing structure-activity relationships and key-factors affecting the catalytic performance, thus defining the reaction mechanisms behind the CO2 conversion and paving the way for follow-up actions of enhanced catalyst stability and productivity. A thermogravimetry analyzer (TGA), able to provide simultaneous measurements of heat flow (differential scanning calorimetry, DSC) and weight loss of material under controlled atmosphere can be interfaced to IR and MS detection for a comprehensive characterization of materials in terms of thermal stability and decomposition mechanism. 

An advanced microscopy zone is getting ready to be supplied with a digital optical microscope for routinary fundamental observations together with two last generation ultra-high resolution microscopes based on scanning and transmission electron microscopy for sub-nanoscale observations. In particular, an Ultra-High Resolution Field Emission Scanning Electron Microscope (UHR FE-SEM) equipped with Focused Ion Beam (FIB) technology and detector STEM (Scanning Transmission Electron Microscopy) will be installed by the end of the year allowing imaging with sub-nano details as well as high-quality sub-surface and 3D characterization. Besides, the facility is already provided with a Transmission Electron Microscope (TEM) of the latest generation, which features high spatial resolution and analytical performance, an easy-to-use operation system for multi-purpose operation and various environmentally friendly energy saving systems. 

The research facility is completed by TRL4-5 test rigs integrating tubular and stirred reactors for producing: i) methanol (MeOH) and/or dimethyl ether (DME) from CO2 or syngas; ii) higher hydrocarbons in the range of transportation fuels. A high throughput set up is under assembling for parallel catalyst screening at a relatively short time and simulated CO2-containing feed mixtures. Catalytic runs under differential or integral conditions can be performed to probe a kinetic or diffusional control in CO2 activation.

The TRL scale of the facility is 2-4.

The research facility is located at the Institute for Advanced Energy Technologies “Nicola Giordano” (ITAE) in Messina, Italy. All the services, installations and auxiliary equipment of the facility are available in support of the research activities performed at the ITAE premises, such as: design, preparation, characterization and testing of unconventional materials for catalytic applications. Additional services include stations for solar fuels and water splitting, electrochemical cells and stacks for photo- and electrocatalysis studies, electrochemical impedance spectroscopy, in-line GCs with automated gas sampling loop for gas analysis.  

Skilled scientists and technicians can assist visiting partners. A large Auditorium (300 seats) is available for conferences and telco services. 

Thanks to a well-connected team of experienced researchers, significant and lasting collaboration relationships can be well established with public and/or private research bodies, Italian and foreign universities or industrial realities. The existing relationships and collaborations with the National and International academic world and with Research Technology Organizations have already allowed to validate on a comparative basis the scientific results obtained in the frame of cooperative actions, to promote training activities, to participate in International research projects, finally leading to publish the joint results according to the principles of Open Science. The lab are frequently attended by master and PhD students. The experimental apparatus have been used in several EU-funded projects dealing with CCU technologies. In the last years, a large scientific production has been delivered on the topic of CO2 hydrogenation for the production of clean alternative fuels. 

Considering that renewable hydrogen is the silver bullet for the short and mid-term energy transition, the expansion of renewable electricity production in the next years is going to claim for the development of drop-in hydrogenation technologies capable of an effective recycle of low-quality CO2-rich waste into useful alternative fuels or liquid organic hydrogen carriers (LOHCs), finally enabling the establishment of a clean circular economy. The possibility to deliver very efficient short-chain technologies, preventing costly intermediate steps, pushes the current research interest towards a deeper understanding of these processes, in terms of enhanced efficiency of current reactor configurations and continuous operation without loss of catalyst performance. While limiting energy consumption, environmental impact as well as CAPEX and OPEX with respect to similar equipment or services elsewhere offered, the access to the facility can offer the unique possibility to train young students or scientists in the field of CCU technologies, also exploring from a multifaced perspective the issues related to the containment of carbon footprint and providing insight on possible successful applications in EU R&D projects. The high degree of innovation allows maintaining constant dialogue and collaboration with both the scientific and industrial community, also favoring a transfer of knowledge between science and industry. 

A long term-experience in the development of hybrid materials for CCU technologies drives the right choses for innovative synthesis routes to prepare multi-functional catalysts suitable for CO2 activation. On this account, 3D robocasting technology represents the innovative powerful tool of the facility for the printing of multichannel catalysts, characterized by fine-tune texture/structure/morphology, homogeneous dispersion of the active sites and unconventional architectures modulating the thickness and distribution of the catalytic layer. The structured catalysts contribute to enhance the process productivity, by maximizing the specific surface areas for a reaction at a high flow rate and increasing at the same time the heat transfer properties, also favouring the heat removal from exothermic processes, such as methanation and methanol/DME synthesis. The geometry of the structure plays a key role in the design of catalysts, being directly involved in mass and heat transfer phenomena. 

The research facility includes TRL4-5 test rigs for producing: i) methanol (MeOH) and/or dimethyl ether (DME) from CO2 or syngas; ii) higher hydrocarbons in the range of transportation fuels. The advancement in the state-of-the-art is represented by the utilization of a multi-reactor system equipped with cutting-edge process control technology in the market. The rig is configured as an advanced modular laboratory system completely automated and able to run at 650 °C/100 bar (up to 800°C at atmospheric pressure) during measurements of catalytic activity for the study of the activity-selectivity pattern and kinetics of chemical reactions. This enables the user to program a series of experiments from the computer, even on the network, so obtaining real-time results with the highest degree of reproducibility and accuracy. 

In a process intensification view, the investigation of the issues related to reactor design and kinetics appears to be crucial. Understanding phenomena associated with reaction mechanism and catalyst deactivation is a very challenging task in green chemistry and molecular catalysis. 

A further potential of this research facility is related to the application of breakthrough characterization techniques applied to study the catalytic processes of CO2 hydrogenation under real conditions. Knowledge of materials under realistic conditions is, in fact, essential for the development of new synthesis routes and the preparation of catalysts with enhanced properties. On this account, in situ/operando DRIFTS measurements will get a deep understanding about the catalytic steps behind methanation, MeOH/DME or higher hydrocarbons synthesis providing crucial information for a rational design of bulk, supported or hybrid catalysts. The Thermo Scientific Nicolet iS50 FTIR Spectrometer uniquely combines multi-tasking capabilities and high performance in an affordable, optimized footprint system. It is equipped a built-in ATR multirange diamond sampling station and automated beamsplitter. It boats the presence of a dynamically aligned interferometer.  

The facility can account for the world’s finest simultaneous DSC/TGA instrument able to guarantee advanced engineering in the measurement set-up with consequent enhancements in every aspect of performance. FT-IR is a well-known technique with enhanced capacity if coupled with thermal analysis, allowing detection of permanent gases such as H2, COX or H2O at reasonable concentration as well as organic molecules released from substrates. The pure real-time simultaneous heat flow and weight data is made possible at ultra high-resolution for the best separation of overlapping weight losses. Thermal capacity and kinetic studies are easily elaborated thus enhancing laboratory workflows and productivity. On the whole, the TGA/IR/MS hyphenation yields a powerful analytical technique that combines the quantitative capabilities of TG and the identification capabilities of both FT-IR and MS spectroscopies. 

New challenges in the design of innovative solid materials are related to the need to highly localized characterization of increasingly complex samples at ever smaller features. On this account, the facility is equipped with a last-generation optical microscope which represents a new era of digital microscopy, combining a large depth of field (20 times greater than conventional optical microscopes) with high resolution able to deliver a new level of observation exceeding conventional imaging tools. However, one of the flagships of the facility is represented by a cutting-edge SEM-FIB microscope which incorporates a suite of state-of-the-art technologies enabling simple and consistent high resolution S/TEM and atom probe tomography (APT) sample preparation, as well as the highest quality sub-surface and 3D characterization even on the most challenging samples. Moreover, the innovative TEM JEM F200 represents a fundamental support for excellence researches in all the different fields of material science.