Geopolymers for process engineering
Hierarchically porous materials, sorbents, membranes and oxygen carriers
Principal investigators: Elena Landi, Valentina Medri, Francesco Miccio, Annalisa Natali Murri, Elettra Papa
Involved personnel: Cesare Melandri, Andreana Piancastelli
The activity of CNR-ISTEC is dedicated to the development of geopolymer matrices and composites for chemical engineering applications such as:
- catalysis (tar reforming);
- filtration and remediation
- composite membranes,
- CO2 selective adsorption,
- Chemichal Looping Combustion
Geopolymers are synthetic inorganic polymers based on alluminosilicates or phosphates chemically bonded at T <300 ° C. Depending on their composition, alkali geopolymers are the amorphous-semicrystalline equivalent of crystalline zeolites. In addition to an intrinsic meso-porosity, micro-meso-macro-ultra-macro porosity may be suitably varied by means of foaming techniques. Particularly for porous geopolymeric materials, four types of products can be identified:
- mesoporous particulate composites with microporous (zeolithic) or macroporous aggregates, or functional metallic oxide;
- mesoporous geopolymers with macro-ultra macro porosity;
- mesoporous geopolymers with unidirectional macro-ultra macro lamellar porosity;
- mesoporous spheres and granules with lamellar, globular porosity and / or metallic functional oxide.
In the frame of international collaborations and national projects such as PON and POR-FESR, as well as industrial research contracts, hierarchically porosities and pre-industrial prototype were developed and / or the composition of the material was settled through the mix design. Some examples:
Within PON01_00375 “PANDION a Loop Heat Pipe evaporator (LHP) has been produced containing two differentiated porous concentric geopolymeric wicks. A heat pipe is a device that can exchange large quantities of heat with a very small temperature difference between the hot and cold interface, by evaporating and condensing a working fluid. An LHP consists of an evaporator (capillary pump), a compensation chamber, a capacitor and lines of steam and liquid. The final device was tested by SAB srl with TRL 5.
In the framework of the POR-FESR TERMOREF project (2016-2018), innovative “green” composite catalysts for the TAR reforming have been developed, consisting of active oxides dispersed in a geopolymeric matrix. The same materials were also positively tested as oxygen carriers in chemical looping combustion processes.
CLC – Chemical Looping Combustion is a technique that allows the inherent separation of CO2 produced from fossil fuel, from combustion air nitrogen through the chemical transport of oxygen. Similarly, the Chemical loop can be used for other processes such as separating O2 from the air or generating pure hydrogen. Metallic oxide functionalized geopolymers can be used in the form of granular or macro-porous monoliths in high temperature cycles for CLC combustion of methane and syngas.
Gas separation / CO2 adsorption. Due to their porosity distributed over different length scales and a zeolite-like molecular structure, geopolymers have good selective adsorption capacity of CO2. Both in the form of granules and as monoliths they can be used in post-combustion CO2 capture equipment with efficiencies slightly below those of other materials (eg active carbons) but with better mechanical strength and shaping properties.
Purification of wastewater from dyes. The wastewater from textile factories contains dyes mixed with various contaminants and are a major cause of environmental pollution. Geopolymers, thanks to their zeolitic structure, can be effectively used in ion exchange absorption, which is one of the most efficient methods for water purification. In particular geopolymer spheres of millimetric size are the simplest to use in an industrial context.
Tools and Processes
Direct and indirect foaming techniques such as blowing agents or ice templating must be suitably adapted to geopolymeric materials by setting process parameters so as to avoid interference with the geopolymerization. The spherification methods (injection and consolidation in PEG, liquid nitrogen and ionotropic gelation) allow the production of millimetric spheres (2-3 mm depending on the process) at different industrial levels, with different porosity, suitable for water remediation processes.
- SPCTS Università di Limoges
- Dipartimento di Chimica industriale “Toso Montanari” Università di Bologna
- Dipartimento di Ingegneria Civile, Chimica, ambientale e dei materiali (DICAM) Università di Bologna
Publications and patents
- “Alternating potential gas separation process with capacitive membranes, and relevant plant” del 26/01/2017. WO2017/013581 A, PCT/IB2016/054285 del 19/07/2016. Priorità Domanda Italiana n. 102015000037715 “Processo ed impianto a potenziale alternato per separazione di gas con membrane capacitive” del 23/07/2015. Inventori UniBO: F. Doghieri, G. C. Sarti, M. Minelli. Inventori CNR: E. Landi, V. Medri, F. Miccio.
- Miccio F, Natali Murri A, Landi E, Synthesis and characterization of geopolymer oxygen carriers for chemical looping combustion, Applied Energy 194 (2017)136-147
- Minelli M., Papa E., Medri V., Miccio F., Benito P., Doghieri F., Landi E., Characterization of novel geopolymer – zeolite composites as solid adsorbents for CO2 capture, Chemical Engineering Journal 341 (2018) 505-515
- Papa E., Medri V., Benito P., Vaccari A., Bugani S., Jaroszewicz J., Swieszkowski W., Landi E., Synthesis of porous hierarchical geopolymer monoliths by ice-templating, Microporous and Mesoporous Materials 215 (2015) 206-214.