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Periodic Report Summary 2 - IOLICAP (Novel IΟnic LΙquid and supported ionic liquid solvents for reversible CAPture of CO2)

Project Context and Objectives:
The IOLICAP project gathers expertise and skills form the domains of chemical synthesis of ILs, molecular simulation/mechanical statistics, phase equilibrium (EoS development), electrochemistry/corrosion, physicochemical characterisation, nanoporous materials & membrane technology and process engineering, aiming at the development optimisation and thorough evaluation of novel TSILs systems as solvents that (a) short-term could replace the alkanolamines in the currently applied PCC technology and (b) long-term would lead to the establishment of a completely novel technology for CO2 capture, based on hybrid absorption bed/membrane systems that will incorporate IL modified porous materials and membranes and alternative ways of regeneration.
The IOLICAP consortium has set the following scientific and technical objectives:
Scientific objectives
1) The development of molecular simulation models for defining the molecular mechanisms that govern the structural, thermodynamic and transport properties of ionic liquids and the development of equations of state (EoS) for modelling the ionic liquids (ILs) phase behaviour in CO2 and other solvents.
2) The synthesis of aminofunctionalised ionic liquids TSILs, protic ionic liquids PILs and poly-ionic liquids (Poly-IL) and the respective IL/solvent systems (mainly water), which have showed promising CO2 capture properties above the 0.5 mol/mol limit for CO2 capture/sequestration. The synthesis of PILs with enhanced proton conductivity properties and of Poly-ILs that can be applied for reversible SO2 capture at the 2 mol/mol level. The synthesis of completely novel ILs based on the guidance from WP1. The optimisation of the solvents properties in what concerns their purity, toxicity and absorption properties.
3) The development of novel techniques for corrosion studies especially focusing to the correlation of the material’s performance data with electrochemical measurements, to assess the suitability of electrochemical approaches for providing rapid screening of materials.
4) The development of advanced techniques for the physicochemical and the thermophysical characterisation of the synthesised ILs as well as the development of experimental techniques for the rapid screening of the CO2 and SO2 absorption capacity under static or dynamic conditions.
Technical objectives
1) The optimisation of a continuous flow micro-reactor technology (MCR) for the up-scaled synthesis of the most promising ILs.
2) The development and application of a novel technology based on using Advanced Guided Elastic Waves Methodology for in-situ monitoring the consequences of corrosion into vessels.
3) The synthesis and characterisation of Supported and/or Grafted IL Phase Systems based on advanced porous materials (Supported Ionic Liquid Systems SILPS) and membranes (Supported Ionic Liquid Membranes SILMS) and the development and study of Non-Thermal Regeneration Methods involving the synthesised hybrid materials.
4) The process engineering and optimisation study of the non-thermal regeneration technology and of the typical scrubbing/stripping technology involving the new solvents. The expected high capture capacity of the new Ionic Liquid solvents, above the 1 mol/mol threshold in combination with the lower temperature needed for their regeneration (80oC instead of 100oC for amines) permits us to predict a 30% reduction of the reboiler duty (less use of steam) and a 20-30% reduction of the units size. The mitigation cost for CO2 capture for a pulverised coal fired power plant is estimated to drop from 41 to 30€ per ton avoided.
5) Construction of a small-scale pilot unit applying the non-thermal regeneration methods and of a typical Scrubbing/Stripping pilot unit for CO2 capture from a 5000Nm3/h flue gas stream where the novel solvents will be tested under real conditions and the Life Cycle Assessment of the process involving the new solvents will be performed.

Project Results:
A large number of Ionic Liquids (ILs) were synthesised and evaluated for their thermo physical and physicochemical properties.
-Protic ILs (3): DBUH Triazolide / Pyrazolide / Imidazolide (DBU=(1,8-Diazabicyclo[5.4.0]undec-7-en))
-Proton Conductive ILs (1): 1-methylimidazole + taurine
-Task specific aminofunctionalised ILs (7): 4-ethyl-4-methylmorpholinium Argininate / Tryptophanate / Serinate, 1-ethyl-3-methylimidazolium Tryptophanate / Serinate / Lysinate, Guanidium tris(pentafluoroethyl)trifluorophosphate
-Poly-Ionic liquids (3): Chitosan ionogels with aminofunctionalised ILs, poly(vinylbenzylpyridinium) bis(trifluoromethylsulfonyl)imide and
poly(dimethylbenzylethylacryloylammonium) bis(trifluoromethylsulfonyl)imide.
-Tricyanomethanide anion based ILs (4): Alkyl methylimidazolium Tricyanomethanides (alkyl= ethyl, butyl, hexyl, octyl)
-Tricyanomethanide anion based ILs with ether groups on their alkyl chain (2).
-Alcohol-ammonium and alkylammonium aminoacid ILs (5): N,N Dimethyl-N,N-diethanolammonium Taurinate /Prolinate, N-Ethyl-N-methyldiethanolammonium β-alaninate, N,N,N-Trimethyl-N-ethylammonium prolinate, N,N,N-Trimethyl-N-propylammonium prolinate
-Lactam cation based ILs (3): Butyrolactam Trifluoroacetate / Acetate / Methanesulphonate
-Silylated ILs (4): 1-methyl-3-(3-triethoxysilylpropyl) imidazolium Tricyanomethanide / Hexafluorophosphate /Arginate/bis-sulphonyl imide
The capture performance of ILs has been examined in their bulk form or in the form of supported ionic liquid phase systems and membranes (SILPs and SILMs). The methods involved had been the “grafted SILP”, with the IL chemically attached to functional groups of the pore surface and the “inverse SILP” where the IL constitutes the larger fraction of the SILP.

Hybrid solvents of binary or tertiary ILs/H2O mixtures and tertiary (ILs/amine/H2O) mixtures have been evaluated in a lab scale scrubbing stripping prototype.
Amino functionalised ILs and Ils involved in the inverse SILPs exhibited CO2 absorption capacity of above 0.7 mol/mol at 1 bar.
Mixtures of the TCM anion ILs with amines and with aminofunctionalised ILs exhibited identical performance with that of the typical 20%v/v DEA solution. Solvent formulations to be used in the Upscaled Unit have been defined.
Corrosion behaviour was studied by immersion of alloys (Mild steel, stainless steel of types 304 and 316, AA-2024 aluminium alloy and super pure iron) in the ionic liquids at elevated temperature and under potentiodynamic and potentiostatic polarisation in aerated conditions. Advanced techniques such as Scanning electron microscopy accompanied by energy dispersive X-ray spectroscopy (EDX), Glow discharge optical emission spectroscopy (GDOES) and Micro Raman mapping have been applied to study the morphology /chemical composition and elemental depth distributions, to visualise the inclusions in the alloys and the corrosion events, to identify corrosion products and understand corrosion processes.
Light scattering methods were successfully developed and applied for the reliable determination of thermophysical properties of pure ILs and their binary mixtures with CO2. The mutual and thermal diffusivity of IL-CO2 mixtures have made accessible by conventional DLS with low uncertainty, typically smaller than ±10%.
Force fields have been tested and optimized for the prediction of transport properties of ILs. The optimized force field parameters were validated by performing long molecular dynamics simulations and comparing with experimental data. They were successfully used for the simulation of macroscopic properties of ILs families and the calculation of the transport properties of gases therein.
The Microreactor technology was optimised and adopted to the production of TCM anion based ILs. 200kg of TCM anion ILs have been produced for the needs of the pilot plant.
The corrosion monitoring technology based on guided lamp waves is ready to be implemented in the scrubber and stripper towers of the power plant.

Potential Impact:
Within the first 36 months, 30+ ILs has been synthesised and characterised and their CO2 capture performance has been evaluated. Three promising solvent formulations have been defined. Solvent 1, (DEA 7%, MDEA 6.9%, TCM- ILs 6.9% (v/v)) had similar performance with 20-30% DEA. Solvent 2, (MDEA 7.77%, TCM anion ILs 7.76%) had better performance compared to MDEA 20%. Solvent 3, ([emim][Lys]/[Ser] 8.5%, TCM anion ILs 10%) exhibited 93% of the capture performance of DEA 20%. These results are very promising. Before claiming the possibility to apply these solvents and refer to their potential impacts, it was essential to investigate several other issues. Amongst them are: Corrosivity, stability (in oxygen and acidic gases) and toxicity.
Corrosion tests revealed that, immersion of MS in the amine-functionalised ILs [emim][Lys] and [emim][Ser] results in the dissolution of metal over the macroscopic mild steel surface. The aggressive behaviour of these amino acid-based ILs and their corrosivity may significantly impair their application for post-combustion CO2 capture. However we must note that Solvent 3 contains only 8.5% of these ILs and 10% of [TCM] anion ILs, the latter being not corrosive, neither in their pristine state nor in mixtures with water. Comparing with the examined Corrosion Rates (MPY) of typical amines: 30% Wt MEA=32>50% Wt DEA=25>15% Wt MEA=13>20% Wt DEA=8>50% Wt MDEA=3 it can be foreseen that the 8.5% composition will trigger very slow corrosion rates. The major impact from the use of Solvent 3 (the same holds for Solvent 1 and Solvent 2) will be the possibility to use cheaper alloys for the construction of the capture plant which can reduce the capital cost by a factor of 5. Moreover amines do gradually evaporate and degrade. The annual emission of amines to the air (due to slippage) for a 400MW plant can vary from 40-160 tonnes and some of them are proved to be toxic and even carcinogenic, especially the degradation by products like Nitrosamines. It is also estimated that the amount of degraded amine per year for a 400MW plant can be up to 690 tones. Replacement with the less volatile (Solvent 3) will have a tremendous environmental impact. 40 tonnes of amine slippage per year means a vapour concentration of below 1ppm in the stream escaping the scrubber. Huge amounts of energy for cooling water in condensers are required to achieve this slow slippage rate. This huge energy expense will be avoided due to the non-volatility of [emim][Lys]/[Ser]. With the current price of DEA (2€/kg), a total annual cost of 1.4M€ can me estimated for replacing degraded solvent. Solvent 1 contains about ¼ of the typical DEA concentration and in this sense a tremendous reduction of annual operation expenses is expected for the plant (about 1M€ can be saved).
In addition the development and application of advanced techniques, to evaluate thermophysical and physicochemical properties with the highest possible accuracy will have a major impact towards the short-term application of the ILs in industrial scale since, knowledge of these properties is needed to be implemented in process simulators to reduce uncertainty in industrial application and to validate force fields through molecular simulation in order to be able in the future to predict thermophysical and physicochechemical properties and identify structure-property relationships: In the absence of such ability, selection of an appropriate IL for a particular separation can become a matter of trial and error.
The European dimension of IOLICAP is signified in technical terms, in terms of developing a trans-national pool of expertise and also from the expected economic benefits resulting from the diffusion of results across complementary business and geographical sectors. The involvement of SMEs together with the multinational character of the partnership is consistent with the spirit of European Cohesion and will make a contribution towards social and economic convergence.

List of Websites:


George Romanos, (Senior Researcher)
Tel.: +302106503972
Fax: +302106511766


Energy Saving
Numero di registrazione: 182670 / Ultimo aggiornamento: 2016-05-17
Fonte d'informazione: SESAM