Deliverables and publications

The present deliverable D7.7 reports the activities of task 7.1 which involves the evaluation of the environmental impact of the overall process of the RECODE project. The RECODE project aims at the recovery of the CO2, present in the flue gas from a rotary kiln in cement manufacturing, to produce high added-value products

In line with the RECODE project plan, a Training Seminar will be organized by month 24 of the project. This document reports on the planning of this event, which will consist of a Summer School organized by the RECODE Consortium (IIT and RUG), in collaboration with other EU project Consortia.

Zeolite Templated Carbons (ZTCs) are a class of materials that feature the textural properties of the template zeolites and the high conductivity of graphene-like structures. These characteristics make ZTCs a valuable candidate for CO2 catalytic reduction. We report here for the first time that metal-free ZTCs obtained from Beta zeolite are a novel valuable energy material for the reduction of CO2 to formic acid, about 10 times better than a reference reduced graphene oxide catalyst. In addition, it is evidenced that the pristine ZTC contains a large amount of oxygen, an aspect largely underestimated in literature. A specific method to reduce this oxygen content was developed, that coupled to an in-depth characterization by multiple techniques of these materials, allows to understand the nature of the oxygen functionalities on ZTCs surface. Moreover, it was evidenced that the change of oxygenated species by combined thermal and NaBH4 treatment of ZTCs affects the catalytic behavior, leading to a remarkable increase in the performances compared to the pristine one. The comparison of the performances and characteristics of two ZTCs, obtained by different BEA nanostructures, allow to correlate better the modification of the type of oxygen species present in ZTCs to the catalytic behavior. The results open new perspectives for the catalytic application of deoxygenated ZTCs.

Cyclic carbonates are a class of versatile compounds that can be prepared using the greenhouse gas carbon dioxide as a building block and that can find applications as green solvents and as a sustainable alternative to toxic reactants currently used in the chemical industry. The current trends in research related to cyclic carbonates are reviewed in this contribution.

This deliverable (D7.6) includes the work done by DVGW, along with help from different project partners, within Task 7.5 ‘Social, pre-normative and regulatory impacts’. Nevertheless, most of this task’s work was carried out within other work packages. From the outset, this task was connected to WP 8 (dissemination) and WP 7 (exploitation) as well as WP 1 (exploitation plan). The related results are reported within different deliverables. In terms of dissemination, this included the gathering of information of past and upcoming events that are related to the RECODE project. Due to delays in the demonstration campaign, the duties of this task focused on the exploitation plan and the final workshop to reach the task’s goals. Also because of increased effort in WP 3, DVGW’s originally budgeted person months for WP 7 were reduced from 5.5 to 3 in the second amendment accordingly.

This document is meant to provide a report on communication, dissemination and Exploitation activities of the RECODE project and to detail the further steps to be taken with respect to these aspects. The report refers to the first year and a half of the project: from August 2017 to January 2018. The present document includes statistics on the reaching potential of the project information by far. It shows also a spreadsheet that collects details regarding the articles news and events where the Project concept and partial results have been shared. Communication has been conducted mainly through the website (www.andy- project.eu) and social media channels (e.g. Twitter), while Dissemination had a more target-specific focus and developed through conference and event participation.

This report is submitted as D8.1 “Project website”. It provides a brief overview of the RECODE public website and platform. For each section, the report provides a description of main features and related content; screenshots for each website section are also included.

This deliverable reports the assessment of the quality increase of cements enabled by the RECODE CO2- derived additives. Synthesized CaCO3 from CO2 through the carbonation route was employed to improve mechanical properties of cementitious materials due to their physical effect such as filling voids and the nucleation effect as well as their chemical reactive. Firstly, the cement content was partially replaced with CaCO3 nanoparticles. Secondly, CaCO3 was added to the cement matrix. The effect of the three polymorphic forms of CaCO3 (calcite, vaterite and aragonite) on the mechanical properties of cement mortars was also investigated. The production of CaCO3 through carbonation is a very promising solution to mitigate CO2 emissions. The application of this approach in the cement industry could allow the development of a circular economy that exploits the CO2 generated in the cement manufacturing process. This circular economy approach could represent 69% of the emissions saving of the cement industry.

Traditionally, environmental science has subscribed to the belief that cement industry is energy and emission intensive. A transition towards deep decarbonisation of these industries is essential [1]. At this respect, CO2 from the flue gases of a rotary kiln in a cement industry (CO2: 25 vol%) could be used for the production of value-added chemicals (acid additives for cement formulations) and materials (CaCO3 nanoparticles to be used as concrete fillers). In RECODE, the CO2 produced by cement manufacturing is re-used in a significant part within the plant itself to produce better cement-related products entailing less energy intensity and related CO2 emissions by a quadratic effect. With this approach, the RECODE project enables a circular-economy system. Its overall sustainability should be yet assessed.

The aim of this work is to study the effect of the presence of different monovalent ions (Na+, NH4 + and K+) on the nucleation and growth rates of CaCO3 precipitation. There is currently great interest in the precipitation of CaCO3 particles reusing CO2 rich flue gases and calcium-rich wastes, which implies the presence of foreign ions that can affect the crystallization process. Unseeded and seeded tests were carried out in a batch system to estimate the nucleation and growth kinetics, respectively. Tests with Na2CO3 and CaCl2 as precursors led to the classical calcite crystallization mechanism via vaterite formation at high supersaturations. On the other hand, the use of (NH4)2CO3 entailed lower pH and the presence of NH4 +, which stabilized the vaterite and avoided its transformation into stable calcite crystals. Thus, faster nucleation kinetics by using Na2CO3 were obtained. To estimate the growth rate, tests with two initial seed loadings and types (micro and nano seed) were performed. The growth rate increased with the crystal size and decreased with the magma density. The results indicate that the ion effect on the growth rate seems to be related to the ionic radius of the foreign ion.

D-glucosamine is investigated as a non-toxic and sustainable carbon/nitrogen (C/N) source for the templated synthesis of nitrogen-containing CMK-8 ordered mesoporous carbons (NOMCs) conceived for selective CO2 uptake. Pyrolysis temperature is varied during nanocasting using the KIT-6 silica hard template to tailor microporosity and nitrogen inclusions. NOMCs exhibit large surface area (600e1000 m2 g-1) and excellent pore ordering. The CO2/adsorbent interaction energy is estimated by the isosteric enthalpy of adsorption (~33e40 kJ mol-1) and Henry's constants. The role of nitrogen content (~7 e12 at.%) and of each type of N-species on CO2 adsorption is studied by X-ray photoelectron spectroscopy, and CO2/N2 selectivity is attributed, being pyridinic functionalities the most effective ones. NOMCs are tested at different temperatures, gas flow compositions, reversibility, and so on; in all tested conditions, they outperform a homologous bare sucrose-derived carbon. Enhancing micropore volume allows achieving maximum adsorption capacity in pure CO2 (1.47 mmol g
1 at 30 C/0.9 bar), whereas increasing surface N-content accounts for the highest selectivity in CO2/N2 mixtures (20/80 v/v) at 35 C/ 1 bar (maximum CO2 uptake 0.82 mmol g
1 ). The combination of a suitable C/N precursor and the hard templating synthetic route is effective for obtaining high-performing, sustainable, and reusable selective CO2 sorbents, without any activation steps or N-doping post-treatments. © 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Choline/amino acid-based ionic liquids were synthetized via ionic metathesis and their CO2 absorption performances evaluated by employing different experimental approaches. In order to overcome any viscosity-related problem, dimethyl sulfoxide (DMSO) was employed as solvent. IL-DMSO solutions with different IL concentrations were evaluated as absorbents for CO2, also investigating their good cyclability as desirable for real industrial CO2 capture technologies. 1 H-NMR and in-situ ATR-IR experiments were the toolbox to study the CO2 chemical fixation mechanism under different experimental conditions, proving the formation of distinct chemical species (carbamic acid and/or ammonium carbamate). In general, these ILs demonstrated molar uptakes higher than classical 0.5 mol CO2/mol IL and the capacity to release CO2 in extremely mild conditions. The possible biological adverse effects were also analyzed, for the first time, in zebrafish (Danio rerio) during the development, by assessing for different toxicological endpoints, proving the non-toxicity and high biocompatibility of these bio-inspired ILs.

The application of packed-bed reactor (PBR) and/or membrane-based precipitator (MBP) technologies for converting CO2 from energy-intensive industry flue gases into carbonates, in a single-step multiphase process, is a key enabler of the circular economy for the cement industry, a major contributor to global industrial CO2 emissions. NanoCaCO3 particles obtained through the carbonation reaction can be directed back into the cement production as fillers for partially substituting cement in high-performance concrete. High CO2 conversion efficiency and a high product quality is achieved in both technologies employed.

To take the circular approach, the captured and purified CO2 of the cement industry is converted to acid additives for cement formulation. To meet future challenges in terms of energy sources for industrial processes, electrochemical synthesis routes are targeted. Due to the significant cost impact of electricity, high Faradaic efficiencies are needed.

Not the cement industry alone, many industries worldwide have the obligation to lower their CO2 emissions. If their processes cannot be adjusted to suppress emissions, CO2 needs to be captured. To do so, ionic liquids can be the key technology.

Membranes, 2021, 11(4), 271

Powder Technology, Volume 377, 2 January 2021, Pages 868-881

Journal of CO2 Utilization, Volume 45, March 2021, 101446

Chem. Commun., 2020,56, 14992-14995

Procedia Structural Integrity, Volume 26, 2020, Pages 155-165