Daniela Zingaretti

Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues

This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO2. This process consists in a first stage in which CO2 is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO2 in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO2 removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO2 uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction.

The fate of MtBE during Fenton-like treatments through laboratory scale column tests

In Situ Chemical Oxidation (ISCO) based on the Fentons process is a proven technology for the treatment of groundwater contaminated by organic compounds. Nevertheless, the application of this treatment process to methyl tert-butyl ether (MtBE) is questioned, as there are concerns about its capacity to achieve complete mineralization. Many existing studies have focused on water contaminated by MtBE and are thus not representative of in situ treatments since they do not consider the presence of soil. In this work, the effectiveness of a Fenton-like process for MtBE treatment was proven in soil column tests performed at operating conditions (i.e., oxidant and contaminant concentration and flow rates) resembling those typically used for in situ applications. No MtBE by-products were detected in any of the tested conditions, thus suggesting that the tert-butyl group of MtBE was completely degraded. A mass balance based on the CO2 produced was used as evidence that most of the MtBE removed was actually mineralized. Finally, the obtained results show that preconditioning of soil with a chelating agent (EDTA) significantly enhanced MtBE oxidation.

Accelerated Carbonation Processes for Carbon Dioxide Capture, Storage and Utilisation

Accelerated carbonation includes a set of processes by which an alkaline material reacts with carbon dioxide forming the corresponding carbonate. This process is applied at pilot scale or full scale for carbon capture from diluted CO2 sources (flue gas or syngas), using (hydr)oxides or carbonates of alkaline metals. Its application to carbon storage has been investigated for more than a decade. Mineralisation of CO2 by reaction with Mg- or Ca-bearing silicate minerals would allow in principle to store CO2 in a safe and definitive manner, without any need of the long-term monitoring required for geological storage. Accelerated carbonation of alkaline industrial residues is also an interesting storage option for specific industrial sectors, such as steelmaking and cement industries. As such, differently from the pure utilisation options discussed in this book, accelerated carbonation may provide an effective contribution to the reduction of CO2 emissions to the atmosphere from stationary sources. Besides, when applied to alkaline residues, it may allow for a beneficial use of these types of waste materials, thus providing a further environmental benefit. This chapter discusses the fundamentals of accelerated carbonation and provides an overview of its main applications proposed so far in the framework of CO2 capture, utilisation and storage (CCUS) and the perspectives for its development in the near future.

Accelerated carbonation of steel slags using CO2 diluted sources: CO2 uptakes and energy requirements

This work presents the results of carbonation experiments performed on Basic Oxygen Furnace (BOF) steel slag samples employing gas mixtures containing 40 and 10% CO2 vol. simulating the gaseous effluents of gasification and combustion processes respectively, as well as 100% CO2 for comparison purposes. Two routes were tested, the slurry phase (L/S=5 l/kg, T=100 °C and Ptot=10 bar) and the thin film (L/S =0.3-0.4 l/kg, T=50 °C and Ptot=7-10 bar) routes. For each one, the CO2 uptake achieved as a function of the reaction time was analyzed and on this basis the energy requirements associated to each carbonation route and gas mixture composition were estimated considering to store the CO2 emissions of a medium size natural gas fired power plant (20 MW). For the slurry phase route, maximum CO2 uptakes ranged from around 8% at 10% CO2, to 21.1% (BOF-a) and 29.2% (BOF-b) at 40% CO2 and 32.5% (BOF-a) and 40.3% (BOF-b) at 100% CO2. For the thin film route, maximum uptakes of 13% (BOF-c) and 19.5% (BOF-d) at 40% CO2, and 17.8% (BOF-c) and 20.2% (BOF-d) at 100% were attained. The energy requirements of the two analyzed process routes appeared to depend chiefly on the CO2 uptake of the slag. For both process route, the minimum overall energy requirements were found for the tests with 40% CO2 flows (i.e. 1400-1600 MJ/t CO2 for the slurry phase and 2220-2550 MJ/t CO2 for the thin film route).

Kinetics of Peroxyacetic Acid Formation and Decomposition in Soil-Slurry Systems

In this work, a comprehensive study on the kinetics of formation and decomposition of peroxyacetic acid in soil-slurry systems is presented. A model of peroxyacetic acid formation and decomposition was developed. It includes the kinetics of formation from hydrogen peroxide and acetic acid, peroxyacetic acid decomposition by hydrolysis and hydrogen peroxide and peroxyacetic acid decomposition due to interactions with soil components. The experimental results were properly described by the proposed model, where all kinetic constants were obtained through independent experiments or by fitting of the experimental data. Three application strategies of the process were compared, showing that the highest peroxyacetic concentration in the system is obtained when the soil is added after equilibrium with acetic acid and hydrogen peroxide is achieved.

Dehalogenation of trichloroethylene vapors by partially saturated zero-valent iron

The reduction of trichloroethylene (TCE) in gas phase by different types of granular zero-valent iron (Fe0) was examined in anaerobic batch vapor systems performed at room temperature. Concentrations of TCE and byproducts were determined at discrete time intervals by analysis of the headspace vapors. Depending on the type of iron used, reductions of TCE gas concentration from 35% up to 99% were observed for treatments of 6 weeks. In line with other experimental studies performed with aqueous solutions, the particle size was found to play a key role in the reactivity of the iron. Namely an increase of the TCE removal up to almost 3 times was observed using iron powders with particle size lower than 425 μm compared to iron powders with particle size lower than 850 μm. The manufacturing process of the iron powder was instead found to play only a limited role. Namely, no significant differences were observed in the TCE reduction by Fe0 obtained using an iron powder attained by water atomization and sieving compared to the removal achieved using an iron powder subjected to a further annealing processes to reduce the content of oxides. Conversely, the pretreatment of the iron powder with HCl was found to enhance the reactivity of the iron. In particular, by washing the iron powder of 425 μm with HCl acid 0.1 M the reduction of TCE after 6 weeks of treatment increase from approximately 80% for the as received material to >99% for the pretreated iron powder. We also performed tests at different humidity of the iron observing that not statistical differences were obtained using a water content of 10% or 50% by weight. In all the experiments, the only detectable byproducts of the reactions were C4-C6 alkenes and alkanes that can be attributed to a hydrogenation of the CCl bond.