Despina Karatza

Study of mercury absorption and desorption on sulfur impregnated carbon

Abstract In this work the attention was focused on the adsorption and desorption of elemental mercuric on HGR activated carbon produced by Calgon-Carbon Corp. The study was performed in an apparatus at laboratory scale in which Hg 0 vapors in a nitrogen gas stream, at a given temperature and mercury concentration, flowed through a fixed bed of adsorbent material. The experiments showed that the adsorption phenomena are faster than the desorption phenomena. SEM micrographs of the fresh carbon and of the carbon after adsorption or desorption had occurred have shown that mercury is adsorbed on the surface on particular sites where high sulfur concentration exists.

Kinetics of Adsorption of Mercuric Chloride Vapors on Sulfur Impregnated Activated Carbon

Abstract Injection of activated carbon impregnated with sulfur or iodine compounds into the flue gases is a promising technique to control mercuric chloride emissions from the combustion of municipal solid wastes. In the present paper the attention is focused on the adsorption of HgCl2 on activated carbon and on the same carbon impregnated with Na2S. The study was performed at laboratory scale, varying the HgCl2 concentration in the inlet stream to the bed in the range of 1–4 mg/m3 and keeping the bed temperature at 150 °C. Three different adsorbents were used, i.e. raw commercially available activated carbon and two impregnated activated carbons (7.8% w/w and 18.7% w/w of Na2S) The experimental runs led to the determination of the breakthrough curves for the fixed bed and of the adsorption isotherms for the three materials at 150 °C. The results showed that, while “raw” activated carbon is capable of removing mercuric compounds, the impregnation process definitely enhances its adsorption capacity, probab...

Degradation of ibuprofen by hydrodynamic cavitation: Reaction pathways and effect of operational parameters

Ibuprofen (IBP) is an anti-inflammatory drug whose residues can be found worldwide in natural water bodies resulting in harmful effects to aquatic species even at low concentrations. This paper deals with the degradation of IBP in water by hydrodynamic cavitation in a convergent-divergent nozzle. Over 60% of ibuprofen was degraded in 60 min with an electrical energy per order (EEO) of 10.77 kWh m(-3) at an initial concentration of 200 μg L(-1) and a relative inlet pressure pin=0.35 MPa. Five intermediates generated from different hydroxylation reactions were identified; the potential mechanisms of degradation were sketched and discussed. The reaction pathways recognized are in line with the relevant literature, both experimental and theoretical. By varying the pressure upstream the constriction, different degradation rates were observed. This effect was discussed according to a numerical simulation of the hydroxyl radical production identifying a clear correspondence between the maximum kinetic constant kOH and the maximum calculated OH production. Furthermore, in the investigated experimental conditions, the pH parameter was found not to affect the extent of degradation; this peculiar feature agrees with a recently published kinetic insight and has been explained in the light of the intermediates of the different reaction pathways.

Silver impregnated carbon for adsorption and desorption of elemental mercury vapors.

The Hg(0) vapor adsorption experimental results on a novel sorbent obtained by impregnating a commercially available activated carbon (Darco G60 from BDH) with silver nitrate were reported. The study was performed by using a fundamental approach, in an apparatus at laboratory scale in which a synthetic flue gas, formed by Hg(0) vapors in a nitrogen gas stream, at a given temperature and mercury concentration, was flowed through a fixed bed of adsorbent material. Breakthrough curves and adsorption isotherms were obtained for bed temperatures of 90, 120 and 150 degrees C and for Hg(0) concentrations in the gas varying in the range of 0.8-5.0 mg/m3. The experimental gas-solid equilibrium data were used to evaluate the Langmuir parameters and the heat of adsorption. The experimental results showed that silver impregnated carbon was very effective to capture elemental mercury and the amount of mercury adsorbed by the carbon decreased as the bed temperature increased. In addition, to evaluate the possibility of adsorbent recovery, desorption was also studied. Desorption runs showed that both the adsorbing material and the mercury could be easily recovered, since at the end of desorption the residue on solid was almost negligible. The material balance on mercury and the constitutive equations of the adsorption phenomenon were integrated, leading to the evaluation of only one kinetic parameter which fits well both the experimentally determined breakthrough and desorption curves.

Sulfite Oxidation Catalyzed by Cobalt Ions in Flue Gas Desulfurization Processes

Abstract This paper presents an experimental study of calcium bisulfite oxidation, a key step in the wet limestone-gypsum flue gas desulfurization (FGD) process, in the presence of catalysts (e.g., cobalt ions and a mixture of ferrous and cobalt ions). A fundamental approach is followed, by reproducing a simplified synthetic FGD liquor in which both catalyst ions, alone or mixed together, are present. A laboratory-scale apparatus is used, in which sulfurous solution is contacted with a gas phase at a fixed oxygen partial pressure (21.3 kPa) and at different temperature levels (25, 45, and 55 °C). The experimental results are analyzed using the theory of gas-liquid mass transfer with chemical reaction, showing that the slow reaction regime is explored and the transition from the kinetic to the diffusional subregime is identified. The experimental results are compared with those obtained in the presence of other catalytic species (manganese and ferrous ions), showing that cobalt is effective in catalyzing the oxidation of calcium bisulfite to sulfate, but to a minor extent with respect to iron and manganese.

Adsorption of elemental mercury vapors from synthetic exhaust combustion gas onto HGR carbon.

ABSTRACT An activated carbon commercially available named HGR, produced by Calgon-Carbon Group, was used to adsorbe metallic mercury. The work is part of a wider research activity by the same group focused on the removal of metallic and divalent mercury from combustion flue gas. With respect to previously published papers, this one is aimed at studying in depth thermodynamic equilibria of metallic mercury adsorption onto a commercial activated carbon. The innovativeness lies in the wider operative conditions explored (temperature and mercury concentrations) and in the evaluation of kinetic and thermodynamic data for a commercially available adsorbing material. In detail, experimental runs were carried out on a laboratory-scale plant, in which Hg° vapors were supplied in a nitrogen gas stream at different temperature and mercury concentration. The gas phase was flowed through a fixed bed of adsorbent material. Adsorbate loading curves for different Hg° concentrations together with adsorption isotherms were achieved as a function of temperature (120, 150, 200°C) and Hg° concentrations (1.0−7.0 mg/m3). Experimental runs demonstrated satisfying results of the adsorption process, while Langmuir parameters were evaluated with gas–solid equilibrium data. Especially, they confirmed that adsorption capacity is a favored process in case of lower temperature and they showed that the adsorption heat was –20 kJ/mol. Furthermore, a numerical integration of differential equations that model the adsorption process was proposed. Scanning electron microscopy (SEM) investigation was an useful tool to investigate about fresh and saturated carbon areas. The comparison between them allowed identification of surface sites where mercury is adsorbed; these spots correspond to carbon areas where sulfur concentration is greater. Implications: Mercury compounds can cause severe harm to human health and to the ecosystem. There are a lot of sources that emit mercury species to the atmosphere; the main ones are exhaust gases from coal combustion and municipal solid waste incineration. Furthermore, certain CO2 capture processes, particularly oxyfuel combustion in a pulverized fuel coal-fired power station, produce a raw CO2 product containing several contaminants, mainly water vapor, oxygen, and nitrogen but also mercury, that have to be almost completely removed; otherwise these would represent a strong drawback to the success of the process.

Extraction of astaxanthin from microalga Haematococcus pluvialis in red phase by using generally recognized as safe solvents and accelerated extraction

Solvent Extraction was tested to extract astaxanthin from Haematococcus pluvialis in red phase (HPR), by investigating effects of solvents, extraction pressure and temperature. Astaxanthin isomers were identified and quantified in the extract. The performances of acetone and ethanol, Generally Recognized As Safe (GRAS) solvents, were explored. Negligible effect of pressure was found, while with increasing extraction temperature astaxanthin recovery increased till a maximum value, beyond which thermal degradation seemed to be greater than the positive effect of temperature on extraction. Furthermore, to maximize the extraction yield of astaxanthin, mechanical pre-treatment of HPR biomass was carried out and several extraction runs were consecutively performed. Experimental results showed that after the mechanical pre-treatment the astaxanthin recovery strongly increased while a single extraction run of 20 min was sufficient to extract more than 99% of total astaxanthin extracted. After pre-treatment, maximum recovery of about 87% was found for acetone (pressure = 100 bar; temperature = 40 °C; total time = 60 min).

Ni-Ti Shape Memory Alloy Coatings for Structural Applications: Optimization of HVOF Spraying Parameters

This work aims at contributing to the development of a revolutionary technology based on shape memory alloy (SMA) coatings deposited on-site to large-scale metallic structural elements, which operate in extreme environmental conditions, such as steel bridges and buildings. The proposed technology will contribute to improve the integrity of metallic civil structures, to alter and control their mechanical properties by external stimuli, to contribute to the stiffness and rigidity of an elastic metallic structure, to safely withstand the expected loading conditions, and to provide corrosion protection. To prove the feasibility of the concept, investigations were carried out by depositing commercial NiTinol Ni50.8Ti (at.%) powder, onto stainless steel substrates by using high-velocity oxygen-fuel thermal spray technology. While the NiTinol has been known since decades, this intermetallic alloy, as well as no other alloy, was ever used as the SMA-coating material. Due to the influence of dynamics of spraying and the impact energy of the powder particles on the properties of thermally sprayed coatings, the effects of the main spray parameters, namely, spray distance, fuel-to-oxygen feed rate ratio, and coating thickness, on the quality and properties of the coating, in terms of hardness, adhesion, roughness, and microstructure, were investigated.

Development and Characterization of High Performance Shape Memory Alloy Coatings for Structural Aerospace Applications

This paper presents an innovative approach, which enables control of the mechanical properties of metallic components by external stimuli to improve the mechanical behavior of aluminum structures in aeronautical applications. The approach is based on the exploitation of the shape memory effect of novel Shape Memory Alloy (SMA) coatings deposited on metallic structural components, for the purpose of relaxing the stress of underlying structures by simple heating at field-feasible temperatures, therefore enhancing their structural integrity and increasing their stiffness and rigidity while allowing them to withstand expected loading conditions safely. Numerical analysis provided an insight in the expected response of the SMA coating and of the SMA-coated element, while the dependence of alloy composition and heat treatment on the experienced shape memory effect were investigated experimentally. A two-phase process is proposed for deposition of the SMA coating in an order that induces beneficial stress relaxation to the underlying structure through the shape memory effect.