Alexander Dimitrov Kroumov

Determination of the mass transfer limiting step of dye adsorption onto commercial adsorbent by using mathematical models

Reactive blue 5G dye removal in a fixed-bed column packed with Dowex Optipore SD-2 adsorbent was modelled. Three mathematical models were tested in order to determine the limiting step of the mass transfer of the dye adsorption process onto the adsorbent. The mass transfer resistance was considered to be a criterion for the determination of the difference between models. The models contained information about the external, internal, or surface adsorption limiting step. In the model development procedure, two hypotheses were applied to describe the internal mass transfer resistance. First, the mass transfer coefficient constant was considered. Second, the mass transfer coefficient was considered as a function of the dye concentration in the adsorbent. The experimental breakthrough curves were obtained for different particle diameters of the adsorbent, flow rates, and feed dye concentrations in order to evaluate the predictive power of the models. The values of the mass transfer parameters of the mathematical models were estimated by using the downhill simplex optimization method. The results showed that the model that considered internal resistance with a variable mass transfer coefficient was more flexible than the other ones and this model described the dynamics of the adsorption process of the dye in the fixed-bed column better. Hence, this model can be used for optimization and column design purposes for the investigated systems and similar ones.

Optimization of the Iron Electro-Coagulation Process of Cr, Ni, Cu, and Zn Galvanization By-Products by Using Response Surface Methodology

An electrocoagulation laboratory scale system was studied for the removal of inorganic pollutants from a mixture of galvanic process-based by-products. Response surface methodology based on a five-level, four-variable central composite rotatable design was employed for optimization with respect to four important variables—reaction time, agitation velocity, current density, and pH. The electrocoagulation process response was evaluated on the basis of chemical oxygen demand (COD), turbidity, total suspended solid, and element concentration values. Interaction effects between reactor operating variables and response variables were evaluated by using 3-D response surface analysis Second-order models were validated by ANOVA. Predicted yields were in a good agreement with the experimental ones. The reactor optimal performance was achieved at 35 min reaction time, 170 rpm agitation velocity, 97.7 Am−2 current density, and 6.5 initial pH. Under these conditions 100% color and turbidity, 90% COD and total suspended solids, 100% chromium and nickel, and almost 99% zinc and copper were removed. A pseudo-first-order rate model was applied to describe the metal removal kinetics. The EC treatment of heavy metal solutions proved to be more cost-effective than the conventional one, indicating clearly that the method of electro-coagulation is a very promising alternative for industrial applications.

Assessment of the banana pseudostem as a low-cost biosorbent for the removal of reactive blue 5G dye.

In this work, the removal of reactive blue 5G (RB5G) dye using the drying biomass of banana pseudostem (BPS) was investigated. The characterization of BPS particles was performed. Improvement in the RB5G dye removal performance at the following sorption conditions was evidenced: pH 1, 30°C sorption temperature and 40 rpm shaking, regardless of the particle size range. Kinetic RB5G dye sorption data obtained at better conditions fit well in an Elovich model. A combined Langmuir–BET isotherm model provides a good representation of the RB5G dye equilibrium sorption data, which shows the evidence of a physical sorption process on the BPS surface. Based on the results, the removal of RB5G dye molecules by BPS is based on a physical sorption process.

Potential of Salvinia auriculata biomass as biosorbent of the Cr(III): directed chemical treatment, modeling and sorption mechanism study

ABSTRACT In this work, the mechanism of the Cr(III) sorption by Salvinia auriculata biosorbent was studied in two stages. To understand the influence of the sorption parameters on the Cr(III) uptake, preliminary tests were performed. First, S. auriculata biomass was separately treated with base and acid solutions. Second, acid and base treatment of samples was performed based on the knowledge data base of our group. It was achieved a higher Cr(III) sorption capacity above 15 mg g-1 as associated to an increase of the micro-pores specific area and biosorbent volume. The obtained kinetic data of raw and treated biosorbents were well described by the intra-particle diffusion model. In this model, Cr(III) adsorption onto treated biomass is progressively improved with appearing of different mass transfer zones from out layer up to micro-porous layers. The equilibrium data of raw biomass were best described by the Langmuir isotherm, whereas the equilibrium data of the treated biomass were best fit by a combination of both Langmuir and Dubinin–Radushkevich isotherms. At low concentrations the adsorption most likely occurred on the outer monolayer, as proposed by the Langmuir model, followed by the adsorption on the micro-porous layers, as validated by the Dubinin–Radushkevich isotherm.

Biosorption of the Reactive Blue 5G Dye in a Fixed Bed Column Packed with Orange Bagasse: Experimental and Mathematical Modelling

The removal of reactive dye in a fixed bed column packed with orange bagasse was modelled using a model that considers the effects of axial dispersion, external and internal mass transfer limitations, and the equilibrium in the liquid-solid interface. The equilibrium and kinetic parameters were obtained through fit the model to the experimental data. In the parameters identification procedure the PSO optimization method was used. The mathematical model showed good performance when describing the dye adsorption process. Furthermore, orange bagasse is an attractive and cost-effective alternative as an adsorbent to remove reactive blue 5G dye from wastewaters.

A comprehensive evaluation of heavy metals removal from battery industry wastewaters by applying bio-residue, mineral and commercial adsorbent materials

We present a feasibility study of different adsorbent materials, namely residual fish scales biosorbent (FS), mineral dolomite (DL) and commercial resin (CR) in the heavy metals removal in multicomponent solution based on the properties of a real effluent from automotive battery recycling industry. Considering the effluent complex characteristics, the materials were assessed aiming to provide not only the heavy metals removal, but also the effluent neutralization and lower sludge generation. For this, all the studied materials were physicochemically and morphologically characterized with the aim of understanding the mechanisms involved in the process. Further, the elemental compositions of the solid and liquid phases generated from each treatment process were assessed by X-ray fluorescence spectrometry. The effluent presented highly acidic characteristics and heavy metals above the legislated limits for discharge (Fe, Zn and Pb). Each adsorbent material followed different mechanisms which led to dissimilar removal and neutralization capacities. The CR showed remarkable heavy metals removal capacity governed by an ion exchange mechanism; conversely, it did not show a neutralization effect. In contrast, FS and DL presented lower removal capacities by complex simultaneous phenomena (ion exchange, precipitation and/or complexation), but a great neutralization potential related to leaching of alkaline constituents. When sludge generation is considered as a key factor, mitigation and enhancement of treated effluent quality could alternatively be addressed by employing the materials in hybrid processes. Hence, the associated use of such materials could be viable yet very challenging for both neutralization and removal of heavy metals from the battery effluent.

Evaluation of hybrid neutralization/biosorption process for zinc ions removal from automotive battery effluent by dolomite and fish scales

ABSTRACT This work focused in the evaluation of Oreochromis niloticus fish scales (FS) as biosorbent material in the removal of Zn from a synthetic effluent based on automotive battery industry effluent and, further, a hybrid neutralization/biosorption process, aiming at a high-quality treated effluent, by a cooperative use of dolomite and FS. For this, a physicochemical and morphological characterization (i.e. SEM–EDX, FTIR, XRD, and TXRF) was performed, which helped to clarify a great heterogeneity of active sites (phosphate, carbonate, amide, and hydroxyl) on the biosorbent; also the inorganic constituents (apatites) leaching from the FS was identified. Biosorption results pointed out to a pH-dependent process due to changes in the functional group’s anionic character (i.e. electrostatic interactions), where an initial pH = 3 favored the Zn uptake. Kinetic and equilibrium studies confirmed the heterogeneous surface and cooperative sorption, wherein experimental data were described by Generalized Elovich kinetic model and the favorable isotherm profile by Langmuir–Freundlich isotherm ( = 15.38 mg g–1 and ). Speciation diagram of Zn species along with the leached species demonstrated that, for the studied pH range, the biosorption was the most likely phenomena rather than precipitation. Finally, the hybrid neutralization/biosorption process showed great potential since both the Zn concentration levels and the pH reached the legislation standards (CZn = 4 mg L–1; pH = 5). Hence, based on the characterization and biosorption results, a comprehensive evaluation of the involved mechanisms in such complex system helped to verify the prospective of FS biosorbent for the Zn treatment from solution, in both individual and hybrid processes.

Complex mathematical analysis of photobioreactor system

Modeling as a tool solves extremely difficult tasks in life sciences. Recently, schemes of culturing of microalgae have received special attention because of its unique features and possible uses in many industrial applications for renewable energy production and high value products isolation. The goal of this review is to present the use of system analysis theory applied to microalgae culturing modeling and process development. The review mainly focuses on the modeling of the key steps of autotrophic growth under the integral biorefinery concept of the microalgae biomass. The system approach follows systematically a procedure showing the difficulties by modeling of sub‐systems. The development of microalgae kinetics and computational fluid dynamics (CFD) studies were analyzed in details as sub‐systems in advanced design of photobioreactor (PBR). This review logically follows the trends of the modeling procedure and clarifies how this approach may save time and money during the research efforts. The result of this work is a successful development of a complex PBR mathematical analysis in the frame of the integral biorefinery concept.

Insights on the criteria of selection of vegetable and mineral dielectric fluids used in power transformers on the basis of their biodegradability and toxicity assessments

Leakage of transformer dielectric fluids is a concern because it may pose a risk of environmental contamination. In this study, the deleterious effects of vegetable and mineral dielectric fluids in water bodies were investigated using biodegradability and acute toxicity tests with Danio rerio and Artemia salina. Regarding biodegradability, all four tested vegetable oils (soy, canola, sunflower and crambe) were considered as easily biodegradable, presenting degradation rates significantly higher than the Lubrax-type mineral fluid. Acute toxicity tests were performed in two separate experiments without solution renewal. In the first experiment, the organisms were exposed in direct contact to different concentrations of vegetable (soy) and mineral (Lubrax) oils. Total soy-type vegetable oil has a higher toxic effect than Lubrax-type mineral oil. In the second experiment, the organisms were exposed to increasing percentages of the water-soluble fraction (WSF) of both types of tested oils. The LC50 values for the water-soluble fraction of the Lubrax-type mineral oil were about 5 and 8% for the Danio rerio and Artemia salina bioindicators, respectively, whereas the vegetable oil did not present toxic effect, regardless of its WSF. These results have shown that a strict selection of dielectric fluids and monitoring the leakage from power transformers is a serious duty of environmental protection agencies.

Soybean plant-based toxicity assessment and phytoremediation of soils contaminated by vegetable and mineral oils used in power electrical transformers

In this work, deleterious effects in soils due to the presence of dielectric fluids were investigated. For this purpose, vegetable (Envirotemp® FR3) and mineral (Lubrax AV 66 IN) oils were used for simulating a set of soils contaminated in different oil contents (0.5, 1.0, 2.0, 2.5, 5.0, 7.5 and 10%) in which three 120-days soybean crop periods (SCP) were carried out using the species Glycine max (L.) Merr. Both soil and soybean plant samples were analysed on following the changes on chemical attributes, content of oils and greases (COG) in soils and phytotechnical characteristics of soybean plant. No significant changes on soil chemical attributes were found. For a 0.5% vegetable oil fraction, COG removals of 35, 60 and 90% were observed after the 1st, 2nd, and 3rd SCPs, respectively, whereas removals of 25, 40 and 70% were observed for 0.5% mineral oil fraction after the 1st, 2nd, and 3rd SCPs, respectively. There was an effectively accumulated removal on all tested oil fractions as being proportional to the integrated 120-days SCPs, suggesting a lesser number of crops for a complete abatement of oil fraction in soil. A 100% recovery on the seedlings emergence fractions was also evidenced, revealing that at least a number of 7 and 9 SCPs should be applied continuously in soils contaminated by vegetable and mineral oils, respectively, in order to no longer jeopardize soybean plant growth. Finally, an empirical prediction of the number of SCPs necessary for the complete removal of oil from the soil was proposed.