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Sharipova, AA, Aidarova SB, Bekturganova NY, Tleuova A, Kerimkulova M, Yessimova O, Kairaliyeva T, Lygina O, Lyubchik S, Miller R.  2017.  Triclosan adsorption from model system by mineral sorbent diatomite. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 532:97-101. AbstractWebsite

Adsorption of model systems of triclosan by mineral sorbent diatomite is studied. The triclosan equilibrium concentration was measured spectrophotometrically, the morphology of the diatomite characterized using scanning electron microscopy and the amount of the adsorbed triclosan on the diatomite quantified by a mass balance. Adsorption isotherms were analyzed according to the linear/nonlinear form of Langmuir, Freundlich, Sips and Toth isotherm models isotherms, using AMPL software. It is shown that nonlinear Langmuir and Sips isotherm model provided suitable fitting results and no pronounced difference in adsorption efficiency between isotherms measured after 1, 2 and 3days adsorption was observed. Determined maximum adsorption capacity of diatomite towards triclosan qs is 140mg/g. Averaged calculated values of ΔG are −9.9 and −9.6kJ/mol for Langmuir and Sips models respectively. The negative sign of such values indicates spontaneous, physical in nature adsorption.

Sharipova, AA, Aidarova SB, Bekturganova NE, Tleuova A, Schenderlein M, Lygina O, Lyubchik S, Miller R.  2016.  Triclosan as model system for the adsorption on recycled adsorbent materials. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 505:193-196. AbstractWebsite

The adsorption of triclosan as model system was studied to qualify activated carbon sorbents recycled from gas masks (civilian gas mask GP5). The triclosan equilibrium concentration was measured spectrophotometrically, the morphology of the activated carbon characterized by scanning electron microscopy, and the amount of the adsorbed triclosan on the activated carbon quantified by a mass balance method. Experimental isotherms were fitted by Langmuir, Freundlich and Sips adsorption models. It was obtained that the contact time is a crucial sorption parameter that provides information on the optimum adsorption efficiency. It was shown that the maximum efficiency of GP5 (88%) is obtained after 10days of adsorption at a maximal concentration of triclosan and carbon loading 1mg/l. No significant adsorption efficiency differences were measured after 5 and 10days of adsorption. The non-linear Sips isotherm, a combined Freundlich–Langmuir model, provides suitable fitting results. The observed remarkable adsorption capacity of activated carbon (GP5) towards triclosan adsorption (∼85mg/g) makes it a viable solution for wastewater treatment.

Silva, CAC, Figueiredo FCA, Rodrigues R, Sairre MI, Gonçalves M, Matos I, Fonseca IM, Mandelli D, Carvalho WA.  2016.  Enhancing the biodiesel manufacturing process by use of glycerin to produce hyacinth fragrance, Jun. Clean Technologies and Environmental Policy. 18:1551–1563., Number 5 AbstractWebsite

Oxidized and sulfonated-activated carbons (AC) were tested in the catalytic conversion of glycerol by acetalization reactions. The solids were treated with concentrated nitric acid and/or fuming sulfuric acid (AC, AC-N, AC-S, and AC-NS). The presence of sulfur and an increase in the acidity of the solids demonstrate the suitability of the oxidation as well as the sulfonation process, especially in the sample treated with concentrated nitric acid and fuming sulfuric acid (AC-NS). The best catalyst for the reaction of glycerol acetalization with phenylacetaldehyde was AC-NS, with a phenylacetaldehyde conversion of 95 {%} after 90 min at 383 K and selectivity of 88 and 12 {%}, respectively, to dioxolane and dioxane. These products can be used as hyacinth fragrance flavoring compounds. Furthermore, a contribution of homogeneous catalysis in these systems was not identified. Thus, we identified a possibility of glycerol conversion, a biodiesel by-product, into value-added products by suitable catalysts produced from activated carbons.

Surra, E, Nogueira MC, Bernardo M, Lapa N, Esteves I, Fonseca I.  2019.  New adsorbents from maize cob wastes and anaerobic digestate for H2S removal from biogas. Waste Management. 94:136-145. AbstractWebsite

Two activated carbons (ACs) were prepared by physical activation of Maize Cob Waste (MCW) with CO2, during 2 and 3 h (MCW(PA)2h and MCW(PA)3h, respectively). Two other ACs were prepared by chemical activation: a) MCW(LD) – MCW was impregnated with anaerobic liquid digestate (LD) and carbonized under N2 atmosphere; and b) CAR-MCW(LD) – previously carbonized MCW was impregnated with LD and carbonized under N2 atmosphere. All ACs were fully characterized for textural and chemical properties, and then used in dynamic H2S removal assays from real biogas samples. Regarding H2S removal, the ACs that were physically activated behaved much better than the impregnated ones: MCW(PA)3h and MCW(PA)2h showed H2S uptake capacities of 15.5 and 0.65 mg g−1, respectively, while MCW(LD) and CAR-MCW(LD) showed values of 0.47 and 0.25 mg g−1, respectively. This may indicate that textural properties (surface area and microporosity) are more important than mineral content in H2S removal. Effectively, both surface area and micropore volume were much higher for the samples of MCW(PA)3h (SBET = 820 m2 g−1 and Vmicro = 0.32 cm3 g−1) and MCW(PA)2h (SBET = 630 m2 g−1 and Vmicro = 0.21 cm3 g−1) than for the ACs that were chemically activated (SBET = 38.0 m2 g−1 and Vmicro = 0.01 cm3 g−1 for MCW(LD); SBET = 8.0 m2 g−1 and Vmicro = 0.01 cm3 g−1 for CAR-MCW(LD)). High oxygen content in MCW(PA)3h favoured the catalytic oxidation reaction of H2S, promoting its removal. The use of MCW as precursor and LD as activating agent of the ACs may contribute for the integrated management of maize wastes and to diversify the applications of anaerobic digestate.

Surra, E, Bernardo M, Lapa N, Esteves I, Fonseca I, Mota JP.  2018.  Maize cob waste pre-treatments to enhance biogas production through co-anaerobic digestion with OFMSW. Waste Management. 72:193-205. AbstractWebsite

In the present work, the enhancement of biogas and methane yields through anaerobic co-digestion of the pre-hydrolised Organic Fraction of Municipal Solid Wastes (hOFMSW) and Maize Cob Wastes (MCW) in a lab-scale thermophilic anaerobic reactor was tested. In order to increase its biodegradability, MCW were submitted to an initial pre-treatment screening phase as follows: (i) microwave (MW) irradiation catalysed by NaOH, (ii) MW catalysed by glycerol in water and alkaline water solutions, (iii) MW catalysed by H2O2 with pH of 9.8 and (iv) chemical pre-treatment at room temperature catalysed by H2O2 with 4 h reaction time. The pre-treatments cataysed by H2O2 were performed with 2% MCW (wMCW/v alkaline water) at ratios of 0.125, 0.25, 0.5 and 1.0 (wH2O2/wMCW). The pre-treatment that presented the most favourable balance between sugars, lignin, cellulose and hemicellulose solubilisations, as well as low production of phenolic compound and furfural (inhibitors), was the chemical pre-treatment catalysed by H2O2, at room temperature, with a ratio of 0.5 wH2O2/wMCW (Pre1). This Pre1 was then optimised testing reaction times of 1, 2 and 3 days at a different pH (11.5) and MCW percentage (10% w/v). The optimised pre-treatment that presented the best results, considering the same criteria defined above, was the one carried out during 3 days, at pH 9.8 and 10% MCW w/v (Pre2). The anaerobic reactor was initially fed with the hOFMSW obtained from the hydrolysis tank of an industrial AD plant. The hOFMSW was than co-digested with MCW submitted to the pre-treatment Pre1. In another assay, hOFMSW was co-digested with MCW submitted pre-treatment Pre 2. The co-digestion of hOFMSW + Pre1 increased the biogas yield by 38.9% and methane yield by 29.7%, when compared to the results obtained with hOFMSW alone. The co-digestion of hOFMSW + Pre2 increased biogas yield by 46.0% and CH4 yield by 36.3%. In both cases, the methane content obtained in the biogas streams was above 66% v/v. These results show that pre-treatment with H2O2, at room temperature, is a promising low cost way to valorize MCW through co-digestion with hOFMSW.

Surra, E, Bernardo M, Lapa N, Esteves IAAC, Fonseca I, Mota JPB.  2019.  Biomethane production through anaerobic co-digestion with Maize Cob Waste based on a biorefinery concept: A review. Journal of Environmental Management. 249:109351. AbstractWebsite

Maize Cob Waste (MCW) is available worldwide in high amounts, as maize is the most produced cereal in the world. MCW is generally left in the crop fields, but due to its low biodegradability it has a negligible impact in soil fertility. Moreover, MCW can be used as substrate to balance the C/N ratio during the Anaerobic co-Digestion (AcoD) with other biodegradable substrates, and is an excellent precursor for the production of Activated Carbons (ACs). In this context, a biorefinery is theoretically discussed in the present review, based on the idea that MCW, after proper pre-treatment is valorised as precursor of ACs and as co-substrate in AcoD for biomethane generation. This paper provides an overview on different scientific and technological aspects that can be involved in the development of the proposed biorefinery; the major topics considered in this work are the following ones: (i) the most suitable pre-treatments of MCW prior to AcoD; (ii) AcoD process with regard to the critical parameters resulting from MCW pre-treatments; (iii) production of ACs using MCW as precursor, with the aim to use these ACs in biogas conditioning (H2S removal) and upgrading (biomethane production), and (iv) an overview on biogas upgrading technologies.

Surra, E, Bernardo M, Lapa N, Esteves IAAC, Fonseca I, Mota JP.  2018.  Enhanced Biogas Production through Anaerobic co-Digestion of OFMSW with Maize Cob Waste Pre-Treated with Hydrogen Peroxide. Chemical Engineering Transactions. 65:121-126.