Chemical Engineering / Kimya Mühendisliği
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Article Citation - WoS: 4Citation - Scopus: 4Novel Hybrid Process for the Conversion of Microcrystalline Cellulose To Value-Added Chemicals: Part 3: Detailed Reaction Pathway(Springer Verlag, 2019) Akın, Okan; Yüksel, AslıIn this study, a novel method of hydrothermal electrolysis of microcrystalline cellulose (MCC) under sub-critical water conditions (200 degrees C) was investigated by applying direct current at constant voltage with the presence of acid catalyst of 5mMH(2)SO(4). Direct current at constant voltage of 2.5V, 4.0V and 8.0V was applied between cylindrical anode (titanium) and cathode (reactor wall). Hydrothermal electrolysis reactions were carried out in a batch reactor (450mL-T316) for the reaction time of 240min. Decomposition products of MCC were analyzed by GC-MS and the decomposition pathway of cellulose under applied voltage was postulated. Levoglucosan and levoglucosenone formations were detected as the first hydrolysis products of MCC and further hydrolysis yielded to formation of glucose and fructose. The major decomposition products of cellulose were detected as levulinic acid (LA), 5-HMF and furfural. Further reactions of LA such as electrochemical decarboxylation, dehydration, hydrogenation, resulted in the formation of 2-butanone, 2-butanone-3-hydroxy, gamma-valerolactone, respectively. Most dramatic results on the product distribution were obtained at applied 2.5V voltage in which LVA and 5-HMF were selectively produced. [GRAPHICS] .Article Citation - WoS: 32Citation - Scopus: 37Mcdm Analysis of Wind Energy in Turkey: Decision Making Based on Environmental Impact(Springer Verlag, 2018) Değirmenci, Sinem; Bingöl, Ferhat; Sofuoğlu, Sait CemilDevelopment of new wind energy projects require complex planning process involving many social, technical, economic, environmental, political concerns, and different agents such as investors, utilities, governmental agencies, or social groups. The aim of this study is to develop a tool combining Geographic Information System (GIS) and Multi-Criteria Decision-Making (MCDM) methodologies, and its application for Turkey as a case study. A variety of constraints and criteria were identified based on a literature review and regulations gathered from variety of agencies, use of which resulted in determination of infeasible sites. Then, pairwise comparisons were carried out using analytic hierarchy process as the MCDM method to estimate relative importance of the criteria, and to visualize a suitability map with three classes. As the final stage, decision making was carried out based on environmental impact where 45.5% of the Turkish territory was found as infeasible area. Sixty percent of the remaining area are covered by the moderate suitability class, followed by the highly suitable area (20.3%) and low suitable area (19.8%). The output of this study can be used by energy planners to estimate the extent that wind energy can be developed based on public perception, administrative, and environmental aspectsArticle Citation - WoS: 34Citation - Scopus: 36Effects of Organo-Modified Clay Addition and Temperature on the Water Vapor Barrier Properties of Polyhydroxy Butyrate Homo and Copolymer Nanocomposite Films for Packaging Applications(Springer Verlag, 2018) Akın, Okan; Tıhmınlıoğlu, FundaPolymer nanocomposites, based on bacterial biodegradable thermoplastic polyester, poly(hydroxy-butyrate) (PHB), poly(hydroxyl-butyrate-co-hydroxy-valerate) (PHBHV), and commercial organo-modified montmorillonite (OMMT-Cloisite 10A) were prepared by solution casting method. This work aims to investigate the effect of Cloisite 10A type clay addition on the water vapour permeability properties of PHB/OMMT, and PHBHV/OMMT nanobiocomposite films. Temperature dependence of water vapor permeabilities of the films were also evaluated at various temperatures, and semi empirical permeability models were used to predict the permeability of polymer systems as a function of clay concentration and aspect ratio of nanoplates. Moreover, thermal, optical, and mechanical properties of the composites were examined by using varieties of techniques including differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), scanning electron microscope (SEM), and thin-film X-ray diffractometer (TF-XRD) respectively. Test results indicated that addition of highly intergallery swollen Cloisite 10A to the PHB/PHBHV, reduced the water vapor permeability up to 41 and 25% compared to native PHB and PHBHV films, respectively. Regarding the all mechanical properties measured, the maximum improvement was achieved for 3 wt% clay loaded samples for both PHB and PHBHV polymer composites. An increase of about 152 and 73% in tensile strength and of 77 and 18% in strain at break was achieved for PHB and PHBHV polymers, respectively. As a result of X-ray diffraction analysis, exfoliated structure was achieved at low clay loaded sample (1% w/w), however at higher concentration (3% w/w) the structure found as intercalated. Therefore, it is an evident that enhancement of characteristic properties highly depend on the dispersion level of clay particles in polymer matrix. The results obtained in this study show the feasibility of improvement of the properties of PHB based polymers with incorporation of nanoclay.Article Citation - WoS: 18Citation - Scopus: 21Polybrominated Diphenyl Ethers (pbdes) in Background Air Around the Aegean: Implications for Phase Partitioning and Size Distribution(Springer Verlag, 2017) Besis, Athanasios; Lammel, Gerhard; Kukucka, Petr; Samara, Constantini; Sofuoğlu, Aysun; Dumanoğlu, Yetkin; Eleftheriadis, Kostas; Kouvarakis, Giorgos; Sofuoğlu, Sait Cemil; Vassilatou, Vassiliki; Voutsa, DimitraThe occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑7PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m−3, respectively) were found at the remote site Finokalia. Partitioning coefficients, KP, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (PL°) and the octanol-air partition coefficient (KOA), were investigated. The equilibrium adsorption (PL°-based) and absorption (KOA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log KOA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log PL° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.Article Citation - WoS: 9Citation - Scopus: 10Novel Hybrid Process for the Conversion of Microcrystalline Cellulose To Value-Added Chemicals: Part 2: Effect of Constant Voltage on Product Selectivity(Springer Verlag, 2017) Akın, Okan; Yüksel, AslıIn this study, electrochemical degradation of microcrystalline cellulose (MCC) under hot-compressed water was investigated via application of constant voltage on reaction medium. Constant voltage ranges from 2.5 to 8.0 V was applied between anode (Titanium) and cathode (reactor wall). As an electrolyte and proton source 5–25 mM of H2SO4 was used. Reactions were carried out in a specially designed batch reactor (450 mL) made of T316 for 240 min at temperature of 200 °C.MCC decomposition products such as glucose, fructose, furfural, 5-HMF and levulinic acid were detected and quantified by High Performance Liquid Chromatography (HPLC). In the absence of electrolyte, applied voltage (2.5 and 4.0 V) decreased the total organic carbon (TOC) yield, in contrast at 8.0 V, TOC yield increased to 13%. Application of 8.0 V in hydrothermal conditions alter MCC decomposition pathway selectively to furfural (15%). Addition of electrolyte (5 mM, H2SO4) and application of 2.5 V potential increased TOC (54%) and changed the decomposition pathway in favor of 5-HMF (30%) and levulinic acid (21%). The structural changes in solid residues of electrochemically reacted MCC was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and found that MCC particles functionalized by carboxylic acid and sulfonated groups by the application of constant voltage to reaction medium. In the presence of electrolyte, under certain voltage (2.5 V), functionalization of solid particles became more obvious in FTIR spectrum results. Therefore, change in the selectivity values of degradation products were conducted with the functionalization of MCC particles due to applied voltage under sub-critical conditions.Article Citation - WoS: 20Citation - Scopus: 26Pops in a Major Conurbation in Turkey: Ambient Air Concentrations, Seasonal Variation, Inhalation and Dermal Exposure, and Associated Carcinogenic Risks(Springer Verlag, 2016) Ugranlı, Tuğba; Güngörmüş, Elif; Kavcar, Pınar; Demircioğlu, Eylem; Odabaşı, Mustafa; Sofuoğlu, Sait Cemil; Lammel, Gerhard; Sofuoglu, AysunSemi-volatile organic compounds were monitored over a whole year, by collection of gas and particle phases every sixth day at a suburban site in Izmir, Turkey. Annual mean concentrations of 32 polychlorinated biphenyls (∑32PCBs) and 14 polycyclic aromatic hydrocarbons (∑14PAHs) were 348 pg/m3 and 36 ng/m3, respectively, while it was 273 pg/m3 for endosulfan, the dominant compound among 23 organochlorine pesticides (OCPs). Monte Carlo simulation was applied to the USEPA exposure-risk models for the estimation of the population exposure and carcinogenic risk probability distributions for heating and non-heating periods. The estimated population risks associated with dermal contact and inhalation routes to ∑32PCBs, ∑14PAHs, and some of the targeted OCPs (α-hexachlorocyclohexane (α-HCH), β-hexachlorocyclohexane (β-HCH), heptachlor, heptachlor epoxide, α-chlordane (α-CHL), γ-chlordane (γ-CHL), and p,p′-dichlorodiphenyltrichloroethane (p,p′-DDT)) were in the ranges of 1.86 × 10−16–7.29 × 10−9 and 1.38 × 10−10–4.07 × 10−6, respectively. The inhalation 95th percentile risks for ∑32PCBs, ∑14PAHs, and OCPs were about 6, 3, and 4–7 orders of magnitude higher than those of dermal route, respectively. The 95th percentile inhalation risk for ∑32PCBs and OCPs in the non-heating period were 1.8- and 1.2–4.6 folds higher than in the heating period, respectively. In contrast, the 95th percentile risk levels for ∑14PAHs in the heating period were 4.3 times greater than that of non-heating period for inhalation, respectively. While risk levels associated with exposure to PCBs and OCPs did not exceed the acceptable level of 1 × 10−6, it was exceeded for 47 % of the population associated with inhalation of PAHs with a maximum value of about 4 × 10−6.Article Citation - WoS: 65Citation - Scopus: 77Air and Seawater Pollution and Air–sea Gas Exchange of Persistent Toxic Substances in the Aegean Sea: Spatial Trends of Pahs, Pcbs, Ocps and Pbdes(Springer Verlag, 2015) Lammel, Gerhard; Audy, Ondrej; Besis, Athanasios; Efstathiou, Christos; Eleftheriadis, Kostas; Kohoutek, Jiri; Kukucka, Petr; Mulder, Marie D.; Pribylova, Petra; Prokes, Roman; Rusina, Tatsiana P.; Samara, Constantini; Sofuoğlu, Aysun; Sofuoğlu, Sait Cemil; Taşdemir, Yücel; Vassilatou, Vassiliki; Voutsa, Dimitra; Vrana, BranislavNear-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air–sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and o,p′-DDT and seawater concentrations of p,p′-DDE and p,p′-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included.Article Citation - WoS: 22Citation - Scopus: 25Indoor Air Quality in a Restaurant Kitchen Using Margarine for Deep-Frying(Springer Verlag, 2015) Sofuoğlu, Sait Cemil; Toprak, Melis; İnal, Fikret; Çimrin, Arif H.Indoor air quality has a great impact on human health. Cooking, in particular frying, is one of the most important sources of indoor air pollution. Indoor air CO, CO2, particulate matter (PM), and volatile organic compound (VOC) concentrations, including aldehydes, were measured in the kitchen of a small establishment where a special deep-frying margarine was used. The objective was to assess occupational exposure concentrations for cooks of such restaurants. While individual VOC and PM2.5 concentrations were measured before, during, and after frying events using active sampling, TVOC, PM10, CO, CO2, temperature, and relative humidity were continuously monitored through the whole period. VOC and aldehyde concentrations did not increase to considerable levels with deep-frying compared to the background and public indoor environment levels, whereas PM10 increased significantly (1.85 to 6.6 folds). The average PM2.5 concentration of the whole period ranged between 76 and 249 μg/m3. Hence, considerable PM exposures could occur during deep-frying with the special margarine, which might be sufficiently high to cause health effects on cooks considering their chronic occupational exposures.Article Citation - WoS: 11Citation - Scopus: 12Novel Hybrid Process for the Conversion of Microcrystalline Cellulose To Value-Added Chemicals: Part 1: Process Optimization(Springer Verlag, 2016) Akın, Okan; Yüksel, AslıIn this paper, a novel hybrid process for the treatment of microcrystalline cellulose (MCC) under hot-compressed water was investigated by applying constant direct current on the reaction medium. Constant current range from 1A to 2A was applied through a cylindrical anode made of titanium to the reactor wall. Reactions were conducted using a specially designed batch reactor (450 mL) made of SUS 316 stainless steel for 30–120 min of reaction time at temperature range of 170–230 °C. As a proton donor H2SO4 was used at concentrations of 1–50 mM. Main hydrolysis products of MCC degradation in HCW were detected as glucose, fructose, levulinic acid, 5-HMF, and furfural. For the quantification of these products, High Performance Liquid Chromatography (HPLC) and Gas Chromatography with Mass Spectroscopy (GC–MS) were used. A ½ fractional factorial design with 2-level of four factors; reaction time, temperature, H2SO4 concentration and applied current with 3 center points were built and responses were statistically analyzed. Response surface methodology was used for process optimization and it was found that introduction of 1A current at 200 °C to the reaction medium increased Total Organic Carbon (TOC) and cellulose conversions to 62 and 81 %, respectively. Moreover, application of current diminished the necessary reaction temperature and time to obtain high TOC and cellulose conversion values and hence decreased the energy required for cellulose hydrolysis to value added chemicals. Applied current had diverse effect on levulinic acid concentration (29.9 %) in the liquid product (230 °C, 120 min., 2 A, 50 mM H2SO4). © 2016, Springer Science+Business Media Dordrecht.Article Citation - WoS: 17Citation - Scopus: 20Preparation and Characterization of Antibacterial Cobalt-Exchanged Natural Zeolite/Poly(vinyl Alcohol) Hydrogels(Springer Verlag, 2014) Narin, Güler; Bulut Albayrak, Çisem; Ülkü, SemraIn the present study, potential application of the local clinoptilolite-rich natural zeolite in formulation of antibacterial hydrogels was investigated. The zeolite powder exchanged with cobalt(II) ions was used in preparation of the zeolite/poly(vinyl alcohol) hydrogel films in different amounts. The films were physically crosslinked by the freezing-thawing method and characterized for their crystallinity, surface and cross sectional morphology, chemical composition, thermal behaviour, mechanical properties, swelling and dissolution behaviours, and antibacterial activities against a Gram-negative bacteria. The films with 0.48 wt% and higher cobalt-exchanged zeolite contents showed antibacterial activity. Addition of the zeolite powder in the formulations did not cause significant changes in the other properties of the films.