Master Degree / Yüksek Lisans Tezleri
Permanent URI for this collectionhttps://hdl.handle.net/11147/3008
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Master Thesis Catalytic Pyrolysis of Virgin and Waste Polyolefins(01. Izmir Institute of Technology, 2023) Çalık, Fatma Defne; Yıldız, Günay; Şeker, ErolThe fact that increasing plastic production and the mismanaged waste released to the environment put the ecosystem at risk. One of the most promising recycling methods developed within this framework has been pyrolysis. In this thesis, a model feedstock mi (No: 119N302). Thermal (batch and continuous) and catalytic pyrolysis (in-situ and ex-situ) techniques were applied to the polyolefins. Silica-alumina-based solid acid catalysts were produced with the simple sol-gel method to compete with commercial ZSM-5 (30) and ZSM-5 (50). Catalyst-to-plastic ratios between 1/100 and 1/1000 were used for in-situ, and 200 h-1 and 500 h-1 WHSVs were used for ex-situ mode. 57 wt.% pyrolysis oil was produced from the thermal pyrolysis of the virgin PO mixture in the batch system. In the ex-situ catalytic pyrolysis experiments by 500 h-1 WHSV and by ZSM-5, silica-alumina, and ZSM-5 supported silica-alumina, 36 wt.%, 56.6% wt.% and 45.2 wt.% liquid, and by 200 h-1 WHSV, 29.9 wt.%, 54.1 wt.%, and 57.9 wt.% pyrolysis oils were collected, respectively. The most successful test in terms of product composition was ES2 with 82.9% gasoline (8.8% BTEX), and 16.7% diesel-range hydrocarbons. The motivation was investigating whether it was suitable to produce liquid hydrocarbons, in the range of C5-C20, as a feedstock in the petrochemical industry. As a result, it has been proven that energy recovery was possible and sustainable by plastics recycling instead of using fossil fuels.Master Thesis Anaerobic Digester Modelling for Production of Biogas From Waste Hazelnut Husk(Izmir Institute of Technology, 2022) Demir, Ozan; Şeker, ErolAnaerobic digestion is a degradation process of complex organic matters into methane and carbon dioxide in an oxygen-free environment maintained by microorganisms. An advantage, besides energy production, is it is a waste management technique. Hazelnut husk is a valuable raw material for the anaerobic digestion process with more than 55 % cellulose and hemicellulose content. Anaerobic Digestion Model No. 1 (ADM1) developed by IWA Group was used in this study. This master thesis modeled biogas production by co-digestion of cattle manure and hazelnut husk process in MATLAB. The goal was to evaluate the methane amount of a household bioreactor. Tanks-in-series model with 3 CSTRs was chosen after residence time distribution (RTD) analysis. Ten different cases were investigated to show the effects of carbon source/manure ratio, temperature, carbon source type, total solid (TS) amount, reactor type, and RTD analysis. The carbon source/manure ratio improves the methane yield as it increases. When the ratio is 1, methane yield is 0.229 L/kgVS whilst yield is 0.224 L/kgVS if the ratio is 0.1. The temperature effect on the process is significant. In the thermophilic case, the methane production is 0.432 L/d which is the highest amount compared to mesophilic and psychrophilic cases. When food waste is used as a carbon source with a ratio of food waste/manure of 0.1, the methane production is 0.410 L/d while it is 0.403 L/d in hazelnut husk digester. When the TS amount is doubled, the methane yield goes down from 0.224 to 0.149 L/kgVS because the residence time is not long enough to digest it as well as in case with lower total organic carbon level. In unmixed, mixed, and Chinese Dome Digester types of reactors, methane productions are 0.403, 0.646, and 0.552 L/d, respectively. In the ideal case, the methane production is 1.525 L/d which indicates the necessity of RTD analysis.Master Thesis Dimethyl Ether Production From Methanol Over Silica-Alumina Catalysts(01. Izmir Institute of Technology, 2021) Tarancı, Ecem; Şeker, ErolThis study aims to investigate the effect of acidic properties of acidic catalysts on the activity, which is required to produce dimethyl ether from methanol. In this study, silica-alumina (SiO2/Al2O3) catalysts with different compositions which are 25/75 wt.%, 50/50 wt.%, 75/25 wt.%, and 3 different calcination temperatures which are 500°C, 700°C, and 900°C were synthesized by the sol-gel method for the methanol dehydration to dimethyl ether reaction. In the further stages of the study, some changes were made in the catalyst formulations of the most active and the least active catalysts in terms of catalytic performance to modify acidic properties. In this regard, the peptizer acid of silica-alumina catalysts was changed from HNO3 to H2SO4, or 0.1 g of ZSM-5 zeolite was added to the silica-alumina sol mixture step. The NH3-TPD analysis was used to understand the acidic properties of all synthesized SiO2/Al2O3 catalysts. The reaction temperatures were 300°C and 400°C for both 30 min. The study has shown that there was a decrease in the acidity of the catalysts calcined at 900°C is observed. The activity of 75%SiO2-25%Al2O3 catalyst decreases significantly as the calcination temperature increases. The activities of all catalysts calcined at 500°C are close to each other, whereas there is a big difference in activity between 25%SiO2-75%Al2O3 and 75%SiO2-25%Al2O3 catalysts calcined at 900°C. As evidence of the NH3-TPD results, 25/75 wt.% catalyst calcined at 900°C was the most active catalyst with approximately 97% methanol conversion, while 75/25 wt.% catalyst calcined at 900°C was the least active catalyst with 63% conversion at 400°C. The 50/50 wt.% catalyst calcined at 900°C is also a very active catalyst with over 90% conversion. While sulfuric acid and/or zeolite exchange increased the performance of the least active catalyst, it did not reveal much difference in the most active catalysts. In addition, the addition of ZSM-5 zeolite increased the acidic strength of the catalysts. All synthesized catalysts are active for methanol dehydration. The DME selectivity for all catalysts is approximately 100%.Master Thesis 1-Octanol Dehydration on Al2o3-Sio2 Catalyst(01. Izmir Institute of Technology, 2021) Uçar, Beyza; Şeker, ErolBu çalışmada, heterojen asit katalizörün 1-oktanol dehidrasyonunda, ürün dağılımına etkisi araştırılmıştır. Kullanılan katalizörler sol-jel yöntemiyle sentezlenmiştir. Sentezlenen katı asit katalizörler ağırlıkça farklı oranlarda (25%-75%, 50%-50% ve 75%-25%) Al2O3-SiO2 katalizörleriydi. Ayrıca, sentezlenen Al2O3-SiO2 katalizörlerin kalsinasyon sıcaklıkları 500 ̊C, 700 ̊C ve 900 ̊C idi. Bu çalışmanın amacı, Al2O3-SiO2 katalizörlerin asidik-bazik özelliklerini ve birincil alkol dehidrasyonu üzerindeki etkisini anlamaktır. Kullanılan bütün katalizörler için dehidrasyon reaksiyonu 150 ̊C ve reaksiyon süresi 4 saat olarak devam etti. Ürünler ve var olan miktarı GC-MS analizi ile belirlenmiştir. Buna ek olarak, katalizörlerin asidik ve bazik özellikleri NH3-TPD ve CO2-TPD analizleri ile açıklanmıştır. Ayrıca katalizörlerin kristalografisi, XRD sonuçlarına göre belirtilmiştir. Bu çalışma, katalizörlerin bileşiminin ve uygulanan kalsinasyon sıcaklıklarının, reaksiyon yollarını etkileyen asidik-bazik kuvvetleri üzerinde etkili olduğunu ortaya koymuştur. Bunun sonucunda ürün dağılımı ve genel dönüşüm değerlendirilmiştir. Ana ürünler oksalik asit 2-etilheksil tetradesil ester, oktil eter, esterler (Formik asit, oktil ester, Asetik asit, oktil ester ve Heptanoik asit, oktil ester) ve oktanal idi. Ürün dağılımının esas olarak Al2O3-SiO2 katalizörlerinin asidik ve bazik güclerine bağlı olduğu gösterildi.Master Thesis Renewable natural gas production via Sabatier reaction(01. Izmir Institute of Technology, 2021) Çamlık, Cansu; Şeker, ErolThis study attempts to understand the effect of support basicity on Sabatier reaction and improve the performance of Ni based catalysts by introducing calcium which is known for its basicity. In accordance with this purpose, Ni-Al2O3-CaO catalysts were synthesized with modified sol-gel method. Effect of Ni loading, calcination temperature and calcium content were investigated. Al2O3-CaO supports were synthesized at three ratios as follows; 70-30 wt.%, 40-60 wt.%, 10-90 wt.% wherein Ni/Al2O3 catalyst was used as reference catalyst. Based on thermodynamic analysis, reaction was conducted at 400oC and 1 atm with inlet composition of CO2/H2=1/4 and total volumetric flow rate of 100 ml/min. Reference catalyst calcined at 700oC was found to be inactive at used reaction conditions due to the presence of inactive NiAl2O4 phase. Increasing Ni loading from 1 wt.% to 10 wt.% increased both CO2 conversion and methane selectivity. Over the catalysts calcined at the temperature of 900oC, maximum methane yield was obtained over 10Ni-70Al-30Ca-900 as 8%. The influence of Ni loading was more pronounced for catalysts calcined at 700oC. In 10Ni-70Al-30Ca-700 catalyst, NiO particles were smaller than 5 nm. Therefore, it is conceivable that the alumina-calcium mixed oxide support could disperse higher loadings of Ni, which could result in higher CO2 conversion. Ca modification was found to have a prominent impact on both methane selectivity and yield. With 10Ni-10Al-90Ca-700, being best performing catalyst, CO2 conversion obtained as 76% and methane yield was 60%. The promotion of catalytic performance might arise from intensifying the CO2 chemisorption supported by XRD and TGA results.Master Thesis Carbon Dioxide Hydrogenation on Alumina Supported Ruthenium Catalysts(Izmir Institute of Technology, 2019) Hamza, Gökmen Oğuzcan; Şeker, ErolIn this study the effect of basicity of catalyst is investigated using different metal oxide supported Nickel and Ruthenium catalyst. The basic strength of catalysts was orchestrated with using different types of metals and different composition of supports. In this study Al2O3-CaO, Al2O3-MgO, Al2O3-BaO supports were used with nickel and ruthenium catalyst, which synthesized with sol-gel method. Different mass ratios of supports were used such as; 100%, 70%/30%, %50/50%, 20%/80% respectively. For all metal oxides Nickel loadings are 1 %, 5% and Ruthenium loading is 0.5%. Calcination temperature was 500 0C with 6 hours. All catalysts were used in methanation reaction with conditions varies between 300-600 0C, inlet ratio of CO2/H2 1/4 to 1/6 and GSHV 5000h-1/10000h-1. The products were analyzed using GC and catalysts were analyzed using XRD NH3-TPD and BET. Nickel load selected as 1%, magnesium supported catalysts' the main crystallites were aluminum oxide and magnesium oxide for 30%,50%,80; respectively. Calcium supported catalyst had had alumina and calcium oxide crystallites for 30%,50% respectively. Barium supported catalysts had had alumina and barium mix oxide crystallites for 30%,50% respectively. For 5% Nickel loaded 70-30% alumina magnesia mix oxide catalyst magnesia and alumina crystallites are found. Aluminum magnesium mix oxide catalysts had higher basicity than aluminum barium mix oxide catalysts for 1% nickel catalysts. Ruthenium based magnesium alumina mix oxide catalyst had higher basicity than nickel-based magnesium alumina catalysts. Ruthenium catalysts had higher total performance towards both of the reverse water gas shift reaction and carbon dioxide methanation than nickel-based catalysts.Master Thesis Investigation of Different Uv Stabilizer Effects on Hdpe Grades(Izmir Institute of Technology, 2019) Germen, Oktay; Şeker, ErolIn this study, a performance Hindered Amin Light Stabilizer (HALS), used to prevent the structure of polymeric materials from UV and thermal degradation, was investigated using High Density Polyethylene (HDPE) injection grade. The primary goal of this study is to understand the effects of different HALS types, that consist of low molecular mass and high molecular mass, on mechanical and physical properties of HDPE using a design of experiment method. In addition, Minitab program was used to analyze the data, obtained with the experimental design, with ANOVA analyses to estimate the OIT and Loss Elongation% responses of the samples made with varying HALS amounts and types. Briefly, Elongation Lost% which is the ratio of Elongation% Before Aging to Elongation % After Aging and OIT(Oxidative Induction Time) were studied in different recipes of HDPE Injection Molding Plaque specimens in order to measure the effect of HALS1 (Tin770), HALS2(Tin622) and HALS3(Chim944) on aging. One-year of aging was simulated using a standard aging chamber. It was observed that synergetic effect of HALS1 with HALS3 was much more effective than thatof HALS2 with HALS3. Moreover, it was determined that the samples containing antioxidant which did not contain any HALS additive were completely degraded at the end of the same aging process. This study showed that OIT results of samples were affected directly by the amount of HALS3 which protected the polymer against long-term exposure to UV radiation and high temperature whereas neither HALS1 nor HALS2 showed the same protection.Master Thesis Development of Kinetic Model for Industrial Ethylene Oxide Catalyst by Using Model-Targeted Experimentation Approach(Izmir Institute of Technology, 2019) Sarrafi, Şahin; Şeker, Erol; Arkun, Ziya YamanEthylene oxide (EO) is produced via selective oxidation of ethylene with oxygen using a Ag supported on -Al2O3 catalyst. The ethylene epoxidation reaction is desired, whereas the ethylene and EO combustion reactions are not. Proposed study is aimed at developing a tailor-made kinetic model in order for making use in the industrial ethylene oxide reactors which are of paramount importance from the viewpoint of process economics and the greenhouse gas (GHG) induced various environmental exposures. With aging of the catalyst, the trade-off between selectivity and productivity becomes gradually more prominent. Along with the compensation of loss of active sites under the favor of increasing of the temperature, catalyst still provides sustainable commercial yields at the expense of excess feedstock consumption which in turns leads to boost GHG emissions by releasing more carbon dioxide (CO2) into the atmosphere. To maintain catalyst activity for a longest period possible, controlling process variables more preciously with a robust model is very demanding issue throughout the last two decades. Within the scope of this thesis, model-targeted experimentation approach was used assisting by gPROMS software in determining intrinsic kinetics of the commercial catalyst in use through integral reactor coupled with gas chromatography. During the course of the kinetic experiments, the effect of VCM used as a promoter together with inhibiting effects of product gases such as CO2 and EO were also investigated and included into the kinetic model to be derived.Master Thesis Biofuels Production Using Canola Oil Over Heterogeneous Catalysts(Izmir Institute of Technology, 2017) Özdoğru, Bertan; Şeker, ErolThe goal of this study was to investigate the activity of Ni loaded on Al2O3-SiO2 supports prepared with different acids for the production of biofuel grade compounds while using canola oil as our feedstock. While keeping the reaction conditions constant, catalyst preparation parameters such as aluminum concentration, nickel concentration, calcination temperature, and acid types investigated with statistical methods by constructing Box Behnken design using three continuous parameters with two levels and one categorical parameter with three level. Responses considered in this study were aldehyde, ester, organic acid and other compound yields calculated from the GC-MS analysis. After ANOVA analysis, empirical models calculated from this analysis used to optimize the catalyst preparation parameters. Three catalysts, one for each acid type, selected to investigate the validity of our model. Analysis did on these catalysts have shown that both 0% Ni/25% Al2O3-75% SiO2 w/H2SO4 at 900oC and 20% Ni/75% Al2O3-25% SiO2 w/H3PO4 at 900oC catalysts gave good ester yields with good organic acid utilization. 20% Ni/75% Al2O3-25% SiO2 w/H3PO4 at 900oC catalyst was exceptional in ester selectivity aspect while 0% Ni/25% Al2O3-75% SiO2 w/H2SO4 at 900oC catalyst was in organic acid utilization aspect. Presence of aluminum phosphate crystal phase observed with XRD resulted in 20% Ni/75% Al2O3-25% SiO2 w/H3PO4 at 900oC catalyst having the highest selectivity towards ester production. Combination of weak and strong acid sites increased the organic acid selectivity while lowering the selectivity towards esters for 0% Ni/25% Al2O3-75% SiO2 w/H2SO4 at 900oC catalyst. From the low organic acid utilization observed with 10% Ni/25% Al2O3-75% SiO2 w/HNO3 at 500oC and, 10% Ni/50% Al2O3-50% SiO2 w/H2SO4 at 700oC catalysts which had high amounts of weak acid sites, it could be said that organic acids can only be reacted over strong acid sites.Master Thesis Biofuels Production Using Starch Over Heterogeneous Catalysts(Izmir Institute of Technology, 2017) Uçaroğlu, Merve; Şeker, ErolIn this study, the effect of acidity and acidic strength on the product distribution in the hydrolysis of starch was investigated on mixed oxide supported Ni catalysts prepared using different types of metal oxides with varying compositions and, the calcination temperatures. SiO2/Al2O3 (mass ratios of 30/70, 50/50, 70/30) and ZnO/TiO2 (mass ratios of 10/90, 30/70, 50/50) catalysts were synthesized using a sol-gel method. For all the ratios and metal oxide types, Ni weight loading was 1%, 5.5% and 10%. The calcination temperatures used for all the SiO2/Al2O3 catalysts were 500 oC, 700 oC and 900 oC. The calcination temperatures used for all the ZnO/TiO2 catalysts were 300 oC, 400 oC and 500 oC. The starch hydrolysis reaction was carried out at 90 oC for the reaction time of 24 h. The concentration of the products was determined using HPLC and acidity/acidic strength of the catalyst were measured using NH3-TPD. This study showed that the product distribution was affected by catalyst compositions and calcination temperatures that resulted varying total acidity and acidic strength. Unidentifiable saccharides, maltotriose, xylose, and glucose were produced during the hydrolysis of starch on all the SiO2/Al2O3 supported Ni catalysts while there were only unidentifiable saccharides on all the ZnO/TiO2 supported Ni catalysts. The products distribution was found to strongly dependent on the nature of the acid type; for instance, Al2(SO4)3 crystalline phase was more active than the acid type on ZnO and TiO2 anatase crystalline phases. In addition, the glucose yield increased on the large Al2(SO4)3 crystallite sizes, e.g. the catalyst having 42 nm of Al2(SO4)3 crystallite size gave ~15% glucose yield whereas that having 10.5 nm of Al2(SO4)3 crystallite size gave 0%. Besides, acidic strength was more important than total acidity for the same acid type. In fact, the lower the acidic strength, such as located at 150 oC, higher the glucose yield was obtained.