Publications without Fulltext
Permanent URI for this collectionhttps://hdl.handle.net/20.500.14288/3
Browse
84 results
Search Results
Publication Metadata only IL-modified MOF-177 filler boosts the CO2/N2 selectivity of Pebax membrane(Elsevier, 2024) Department of Chemical and Biological Engineering; Habib, Nitasha; Tarhanlı, İlayda; Şenses, Erkan; Keskin, Seda; Uzun, Alper; Department of Chemical and Biological Engineering; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); Koç University Boron and Advanced Materials Application and Research Center (KUBAM) / Koç Üniversitesi Bor ve İleri Malzemeler Uygulama ve Araştırma Merkezi (KUBAM); Graduate School of Sciences and Engineering; College of EngineeringMixed matrix membranes (MMMs) having ionic liquid (IL) modified metal-organic frameworks (MOF) as fillers present a broad potential for enhancing the separation properties of the polymers. Here, we incorporated an IL, 1butyl-1-methyl-pyrrolidinium tricyanomethanide [BMPyr][TCM], into MOF-177 and used the corresponding composite as filler in Pebax polymer to fabricate IL/MOF-177/Pebax MMMs at different filler loadings. These MMMs along with those prepared by using pristine MOF-177 as a filler were then tested for CO2/N2 separation by measuring their CO2 and N2 permeabilities at 35 degrees C and 1 bar. The [BMPyr][TCM]/MOF-177/Pebax MMM having 10 wt.% filler loading showed remarkable improvements in both CO2 permeability (137 f 2.0 Barrer) and CO2/N2 selectivity (622 f 105) compared to the neat Pebax membrane having corresponding performance values of 98.0 f 2.0 Barrer and 64.5 f 6.0, respectively. This simultaneous improvement in both CO2 permeability and CO2/N2 selectivity breaks the trade-off limitation of polymer membranes. Besides, the MMMs having 10 and 15 wt.% loadings of fillers were located well above the updated Robeson's upper bound, demonstrating the great promise of [BMPyr][TCM]/MOF-177/Pebax MMMs for CO2/N2 separation.Publication Metadata only Atomically dispersed zeolite-supported rhodium complex: selective and stable catalyst for acetylene semi-hydrogenation(Academic Press Inc., 2024) Su Yordanli, Melisa; Hoffman, Adam S.; Hong, Jiyun; Perez-Aguilar, Jorge E.; Saltuk, Aylin; Akgül, Deniz; Demircan, Oktay; Ateşin, Tülay A.; Aviyente, Viktorya; Gates, Bruce C.; Bare, Simon R.; Department of Chemical and Biological Engineering; Zhao, Yuxin; Bozkurt, Özge Deniz; Öztulum, Samira Fatma Kurtoğlu; Uzun, Alper; Department of Chemical and Biological Engineering; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); Graduate School of Sciences and Engineering; College of EngineeringSupported rhodium catalysts are known to be unselective for semi-hydrogenation reactions. Here, by tuning the electronic structure of supported mononuclear rhodium sites determined by the metal nuclearity and the electron-donor properties of the support, we report that atomically dispersed HY zeolite-supported rhodium with reactive acetylene ligands affords a stable ethylene selectivity > 90 % for acetylene semi-hydrogenation at 373 K and atmospheric pressure, even when ethylene is present in a large excess over acetylene. Infrared and X-ray absorption spectra and measurements of rates of the catalytic reaction complemented with calculations at the level of density functional theory show how the catalyst performance depends on the electronic structure of the rhodium, influenced by the support as a ligand that is a weak electron donor.Publication Metadata only [BMIM][OAc] coating layer makes activated carbon almost completely selective for CO2(Elsevier Science Sa, 2022) N/A; N/A; Department of Chemical and Biological Engineering; Department of Chemical and Biological Engineering; Durak, Özce; Zeeshan, Muhammad; Keskin, Seda; Uzun, Alper; Master Student; PhD Student; Faculty Member; Faculty Member; Department of Chemical and Biological Engineering; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); Graduate School of Sciences and Engineering; Graduate School of Sciences and Engineering; College of Engineering; College of Engineering; N/A; N/A; 40548; 59917Tuning the molecular affinity of porous materials towards desired gases is important to achieve superior selectivity for a target separation. Herein, we report a novel composite, prepared by coating an ordinary activated carbon (AC) with an ionic liquid (IL) (1-butyl-3-methylimidazolium acetate, [BMIM][OAc]) offering an almost complete CO2 selectivity over N-2 and CH4. Data indicated that pore blockage by the IL accompanied with the enhancement in polarity and reduction in the hydrophobic character of the surface hindered the sorption of N-2 and CH4. For CO2, on the other hand, new chemisorption and physisorption sites became available associated with the IL layer on the surface, making the composite material significantly selective. Newly formed chemisorption sites attributed to the cation's acidic C2H sites, which become available with bi-layer formation. Presence of multiple competitive sorption sites with different energies was further proven with thermal analysis and detailed spectroscopic analysis. Data showed that CO2/CH4 and CO2/N-2 ideal selectivities boosted from 3.3 to 688.3 (2.3 to 54.7) and from 15.6 to 903.7 (7.1 to 74.3) at 0.1 (1) bar and 25 degrees C, respectively, upon the deposition of IL layer. Especially at lower pressures, the IL/AC material became almost fully selective for CO2 offering ideal selectivities in the order of several tens of thousands. To the best of our knowledge, the remarkable enhancement in the ideal CO2 selectivity by a straightforward post-synthesis modification of an ordinary AC, as reported here, sets a new benchmark in high-performance and efficient gas separation for similar porous materials.Publication Metadata only Computational assessment of MOF membranes for CH4/H2 separations(Elsevier, 2016) N/A; Department of Chemical and Biological Engineering; Eruçar, İlknur; Keskin, Seda; PhD Student; Faculty Member; Department of Chemical and Biological Engineering; Graduate School of Sciences and Engineering; College of Engineering; 260094; 40548MOFs have received significant attention as gas separation membranes due to their wide range of pore sizes, permanent porosities and high surface areas. Thousands of MOFs have been reported to date. However, membrane performance of only a small number of MOFs has been experimentally reported since fabrication of thin-film MOF membranes is challenging. In this study, we used atomically-detailed simulations to assess membrane-based CH4/H-2 separation performances of 172 different MOF structures. Adsorption selectivity, diffusion selectivity, membrane selectivity and gas permeability of MOFs were calculated using atomically-detailed simulations to identify the most promising membrane materials. Our results show that a significant number of MOF membranes exhibits high CH4 selectivity over H-2 and a small number of MOF membranes exhibits mediocre H-2 selectivity over CH4. Gas permeabilities and selectivities of MOF membranes were compared with traditional membranes such as polymers and zeolites. Several MOFs were identified to exceed the upper bound established for polymeric membranes and many MOF membranes showed higher gas permeabilities and selectivities than zeolites LTA, ITQ-29 and MFI. We also carried out flexible molecular dynamics simulations to examine the effect of MOF's flexibility on the predicted membrane performance. Considering flexibility of the framework made a negligible effect on the gas permeability and selectivity of the material having large pores whereas more pronounced changes were seen in gas permeabilities of the material having narrow pores. The results of this computational study will be helpful to guide the experiments to the most promising MOF membranes for CH4/H-2 separations. (C) 2016 Elsevier B.V. All rights reserved.Publication Metadata only Transformation of reduced graphene aerogel-supported atomically dispersed iridium into stable clusters approximated as Ir-6 during ethylene hydrogenation catalysis(Elsevier, 2022) Zhao, Yuxin; Hoffman, Adam S.; Gates, Bruce C.; Bare, Simon R.; Department of Chemistry; Department of Chemical and Biological Engineering; N/A; N/A; N/A; Ünal, Uğur; Uzun, Alper; Öztulum, Samira Fatma Kurtoğlu; Yalçın, Kaan; Çağlayan, Hatice Pelin; Faculty Member; Faculty Member; PhD Student; Master Student; Master Student; Department of Chemistry; Department of Chemical and Biological Engineering; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); College of Sciences; College of Engineering; Graduate School of Sciences and Engineering; Graduate School of Sciences and Engineering; Graduate School of Sciences and Engineering; 42079; 59917; 384798; N/A; N/ATransformation of atomically dispersed reduced graphene aerogel (rGA)-supported complexes, Ir-I(C2H4)(2)(+), with an iridium loading of 9.9 wt%, to form low-nuclearity clusters was investigated during ethylene hydrogenation catalysis. Continuous-scan X-ray absorption spectra demonstrate the formation of clusters well approximated as Ir-4 during reaction at 100 degrees C in flowing equimolar ethylene and H-2. The Ir-4 clusters transformed into clusters well approximated as Ir 6 when the feed molar ratio was switched to H-2: C2H4 = 2 and remained stable in pure H-2 at 100 degrees C. Catalyst performance data show that hydrogenation activity increased with metal nuclearity in the order of atomically dispersed iridium/rGA << Ir-4/rGA < Ir-6/ rGA. Continuous scan X-ray absorption data, complemented with aberration-corrected scanning transmission electron microscopy images, demonstrate that the supported clusters approximated as Ir-6 are stable even in H-2 at atmospheric pressure and 100 degrees C. These supported iridium clusters are among the ones having the highest metal loadings reported for a supported metal cluster catalyst.Publication Metadata only Atomically detailed models for transport of gas mixtures in ZIF membranes and ZIF/polymer composite membranes(amer Chemical Soc, 2012) N/A; Department of Chemical and Biological Engineering; Atcı, Erhan; Keskin, Seda; Master Student; Faculty Member; Department of Chemical and Biological Engineering; Graduate School of Sciences and Engineering; College of Engineering; N/A; 40548In this work, we introduced atomic models for transport of single component gases (CH4, CO2, H-2, and N-2) and binary gas mixtures (H-2/CO2, H-2/N-2, H-2/CH4) in zeolite imidazolate framework (ZIF) membranes and ZIF/polymer composite membranes. the predictions of atomic models were validated by comparing with the available experimental data for a ZIF-90 membrane. Motivated from the good agreement between experimental measurements and predictions of our molecular simulations for single gas and mixture permeances, we extended atomic modeling methods to an unfabricated ZIF membrane, ZIF-65, for predicting its separation performance. Various selectivities of ZIF membranes such as ideal selectivity, mixture selectivity, Adsorption selectivity, and diffusion selectivity were computed for a wide range of operating conditions to assess the potential of ZIF membranes in H-2/CO2 separations. We then combined atomic simulations with continuum modeling to estimate the performance of ZIF-90/Matrimid and ZIF-90/Ultem composite membranes for gas separations. Our theoretical predictions agreed very well with the experimental measurements for these two composite membranes, and therefore, we assessed the performances of several ZIF/polymer membranes composed of various polymers, ZIF-90 and ZIF-65, for separation of H-2 from CO2.Publication Metadata only Plant-wide hierarchical optimization and control of an industrial hydrocracking process(Elsevier Sci Ltd, 2013) Çakal, Berna; Gökçe, Dila; Kuzu, Emre; N/A; Department of Chemical and Biological Engineering; Şıldır, Hasan; Arkun, Yaman; PhD Student; Faculty Member; Department of Chemical and Biological Engineering; Graduate School of Sciences and Engineering; College of Engineering; 242076; 108526Hydrocracking is a crucial refinery process in which heavy hydrocarbons are converted to more valuable, low-molecular weight products. Hydrocracking plants operate with large throughputs and varying feedstocks. In addition the product specifications change due to varying economic and market conditions. In such a dynamic operating environment, the potential gains of real-time optimization (RTO) and control are quite high. At the same time, real-time optimization of hydrocracking plants is a challenging task. A complex network of reactions, which are difficult to characterize, takes place in the hydrocracker. The reactor effluent affects the operation of the fractionator downstream and the properties of the final products. In this paper, a lumped first-principles reactor model and an empirical fractionation model are used to predict the product distribution and properties on-line. Both models have been built and validated using industrial data. A cascaded model predictive control (MPC) structure is developed in order to operate both the reactor and fractionation column at maximum profit. In this cascade structure, reactor and fractionation units are controlled by local decentralized MPC controllers whose set-points are manipulated by a supervisory MPC controller. The coordinating action of the supervisory MPC controller accomplishes the transition between different optimum operating conditions and helps to reject disturbances without violating any constraints. Simulations illustrate the applicability of the proposed method on the industrial process.Publication Metadata only Consequences of simple acid-pretreatments on geopolymerization and thermal stability of red mud-based geopolymers(Amer Chemical Soc, 2018) Kaya, Kardelen; Soyer Uzun, Sezen; N/A; Department of Chemical and Biological Engineering; Öztulum, Samira Fatma Kurtoğlu; Uzun, Alper; Researcher; Faculty Member; Department of Chemical and Biological Engineering; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Graduate School of Sciences and Engineering; College of Engineering; N/A; 59917Red mud, a solid waste residue that forms as a by-product of the Bayer process in alumina production, is structurally modified by simple acid treatments (using 2 and 6 M HCl with digestion temperatures of 85 and 220 degrees C, respectively) followed by calcination at 800 degrees C prior to employing it as a raw material in geopolymer synthesis. The raw materials and their geopolymers are characterized by combining X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence spectroscopy, thermogravimetric analysis, pore volume and surface area analysis, and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. Results reveal that acid modification of red mud followed by calcination plays an important role in activating red mud, significantly leading to enhanced geopolymerization and increased thermal stability of the corresponding geopolymers. The findings presented here can offer new opportunities for effective large-scale utilization of other waste material-based systems in geopolymerization.Publication Metadata only Investigation of the effect of gel properties on supercritical drying kinetics of ionotropic alginate gel particles(Elsevier, 2019) Uzunlar, Erdal; N/A; Department of Chemical and Biological Engineering; Şahin, İbrahim; Erkey, Can; PhD Student; Faculty Member; Department of Chemical and Biological Engineering; Graduate School of Sciences and Engineering; College of Engineering; N/A; 29633A series of spherical ionotropic alginate gel particles with different diameters ranging from 2.8mm to 5.0mm and porosities ranging from 0.899 to 0.976 were prepared by dripping a Na-alginate solution into a solution of salts of divalent cations (Ca2+, Mn2+, Ni2+, Co2+, Cu2+ and Zn2+). After solvent exchange with ethanol, kinetics of supercritical drying of these ionotropic alginate gel particles in a packed bed was investigated at 308-338 K and 100-120 bar. Experimental data were compared with predictions of a model which considers diffusive transport inside the pores and convection in the flowing fluid stream. The model predicted drying profiles by taking into account only the changes in porosity and diameter of the gel particles. A convective mass transfer coefficient correlation that was originally developed for supercritical drying of Ca-alginate gel particles was found to be suitable for M-alginate gel particles. (C) 2019 Elsevier B.V. All rights reserved.Publication Metadata only Adsorption of Pt(cod)me(2) onto organic aerogels from supercritical solutions for the synthesis of supported platinum nanoparticles(Elsevier Science Bv, 2011) Yasar, N. S.; Zhang, L. C.; Aindow, M.; N/A; Department of Chemical and Biological Engineering; Bozbağ, Selmi Erim; Erkey, Can; Researcher; Faculty Member; Department of Chemical and Biological Engineering; College of Engineering; College of Engineering; N/A; 29633The thermodynamics and kinetics of adsorption of Pt(cod)me(2) onto resorcinol-formaldehyde aerogel (RFA) from supercritical carbon dioxide (scCO(2)) was investigated by using high performance liquid chromatography (HPLC) to measure Pt(cod)me(2) concentrations in the fluid phase. It was found that the adsorption isotherms of Pt(cod)me(2) at 35 degrees C for different CO2 pressures could be represented by modified Langmuir isotherms. The kinetics of adsorption was determined by following the Pt(cod)me(2) uptake of the RFA spheres; these data correspond closely to the behavior from a mass transfer model based on diffusion within the pore volume with the assumption of local equilibrium at the solid-fluid interface. The adsorbed Pt(cod)me(2) molecules were reduced at atmospheric pressure under flowing hydrogen at 200 degrees C. The resultant Pt nanoparticles were distributed uniformly on the surface and had narrow size distributions. The average particle size of the nanoparticles increased with platinum loading from 2.0 nm at 10 wt.% to 3.3 nm at 34 wt.%. The Pt nanoparticles in an RFA pellet had a uniform radial size distribution, even though the pellet was impregnated with Pt(cod)me(2) for too short a short period of time for the system to reach adsorption equilibrium. The high mobility of the atomic Pt evolved during the reduction process is believed to be responsible for this phenomenon. Performing the adsorption of Pt(cod)me(2) onto RFA at 80 degrees C led to concurrent reduction and Pt nanoparticle growth. (C) 2010 Elsevier B.V. All rights reserved.