• Clean Technology
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• v.25 no.1
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• pp.1-6
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• 2019

Effects of the Cu and K addition and the reduction condition of Fe-based catalysts for Fischer-Tropsch reaction are studied in a continuous flow reactor in this research. The catalysts for the reaction were prepared by homogeneous precipitation followed by incipient wetness impregnation. Physicochemical properties of the $Al_2O_3$ supported Fe-based catalysts are characterized by various methods including X-ray diffraction (XRD), temperature programmed reduction (TPR), and scanning electron microscopy (SEM). Catalytic activities and stabilities of the Fe/Cu/K catalyst are investigated in time-on-stream for an extended reaction time over 216 h. It is found that a reduction of the catalysts using a mixture of CO and $H_2$ can promote their catalytic activities, attributed to the iron carbides formed on the catalysts surface by X-ray diffraction analysis. The addition of Cu induces a fast stabilization of the reaction reducing the time to reach at the steady state by enhancement of catalytic reduction. The addition of K to the catalysts increases the CO conversion, while the physical stability of catalyst decreases with potassium loading up to 5%. The Fe/Cu (5%)/K (1%) catalyst shows an enhanced long term stability for the Fischer-Tropsch reaction under the practical reaction condition, displaying about 15% decrease in the CO conversion after 120 h of the operation.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.888-888
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• 2009

A simulation study on SCR (Steam Carbon dioxide Reforming) process in gas-to-liquid (natural gas to Fischer-Tropsch synthetic fuel) process was carried out in order to find optimum reaction conditions for GTL (gas-to-liquid) process reaction. Optimum SCR operating conditions for synthesis gas to FT (Fischer-Tropsch) process were determined by changing reaction variables such as feed temperature and pressure. During the simulation, overall synthesis process was assumed to proceed under steady-state conditions. It was also assumed that physical properties of reaction medium were governed by RKS (Redlich-Kwong-Soave) equation. SCR process was considered as reaction models for synthesis gas in GTL proess. The effect of temperature and pressure on SCR process $H_2$/CO ratio and the effect of reaction pressure on SCR reaction were mainly examined. Simulation results were also compared to experimental results to confirm the reliability of simulation model. Simulation results were reasonably well matched with experimental results.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.133.2-133.2
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• 2010

Fischer-Tropsch synthesis (FTS) was carried out in heat-exchanger typed reactor with cobalt metallic foam catalyst. Considering the heat and mass transfer limitations in the cobalt catalyst, a Co-foam catalyst with an inner metallic foam frame and an outer cobalt catalyst was developed. The Co-foam catalyst was highly selective toward liquid hydrocarbon production and the liquid hydrocarbon productivity at $203^{\circ}C$ reached to $52.5ml/(kg_{cat}{\cdot}h)$, which was higher than that obtained by the Co-pellet. Furthermore, the heat-exchanger typed reactor was developed to efficiently control the highly exothermic reaction heat. The reaction heat generated in the FTS reaction on the cobalt active site was easily transferred to reactor wall by the metallic foam in the catalyst and the transferred reaction heat was directly removed by the hot oil which circulated the wall side of the heat-exchanger typed reactor.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.358-364
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• 2012

The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.

• Journal of the Korean Chemical Society
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• v.55 no.5
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• pp.824-829
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• 2011

In Fischer-Tropsch Synthesis, because of few reactants ($H_2$, CO), scarce operating parameters affected on efficiency especially the selectivity of products. In this research, effect of operating parameters on the selectivity of Co-Mn-$TiO_2$ Fischer-Tropsch synthesis catalyst were studied by design of experimental procedure and Taguchi method. According to this research, interactions between operating factors have a crucial effect on light products selectivity. Among these interactions, (temperature${\times}$feed ratio) has the main influence on light hydrocarbons selectivity. It was concluded that temperature and feed ratio ($H_2$/CO) were the most integral operating parameters for much greater selectivity of light hydrocarbons.

• Journal of the Korean Applied Science and Technology
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• v.30 no.4
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• pp.726-739
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• 2013

Fischer-Tropsch synthesis (FTS) converts synthesis gas (CO and $H_2$) into longer chain hydrocarbons by a surface polymerization reaction. Cobalt- or iron-based catalysts normally show excellent activity for syngas conversion to petroleum products leading to super clean diesel fuels. The catalytic activities of the catalysts in FTS depend on the number of active sites on the surface. The number of active site was determined by the active metal particle size, loading amount, reduction degree and support-active metal interaction. The investigation adopts new methodology in preparing FT catalyst, which contains the controlled synthesis of active metal. The main focus of this paper is to give an overview of the types of catalysts, also including their preparation and reduction; the types of FT reactors; and also including the reaction conditions.

• Journal of the Korean Institute of Gas
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• v.20 no.4
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• pp.65-77
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• 2016

Modeling for complex reacting flow in Fischer-Tropsch reactor is one of the challenges in the field of Computational Fluid Dynamics (CFD). It is hard to derive each and every reaction rate for all chemical species because Fisher-Tropsch reaction produces many kinds of hydrocarbons which include lots of isomers. To overcome this problem, after analyzing the existing methodologies for reaction rate modeling, non-Anderson-Schulz-Flory methodology is selected to model the detailed reaction rates. In addition, the inside flow has feature of multi-phase flow, and the methodologies for modeling multi-phase flow depend on the interference between the phases, distribution of the dispersed phase, flow pattern, etc. However, existing studies have used a variety of inside flow modeling methodologies with no basis or rationale for the feasibility. Modeling inside flow based on the experimental observation of the flow would be the best way, however, with limited resources we infer the probable regime of inside flow based on conventional fluid dynamics theory; select the appropriate methodology of Mixture model; and perform systematic CFD modeling. The model presented in this study is validated through comparisons between experimental data and simulation results for 10 experimental conditions.

• Bulletin of the Korean Chemical Society
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• v.28 no.4
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• pp.529-532
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• 2007

Combined temperature programmed reaction (TPR) and infrared (IR) spectroscopic studies for Fischer- Tropsch reaction have been performed over Ru/SiO2 and Ru-Ag/SiO2 supported catalysts. Reaction of linearly absorbed CO with hydrogen starts at 375 K over Ru/SiO2 catalyst and reaches maximum at 420 K accompanied with an intensity decrease of linear CO absorption. The reaction with bridged absorbed CO peaks around 510-535 K. Addition of Ag yields mixed Ru-Ag bimetallic sites while it suppresses the formation of bridged bonded CO. Formation of methane on this modified surface occurs at 390 K and reaches maximum at 444 K. Suppression of hydrogen on the Ag-doped surface also occurs resulting in the formation of unsaturated hydrocarbons and of CHx intermediates not observed with Ru/SiO2 catalyst. Such intermediates are believed to be the building blocks of higher hydrocarbons during the Fischer-Tropsch synthesis. Linearly absorbed CO is found to be more reactive as compared to bridged CO. The Ag-modified surface also produces CO2 and carbon. On this surface, hydrogenation of CO begins at 390 K and reaches maximum at 494 K. The high temperature for hydrogenation of absorbed CO and C over Ru-Ag/SiO2 catalyst as compared to Ru/SiO2 catalyst is due to the formation of Ru-Ag bimetallic surfaces impeding hydrogen adsorption.

• International Journal of Internet, Broadcasting and Communication
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• v.7 no.2
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• pp.96-104
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• 2015

Fischer Tropsch reaction is one of the interesting topic for renewable and clean energy. Polymerization of carbon monoxide or carbon dioxide with hydrogen over metal supported catalyst can produce long chain hydrocarbons. Synthetic liquid hydrocarbons are promising alternative to fossil fuels. This research work has been focused on the synthesis of Fe based catalyst for Fischer Tropsch reaction. Mesoporous silica (MS) support prepared by a precipitation method using two different washing solution, distilled water (DW) and acid in ethanol solution (ET), and different calcination temperature. Then, Fe/MS was prepared by an incipient wetness impregnation method. All of samples were systematically characterized using various physical and chemical techniques. TEM and XRD analysis were used to ensure that the cubic Ia3d mesostructure is stable after calcination. FTIR spectra are useful to ascertain the existence of template in the support. TPR studies were also used to understand the nature of Fe species and their reducibility. The results reveal that washing the support with distilled water and calcination at $550^{\circ}C$ can efficiently remove the triblock copolymer templates. The existence of template in the support affects the textural properties of all catalyst investigated.

• Journal of the Korean Chemical Society
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• v.57 no.6
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• pp.769-777
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• 2013

The effect of operating conditions (temperature and the partial pressures of H2 and CO) on the reaction rate of Fischer-Tropsch synthesis (FTS) were investigated by carrying out experiments according to a Box-Behnken design (BBD), and were mathematically modeled by using response surface methodology (RSM). The catalyst used was a nano-structured cobalt/manganese oxide catalyst, which was prepared by thermal decomposition. The rate of synthesis was measured in a fixed-bed micro reactor with $H_2/CO$ molar feed ratio of 0.32-3.11 and reactor pressure in the range of 3-9.33 bar at space velocity of $3600h^{-1}$ and a temperature range of 463.15-503.15 K, under differential conditions (CO conversion below 2%). The results indicated that in the present experimental setup, the temperature and the partial pressure of CO were the most significant variables affecting reaction rate. Based on statistical analysis the quadratic model of reaction rate of FTS was highly significant as p-value 0.0002.