Search results for: syngas%20based%20DRI
Commenced in January 2007
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Edition: International
Paper Count: 20

Search results for: syngas%20based%20DRI

20 Combustion and Emissions Performance of Syngas Fuels Derived from Palm Kernel Shell and Polyethylene (PE) Waste via Catalytic Steam Gasification

Authors: Chaouki Ghenai

Abstract:

Computational fluid dynamics analysis of the burning of syngas fuels derived from biomass and plastic solid waste mixture through gasification process is presented in this paper. The syngas fuel is burned in gas turbine can combustor. Gas turbine can combustor with swirl is designed to burn the fuel efficiently and reduce the emissions. The main objective is to test the impact of the alternative syngas fuel compositions and lower heating value on the combustion performance and emissions. The syngas fuel is produced by blending palm kernel shell (PKS) with polyethylene (PE) waste via catalytic steam gasification (fluidized bed reactor). High hydrogen content syngas fuel was obtained by mixing 30% PE waste with PKS. The syngas composition obtained through the gasification process is 76.2% H2, 8.53% CO, 4.39% CO2 and 10.90% CH4. The lower heating value of the syngas fuel is LHV = 15.98 MJ/m3. Three fuels were tested in this study natural gas (100%CH4), syngas fuel and pure hydrogen (100% H2). The power from the combustor was kept constant for all the fuels tested in this study. The effect of syngas fuel composition and lower heating value on the flame shape, gas temperature, mass of carbon dioxide (CO2) and nitrogen oxides (NOX) per unit of energy generation is presented in this paper. The results show an increase of the peak flame temperature and NO mass fractions for the syngas and hydrogen fuels compared to natural gas fuel combustion. Lower average CO2 emissions at the exit of the combustor are obtained for the syngas compared to the natural gas fuel.

Keywords: CFD, Combustion, Emissions, Gas Turbine Combustor, Gasification, Solid Waste, Syngas and Waste to Energy.

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19 La promoted Ni/α-Al2O3 Catalysts for Syngas Methanation

Authors: Anmin Zhao, Weiyong Yingı , Haitao Zhang, Hongfang Ma, Dingye Fang

Abstract:

The Ni/α-Al2O3 catalysts with different amounts of La as promoter from 0 to 4 wt % were prepared, characterized and their catalytic activity was investigated in syngas methanation reaction. Effects of reaction temperature and lanthanum loading on carbon oxides conversion and methane selectivity were also studied. Adding certain amount of lanthanum to 10Ni /α-Al2O3 catalysts can decrease the average NiO crystallite diameter which leads to higher activity and stability while excessive addition would cause deactivation quickly. Stability on stream towards deactivation was observed up to 800 min at 500 °C, 0.1MPa and 600000 mL·g-1·h-1.

Keywords: Methanation; Nickel catalysts; Syngas methanation

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18 Na Promoted Ni/γ-Al2O3 Catalysts Prepared by Solution Combustion Method for Syngas Methanation

Authors: Yan Zeng, Hongfang Ma, Haitao Zhang, Weiyong Ying

Abstract:

Ni-based catalysts with different amounts of Na as promoter from 2 to 6 wt % were prepared by solution combustion method. The catalytic activity was investigated in syngas methanation reaction. Carbon oxides conversion and methane selectivity are greatly influenced by sodium loading. Adding 2 wt% Na remarkably improves catalytic activity and long-term stability, attributed to its smaller mean NiO particle size, better distribution, and milder metal-support interaction. However, excess addition of Na results in deactivation distinctly due to the blockage of active sites.

Keywords: Nickel catalysts, Syngas methanation, Sodium, Solution combustion method.

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17 Investigation of Syngas Production from Waste Gas and Ratio Adjustment using a Fischer-Tropsch Synthesis Reactor

Authors: E.Darzi

Abstract:

In this study, a reformer model simulation to use refinery (Farashband refinery, Iran) waste natural gas. In the petroleum and allied sectors where natural gas is being encountered (in form of associated gas) without prior preparation for its positive use, its combustion (which takes place in flares, an equipment through which they are being disposed) has become a great problem because of its associated environmental problems in form of gaseous emission. The proposed model is used to product syngas from waste natural gas. A detailed steady model described by a set of ordinary differential and algebraic equations was developed to predict the behavior of the overall process. The proposed steady reactor model was validated against process data of a reformer synthesis plant recorded and a good agreement was achieved. H2/CO ratio has important effect on Fischer- Tropsch synthesis reactor product and we try to achieve this parameter with best designing reformer reactor. We study different kind of reformer reactors and then select auto thermal reforming process of natural gas in a fixed bed reformer that adjustment H2/CO ratio with CO2 and H2O injection. Finally a strategy was proposed for prevention of extra natural gas to atmosphere.

Keywords: Fischer-Tropsch, injection, reformer, syngas, waste natural gas.

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16 Impact of Zn/Cr Ratio on ZnCrOx-SAPO-34 Bifunctional Catalyst for Direct Conversion of Syngas to Light Olefins

Authors: Yuxuan Huang, Weixin Qian, Hongfang Ma, Haitao Zhang, Weiyong Ying

Abstract:

Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrOx was prepared by co-precipitation method and (NH4)2CO3 was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrOx and SAPO-34. Catalytic reactions were carried out under H2/CO=2, 380 ℃, 1 MPa and 6000 mL·gcat-1·h-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C2-4= distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.

Keywords: Light olefins, OX-ZEO, syngas, ZnCrOx.

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15 Production of Pre-Reduction of Iron Ore Nuggets with Lesser Sulphur Intake by Devolatisation of Boiler Grade Coal

Authors: Chanchal Biswas, Anrin Bhattacharyya, Gopes Chandra Das, Mahua Ghosh Chaudhuri, Rajib Dey

Abstract:

Boiler coals with low fixed carbon and higher ash content have always challenged the metallurgists to develop a suitable method for their utilization. In the present study, an attempt is made to establish an energy effective method for the reduction of iron ore fines in the form of nuggets by using ‘Syngas’. By devolatisation (expulsion of volatile matter by applying heat) of boiler coal, gaseous product (enriched with reducing agents like CO, CO2, H2, and CH4 gases) is generated. Iron ore nuggets are reduced by this syngas. For that reason, there is no direct contact between iron ore nuggets and coal ash. It helps to control the minimization of the sulphur intake of the reduced nuggets. A laboratory scale devolatisation furnace designed with reduction facility is evaluated after in-depth studies and exhaustive experimentations including thermo-gravimetric (TG-DTA) analysis to find out the volatile fraction present in boiler grade coal, gas chromatography (GC) to find out syngas composition in different temperature and furnace temperature gradient measurements to minimize the furnace cost by applying one heating coil. The nuggets are reduced in the devolatisation furnace at three different temperatures and three different times. The pre-reduced nuggets are subjected to analytical weight loss calculations to evaluate the extent of reduction. The phase and surface morphology analysis of pre-reduced samples are characterized using X-ray diffractometry (XRD), energy dispersive x-ray spectrometry (EDX), scanning electron microscopy (SEM), carbon sulphur analyzer and chemical analysis method. Degree of metallization of the reduced nuggets is 78.9% by using boiler grade coal. The pre-reduced nuggets with lesser sulphur content could be used in the blast furnace as raw materials or coolant which would reduce the high quality of coke rate of the furnace due to its pre-reduced character. These can be used in Basic Oxygen Furnace (BOF) as coolant also.

Keywords: Alternative ironmaking, coal devolatisation, extent of reduction, nugget making, syngas based DRI, solid state reduction.

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14 Fluidised Bed Gasification of Multiple Agricultural Biomass Derived Briquettes

Authors: Rukayya Ibrahim Muazu, Aiduan Li Borrion, Julia A. Stegemann

Abstract:

Biomass briquette gasification is regarded as a promising route for efficient briquette use in energy generation, fuels and other useful chemicals. However, previous research has been focused on briquette gasification in fixed bed gasifiers such as updraft and downdraft gasifiers. Fluidised bed gasifier has the potential to be effectively sized to medium or large scale. This study investigated the use of fuel briquettes produced from blends of rice husks and corn cobs biomass, in a bubbling fluidised bed gasifier. The study adopted a combination of numerical equations and Aspen Plus simulation software, to predict the product gas (syngas) composition base on briquette density and biomass composition (blend ratio of rice husks to corn cobs). The Aspen Plus model was based on an experimentally validated model from the literature. The results based on a briquette size 32 mm diameter and relaxed density range of 500 to 650kg/m3, indicated that fluidisation air required in the gasifier increased with increase in briquette density, and the fluidisation air showed to be the controlling factor compared with the actual air required for gasification of the biomass briquettes. The mass flowrate of CO2 in the predicted syngas composition increased with an increase in air flow, in the gasifier, while CO decreased and H2 was almost constant. The ratio of H2 to CO for various blends of rice husks and corn cobs did not significantly change at the designed process air, but a significant difference of 1.0 was observed between 10/90 and 90/10 % blend of rice husks and corn cobs.

Keywords: Briquettes, fluidised bed, gasification, Aspen Plus, syngas.

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13 Processes Simulation Study of Coal to Methanol Based on Gasification Technology

Authors: Po-Chuang Chen, Hsiu-Mei Chiu, Yau-Pin Chyou, Chiou-Shia Yu

Abstract:

This study presents a simulation model for converting coal to methanol, based on gasification technology with the commercial chemical process simulator, Pro/II® V8.1.1. The methanol plant consists of air separation unit (ASU), gasification unit, gas clean-up unit, and methanol synthetic unit. The clean syngas is produced with the first three operating units, and the model has been verified with the reference data from United States Environment Protection Agency. The liquid phase methanol (LPMEOHTM) process is adopted in the methanol synthetic unit. Clean syngas goes through gas handing section to reach the reaction requirement, reactor loop/catalyst to generate methanol, and methanol distillation to get desired purity over 99.9 wt%. The ratio of the total energy combined with methanol and dimethyl ether to that of feed coal is 78.5% (gross efficiency). The net efficiency is 64.2% with the internal power consumption taken into account, based on the assumption that the efficiency of electricity generation is 40%.

Keywords: Gasification, Methanol, LPMEOH, System-levelsimulation.

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12 Mathematical Simulation of Bubble Column Slurry Reactor for Direct Dimethyl Ether Synthesis Process from Syngas

Authors: Zhen Chen, Haitao Zhang, Weiyong Ying, Dingye Fang

Abstract:

Based on a global kinetics of direct dimethyl ether (DME) synthesis process from syngas, a steady-state one-dimensional mathematical model for the bubble column slurry reactor (BCSR) has been established. It was built on the assumption of plug flow of gas phase, sedimentation-dispersion model of catalyst grains and isothermal chamber regardless of reaction heats and rates for the design of an industrial scale bubble column slurry reactor. The simulation results indicate that higher pressure and lower temperature were favorable to the increase of CO conversion, DME selectivity, products yield and the height of slurry bed, which has a coincidence with the characteristic of DME synthesis reaction system, and that the height of slurry bed is lessen with the increasing of operation temperature in the range of 220-260℃. CO conversion, the optimal operation conditions in BCSR were proposed. 

Keywords: Alcohol/ether fuel, bubble column slurry reactor, global kinetics, mathematical model.

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11 Global Kinetics of Direct Dimethyl Ether Synthesis Process from Syngas in Slurry Reactor over a Novel Cu-Zn-Al-Zr Slurry Catalyst

Authors: Zhen Chen, Haitao Zhang, Weiyong Ying, Dingye Fang

Abstract:

The direct synthesis process of dimethyl ether (DME) from syngas in slurry reactors is considered to be promising because of its advantages in caloric transfer. In this paper, the influences of operating conditions (temperature, pressure and weight hourly space velocity) on the conversion of CO, selectivity of DME and methanol were studied in a stirred autoclave over Cu-Zn-Al-Zr slurry catalyst, which is far more suitable to liquid phase dimethyl ether synthesis process than bifunctional catalyst commercially. A Langmuir- Hinshelwood mechanism type global kinetics model for liquid phase DME direct synthesis based on methanol synthesis models and a methanol dehydration model has been investigated by fitting our experimental data. The model parameters were estimated with MATLAB program based on general Genetic Algorithms and Levenberg-Marquardt method, which is suitably fitting experimental data and its reliability was verified by statistical test and residual error analysis.

Keywords: alcohol/ether fuel, Cu-Zn-Al-Zr slurry catalyst, global kinetics, slurry reactor

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10 Comparison of Cyclone Design Methods for Removal of Fine Particles from Plasma Generated Syngas

Authors: Mareli Hattingh, I. Jaco Van der Walt, Frans B. Waanders

Abstract:

A waste-to-energy plasma system was designed by Necsa for commercial use to create electricity from unsorted municipal waste. Fly ash particles must be removed from the syngas stream at operating temperatures of 1000 °C and recycled back into the reactor for complete combustion. A 2D2D high efficiency cyclone separator was chosen for this purpose. During this study, two cyclone design methods were explored: The Classic Empirical Method (smaller cyclone) and the Flow Characteristics Method (larger cyclone). These designs were optimized with regard to efficiency, so as to remove at minimum 90% of the fly ash particles of average size 10 μm by 50 μm. Wood was used as feed source at a concentration of 20 g/m3 syngas. The two designs were then compared at room temperature, using Perspex test units and three feed gases of different densities, namely nitrogen, helium and air. System conditions were imitated by adapting the gas feed velocity and particle load for each gas respectively. Helium, the least dense of the three gases, would simulate higher temperatures, whereas air, the densest gas, simulates a lower temperature. The average cyclone efficiencies ranged between 94.96% and 98.37%, reaching up to 99.89% in individual runs. The lowest efficiency attained was 94.00%. Furthermore, the design of the smaller cyclone proved to be more robust, while the larger cyclone demonstrated a stronger correlation between its separation efficiency and the feed temperatures. The larger cyclone can be assumed to achieve slightly higher efficiencies at elevated temperatures. However, both design methods led to good designs. At room temperature, the difference in efficiency between the two cyclones was almost negligible. At higher temperatures, however, these general tendencies are expected to be amplified so that the difference between the two design methods will become more obvious. Though the design specifications were met for both designs, the smaller cyclone is recommended as default particle separator for the plasma system due to its robust nature.

Keywords: Cyclone, design, plasma, renewable energy, solid separation, waste processing.

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9 Effect of Leaks in Solid Oxide Electrolysis Cells Tested for Durability under Co-Electrolysis Conditions

Authors: Megha Rao, Søren H. Jensen, Xiufu Sun, Anke Hagen, Mogens B. Mogensen

Abstract:

Solid oxide electrolysis cells have an immense potential in converting CO2 and H2O into syngas during co-electrolysis operation. The produced syngas can be further converted into hydrocarbons. This kind of technology is called power-to-gas or power-to-liquid. To produce hydrocarbons via this route, durability of the cells is still a challenge, which needs to be further investigated in order to improve the cells. In this work, various nickel-yttria stabilized zirconia (Ni-YSZ) fuel electrode supported or YSZ electrolyte supported cells, cerium gadolinium oxide (CGO) barrier layer, and an oxygen electrode are investigated for durability under co-electrolysis conditions in both galvanostatic and potentiostatic conditions. While changing the gas on the oxygen electrode, keeping the fuel electrode gas composition constant, a change in the gas concentration arc was observed by impedance spectroscopy. Measurements of open circuit potential revealed the presence of leaks in the setup. It is speculated that the change in concentration impedance may be related to the leaks. Furthermore, the cells were also tested under pressurized conditions to find an inter-play between the leak rate and the pressure. A mathematical modeling together with electrochemical and microscopy analysis is presented.

Keywords: Co-electrolysis, solid oxide electrolysis cells, leaks, durability, gas concentration.

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8 Analysis of a Secondary Autothermal Reformer Using a Thermodynamic POX Model

Authors: Akbar Zamaniyan, Alireza Behroozsarand, Hadi Ebrahimi

Abstract:

Partial oxidation (POX) of light hydrocarbons (e.g. methane) is occurred in the first part of the autothermal reformer (ATR). The results of the detailed modeling of the reformer based on the thermodynamic model of the POX and 1D heterogeneous catalytic model for the fixed bed section are considered here. According to the results, the overall performance of the ATR can be improved by changing the important feed parameters.

Keywords: Autothermal Reformer, Partial Oxidation, Mathematical Modeling, Process Simulation, Syngas.

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7 A Comparison between Heterogeneous and Homogeneous Gas Flow Model in Slurry Bubble Column Reactor for Direct Synthesis of DME

Authors: Sadegh Papari, Mohammad Kazemeini, Moslem Fattahi

Abstract:

In the present study, a heterogeneous and homogeneous gas flow dispersion model for simulation and optimisation of a large-scale catalytic slurry reactor for the direct synthesis of dimethyl ether (DME) from syngas and CO2, using a churn-turbulent regime was developed. In the heterogeneous gas flow model the gas phase was distributed into two bubble phases: small and large, however in the homogeneous one, the gas phase was distributed into only one large bubble phase. The results indicated that the heterogeneous gas flow model was in more agreement with experimental pilot plant data than the homogeneous one.

Keywords: Modelling, Slurry bubble column, Dimethyl ether synthesis, Homogeneous gas flow, Heterogeneous gas flow

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6 Evaluation of Biomass Introduction Methods in Coal Co-Gasification

Authors: Ruwaida Abdul Rasid, Kevin J. Hughes, Peter J. Heggs, Mohamed Pourkashanian

Abstract:

Heightened concerns over the amount of carbon emitted from coal-related processes are generating shifts to the application of biomass. In co-gasification, where coal is gasified along with biomass, the biomass may be fed together with coal (cofeeding) or an independent biomass gasifier needs to be integrated with the coal gasifier. The main aim of this work is to evaluate the biomass introduction methods in coal co-gasification. This includes the evaluation of biomass concentration input (B0 to B100) and its gasification performance. A process model is developed and simulated in Aspen HYSYS, where both coal and biomass are modelled according to its ultimate analysis. It was found that the syngas produced increased with increasing biomass content for both co-feeding and independent schemes. However, the heating values and heat duties decreases with biomass concentration as more CO2 are produced from complete combustion.

Keywords: Aspen HYSYS, biomass, coal, co-gasification modelling and simulation.

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5 Combustion Characteristics of Syngas and Natural Gas in Micro-pilot Ignited Dual-fuel Engine

Authors: Ulugbek Azimov, Eiji Tomita, Nobuyuki Kawahara, Sharul Sham Dol

Abstract:

The objective of this study is to investigate the combustion in a pilot-ignited supercharged dual-fuel engine, fueled with different types of gaseous fuels under various equivalence ratios. It is found that if certain operating conditions are maintained, conventional dual-fuel engine combustion mode can be transformed to the combustion mode with the two-stage heat release. This mode of combustion was called the PREMIER (PREmixed Mixture Ignition in the End-gas Region) combustion. During PREMIER combustion, initially, the combustion progresses as the premixed flame propagation and then, due to the mixture autoignition in the end-gas region, ahead of the propagating flame front, the transition occurs with the rapid increase in the heat release rate.

Keywords: Combustion, dual-fuel engine, end-gas autoignition, PREMIER.

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4 Microwave Plasma Dry Reforming of Methane at High CO2/CH4 Feed Ratio

Authors: Nabil Majd Alawi, Gia Hung Pham, Ahmed Barifcani

Abstract:

Dry reforming of methane that converts two greenhouses gases (CH4 and CO2) to synthesis gas (a mixture of H2 and CO) was studied in a commercial bench scale microwave (MW) plasma reactor system at atmospheric pressure. The CO2, CH4 and N2 conversions; H2, CO selectivities and yields, and syngas ratio (H2/CO) were investigated in a wide range of total feed flow rate (0.45 – 2.1 L/min), MW power (700 – 1200 watt) and CO2/CH4 molar ratio (2 – 5). At the feed flow rates of CH4, CO2 and N2 of 0.2, 0.4 and 1.5 L/min respectively, and the MWs input power of 700 W, the highest conversions of CH4 and CO2, selectivity and yield of H2, CO and H2/CO ratio of 79.35%, 44.82%, 50.12, 58.42, 39.77%, 32.89%, and 0.86, respectively, were achieved. The results of this work show that the product ratio increases slightly with the increasing total feed flow rate, but it decreases significantly with the increasing MW power and feeds CO2/CH4 ratio.

Keywords: Atmospheric pressure, methane dry reforming, microwave plasma, synthesis gas production.

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3 Water Vapor Plasma Torch: Design, Characteristics and Applications

Authors: A. Tamošiūnas, P. Valatkevičius, V. Grigaitiene, V. Valinčius

Abstract:

The atmospheric pressure plasma torch with a direct current arc discharge stabilized by water vapor vortex was experimentally investigated. Overheated up to 450K water vapor was used as plasma forming gas. Plasma torch design is one of the most important factors leading to a stable operation of the device. The electrical and thermal characteristics of the plasma torch were determined during the experimental investigations. The design and the basic characteristics of the water vapor plasma torch are presented in the paper. Plasma torches with the electric arc stabilized by water vapor vortex provide special performance characteristics in some plasma processing applications such as thermal plasma neutralization and destruction of organic wastes enabling to extract high caloric value synthesis gas as by-product of the process. Syngas could be used as a surrogate fuel partly replacing the dependence on the fossil fuels or used as a feedstock for hydrogen, methanol production.

Keywords: Arc discharge, atmospheric pressure thermal plasma, plasma torch, water vapor.

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2 Numerical Simulation of Different Configurations for a Combined Gasification/Carbonization Reactors

Authors: Mahmoud Amer, Ibrahim El-Sharkawy, Shinichi Ookawara, Ahmed Elwardany

Abstract:

Gasification and carbonization are two of the most common ways for biomass utilization. Both processes are using part of the waste to be accomplished, either by incomplete combustion or for heating for both gasification and carbonization, respectively. The focus of this paper is to minimize the part of the waste that is used for heating biomass for gasification and carbonization. This will occur by combining both gasifiers and carbonization reactors in a single unit to utilize the heat in the product biogas to heating up the wastes in the carbonization reactors. Three different designs are proposed for the combined gasification/carbonization (CGC) reactor. These include a parallel combination of two gasifiers and carbonized syngas, carbonizer and combustion chamber, and one gasifier, carbonizer, and combustion chamber. They are tested numerically using ANSYS Fluent Computational Fluid Dynamics to ensure homogeneity of temperature distribution inside the carbonization part of the CGC reactor. 2D simulations are performed for the three cases after performing both mesh-size and time-step independent solutions. The carbonization part is common among the three different cases, and the difference among them is how this carbonization reactor is heated. The simulation results showed that the first design could provide only partial homogeneous temperature distribution, not across the whole reactor. This means that the produced carbonized biomass will be reduced as it will only fill a specified height of the reactor. To keep the carbonized product production high, a series combination is proposed. This series configuration resulted in a uniform temperature distribution across the whole reactor as it has only one source for heat with no temperature distribution on any surface of the carbonization section. The simulations provided a satisfactory result that either the first parallel combination of gasifier and carbonization reactor could be used with a reduced carbonized amount or a series configuration to keep the production rate high.

Keywords: Numerical simulation, carbonization, gasification, reactor, biomass.

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1 O-Functionalized CNT Mediated CO Hydro-Deoxygenation and Chain Growth

Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

Abstract:

Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H2, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO hydro-deoxygenation, DFT, liquid fuels, XPS, XTL.

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