Search results for: coke formation

Authors: Thidaya Thitiapichart

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The effect of additional magnesium oxide (MgO) was investigated by using the tungsten oxide supported on silica catalyst (WOx/SiO2) physically mixed with MgO in a weight ratio 1:1. The both fresh and spent catalysts were characterized by FT-Raman spectrometer, UV-Vis spectrometer, X-Ray diffraction (XRD), and temperature programmed oxidation (TPO). The results indicated that the additional MgO could enhance the conversion of trans-2-butene due to isomerization reaction. However, adding MgO would increase the amount of coke deposit on the WOx/SiO2 catalyst. The TPO profile presents two peaks when the WOx/SiO2 catalyst was physically mixed with MgO. The further peak was suggested to be coming from the coke precursor that could be produced by isomerization reaction of the undesired product. Then, the occurred coke precursor could deposit and form coke on the acid catalyst.

Keywords: coke formation, metathesis, magnesium oxide, physically mix

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Authors: Yadong Liu

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The experimental study on reduction carbonization of coke containing iron respectively with the particle size of <0.3mm, 0.3-0.6mm and 0.6-0.9mm and synthetic sea sand ore smelting reduction titanium-bearing slag as material were studied under the conditions of holding 6h at most at 1500℃. The effects of coke containing iron particle size and heat preservation time on the formation of TiC and the size of TiC crystal were studied by XRD, SEM and EDS. The results show that it is not good for the formation, concentration and growth of TiC crystal when the particle size of coke containing iron is too small or too large. The suitable particle size is 0.3~0.6mm. The heat preservation time of 2h basically ensures that all the component TiO2 in the slag are reduced and carbonized and converted to TiC. The size of TiC crystal will increase with the prolongation of heat preservation time. The thickness of the TiC layer can reach 20μm when the heat preservation time is 6h.

Keywords: coke containing iron, formation and concentration and growth of TiC, reduction and carbonization, titanium-bearing slag

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Authors: Uzu-Kuei Hsu, Keh-Chin Chang, Joo-Guan Hang, Chang-Hsien Tai

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Carbon Deposits are often occurred inside the industrial coke oven during the coking process. Accumulation of carbon deposits may cause a big issue, which seriously influences the coking operation. The carbon is burning off by injecting fresh air through pipes into coke oven which is an efficient way practically operated in industries. The burning off carbon deposition in coke oven performed by Computational Fluid Dynamics (CFD) method has provided an evaluation of the feasibility study. A three-dimensional, transient, turbulent reacting flow simulation has performed with three different injecting air flow rate and another kind of injecting configuration. The result shows that injection higher air flow rate would effectively reduce the carbon deposits. In the meantime, the opened charging holes would suck extra oxygen from the atmosphere to participate in reactions. In term of coke oven operating limits, the wall temperatures are monitored to prevent over-heating of the adiabatic walls during the burn-off process.

Keywords: coke oven, burning off, carbon deposits, carbon combustion, CFD

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Authors: Adisak Guntida

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Propylene self-metathesis to ethylene and butene was studied over WOx/SiO2 catalysts at 450 °C and atmospheric pressure. The WOx/SiO2 catalysts were prepared by incipient wetness impregnation of ammonium metatungstate aqueous solution. It was found that, adding nano-sized extra supports (SiO2 and TiO2) by physical mixing with the WOx/SiO2 enhanced propylene conversion. The UV-Vis and FT-Raman results revealed that WOx could migrate from the original silica support to the extra support, leading to a better dispersion of WOx. The ICP-OES results also indicate that WOx existed on the extra support. Coke formation was investigated on the catalysts after 10 h time-on-stream by TPO. However, adding nano-sized extra supports led to higher coke formation which may be related to acidity as characterized by NH3-TPD.

Keywords: extra support, nanomaterial, propylene self-metathesis, tungsten oxide

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Authors: Jianjun Wu, Fanhui Guo, Yixin Zhang

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In this study, gasification-coke were produced by blending the middlings (MC), and coking coal (CC) and a large proportion of long flame coal (Shenfu coal, SC), the effects of blending ratio were investigated. Mineral evolution and crystalline order obtained by XRD methods were reproduced within reasonable accuracy. Structure characteristics of partially gasification-coke such as surface area and porosity were determined using the N₂ adsorption and mercury porosimetry. Experimental data of gasification-coke was dominated by the TGA results provided trend, reactivity differences between gasification-cokes are discussed in terms of structure characteristic, crystallinity, and alkali index (AI). The first-order reaction equation was suitable for the gasification reaction kinetics of CO₂ atmosphere which was represented by the volumetric reaction model with linear correlation coefficient above 0.985. The differences in the microporous structure of gasification-coke and catalysis caused by the minerals in parent coals were supposed to be the main factors which affect its reactivity. The addition of MC made the samples enriched with a large amount of ash causing a higher surface area and a lower crystalline order to gasification-coke which was beneficial to gasification reaction. The higher SiO₂ and Al₂O₃ contents, causing a decreasing AI value and increasing activation energy, which reduced the gasification reaction activity. It was found that the increasing amount of MC got a better performance on the coke gasification reactivity by blending > 30% SC with this coking process.

Keywords: low-rank coal, middlings, structure characteristic, mineral evolution, alkali index, gasification-coke, gasification kinetics

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Authors: Deepti Mishra, Arindam Modak, K. K. Pant, Xiu Song Zhao

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The promotional effect of mixed ceria-zirconia oxides (CZO) over the Mo/HZSM-5 catalyst for methane dehydroaromatization (MDA) reaction was studied. The surface and structural properties of the synthesized catalyst were characterized using a range of spectroscopic and microscopic techniques, and the correlation between catalytic properties and its performance for MDA reaction is discussed. The impregnation of CZO solid solution on Mo/HZSM-5 was observed to give an excellent catalytic performance and improved benzene formation rate (4.5 μmol/gcat. s) as compared to the conventional Mo/HZSM-5 (3.1 μmol/gcat. s) catalyst. In addition, a significant reduction in coke formation was observed in the CZO-modified Mo/HZSM-5 catalyst. The prevailing comprehension for higher catalytic activity could be because of the redox properties of CZO deposited Mo/HZSM-5, which acts as a selective oxygen supplier and performs hydrogen combustion during the reaction, which is indirectly probed by O₂-TPD and H₂-TPR analysis. The selective hydrogen combustion prevents the over-oxidation of aromatic species formed during the reaction while the generated steam helps in reducing the amount of coke generated in the MDA reaction. Thus, the advantage of CZO incorporated Mo/HZSM-5 is manifested as it promotes the reaction equilibrium to shift towards the formation of benzene which is favourable for MDA reaction.

Keywords: Mo/HZSM-5, ceria-zirconia (CZO), in-situ combustion, methane dehydroaromatization

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Authors: Lin Huang, Bo Wang, Armando Borgna

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Dehydration of glycerol to acrolein was conducted with solid acid catalysts in liquid phase in a batch reactor and in gas phase in a fix-bed reactor, respectively. In the liquid-phase reaction, ZSM-5, H3PO4-modified ZSM-5 and heteropolyacids including H3PW12O40•xH2O (HPW) and Cs2.5H0.5PW12O40 (CsPW) were studied as catalysts. High temperatures and high boiling point solvents such as sulfolane improved the selectivity to acrolein through suppressing the formation of polyglycerols and coke. Catalytic results and temperature-programmed desorption of ammonia showed that the yield of acrolein increased with increasing catalyst acidity within the range of weak acid strength. Weak acid sites favored the selectivity to acrolein whereas strong acid sites promoted the formation of coke. ZSM-5 possessing only acid sites led to a high acrolein yield, while heteropolyacid catalysts with strong acid sites produced a low acrolein yield. In the gas-phase reaction, HPW and CsPW supported on metal oxides such as SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2 and silicate TUD-1 were studied as catalysts. HPW/TUD-1 was most active for the production of acrolein, followed by HPW/SiO2. An acrolein yield of 61 % was obtained over HPW/TUD-1. X-ray diffraction study suggested that HPW and CsPW were stable and more dispersed on SiO2, silicate TUD-1 and SiO2-Al2O3. It was found that the structures of HPW and CsPW were destroyed by interaction with γ-Al2O3 and ZrO2. Compared to CsPW/TUD-1, the higher acrolein yield with HPW/TUD-1 may be attributed to more Brønsted acid sites on HPW/TUD-1, based on preliminary pyridine adsorption IR study.

Keywords: dehydration, glycerol, acrolein, solid acid catalysts, gas-phase, liquid-phase

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Authors: Sewon Kim, Minjun Kwon, Changyeop Lee

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This study is aimed to study combustion characteristics of low NOx burner using petroleum cokes as fuel. The petroleum coke, which is produced through the oil refining process, is an attractive fuel in terms of its high heating value and low price. But petroleum coke is a challenging fuel because of its low volatile content, high sulfur and nitrogen content, which give rise to undesirable emission characteristics and low ignitability. Therefore, the research and development regarding the petroleum coke burner is needed for applying this industrial system. In this study, combustion and emission characteristics of petroleum cokes burner are experimentally investigated in an industrial steam boiler. The low NOx burner is designed to control fuel and air mixing to achieve staged combustion, which, in turn reduces both flame temperature and oxygen. Air distribution ratio of triple staged air are optimized experimentally. The result showed that NOx concentration is lowest when overfire air is used, and the burner function at a fuel rich condition. That is, the burner is operated at the equivalence ratio of 1.67 and overall equivalence ratio including overfire air is kept 0.87.

Keywords: petroleum cokes, low NOx, combustion, equivalence ratio

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Authors: Richard, Iyan Subiyanto, Chairul Hudaya

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Activated carbon has been playing a significant role for many applications, especially in energy storage devices. However, commercially activated carbons generally require complicated processes and high production costs. Therefore, in this study, an activated carbon originating from green coke waste, that is economically affordable will be used as a carbon source. To synthesize activated carbon, KOH as an activator was employed with variation of C:KOH in ratio of 1:2, 1:3, 1:4, and 1:5, respectively, with an activation temperature of 700°C. The characterizations of activated carbon are obtained from Scanning Electron Microscopy, Energy Dispersive X-Ray, Raman Spectroscopy, and Brunauer-Emmett-Teller. The optimal activated carbon sample with specific surface area of 2,024 m²/g with high carbon content ( > 80%) supported by the high porosity carbon image obtained by SEM was prepared at C:KOH ratio of 1:4. The result shows that the synthesized activated carbon would be an ideal choice for energy storage device applications. Therefore, this study is expected to reduce the costs of activated carbon production by expanding the utilization of petroleum waste.

Keywords: activated carbon, energy storage material, green coke, specific surface area

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Authors: Krishnendu Mukhopadhyay, Subhashis Kundu, Mayank Tiwari, Sameeran Pani, Padmapal, Uttam Singh

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Blast Furnace is a counter current process where burden descends from top and hot gases ascend from bottom and chemically reduce iron oxides into liquid hot metal. One of the major problems of blast furnace operation is the erratic burden descent inside furnace. Sometimes this problem is so acute that burden descent stops resulting in Hanging and instability of the furnace. This problem is very frequent in blast furnaces worldwide and results in huge production losses. This situation becomes more adverse when blast furnaces are operated at low coke rate and high coal injection rate with adverse raw materials like high alumina ore and high coke ash. For last three years, H-Blast Furnace Tata Steel was able to reduce coke rate from 450 kg/thm to 350 kg/thm with an increase in coal injection to 200 kg/thm which are close to world benchmarks and expand profitability. To sustain this regime, elimination of irregularities of blast furnace like hanging, channeling, and scaffolding is very essential. In this paper, sustaining of zero hanging spell for consecutive three years with low coke rate operation by improvement in burden characteristics, burden distribution, changes in slag regime, casting practices and adequate automation of the furnace operation has been illustrated. Models have been created to comprehend and upgrade the blast furnace process understanding. A model has been developed to predict the process of maintaining slag viscosity in desired range to attain proper burden permeability. A channeling prediction model has also been developed to understand channeling symptoms so that early actions can be initiated. The models have helped to a great extent in standardizing the control decisions of operators at H-Blast Furnace of Tata Steel, Jamshedpur and thus achieving process stability for last three years.

Keywords: hanging, channelling, blast furnace, coke

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Authors: L. Angiuli, L. Trizio, R. Giua, A. Digilio, M. Tutino, P. Dambruoso, F. Mazzone, C. M. Placentino

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In the winter of 2014 a series of measurements were performed to evaluate the behavior of real-time PAHs and black carbon analyzers in a coke oven plant located in Taranto, a city of Southern Italy. Data were collected both insides than outside the plant, at air quality monitoring sites. Contemporary measures of PM2.5 and PM1 were performed. Particle-bound PAHs were measured by two methods: (1) aerosol photoionization using an Ecochem PAS 2000 analyzer, (2) PM2.5 and PM1 quartz filter collection and analysis by gas chromatography/mass spectrometry (GC/MS). Black carbon was determined both in real-time by Magee Aethalometer AE22 analyzer than by semi-continuous Sunset Lab EC/OC instrument. Detected PM2.5 and PM1 levels were higher inside than outside the plant while PAHs real-time values were higher outside than inside. As regards PAHs, inside the plant Ecochem PAS 2000 revealed concentrations not significantly different from those determined on the filter during low polluted days, but at increasing concentrations the automated instrument underestimated PAHs levels. At the external site, Ecochem PAS 2000 real-time concentrations were steadily higher than those on the filter. In the same way, real-time black carbon values were constantly lower than EC concentrations obtained by Sunset EC/OC in the inner site, while outside the plant real-time values were comparable to Sunset EC values. Results showed that in a coke plant real-time analyzers of PAHs and black carbon in the factory configuration provide qualitative information, with no accuracy and leading to the underestimation of the concentration. A site specific calibration is needed for these instruments before their installation in high polluted sites.

Keywords: black carbon, coke oven plant, PAH, PAS, aethalometer

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Authors: Ulugbek Azimov, Nearchos Stylianidis, Nobuyuki Kawahara, Eiji Tomita

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A chemical kinetics and computational fluid-dynamics (CFD) analysis was performed to evaluate the combustion of syngas derived from biomass and coke-oven solid feedstock in a micro-pilot ignited supercharged dual-fuel engine under lean conditions. For this analysis, a new reduced syngas chemical kinetics mechanism was constructed and validated by comparing the ignition delay and laminar flame speed data with those obtained from experiments and other detail chemical kinetics mechanisms available in the literature. The reaction sensitivity analysis was conducted for ignition delay at elevated pressures in order to identify important chemical reactions that govern the combustion process. The chemical kinetics of NOx formation was analyzed for H2/CO/CO2/CH4 syngas mixtures by using counter flow burner and premixed laminar flame speed reactor models. The new mechanism showed a very good agreement with experimental measurements and accurately reproduced the effect of pressure, temperature and equivalence ratio on NOx formation. In order to identify the species important for NOx formation, a sensitivity analysis was conducted for pressures 4 bar, 10 bar and 16 bar and preheat temperature 300 K. The results show that the NOx formation is driven mostly by hydrogen based species while other species, such as N2, CO2 and CH4, have also important effects on combustion. Finally, the new mechanism was used in a multidimensional CFD simulation to predict the combustion of syngas in a micro-pilot-ignited supercharged dual-fuel engine and results were compared with experiments. The mechanism showed the closest prediction of the in-cylinder pressure and the rate of heat release (ROHR).

Keywords: syngas, chemical kinetics mechanism, internal combustion engine, NOx formation

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Authors: Gökhan Polat, Dicle Kocaoğlu Yılmazer, Muhlis Nezihi Sarıdede

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Iron oxides are the main input to produce iron in integrated iron and steel plants. During production of iron from iron oxides, some wastes with high iron content occur. These main wastes can be classified as basic oxygen furnace (BOF) sludge, flue dust and rolling scale. Recycling of these wastes has a great importance for both environmental effects and reduction of production costs. In this study, recycling experiments were performed on basic oxygen furnace sludge, flue dust and rolling scale which contain 53.8%, 54.3% and 70.2% iron respectively. These wastes were mixed together with coke as reducer and these mixtures are pressed to obtain cylindrical briquettes. These briquettes were pressed under various compacting forces from 1 ton to 6 tons. Also, both stoichiometric and twice the stoichiometric cokes were added to investigate effect of coke amount on reduction properties of the waste mixtures. Then, these briquettes were reduced at 1000°C and 1100°C during 30, 60, 90, 120 and 150 min in a muffle furnace. According to the results of reduction experiments, the effect of compacting force, temperature and time on reduction ratio of the wastes were determined. It is found that 1 ton compacting force, 150 min reduction time and 1100°C are the optimum conditions to obtain reduction ratio higher than 75%.

Keywords: Coke, iron oxide wastes, recycling, reduction

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Authors: Adefarati Oloruntoba, Yongmin Zhang, Hongliang Xiao

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An annular fluidized bed (AFB) is gaining extensive application in the process industry due to its efficient gas-solids contacting. But a direct evaluation of its reaction performance is still lacking. In this paper, comparative 3D Euler–Lagrange multiphase-particle-in-cell (MP-PIC) computations are performed to assess the reaction performance of AFB relative to a bubbling fluidized bed (BFB) in an FCC regeneration process. By using the energy-minimization multi-scale (EMMS) drag model with a suitable heterogeneity index, the MP-PIC simulation predicts the typical fountain region in AFB and solids holdup of BFB, which is consistent with an experiment. Coke combustion rate, flue gas and temperature profile are utilized as the performance indicators, while related bed hydrodynamics are explored to account for the different performance under varying superficial gas velocities (0.5 m/s, 0.6 m/s, and 0.7 m/s). Simulation results indicate that the burning rates of coke and its species are relatively the same in both beds, albeit marginal increase in BFB. Similarly, the shape and evolution time of flue gas (CO, CO₂, H₂O and O₂) curves are indistinguishable but match the coke combustion rates. However, AFB has high proclivity to high temperature-gradient as higher gas and solids temperatures are predicted in the freeboard. Moreover, for both beds, the effect of superficial gas velocity is only conspicuous on the temperature but negligible on combustion efficiency and effluent gas emissions due to constant gas volumetric flow rate and bed loading criteria. Cross-flow of solids from the annulus to the spout region as well as the high primary gas in the AFB directly assume the underlying mechanisms for its unique gas-solids hydrodynamics (pressure, solids holdup, velocity, mass flux) and local spatial homogeneity, which in turn influence the reactor performance. Overall, the study portrays AFB as a cheap alternative reactor to BFB for catalyst regeneration.

Keywords: annular fluidized bed, bubbling fluidized bed, coke combustion, flue gas, fountaining, CFD, MP-PIC, hydrodynamics, FCC regeneration

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Authors: Zhang Haitao

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The different size of nanoparticle mordenite zeolites were prepared by adding different soft template during hydrothermal process for carbonylation of dimethyl ether (DME) to methyl acetate (MA). The catalysts were characterized by X-ray diffraction, Ar adsorption-desorption, high-resolution transmission electron microscopy, NH3-temperature programmed desorption, scanning electron microscopy and Thermogravimetric. The characterization results confirmed that mordenite zeolites with small nanoparticle showed more strong acid sites which was the active site for carbonylation thus promoting conversion of DME and MA selectivity. Furthermore, the nanoparticle mordenite had increased the mass transfer efficiency which could suppress the formation of coke.

Keywords: nanoparticle mordenite, carbonylation, dimethyl ether, methyl acetate

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Authors: Amit Kumar Bhandary, Prithviraj Gupta, Siddhartha Mukherjee, Mahua Ghosh Chaudhuri, Rajib Dey

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Chromite ores are primarily used for extraction of chromium, which is an expensive metal. For low grade chromite ores (containing less than 40% Cr₂O₃), the chromium extraction is not usually economically viable. India possesses huge quantities of low grade chromite reserves. This deposit can be utilized after proper physical beneficiation. Magnetic separation techniques may be useful after reduction for the beneficiation of low grade chromite ore. The sample collected from the sukinda mines is characterized by XRD which shows predominant phases like maghemite, chromite, silica, magnesia and alumina. The raw ore is crushed and ground to below 75 micrometer size. The microstructure of the ore shows that the chromite grains surrounded by a silicate matrix and porosity observed the exposed side of the chromite ore. However, this ore may be utilized in refractory applications. Chromite ores contain Cr₂O₃, FeO, Al₂O₃ and other oxides like Fe-Cr, Mg-Cr have a high tendency to form spinel compounds, which usually show high refractoriness. Initially, the low grade chromite ore (containing 34.8% Cr₂O₃) was reduced at 1200 ⁰C for 80 minutes with 30% coke fines by weight, before being subjected to magnetic separation. The reduction by coke leads to conversion of higher state of iron oxides converted to lower state of iron oxides. The pre-reduced samples are then characterized by XRD. The magnetically inert mass was then reacted with 20% MgO by weight at 1450 ⁰C for 2 hours. The resultant product was then tested for various refractoriness parameters like apparent porosity, slag resistance etc. The results were satisfactory, indicating that the resultant spinel compounds are suitable for refractory applications for elevated temperature processes.

Keywords: apparent porosity, beneficiation, low-grade chromite, refractory, spinel compounds, slag resistance

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Authors: Kriangkrai Aranyarat

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The effect of N2 pretreatment on the catalytic activity of tungsten-based catalysts was investigated in the metathesis of ethylene and trans-2-butene at 450oC and atmospheric pressure. The presence of tungsten active species was confirmed by UV-Vis and Raman spectroscopy. Compared to the WO3-based catalysts treated in air, higher amount of WO42- tetrahedral species and lower amount of WO3 crystalline species were observed on the N2-treated ones. These contribute to the higher conversion of 2-butene and propylene selectivity during 10 h time-on-stream. Moreover, N2 treatment led to lower amount of coke formation as revealed by TPO of the spent catalysts.

Keywords: metathesis, pretreatment, propylene, tungsten

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Authors: Abubakar Rashid, Muhammad Saad, Faheem Ahmed

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This paper provides a comprehensive study pertaining to diagnosis of intermittent high vibrations on an industrial gas turbine using detailed vibrations analysis, followed by its rectification. Engro Polymer & Chemicals Limited, a Chlor-Vinyl complex located in Pakistan has a captive combined cycle power plant having two 28 MW gas turbines (make Hitachi) & one 15 MW steam turbine. In 2018, the organization faced an issue of high vibrations on one of the gas turbines. These high vibration peaks appeared intermittently on both compressor’s drive end (DE) & turbine’s non-drive end (NDE) bearing. The amplitude of high vibration peaks was between 150-170% on the DE bearing & 200-300% on the NDE bearing from baseline values. In one of these episodes, the gas turbine got tripped on “High Vibrations Trip” logic actuated at 155µm. Limited instrumentation is available on the machine, which is monitored with GE Bently Nevada 3300 system having two proximity probes installed at Turbine NDE, Compressor DE &at Generator DE & NDE bearings. Machine’s transient ramp-up & steady state data was collected using ADRE SXP & DSPI 408. Since only 01 key phasor is installed at Turbine high speed shaft, a derived drive key phasor was configured in ADRE to obtain low speed shaft rpm required for data analysis. By analyzing the Bode plots, Shaft center line plot, Polar plot & orbit plots; rubbing was evident on Turbine’s NDE along with increased bearing clearance of Turbine’s NDE radial bearing. The subject bearing was then inspected & heavy deposition of carbonized coke was found on the labyrinth seals of bearing housing with clear rubbing marks on shaft & housing covering at 20-25 degrees on the inner radius of labyrinth seals. The collected coke sample was tested in laboratory & found to be the residue of lube oil in the bearing housing. After detailed inspection & cleaning of shaft journal area & bearing housing, new radial bearing was installed. Before assembling the bearing housing, cleaning of bearing cooling & sealing air lines was also carried out as inadequate flow of cooling & sealing air can accelerate coke formation in bearing housing. The machine was then taken back online & data was collected again using ADRE SXP & DSPI 408 for health analysis. The vibrations were found in acceptable zone as per ISO standard 7919-3 while all other parameters were also within vendor defined range. As a learning from subject case, revised operating & maintenance regime has also been proposed to enhance machine’s reliability.

Keywords: ADRE, bearing, gas turbine, GE Bently Nevada, Hitachi, vibration

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Z. Kadivar, M. Vahidinia, A. Mousavinia

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Kopet-Dagh Mountain Range is located in the north and northeast of Iran. Mozduran Formation in the east of Kopet-Dagh is mainly composed of limestone, dolomite, with shale and sandstone interbedded. Mozduran Formation is reservoir rock of the Khangiran gas field. The location of the study was east Kopet-Dagh basin (Northeast Iran) where the deliberate thickness of formation is 418 meters. In the present study, a total of 57 samples were gathered. Moreover, 100 thin sections were made out of 52 samples. According to the findings of the thin section study, 18 genera and nine species of foraminifera and algae were identified. Based on the index fossils, the age of the Mozduran Formation was identified as Upper Jurassic (Kimmerdgian-Tithonian) in the east of Kopet-Dagh basin. According to the magnetite data (total intensity and RTP map), there is a disconformity (low intensity) between the Kashaf-Rood Formation and Mozduran Formation. At the top, where among Mozduran Formation and Shurijeh Formation, is high intensity and a widespread disconformity (high intensity).

Keywords: upper jurassic, magnetometre, mozduran formation, stratigraphy

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Authors: R. K. Agrawal, Shiv Agrawal

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Fines and micro create fundamental problems of respiration. From mines to mills steel plants generate lot of pollutants. Legislation & Government laws are stricter day by day & each plant has to think of recycling, reuse &reintegration of pollutants generated during the process of steel making. This paper deals with experiments conducted in Bhilai Steel Plant and Real Ispat and Power Limited for reuse, recycle & reintegrate some of the steel making process fines. Iron ore fines with binders have been agglomerated to be used as a part of the charge for small furnaces. This will improve yield at nominal cost. Rolling mill fines have been recycled to increase the yield of sinter making. This will solve the problems of fine disposal. Huge saving on account of recycling will be achieved. Lime fines after briquetting is used along with prime lime. Lime fines have also been used as a binding material during production of fly ash bricks. These fines serve as low-cost binder. Experiments have been conducted along with coke breeze & gas cleaning plant sludge. As a result, the anti-sloping compound has been developed for converter vessels. Dolo char and Char during Sponge Iron production have been successfully used in power generation and brick making. Pellets have been made with ventilation dust & flue dust. These samples have been tried as a coolant in the converter. Pellets have been made with Sinter Plant electrostatic precipitator micro fines with liquid binder. Trials have been conducted to reuse these pellets in sinter making. Coke breeze from coke-ovens fines and mill scale along with binders were agglomerated. This was used in furnace after attaining required screening and reactivity index. These actions will definitely bring social, economic and environment-friendly universe.

Keywords: briquette, dolo char, electrostatic precipitator, pellet, sinter

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Authors: Hadda Krarcha, S. Messaasdi

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In order to investigate Hafnium transition metal alloys HfM (M= Co, Ir, Os,Pt, Rh, Ru) phase diagrams in the region of 50/50% atomic ratio, we performed ab initio Full-Potential Linearized Augmented Plane Waves calculations of the enthalpies of formation of HfM compounds at B2 (CsCl) structure type. The obtained enthalpies of formation are discussed and compared to some of the existing models and available experimental data.

Keywords: enthalpy of formation, transition metal, binarry compunds, hafnium

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Authors: Deepti Mishra, K. K Pant, Xiu Song Zhao, Muxina Konarova

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Catalytic transformation of simplest hydrocarbon methane into benzene and valuable chemicals over Mo/HZSM-5 has a great economic potential, however, it suffers serious hurdles due to the blockage in the micropores because of extensive coking at high temperature during methane dehydroaromatization (MDA). Under such conditions, it necessitates the design of micro/mesoporous ZSM-5, which has the advantages viz. uniform dispersibility of MoOx species, consequently the formation of active Mo sites in the micro/mesoporous channel and lower carbon deposition because of improved mass transfer rate within the hierarchical pores. In this study, we report a unique strategy to control the porous structures of ZSM-5 through a dual templating approach, utilizing C6 and C12 -surfactants as porogen. DFT studies were carried out to correlate the ZSM-5 framework development using the C6 and C12 surfactants with structure directing agent. The structural and morphological parameters of the synthesized ZSM-5 were explored in detail to determine the crystallinity, porosity, Si/Al ratio, particle shape, size, and acidic strength, which were further correlated with the physicochemical and catalytic properties of Mo modified HZSM-5 catalysts. After Mo incorporation, all the catalysts were tested for MDA reaction. From the activity test, it was observed that C6 surfactant-modified hierarchically porous Mo/HZSM-5(H) showed the highest benzene formation rate (1.5 μmol/gcat. s) and longer catalytic stability up to 270 min of reaction as compared to the conventional microporous Mo/HZSM-5(C). In contrary, C12 surfactant modified Mo/HZSM-5(D) is inferior towards MDA reaction (benzene formation rate: 0.5 μmol/gcat. s). We ascribed that the difference in MDA activity could be due to the hierarchically interconnected meso/microporous feature of Mo/HZSM-5(H) that precludes secondary reaction of coking from benzene and hence contributing substantial stability towards MDA reaction.

Keywords: hierarchical pores, Mo/HZSM-5, methane dehydroaromatization, coke deposition

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Authors: Junhai Liao, Yansong Shen, Aibing Yu

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A 3D numerical model is developed to simulate the complicated in-furnace combustion phenomena in the lower part of an ironmaking blast furnace (BF) while using pulverized coal injection (PCI) technology to reduce the consumption of relatively expensive coke. The computational domain covers blowpipe-tuyere-raceway-coke bed in the BF. The model is validated against experimental data in terms of gaseous compositions and coal burnout. Parameters, such as coal properties and some key operational variables, play an important role on the performance of coal combustion. Their diverse effects on different combustion characteristics are examined in the domain, in terms of gas compositions, temperature, and burnout. The heat generated by the combustion of upgraded Victorian brown coal is able to meet the heating requirement of a BF, hence making upgraded brown coal injected into BF possible. It is evidenced that the model is suitable to investigate the mechanism of the PCI operation in a BF. Prediction results provide scientific insights to optimize and control of the PCI operation. This model cuts the cost to investigate and understand the comprehensive combustion phenomena of upgraded Victorian brown coal in a full-scale BF.

Keywords: blast furnace, numerical study, pulverized coal injection, Victorian brown coal

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Authors: Khaled Ramadan Elbeydi

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This study is carried out to provide an insight into the analysis of the impact of selected macro-economic variables on gross fixed capital formation in Libya using annual data over the period (1970-2010). The importance of this study comes from the ability to show the relative important factors that impact the Libyan gross fixed capital formation. This understanding would give indications to decision makers on which policy they must focus to stimulate the economy. An Auto-Regressive Distributed Lag (ARDL) modeling process is employed to investigate the impact of the gross domestic product, monetary base, and trade openness on gross fixed capital formation in Libya. The results of this study reveal that there is an equilibrium relationship between capital formation and its determinants. The results also indicate that GDP and trade openness largely explain the pattern of capital formation in Libya. The findings and recommendations provide vital information relevant for policy formulation and implementation aimed to improve capital formation in Libya.

Keywords: ARDL, bounds test, capital formation, co-integration, Libya

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Authors: Gulcan Sahal, Isil Seyis Bilkay

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Candida species which often exist as commensal microorganisms in healthy individuals are major causes of important infections, especially in AIDS and immunocompromised patients, by means of their biofilm formation abilities. Therefore, in this study, determination of biofilm formation in different clinical strains of Candida species, investigation of strong biofilm forming Candida strains, examination of clinical information of each strong and weak biofilm forming Candida strains and investigation of some plant substances’ effects on biofilm formation of strong biofilm forming strains were aimed. In this respect, biofilm formation of Candida strains was analyzed via crystal violet binding assay. According to our results, biofilm levels of strains belong to different Candida species were different from each other. Additionally, it is also found that some plant substances effect biofilm formation. All these results indicate that, as well as C. albicans strains, other non-albicans Candida species also emerge as causative agents of infections and have biofilm formation abilities. In addition, usage of some plant substances in different concentrations may provide a new treatment against biofilm related Candida infections.

Keywords: anti-biofilm, biofilm formation, Candida species, biosystems engineering

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Authors: Amin Abbasi, Mahdi Asghari Ozma

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Background and Objective:Enterococcus faecium is a normal flora of the human gastrointestinal tract that causes infection in the host body under conditions such as biofilm formation, in which the use of antibiotics causes changes in these pathogenic mechanisms. In this study, we aimed to evaluate comprehensively the changes in E.faecium when exposed to sub-MIC of the gentamicin,especiallythe biofilm formation rate. Materials and Methods: For this study, the keywords "Enterococcus faecium ", "Biofilm", and "Gentamicin" in the databases PubMed, Google Scholar, Sid, and MagIran between 2015 and 2021 were searched, and 14 articles were chosen, studied, and analyzed. Results: Gentamicin significantly had increased biofilm formation in most of the isolates in the studies. Increased expression of the genes (efaA and esp) and proteins involved in biofilm formation and decreased expression of the genes (gelE and cylA) involved in spreading and proteins involved in metabolism and cell division in E.faecium were the most significant cause of the biofilm formation, which were increased in sub-MIC gentamicin-treated situation. Conclusion: Inadequate use of gentamicin intensify biofilm formation of E.faecium, which can make the treatment of infections caused by this bacterium difficult.

Keywords: biofilm, enterococcus faecium, gentamicin, proteome

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Authors: Selvan Bellan, Koji Matsubara, Nobuyuki Gokon, Tatsuya Kodama, Hyun Seok-Cho

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In concentrated solar thermal industry, fluidized-bed technology has been used to produce hydrogen by thermochemical two step water splitting cycles, and synthetic gas by gasification of coal coke. Recently, couple of fluidized bed reactors have been developed and tested at Niigata University, Japan, for two-step thermochemical water splitting cycles and coal coke gasification using Xe light, solar simulator. The hydrodynamic behavior of the gas-solid flow plays a vital role in the aforementioned fluidized bed reactors. Thus, in order to study the dynamics of dense gas-solid flow, a CFD-DEM model has been developed; in which the contact forces between the particles have been calculated by the spring-dashpot model, based on the soft-sphere method. Heat transfer and hydrodynamics of a solar thermochemical fluidized bed reactor filled with ceria particles have been studied numerically and experimentally for beam-down solar concentrating system. An experimental visualization of particles circulation pattern and mixing of two-tower fluidized bed system has been presented. Simulation results have been compared with experimental data to validate the CFD-DEM model. Results indicate that the model can predict the particle-fluid flow of the two-tower fluidized bed reactor. Using this model, the key operating parameters can be optimized.

Keywords: solar reactor, CFD-DEM modeling, fluidized bed, beam-down solar concentrating system

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Authors: Antonios Katsianis

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I present the evolution of the galaxy Star Formation Rate Function (SFRF), star formation rate-stellar mass relation (SFR-M*) and Cosmic Star Formation Rate Density (CSFRD) of z = 0-8 galaxies employing both the Evolution and Assembly of GaLaxies and their Environments (EAGLE) simulations and a compilation of UV, Ha, radio and IR data. While I present comparisons between the above, I evaluate the effect and importance of supernovae/active galactic nuclei feedback. The relation between the star formation rate and stellar mass of galaxies represents a fundamental constraint on galaxy formation, and has been studied extensively both in observations and cosmological hydrodynamic simulations. However, a tension between the above is reported in the literature. I present the evolution of the SFR-M* relation and demonstrate the inconsistencies between observations that are retrieved using different methods. I employ cosmological hydrodynamic simulations combined with radiative transfer methods and compare these with a range of observed data in order to investigate further the root of this tension. Last, I present insights about the scatter of the SFR-M* relation and investigate which mechanisms (e.g. feedback) drive its shape and evolution.

Keywords: cosmological simulations, galaxy formation and evolution, star formation rate, stellar masses

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Authors: Naveen Kumar

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Microplastics, tiny plastic particles less than 5 mm in size formed by the disposal and breakdown of industrial and consumer products, have become a primary environmental concern due to their ubiquitous presence and application in the environment and their potential to cause harm to the ecosystem, wildlife and human health. In this, we study the ability of the fungus Rasamsonia emersonii IMI 393752 to degrade the rigid microplastics of Coke bottles. Microplastics were extracted from Coke bottles and incubated with Rasamsonia emersonii in Sabouraud dextrose agar media. Microplastics were pre-sterilized without altering the chemistry of microplastic. Preliminary analysis was performed by observing radial growth assessment of microplastic-containing media enriched with fungi vs. control. The assay confirmed no impedance or change in the fungi's growth pattern and rate by introducing microplastics. The degradation of the microplastics was monitored over time using microscopy and FTIR, and biodegradation/deterioration on the plastic surface was observed. Furthermore, the liquid assay was performed. HPLC and GCMS will be conducted to check the biodegradation and presence of enzyme release by fungi to counteract the presence of microplastics. These findings have important implications for managing plastic waste, as they suggest that fungi such as Rasamsonia emersonii can potentially degrade microplastics safely and effectively. However, further research to optimise the conditions for microplastic degradation by Rasamsonia emersonii and to develop strategies for scaling up the process for industrial applications will be beneficial.

Keywords: bioremediation, mycoremediation, plastic degradtion, polyethylene terephthalate

Procedia PDF Downloads 95