Search results for: butene catalytic cracking

Authors: Ali Haghiri

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This research has been to investigate the cause of the stress corrosion cracking on dryer equipment (2DR-1745 and DR-1402) in Shahid Tondguyan Petrochemical Company (STPC). These dryers are as a drying powder Terphetalic acid in CTA2 and CTA1 unit. After passing through RVF equipment, wet cake moisture content of about 14% and temperature of 90C changed into a dry cake with a moisture content of less than 0.1% and the final temperature of about 140C and sent out Final Silo (FS-1820). After the declaration of the operation department concerning the observation of acid leakage under the primary insulation was decided that at the first opportunity, this issue must be investigated. So, after the shutdown of a unit at the date 2012/10/20 (2DR-1745) and 2021/11/24 (DR-1402) and after washing the dryer wall, insulation around the wall opened and it was found to crack and leakage from some points.

Keywords: stress corrosion cracking, residual stress, austenitic stainless steel, Br- ion

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Authors: Mikael M. Johansson, Peter Stenvall, Leif Karlsson, Joel Andersson

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Sandvik Sanicro 25, UNS S31035, is an advanced high temperature austenitic stainless steel that potentially can be used in super-heaters and reheaters in the next generation of advanced ultra-super critical power plants. The material possesses both high creep strength and good corrosion resistance at temperatures up to 700°C. Its high temperature properties are positioned between other commercially available high temperature austenitic stainless steels and nickel-based alloys. It is, however, well known that an austenitic solidification mode combined with a fully austenitic microstructure exacerbate susceptibility towards hot cracking. The problem increases even more for thick walled material in multipass welding and could compromise the integrity of the welded component. Varestraint weldability testing is commonly used to evaluate susceptibility towards hot cracking of materials. In this paper, Varestraint test results are evaluated for base material of both UNS S31035 steel and are compared to those of the well-known and well-characterized UNS S31008 grade. The more creep resistant alloy, UNS S31035, is metallurgically more complicated than the UNS S31008 grade and has additions of several alloying elements to improve its high temperature properties. It benefits from both solid solution hardening as well as precipitation hardening. This investigation therefore attempts, based on the Varestraint weldability test, to understand if there are any differences in cracking mechanisms between these two grades due to the additional alloying elements used in UNS S31035. Results from Varestraint testing and crack type investigations will be presented and discussed in some detail. It is shown that hot cracking susceptibility of the UNS S31035 steel is only slightly higher than that of UNS S31008 despite the more complicated metallurgy. Weldability of the two alloys is therefore judged to be comparable making the newer alloy well suited also for critical applications.

Keywords: austenitic stainless steel, hot cracking susceptibility, UNS S31035, UNS S31008, varestraint weldability testing

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Authors: Yalçın Kılıç, İbrahim Kani

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In recent years, interest in the synthesis of coordination compounds has greatly increased due to various application areas (such as catalysis, gas storage, luminescence). Dicarboxylic acids are often used in the synthesis of metal complexes. Bis-thiosalicylate derivative ligands contribute to the synthesis of structures of crystal engineering interest, as they can have both rigid and flexible properties. In addition, these ligands have great potential in terms of catalytic applications with the sulfur and oxygen donor atoms in their structures. In this study, we synthesized a Cu(II) complex [Cu(tsaxyl)(phen)2]•CH3OH (where tsaxyl = 2,2'-(1,2-phylenebis(methylene))bis(sulfanedyl)dibenzoate, phen = 1,10-phenantroline) and characterized through X-ray crystallography. The catalytic activities of Cu(II) complex on oxidation of ethylbenzene, cyclohexane, diphenylmethane, p-xylene were performed in acetonitrile with t-BuOOH as the source of oxygen.

Keywords: complex, crystallography, catalysis, oxidation

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Authors: Seyed Mohamad Rasool Mirkarimi, David Chiaramonti, Samir Bensaid

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Catalytic methane decomposition (CMD, reaction 4) is a one-step process for hydrogen production where carbon in the methane molecule is sequestered in the form of stable and higher-value carbon materials. Metallic catalysts and carbon-based catalysts are two major types of catalysts utilized for the CDM process. Although carbon-based catalysts have lower activity compared to metallic ones, they are less expensive and offer high thermal stability and strong resistance to chemical impurities such as sulfur. Also, it would require less costly separation methods as some of the carbon-based catalysts may not have an active metal component in them. Since the regeneration of metallic catalysts requires burning of the C on their surfaces, which emits CO/CO2, in some cases, using carbon-based catalysts would be recommended because regeneration can be completely avoided, and the catalyst can be directly used in other processes. This work focuses on the effect of biochar as a carbon-based catalyst for the conversion of methane into hydrogen and carbon. Biochar produced from the pyrolysis of poplar wood and activated biochar are used as catalysts for this process. In order to observe the impact of carbon-based catalysts on methane conversion, methane cracking in the absence and presence of catalysts for a gas stream with different levels of methane concentration should be performed. The results of these experiments prove conversion of methane in the absence of catalysts at 900 °C is negligible, whereas in the presence of biochar and activated biochar, significant growth has been observed. Comparing the results of the tests related to using char and activated char shows the enhancement obtained in BET surface area of the catalyst through activation leads to more than 10 vol.% methane conversion.

Keywords: hydrogen production, catalytic methane decomposition, biochar, activated biochar, carbon-based catalyts

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Authors: Hana Gebremariam Liliso

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This study investigates the factors contributing to the deterioration of thick asphalt pavements, such as rutting and cracking. We focus on the combined influence of traffic loads and pavement structure. This study uses a three-dimensional finite element model with a Mohr-Coulomb failure criterion to analyze the stress levels near the pavement's surface under realistic conditions. Our model considers various factors, including tire-pavement contact stresses, asphalt properties, moving loads, and dynamic analysis. This research suggests that cracking tends to occur between dual tires. Some key discoveries include the risk of cracking increases as temperatures rise; surface cracking at high temperatures is associated with distortional deformation; using a uniform contact stress distribution underestimates the risk of failure compared to realistic three-dimensional tire contact stress, particularly at high temperatures; the risk of failure is higher near the surface when there is a negative temperature gradient in the asphalt layer; and debonding beneath the surface layer leads to increased shear stress and premature failure around the interface.

Keywords: asphalt pavement, surface failure, 3d finite element model, multiaxial stress states, Mohr-Coulomb failure criterion

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Authors: I. Yordanova, H. Kolev, S. Todorova, Z. Cherkezova-Zheleva

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Catalysis plays a key role in solving many environmental problems by establishing efficient catalytic systems for environmental protection and reducing emissions of greenhouse gases from industry. Volatile organic compounds are major air pollutants. There are several ways to dispose of emissions like - adsorption, condensation, absorption, bio-filtration, thermal, catalytic, plasma and ultraviolet oxidation. The catalytic oxidation has more advantages over other methods. For example - lower energy consumption; the concentration of the organic contaminant may be low or may vary within wide limits. Catalysts for complete oxidation of VOCs can be classified into three categories: noble metal, metal oxides or supported metal oxides and mixture of noble metals and metal oxides. Most of the catalysts for the complete catalytic oxidation are based on Pt, Pd, Rh or a combination thereof. The oxides of the transition metal are one of the alternatives to noble metal catalysts for these reactions. They are less active at low temperatures, but at higher - their activity is similar. The properties of the catalyst depend on the distribution of the active phase, the medium type of the pre-treatment, the interaction between the active phase and the support and the interaction between the active phase and the reaction medium. Supported mono-component Mn and bi-component Mn-Co systems are examined in present study. The samples are prepared using co-precipitation method. SiO2 (Aerosil) is used as a support. The studied samples were precipitated by NH4OH. The synthesized samples were characterized by XRD, XPS, TPR and tested in the catalytic reaction of complete oxidation of n-hexane, propane, methanol, ethanol and propanol.

Keywords: catalytic oxidation, Co-Mn oxide, oxidation of hydrocarbons and alcohols, environmental protection

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Authors: Mahdi Saadat, Abbas Taheri

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Understanding the cracking response of crystalline rocks at mineralogical scale is of great importance during the design procedure of mining structures. A grain-based distinct element model (GBM) is employed to numerically study the cracking response of Barre granite at micro- and macro-scales. The GBM framework is augmented with a proposed distinct element-based cohesive model to reproduce the micro-cracking response of the inter- and intra-grain contacts. The cohesive GBM framework is implemented in PFC2D distinct element codes. The microstructural properties of Barre granite are imported in PFC2D to generate synthetic specimens. The microproperties of the model is calibrated against the laboratory uniaxial compressive and Brazilian split tensile tests. The calibrated model is then used to simulate the fracturing behaviour of pre-cracked Barre granite with different flaw configurations. The numerical results of the proposed model demonstrate a good agreement with the experimental counterparts. The GBM framework proposed thus appears promising for further investigation of the influence of grain microstructure and mineralogical properties on the cracking behaviour of crystalline rocks.

Keywords: discrete element modelling, cohesive grain-based model, crystalline rock, fracturing behavior

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Authors: Blaž Likozar, Andraž Pavlišič, Matic Pavlin, Taja Žibert, Aleksandra Zamljen, Sašo Gyergyek, Matej Huš

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Ammonia is gaining recognition as a carbon-free fuel for energy-intensive applications, particularly transportation, industry, and power generation. Due to its physical properties, high energy density of 3 kWh kg-1, and high gravimetric hydrogen capacity of 17.6 wt%, ammonia is an efficient energy vector for green hydrogen, capable of mitigating hydrogen’s storage, distribution, and infrastructure deployment limitations. Chemicalstorage in the form of ammonia provides an efficient and affordable solution for energy storage, which is currently a critical step in overcoming the intermittency of abundant renewable energy sources with minimal or no environmental impact. Experiments were carried out to validate the modelling in a packed bed reactor, which proved to be agreeing.

Keywords: hydrogen, ammonia, catalysis, modelling, kinetics

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Authors: W. Nataniel, B. Lima, J. Manoel, M. P. Filho, H. Marcos, Oliveira Mauricio, P. Ferreira

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Headed reinforcement bars are increasingly used for anchorage in concrete structures. Applications include connections in composite steel-concrete structures, such as beam-column joints, in several strengthening situations as well as in more traditional uses in cast-in-place and precast structural systems. This paper investigates the reduction in the ultimate tensile capacity of embedded cast-in headed anchors due to concrete cracking. A series of nine laboratory tests are carried out to evaluate the influence of cracking on the concrete breakout strength in tension. The experimental results show that cracking affects both the resistance and load-slip response of the headed bar anchors. The strengths measured in these tests are compared to theoretical resistances calculated following the recommendations presented by fib Bulletin no. 58 (2011), ETAG 001 (2010) and ACI 318 (2014). The influences of parameters such as the effective embedment depth (h_ef), bar diameter (d_s), and the concrete compressive strength (f_c) are analysed and discussed. The theoretical recommendations are shown to be over-conservative for both embedment depths and were, in general, inaccurate in comparison to the experimental trends. The ACI 318 (2014) was the design code which presented the best performance regarding to the predictions of the ultimate load, with an average of 1.42 for the ratio between the experimental and estimated strengths, standard deviation of 0.36, and coefficient of variation equal to 0.25.

Keywords: cast-in headed anchors, concrete cone failure, uncracked concrete, cracked concrete

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Authors: Xiaoquan Huang, Congcong Li, Tingting Wei, Changcun Bai, Na Liu, Meng Tang

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Silver is often doped on nano-titanium dioxide photocatalysts (Ag-TiO₂) by photodeposition method to improve their utilization of visible-light while increasing the toxicity of TiO₂。 However, it is not known what factors influence this toxicity and how to reduce toxicity while maintaining the maximum catalytic activity. In this study, Ag-TiO₂ photocatalysts were synthesized by the photodeposition method with different silver content (AgC) and photodeposition time (PDT). Characterization and catalytic experiments demonstrated that silver was well assembled on TiO₂ with excellent visible-light catalytic activity, and the size of silver increased with PDT. In vitro, the cell viability of lung epithelial cells A549 and BEAS-2B showed that the higher content and smaller size of silver doping caused higher toxicity. In vivo, Ag-TiO₂ catalysts with lower AgC or larger silver particle size obviously caused less pulmonary pro-inflammatory and pro-fibrosis responses. However, the visible light catalytic activity decreased with the increase in silver size. Therefore, in order to optimize the Ag-TiO₂ photocatalyst with the lowest pulmonary toxicity and highest catalytic performance, response surface methodology (RSM) was further performed to optimize the two independent variables of AgC and PDT. Visible-light catalytic activity was evaluated by the degradation rate of Rhodamine B, the antibacterial property was evaluated by killing log value for Escherichia coli, and cytotoxicity was evaluated by IC50 to BEAS-2B cells. As a result, the RSM model showed that AgC and PDT exhibited an interaction effect on catalytic activity in the quadratic model. AgC was positively correlated with antibacterial activity. Cytotoxicity was proportional to AgC while inversely proportional to PDT. Finally, the optimization values were AgC 3.08 w/w% and PDT 28 min. Under this optimal condition, the relatively high silver proportion ensured the visible-light catalytic and antibacterial activity, while the longer PDT effectively reduced the cytotoxicity. This study is of significance for the safe and efficient application of silver-doped TiO₂ photocatalysts.

Keywords: Ag-doped TiO₂, cytotoxicity, inflammtion, fibrosis, response surface methodology

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Authors: Seyed Amin Vakili, Sahar Sadat Vakili, Seyed Ehsan Vakili, Nader Abdoli Yazdi

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The aim of this paper is to examine the behavior of elastic stability of reinforced and composite concrete struts with axial loads. The objective of this study is to verify the ability of the Modified Newmark Method to include geometric non-linearity in addition to non-linearity due to cracking, and also to show the advantage of the established method to reconsider an ignored minor parameter in mathematical modeling, such as the effect of the cracking by extra geometric bending moment Ny on cross-section properties. The purpose of this investigation is not to present some new results for the instability of reinforced or composite concrete columns. Therefore, no kinds of non-linearity involved in the problem are considered here. Only as mentioned, it is a part of the verification of the new established method to solve two kinds of non-linearity P- δ effect and cracking together simultaneously. However, the Modified Newmark Method can be used to solve non-linearity of materials and time-dependent behavior of concrete. However, since it is out of the scope of this article, it is not considered.

Keywords: stability, buckling, modified newmark method, reinforced

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Authors: Leal Leonardo, Pires Carlos Augusto de Moraes, Casiraghi Magela

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In this work were realized the modeling and simulation of the catalytic reformer process, of ample form, considering all the equipment that influence the operation performance. Considered it a semi-regenerative reformer, with four reactors in series intercalated with four furnaces, two heat exchanges, one product separator and one recycle compressor. A simplified reactional system was considered, involving only ten chemical compounds related through five reactions. The considered process was the applied to aromatics production (benzene, toluene, and xylene). The models developed to diverse equipment were interconnecting in a simulator that consists of a computer program elaborate in FORTRAN 77. The simulation of the global model representative of reformer unity achieved results that are compatibles with the literature ones. It was then possible to study the effects of operational variables in the products concentration and in the performance of the unity equipment.

Keywords: catalytic reforming, modeling, simulation, petrochemical engineering

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Authors: A. Taoufyq, B. Bakiz, A. Benlhachemi, L. Patout, D. V. Chokouadeua, F. Guinneton, G. Nolibe, A. Lyoussi, J-R. Gavarri

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Currently, the photo catalytic reactions occurring under solar illumination have attracted worldwide attentions due to a tremendous set of environmental problems. Taking the sunlight into account, it is indispensable to develop highly effective visible-light-driver photo catalysts. Nano structured materials such as MxM’1-xWO6 system are widely studied due to its interesting piezoelectric, dielectric and catalytic properties. These materials can be used in photo catalysis technique for environmental applications, such as waste water treatments. The aim of this study was to investigate the photo catalytic activity of polycrystalline phases of bismuth tungstate of formula Bi2WO6. Polycrystalline samples were elaborated using a coprecipitation technique followed by a calcination process at different temperatures (300, 400, 600 and 900°C). The obtained polycrystalline phases have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Crystal cell parameters and cell volume depend on elaboration temperature. High-resolution electron microscopy images and image simulations, associated with X-ray diffraction data, allowed confirming the lattices and space groups Pca21. The photo catalytic activity of the as-prepared samples was studied by irradiating aqueous solutions of Rhodamine B, associated with Bi2WO6 additives having variable crystallite sizes. The photo catalytic activity of such bismuth tungstates increased as the crystallite sizes decreased. The high specific area of the photo catalytic particles obtained at 300°C seems to condition the degradation kinetics of RhB.

Keywords: Bismuth tungstate, crystallite sizes, electron microscopy, photocatalytic activity, X-ray diffraction.

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Authors: Malee Santikunaporn, Neera Wongtyanuwat, Channarong Asavatesanupap

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Pyrolysis of waste oil is an effective process to produce high quality liquid fuels. In this work, pyrolysis experiments of waste oil over Y zeolite were carried out in a semi-batch reactor under a flow of nitrogen at atmospheric pressure and at different reaction temperatures (350-450 ^oC). The products were gas, liquid fuel, and residue. Only liquid fuel was further characterized for its composition and properties by using gas chromatography, thermogravimetric analyzer, and bomb calorimeter. Experimental results indicated that the pyrolysis reaction temperature significantly affected both yield and composition distribution of pyrolysis oil. An increase in reaction temperature resulted in increased fuel yield, especially gasoline fraction. To obtain high amount of fuel, the optimal reaction temperature should be higher than 350 ^oC. A presence of Y zeolite in the system enhanced the cracking activity. In addition, the pyrolysis oil yield is proportional to the catalyst quantity.

Keywords: gasoline, diesel, pyrolysis, waste oil, Y zeolite

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Authors: Mohamed Gar Alalm, Ahmed Tawfik

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In this study, photo-catalytic degradation of phenol by titanium dioxide (TiO2) in aqueous solution was evaluated. The UV energy of solar light was utilized by compound parabolic collectors (CPCs) technology. The effect of irradiation time, initial pH, and dosage of TiO2 were investigated. Aromatic intermediates (catechol, benzoquinone, and hydroquinone) were quantified during the reaction to study the pathways of the oxidation process. 94.5% degradation efficiency of phenol was achieved after 150 minutes of irradiation when the initial concentration was 100 mg/L. The dosage of TiO2 significantly affected the degradation efficiency of phenol. The observed optimum pH for the reaction was 5.2. Phenol photo-catalytic degradation fitted to the pseudo-first order kinetic according to Langmuir–Hinshelwood model.

Keywords: compound parabolic collectors, phenol, photo-catalytic, titanium dioxide

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Authors: Behzad Behnia, Noah LaRussa-Trott

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In recent years, fibers have been successfully used as an additive to reinforce asphalt concrete materials and to enhance the sustainability and resiliency of transportation infrastructure. Roads covered with fiber-reinforced asphalt concrete (FRAC) require less frequent maintenance and tend to have a longer lifespan. The present work investigates the application of sasobit-coated aramid fibers in asphalt pavements and employs machine learning to develop prediction models to evaluate the cracking performance of FRAC materials. For the experimental part of the study, the effects of several important parameters such as fiber content, fiber length, and testing temperature on fracture characteristics of FRAC mixtures were thoroughly investigated. Two mechanical performance tests, i.e., the disk-shaped compact tension [DC(T)] and indirect tensile [ID(T)] strength tests, as well as the non-destructive acoustic emission test, were utilized to experimentally measure the cracking behavior of the FRAC material in both macro and micro level, respectively. The experimental results were used to train the supervised machine learning approach in order to establish prediction models for fracture performance of the FRAC mixtures in the field. Experimental results demonstrated that adding fibers improved the overall fracture performance of asphalt concrete materials by increasing their fracture energy, tensile strength and lowering their 'embrittlement temperature'. FRAC mixtures containing long-size fibers exhibited better cracking performance than regular-size fiber mixtures. The developed prediction models of this study could be easily employed by pavement engineers in the assessment of the FRAC pavements.

Keywords: fiber reinforced asphalt concrete, machine learning, cracking performance tests, prediction model

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Authors: Shyaka Eugene

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The efficient and safe demolition of structures is a critical challenge in civil engineering and construction. This study focuses on the development of optimal demolition strategies by investigating the crack propagation behavior in beams induced by soundless cracking agents. It is commonly used in controlled demolition and has gained prominence due to its non-explosive and environmentally friendly nature. This research employs a comprehensive experimental and computational approach to analyze the crack initiation, propagation, and eventual failure in beams subjected to soundless cracking agents. Experimental testing involves the application of various cracking agents under controlled conditions to understand their effects on the structural integrity of beams. High-resolution imaging and strain measurements are used to capture the crack propagation process. In parallel, numerical simulations are conducted using advanced finite element analysis (FEA) techniques to model crack propagation in beams, considering various parameters such as cracking agent composition, loading conditions, and beam properties. The FEA models are validated against experimental results, ensuring their accuracy in predicting crack propagation patterns. The findings of this study provide valuable insights into optimizing demolition strategies, allowing engineers and demolition experts to make informed decisions regarding the selection of cracking agents, their application techniques, and structural reinforcement methods. Ultimately, this research contributes to enhancing the safety, efficiency, and sustainability of demolition practices in the construction industry, reducing environmental impact and ensuring the protection of adjacent structures and the surrounding environment.

Keywords: expansion pressure, energy release rate, soundless chemical demolition agent, crack propagation

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Authors: Sushil Kumar Saraswat, K. K. Pant

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Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nano materials. The catalytic runs were carried out from 550-800 oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, TPR, XRD, SEM, TEM, and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity and stability up to 10 h time-on-stream at 750 oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at a higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs, and branched CNFs depending on the catalyst composition and reaction temperature, were obtained. The TG data showed that a higher yield of MWCNTs was achieved over 50% Co/Al2O3 catalyst compared to other catalysts.

Keywords: carbon nanotubes, cobalt, hydrogen production, methane decomposition

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Authors: G. Massaad, E. Roziere, A. Loukili, L. Izoret

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Based on the monitoring of mass, hydrostatic weighing, and the amount of leached OH- we deduced the nature of leached and precipitated minerals, the amount of lost aggregates and the evolution of porosity and cracking during the sulphate attack. Using these information, we are able to draw the volume / mass changes brought by mineralogical variations and cracking of the cement matrix. Then we defined a new performance indicator, the averaged density, capable to resume along the test of sulphate attack the occurred physicochemical variation occurred in the cementitious matrix and then highlight.

Keywords: monitoring strategy, performance indicator, sulphate attack, mechanism of degradation

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Authors: Mokhtari Karchegani Amir, Maboudi Samad, Azadi Reza, Dastanian Raoof

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Marun's petrochemical cracking furnaces have a very comprehensive operating control system for combustion and related equipment, utilizing advanced instrument circuits. However, after several years of operation, numerous problems arose in the pyrolysis furnaces. A team of experts conducted an audit, revealing that the furnaces were over-designed, leading to excessive consumption of air and fuel. This issue was related to the burners' shutter settings, which had not been configured properly. The operations department had responded by increasing the induced draft fan speed and forcing the instrument switches to counteract the wind effect in the combustion chamber. Using Fluent and Gambit software, the furnaces were analyzed. The findings indicated that this situation elevated the convection part's temperature, causing uneven heat distribution inside the furnace. Consequently, this led to overheating in the convection section and excessive cracking within the coils in the radiation section. The increased convection temperature damaged convection parts and resulted in equipment blockages downstream of the furnaces due to the production of more coke and tar in the process. To address these issues, corrective actions were implemented. The excess air for burners and combustion chambers was properly set, resulting in improved efficiency, reduced emissions of environmentally harmful gases, prevention of creep in coils, decreased fuel consumption, and lower maintenance costs.

Keywords: furnace, coke, CFD analysis, over cracking

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Authors: Hafiz Muhammad Adeel Sharif, Tian Li, Changping Li

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Recently, the emission of nitrogen-sulphur oxides (NOₓ, SO₂) has become a global issue and causing serious threats to health and the environment. Catalytic reduction of NOx and SOₓ gases into friendly gases is considered one of the best approaches. However, regeneration of the catalyst, higher bond-dissociation energy for NOx, i.e., 150.7 kcal/mol, escape of intermediate gas (N₂O, a greenhouse gas) with treated flue-gas, and limited activity of catalyst remains a great challenge. Here, a cheap, binderless naturally-extracted bass-wood thin carbon electrode (TCE) is presented, which shows excellent catalytic activity towards NOx reduction. The bass-wood carbonization at 900 ℃ followed by thermal activation in the presence of CO2 gas at 750 ℃. The thermal activation resulted in an increase in epoxy groups on the surface of the TCE and enhancement in the surface area as well as the degree of graphitization. The TCE unique 3D strongly inter-connected network through hierarchical micro/meso/macro pores that allow large electrode/electrolyte interface. Owing to these characteristics, the TCE exhibited excellent catalytic efficiency towards NOx (~83.3%) under ambient conditions and enhanced catalytic response under pH and sulphite exposure as well as excellent stability up to 168 hours. Moreover, a temperature-dependent activity trend was found where the highest catalytic activity was achieved at 80 ℃, beyond which the electrolyte became evaporative and resulted in a performance decrease. The designed electrocatalyst showed great potential for effective NOx-reduction, which is highly cost-effective, green, and sustainable.

Keywords: electrocatalyst, NOx-reduction, bass-wood electrode, integrated wet-scrubbing, sustainable

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Authors: Yijin Kang

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Chemical-electrical energy conversion and storage are greatly attractive for the development of sustainable energy. Catalytic processes are heavily involved in such energy conversion and storage. Development of high-performance catalyst nanomaterials relies on tuning material structures at nanoscale. This is in particular manifested in the design of catalysts demanding both high activity and durability. Here, a research system will be presented that connects fundamental investigation on well-defined extended surfaces (e.g. single crystal surfaces), extrapolation onto nanocrystals with highly controlled shape and size, exploration of interfacial interaction using novel nanocrystal superlattices as platform, and finally design of high performance catalysts in which all the possible beneficial properties from complex functional structures are implemented. Using recently published results, it will be demonstrated that optimal and fine balanced activity and durability, as well as tunable functionality, can be achieved by carefully tailoring the nanostructure of catalytic nanomaterials.

Keywords: energy, nanomaterials, catalysis, electrocatalysis

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Authors: Vishnu S. Prasad, Preeti Aghalayam

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The major harmful automobile exhausts are nitric oxide (NO) and unburned hydrocarbon (HC). Reduction of NO using unburned fuel HC as a reductant is the technique used in hydrocarbon-selective catalytic reduction (HC-SCR). In this work, we study the microkinetic modelling of NO reduction using propene as a reductant on Pt catalysts. The selectivity of NO reduction to N₂O is detected in some ranges of operating conditions, whereas the effect of inlet O₂% causes a number of changes in the feasible regimes of operation.

Keywords: microkinetic modelling, NOx, platinum on alumina catalysts, selective catalytic reduction

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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: Anıl Dinçer, Dilek Duranoğlu

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Ketones, which are widely used as solvent and chemical intermediates in chemical process industry, are commercially produced by using catalytic dehydrogenation of secondary alcohols at higher temperature (300-500ºC), and pressure (1-5 bar). Although it is possible to obtain high conversion values (60-87%) via gas phase catalytic dehydrogenation, working high temperature and pressure can result in side reactions and shorten the catalyst life. In order to overcome these challenges, catalytic dehydrogenation in the presence of an appropriate liquid solvent has been started to use. Hence, secondary alcohols can be converted to respective ketones at relatively low temperature (150-200ºC) under atmospheric pressure. In this study, methyl ethyl ketone and acetone was produced via catalytic dehydrogenation of appropriate secondary alcohols (isopropyl alcohol and sec-butyl alcohol) in the presence of liquid solvent at 160-190ºC. Obtained methyl ethyl ketone and acetone were analyzed by using FTIR and GC spectrometer. Effects of temperature, amount of catalyst and solvent on conversion and reaction rate were investigated. Optimum process conditions, which gave high conversion and reaction rate, were determined. According to GC results, 70% of secondary butyl alcohol and 42% of isopropyl alcohol was converted to related ketone (methyl ethyl ketone and acetone, respectively) at optimum process conditions. After distillation, 99.13% methyl ethyl ketone and 99.20% acetone was obtained. Consequently, liquid phase dehydrogenation process, which can compete with commercial gas phase process, was developed.

Keywords: dehydrogenation, liquid phase, methyl ethyl ketone, secondary alcohol

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Authors: Su-Ning Wang, Yao-Qiang Chen

Abstract:

The CeO2-ZrO2-La2O3-Al2O3 composite oxides are synthesized using co-precipitation method by two different reactors (i.e. continuous stirred-tank reactor and batch reactor), and the corresponding Rh-only three-way catalysts are obtained by wet-impregnation approach. The textural, structural, morphology and redox properties of the support materials, as well as the catalytic performance of the Rh-only catalyst are investigated systematically. The results reveal that the materials (CZLA-C) synthesized by continuous stirred-tank reactor have a better physic-chemical properties than the counterpart material (CZLA-B) prepared by batch reactor. After aging treatment at 1000 ℃ for 5 h, the BET surface area and pore volume of S1 reach up to 76 m2 g-1 and 0.36 mL/g, respectively, which is higher than that of S2. The XRD and Raman results demonstrate that a high structural stability is obtained by S1 because of the negligible lattice variation and the slight grain growth after aging treatment. The SEM and TEM images display that the morphology of S1 is assembled by many homogeneous primary nanoparticles (about 6.12 nm) that are connected to form mesoporous structure The TPR measurement shows that S1 possesses a higher reduction ability than S2. Compared with the catalyst supported on the CZLA-B, the as-prepared CZLA-C demonstrates an improved three-way catalytic activity both before and after aging treatment.

Keywords: composite oxides, reactor, catalysis, catalytic performance

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Authors: M. Amanipour, J. Towfighi, E. Ganji Babakhani, M. Heidari

Abstract:

Cylindrical alumina microfiltration membrane (GMITM Corporation, inside diameter=9 mm, outside diameter=13 mm, length= 50 mm) with an average pore size of 0.5 micrometer and porosity of about 0.35 was used as the support for membrane reactor. This support was soaked in boehmite sols, and the mean particle size was adjusted in the range of 50 to 500 nm by carefully controlling hydrolysis time, and calcined at 650 °C for two hours. This process was repeated with different boehmite solutions in order to achieve an intermediate layer with an average pore size of about 50 nm. The resulting substrate was then coated with a thin and dense layer of silica by counter current chemical vapour deposition (CVD) method. A boehmite sol with 10 wt.% of nickel which was prepared by a standard procedure was used to make the catalytic layer. BET, SEM, and XRD analysis were used to characterize this layer. The catalytic membrane reactor was placed in an experimental setup to evaluate the permeation and hydrogen separation performance for a steam reforming reaction. The setup consisted of a tubular module in which the membrane was fixed, and the reforming reaction occurred at the inner side of the membrane. Methane stream, diluted with nitrogen, and deionized water with a steam to carbon (S/C) ratio of 3.0 entered the reactor after the reactor was heated up to 500 °C with a specified rate of 2 °C/ min and the catalytic layer was reduced at presence of hydrogen for 2.5 hours. Nitrogen flow was used as sweep gas through the outer side of the reactor. Any liquid produced was trapped and separated at reactor exit by a cold trap, and the produced gases were analyzed by an on-line gas chromatograph (Agilent 7890A) to measure total CH₄ conversion and H₂ permeation. BET analysis indicated uniform size distribution for catalyst with average pore size of 280 nm and average surface area of 275 m².g^-1. Single-component permeation tests were carried out for hydrogen, methane, and carbon dioxide at temperature range of 500-800 °C, and the results showed almost the same permeance and hydrogen selectivity values for hydrogen as the composite membrane without catalytic layer. Performance of the catalytic membrane was evaluated by applying membranes as a membrane reactor for methane steam reforming reaction at gas hourly space velocity (GHSV) of 10,000 h⁻¹ and 2 bar. CH₄ conversion increased from 50% to 85% with increasing reaction temperature from 600 °C to 750 °C, which is sufficiently above equilibrium curve at reaction conditions, but slightly lower than membrane reactor with packed nickel catalytic bed because of its higher surface area compared to the catalytic layer.

Keywords: catalytic membrane, hydrogen, methane steam reforming, permeance

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Authors: S. Shanthi

Abstract:

Catalyzed oxidation processes show extraordinary guarantee for application in numerous wastewater treatment ranges. Advanced oxidation processes are emerging innovation that might be utilized for particular objectives in wastewater treatment. This research work provides a solution for removal a refractory organic compound 2,4-dichlorophenoxyaceticacid a common water pollutant. All studies were done in batch mode in a constantly stirred reactor. Alternative ozonation processes catalysed by transition metals or granular activated carbon have been investigated for degradation of organics. Catalytic ozonation under study are homogeneous catalytic ozonation, which is based on ozone activation by transition metal ions present in aqueous solution, and secondly as heterogeneous catalytic ozonation in the presence of Granular Activated Carbon (GAC). The present studies reveal that heterogeneous catalytic ozonation using GAC favour the ozonation of 2,4-dichlorophenoxyaceticacid by increasing the rate of ozonation and a much higher degradation of substrates were obtained in a given time. Be that it may, Fe2+and Fe3+ ions decreased the rate of degradation of 2,4-dichlorophenoxyaceticacid indicating that it acts as a negative catalyst. In case of heterogeneous catalytic ozonation using GAC catalyst it was found that during the initial 5 minutes of contact solution concentration decreased significantly as the pollutants were adsorbed initially. Thereafter the substrate started getting oxidized and ozonation became a dominates the treatment process. The exhausted GAC was found to be regenerated in situ. The percentage reduction of the substrate was maximum achieved in minimum possible time when GAC catalyst is employed.

Keywords: ozonation, homogeneous catalysis, heterogeneous catalysis, granular activated carbon

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Authors: N. Stoeva, I. Spassova, R. Nickolov, M. Khristova

Abstract:

Exhaust gases from stationary and mobile combustion sources contain nitrogen oxides that cause a variety of environmentally harmful effects. The most common approach of their elimination is the catalytic reaction in the exhaust using various reduction agents such as NH3, CO and hydrocarbons. Transition metals (Co, Ni, Cu, etc.) are the most widely used as active components for deposition on various supports. However, since the interaction between different catalyst components have been extensively studied in different types of reaction systems, the possible cooperation between active components and the support material and the underlying mechanisms have not been thoroughly investigated. The support structure may affect how these materials maintain an active phase. The objective is to investigate the addition of carbonaceous materials with different nature and texture characteristics on the properties of the resulting silica-carbon support and how it influences of the catalytic properties of the supported copper and cobalt catalysts for reduction of NO with CO. The versatility of the physico-chemical properties of the composites and the supported copper and cobalt catalysts are discussed with an emphasis on the relationship of the properties with the catalytic performance. The catalysts were prepared by sol-gel process and were characterized by XRD, XPS, AAS and BET analysis. The catalytic experiments were carried out in catalytic flow apparatus with isothermal flow reactor in the temperature range 20–300оС. After the catalytic test temperature-programmed desorption (TPD) was carried out. The transient response method was used to study the interaction of the gas phase with the catalyst surface. The role of the interaction between the support and the active phase on the catalyst’s activity in the studied reaction was discussed. We suppose the carbon particles with small sizes to participate in the formation of the active sites for the reduction of NO with CO along with their effect on the kind of deposited metal oxide phase. The existence of micropore texture for some of composites also influences by mass-transfer limitations.

Keywords: catalysts, no reduction, composites, bet analysis

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Authors: Joanna Drzeżdżon

Abstract:

Polyvinyl alcohol and its derivatives such as 2-chloro-2-propen-1-ol have found application in many industries. They are mainly used for the production of adhesives, thickeners and stabilizers of emulsion paints, and surgical threads. Moreover, polyvinyl alcohol derivatives are indispensable reagents in the synthesis of hemiacetals. Polyolefins derived from polyvinyl alcohol are obtained by using catalysts belonging to complex compounds of transition metal ions. The aim of the studies is to the synthesis of a new complex, i.e. dipicolinate oxovanadium(IV) complex with 4,4’-dimethoxy-2,2’-bipyridyl, and to determine its catalytic activities. Moreover, the another aim of the studies was to set conditions for 2-chloro-2-propen-1-ol oligomerization. The catalytic system has been based on the dipicolinate complex of oxovanadium(IV) with 4,4’-dimethoxy-2,2’-bipyridyl and MMAO-12. The results of the studies showed that how a new oxovanadium(IV) complex compound effects on the 2-chloro-2-propen-1-ol oligomerization. Moreover, the results revealed that new catalytic material is a highly active catalyst for the investigated oligomerization.

Keywords: 2-chloro-2-propen-1-ol, oligomerization, dipicolinate, vanadium, methylaluminoxane

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