Search results for: catalytic cracking
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 863

Search results for: catalytic cracking

863 Catalytic Cracking of Butene to Propylene over Modified HZSM-5 Zeolites

Authors: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

Abstract:

Catalytic cracking of butene to propylene was carried out in a continuous-flow fixed-bed reactor over HZSM-5 catalysts modified by nickel and phosphorus. The structure and acidity of catalysts were measured by N2 adsorption, NH3-TPD and XPS. The results revealed that surface area and strong acid sites both decreased with increasing phosphorus loadings. The increment of phosphorus loadings reduced the butene conversion but enhanced the propylene selectivity and catalyst stability.

Keywords: butene, catalytic cracking, HZSM-5, modification

Procedia PDF Downloads 355
862 Catalytic Cracking of Hydrocarbon over Zeolite Based Catalysts

Authors: Debdut Roy, Vidyasagar Guggilla

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In this research, we highlight our exploratory work on modified zeolite based catalysts for catalytic cracking of hydrocarbons for production of light olefin i.e. ethylene and propylene. The work is focused on understanding the catalyst structure and activity correlation. Catalysts are characterized by surface area and pore size distribution analysis, inductively coupled plasma optical emission spectrometry (ICP-OES), Temperature Programmed Desorption (TPD) of ammonia, pyridine Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermo-gravimetric Analysis (TGA) and correlated with the catalytic activity. It is observed that the yield of lighter olefins increases with increase of Bronsted acid strength.

Keywords: catalytic cracking, zeolite, propylene, structure-activity correlation

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861 Butene Catalytic Cracking to Propylene over Iron and Phosphorus Modified HZSM-5

Authors: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

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HZSM-5 zeolites modified by iron and phosphorus were applied in catalytic cracking of butene. N2 adsorption and NH3-TPD were employed to measure the structure and acidity of catalysts. The results indicate that increasing phosphorus loading decreased surface area, pore volume and strong acidity of catalysts. The introduction of phosphorus significantly decreased butene conversion and promoted propylene selectivity. The catalytic performance of catalyst was strongly dependent on the reaction conditions. Appropriate reaction conditions could suppress side reactions and enhance propylene selectivity.

Keywords: butene catalytic cracking, HZSM-5, modification, reaction conditions

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860 Simulation of a Fluid Catalytic Cracking Process

Authors: Sungho Kim, Dae Shik Kim, Jong Min Lee

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Fluid catalytic cracking (FCC) process is one of the most important process in modern refinery indusrty. This paper focuses on the fluid catalytic cracking (FCC) process. As the FCC process is difficult to model well, due to its nonlinearities and various interactions between its process variables, rigorous process modeling of whole FCC plant is demanded for control and plant-wide optimization of the plant. In this study, a process design for the FCC plant includes riser reactor, main fractionator, and gas processing unit was developed. A reactor model was described based on four-lumped kinetic scheme. Main fractionator, gas processing unit and other process units are designed to simulate real plant data, using a process flowsheet simulator, Aspen PLUS. The custom reactor model was integrated with the process flowsheet simulator to develop an integrated process model.

Keywords: fluid catalytic cracking, simulation, plant data, process design

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859 Modeling and Simulation of Fluid Catalytic Cracking Process

Authors: Sungho Kim, Dae Shik Kim, Jong Min Lee

Abstract:

Fluid catalytic cracking (FCC) process is one of the most important process in modern refinery industry. This paper focuses on the fluid catalytic cracking (FCC) process. As the FCC process is difficult to model well, due to its non linearities and various interactions between its process variables, rigorous process modeling of whole FCC plant is demanded for control and plant-wide optimization of the plant. In this study, a process design for the FCC plant includes riser reactor, main fractionator, and gas processing unit was developed. A reactor model was described based on four-lumped kinetic scheme. Main fractionator, gas processing unit and other process units are designed to simulate real plant data, using a process flow sheet simulator, Aspen PLUS. The custom reactor model was integrated with the process flow sheet simulator to develop an integrated process model.

Keywords: fluid catalytic cracking, simulation, plant data, process design

Procedia PDF Downloads 486
858 N-Heptane as Model Molecule for Cracking Catalyst Evaluation to Improve the Yield of Ethylene and Propylene

Authors: Tony K. Joseph, Balasubramanian Vathilingam, Stephane Morin

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Currently, the refiners around the world are more focused on improving the yield of light olefins (propylene and ethylene) as both of them are very prominent raw materials to produce wide spectrum of polymeric materials such as polyethylene and polypropylene. Henceforth, it is desirable to increase the yield of light olefins via selective cracking of heavy oil fractions. In this study, zeolite grown on SiC was used as the catalyst to do model cracking reaction of n-heptane. The catalytic cracking of n-heptane was performed in a fixed bed reactor (12 mm i.d.) at three different temperatures (425, 450 and 475 °C) and at atmospheric pressure. A carrier gas (N₂) was mixed with n-heptane with ratio of 90:10 (N₂:n-heptane), and the gaseous mixture was introduced into the fixed bed reactor. Various flow rate of reactants was tested to increase the yield of ethylene and propylene. For the comparison purpose, commercial zeolite was also tested in addition to Zeolite on SiC. The products were analyzed using an Agilent gas chromatograph (GC-9860) equipped with flame ionization detector (FID). The GC is connected online with the reactor and all the cracking tests were successfully reproduced. The entire catalytic evaluation results will be presented during the conference.

Keywords: cracking, catalyst, evaluation, ethylene, heptane, propylene

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857 Fluid Catalytic Cracking: Zeolite Catalyzed Chemical Industry Processes

Authors: Mithil Pandey, Ragunathan Bala Subramanian

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One of the major conversion technologies in the oil refinery industry is Fluid catalytic cracking (FCC) which produces the majority of the world’s gasoline. Some useful products are generated from the vacuum gas oil, heavy gas oil and residue feedstocks by the FCC unit in an oil refinery. Moreover, Zeolite catalysts (zeo-catalysts) have found widespread applications and have proved to be substantial and paradigmatic in oil refining and petrochemical processes, such as FCC because of their porous features. Several famous zeo-catalysts have been fabricated and applied in industrial processes as milestones in history, and have brought on huge changes in petrochemicals. So far, more than twenty types of zeolites have been industrially applied, and their versatile porous architectures with their essential features have contributed to affect the catalytic efficiency. This poster depicts the evolution of pore models in zeolite catalysts which are accompanied by an increase in environmental and demands. The crucial roles of modulating pore models are outlined for zeo-catalysts for the enhancement of their catalytic performances in various industrial processes. The development of industrial processes for the FCC process, aromatic conversions and olefin production, makes it obvious that the pore architecture plays a very important role in zeo-catalysis processes. By looking at the different necessities of industrial processes, rational construction of the pore model is critically essential. Besides, the pore structure of the zeolite would have a substantial and direct effect on the utilization efficiency of the zeo-catalyst.

Keywords: catalysts, fluid catalytic cracking, industrial processes, zeolite

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856 Direct Conversion of Crude Oils into Petrochemicals under High Severity Conditions

Authors: Anaam H. Al-ShaikhAli, Mansour A. Al-Herz

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The research leverages the proven HS-FCC technology to directly crack crude oils into petrochemical building blocks. Crude oils were subjected to an optimized hydro-processing process where metal contaminants and sulfur were reduced to an acceptable level for feeding the crudes into the HS-FCC technology. The hydro-processing is achieved through a fixed-bed reactor which is composed of 3 layers of catalysts. The crude oil is passed through a dementalization catalyst followed by a desulfurization catalyst and finally a de-aromatization catalyst. The hydroprocessing was conducted at an optimized liquid hourly space velocity (LHSV), temperature, and pressure for an optimal reduction of metals and sulfur from the crudes. The hydro-processed crudes were then fed into a micro activity testing (MAT) unit to simulate the HS-FCC technology. The catalytic cracking of crude oils was conducted over tailored catalyst formulations under an optimized catalyst/oil ratio and cracking temperature for optimal production of total light olefins.

Keywords: petrochemical, catalytic cracking, catalyst synthesis, HS-FCC technology

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855 Biodiesel Synthesis Using Animal Excreta-Based Biochar and Waste Cooking Oil

Authors: Sang-Ryong Lee, Min-Woon Jung, Deugwoo Han, Kiyong Kim

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This study laid an emphasis on the possible employment of biochar generated from pyrolysis of animal excreta to establish a green platform for producing biodiesel. To this end, the pseudo-catalytic transesterification reaction using chicken manure biochar and waste cooking oil was investigated. Compared with a commercial porous material (SiO2), chicken manure biochar generated from 350 C showed better performance, resulting in 95.6% of the FAME yield at 350C. The Ca species in chicken manure biochar imparted strong catalytic capability by providing the basicity for transesterification. The identified catalytic effect also led to the thermal cracking of unsaturated FAMEs, which decreased the overall FAME yield. For example, 40–60% of converted FAMEs were thermally degraded. To avoid undesirable thermal cracking arising from the high content of the Ca species in chicken manure biochar, the fabrication of chicken manure biochar at temperatures ≥350C was highly recommended.

Keywords: Trasesterification, Animal excreta, FAME, Biochar, Chicken manure

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854 A Rational Strategy to Maximize the Value-Added Products by Selectively Converting Components of Inferior Heavy Oil

Authors: Kashan Bashir, Salah Naji Ahmed Sufyan, Mirza Umar Baig

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In this study, n-dodecane, tetralin, decalin, and tetramethybenzene (TMBE) were used as model compounds of alkanes, naphthenic-aromatic, cycloalkanes and alkyl-benzenes presented in hydro-diesel. The catalytic cracking properties of four model compounds over Y zeolite catalyst (Y-Cat.) and ZSM-5 zeolite catalysts (ZSM-5-Cat.) were probed. The experiment results revealed that high conversion of macromolecular paraffin and naphthenic aromatics were achieved over Y-Cat, whereas its low cracking activity of intermediate products micromolecules paraffin and olefin and high activity of hydride transfer reaction goes against the production of value-added products (light olefin and gasoline). In contrast, despite the fact that the hydride transfer reaction was greatly inhabited over ZSM-5-Cat, the low conversion of macromolecules was observed attributed to diffusion limitations. Interestingly, the mixed catalyst compensates for the shortcomings of the two catalysts, and a “relay reaction” between Y-Cat and ZSM-5-Cat was proposed. Specifically, the added Y-Cat acts as a “pre-cracking booster site” and promotes macromolecules conversion. The addition of ZSM-5-Cat not only significantly suppresses the hydride transfer reaction but also contributes to the cracking of immediate products paraffin and olefin into ethylene and propylene, resulting in a high yield of alkyl-benzene (gasoline), ethylene, and propylene with a low yield of naphthalene (LCO) and coke. The catalytic cracking evaluation experiments of mixed hydro-LCO were also performed to further clarify the “relay reaction” above, showing the highest yield of LPG and gasoline over mixed catalyst. The results indicate that the Y-cat and ZSM-5-cat have a synergistic effect on the conversion of hydro-diesel and corresponding value-added product yield and selective coke yield.

Keywords: synergistic effect, hydro-diesel cracking, FCC, zeolite catalyst, ethylene and propylene

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853 Rational Probabilistic Method for Calculating Thermal Cracking Risk of Mass Concrete Structures

Authors: Naoyuki Sugihashi, Toshiharu Kishi

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The probability of occurrence of thermal cracks in mass concrete in Japan is evaluated by the cracking probability diagram that represents the relationship between the thermal cracking index and the probability of occurrence of cracks in the actual structure. In this paper, we propose a method to directly calculate the cracking probability, following a probabilistic theory by modeling the variance of tensile stress and tensile strength. In this method, the relationship between the variance of tensile stress and tensile strength, the thermal cracking index, and the cracking probability are formulated and presented. In addition, standard deviation of tensile stress and tensile strength was identified, and the method of calculating cracking probability in a general construction controlled environment was also demonstrated.

Keywords: thermal crack control, mass concrete, thermal cracking probability, durability of concrete, calculating method of cracking probability

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852 Characteristics-Based Lq-Control of Cracking Reactor by Integral Reinforcement

Authors: Jana Abu Ahmada, Zaineb Mohamed, Ilyasse Aksikas

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The linear quadratic control system of hyperbolic first order partial differential equations (PDEs) are presented. The aim of this research is to control chemical reactions. This is achieved by converting the PDEs system to ordinary differential equations (ODEs) using the method of characteristics to reduce the system to control it by using the integral reinforcement learning. The designed controller is applied to a catalytic cracking reactor. Background—Transport-Reaction systems cover a large chemical and bio-chemical processes. They are best described by nonlinear PDEs derived from mass and energy balances. As a main application to be considered in this work is the catalytic cracking reactor. Indeed, the cracking reactor is widely used to convert high-boiling, high-molecular weight hydrocarbon fractions of petroleum crude oils into more valuable gasoline, olefinic gases, and others. On the other hand, control of PDEs systems is an important and rich area of research. One of the main control techniques is feedback control. This type of control utilizes information coming from the system to correct its trajectories and drive it to a desired state. Moreover, feedback control rejects disturbances and reduces the variation effects on the plant parameters. Linear-quadratic control is a feedback control since the developed optimal input is expressed as feedback on the system state to exponentially stabilize and drive a linear plant to the steady-state while minimizing a cost criterion. The integral reinforcement learning policy iteration technique is a strong method that solves the linear quadratic regulator problem for continuous-time systems online in real time, using only partial information about the system dynamics (i.e. the drift dynamics A of the system need not be known), and without requiring measurements of the state derivative. This is, in effect, a direct (i.e. no system identification procedure is employed) adaptive control scheme for partially unknown linear systems that converges to the optimal control solution. Contribution—The goal of this research is to Develop a characteristics-based optimal controller for a class of hyperbolic PDEs and apply the developed controller to a catalytic cracking reactor model. In the first part, developing an algorithm to control a class of hyperbolic PDEs system will be investigated. The method of characteristics will be employed to convert the PDEs system into a system of ODEs. Then, the control problem will be solved along the characteristic curves. The reinforcement technique is implemented to find the state-feedback matrix. In the other half, applying the developed algorithm to the important application of a catalytic cracking reactor. The main objective is to use the inlet fraction of gas oil as a manipulated variable to drive the process state towards desired trajectories. The outcome of this challenging research would yield the potential to provide a significant technological innovation for the gas industries since the catalytic cracking reactor is one of the most important conversion processes in petroleum refineries.

Keywords: PDEs, reinforcement iteration, method of characteristics, riccati equation, cracking reactor

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851 The Role of Fluid Catalytic Cracking in Process Optimisation for Petroleum Refineries

Authors: Chinwendu R. Nnabalu, Gioia Falcone, Imma Bortone

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Petroleum refining is a chemical process in which the raw material (crude oil) is converted to finished commercial products for end users. The fluid catalytic cracking (FCC) unit is a key asset in refineries, requiring optimised processes in the context of engineering design. Following the first stage of separation of crude oil in a distillation tower, an additional 40 per cent quantity is attainable in the gasoline pool with further conversion of the downgraded product of crude oil (residue from the distillation tower) using a catalyst in the FCC process. Effective removal of sulphur oxides, nitrogen oxides, carbon and heavy metals from FCC gasoline requires greater separation efficiency and involves an enormous environmental significance. The FCC unit is primarily a reactor and regeneration system which employs cyclone systems for separation.  Catalyst losses in FCC cyclones lead to high particulate matter emission on the regenerator side and fines carryover into the product on the reactor side. This paper aims at demonstrating the importance of FCC unit design criteria in terms of technical performance and compliance with environmental legislation. A systematic review of state-of-the-art FCC technology was carried out, identifying its key technical challenges and sources of emissions.  Case studies of petroleum refineries in Nigeria were assessed against selected global case studies. The review highlights the need for further modelling investigations to help improve FCC design to more effectively meet product specification requirements while complying with stricter environmental legislation.

Keywords: design, emission, fluid catalytic cracking, petroleum refineries

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850 Password Cracking on Graphics Processing Unit Based Systems

Authors: N. Gopalakrishna Kini, Ranjana Paleppady, Akshata K. Naik

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Password authentication is one of the widely used methods to achieve authentication for legal users of computers and defense against attackers. There are many different ways to authenticate users of a system and there are many password cracking methods also developed. This paper is mainly to propose how best password cracking can be performed on a CPU-GPGPU based system. The main objective of this work is to project how quickly a password can be cracked with some knowledge about the computer security and password cracking if sufficient security is not incorporated to the system.

Keywords: GPGPU, password cracking, secret key, user authentication

Procedia PDF Downloads 243
849 Structural Engineering Forensic Evaluation of Misdiagnosed Concrete Masonry Wall Cracking

Authors: W. C. Bracken

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Given that concrete masonry walls are expected to experience shrinkage combined with thermal expansion and contraction, and in some cases even carbonation, throughout their service life, cracking is to be expected. However, after concrete masonry walls have been placed into service, originally anticipated and accounted for cracking is often misdiagnosed as a structural defect. Such misdiagnoses often result in or are used to support litigation. This paper begins by discussing the causes and types of anticipated cracking within concrete masonry walls followed by a discussion on the processes and analyses that exists for properly evaluating them and their significance. From here, the paper then presents a case of misdiagnosed concrete masonry cracking and the flawed logic employed to support litigation.

Keywords: concrete masonry, masonry wall cracking, structural defect, structural damage, construction defect, forensic investigation

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848 Reaction Rate Behavior of a Methane-Air Mixture over a Platinum Catalyst in a Single Channel Catalytic Reactor

Authors: Doo Ki Lee, Kumaresh Selvakumar, Man Young Kim

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Catalytic combustion is an environmentally friendly technique to combust fuels in gas turbines. In this paper, the behavior of surface reaction rate on catalytic combustion is studied with respect to the heterogeneous oxidation of methane-air mixture in a catalytic reactor. Plug flow reactor (PFR), the simplified single catalytic channel assists in investigating the catalytic combustion phenomenon over the Pt catalyst by promoting the desired chemical reactions. The numerical simulation with multi-step elementary surface reactions is governed by the availability of free surface sites onto the catalytic surface and thereby, the catalytic combustion characteristics are demonstrated by examining the rate of the reaction for lean fuel mixture. Further, two different surface reaction mechanisms are adopted and compared for surface reaction rates to indicate the controlling heterogeneous reaction for better fuel conversion. The performance of platinum catalyst under heterogeneous reaction is analyzed under the same temperature condition, where the catalyst with the higher kinetic rate of reaction would have a maximum catalytic activity for enhanced methane catalytic combustion.

Keywords: catalytic combustion, heterogeneous reaction, plug flow reactor, surface reaction rate

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847 Toluene Methylation with Methanol Using Synthesized HZSM-5 Catalysts Modified by Silylation and Dealumination

Authors: Weerachit Pulsawas, Thirasak Rirksomboon

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Due to its abundance from catalytic reforming and thermal cracking of naphtha, toluene could become more value-added compound if it is converted into xylenes, particularly p-xylene, via toluene methylation. Attractively, toluene methylation with methanol is an alternative route to produce xylenes in the absence of other hydrocarbon by-products for which appropriate catalyst would be utilized. In this study, HZSM-5 catalysts with Si/Al molar ratio of 100 were synthesized via hydrothermal treatment and modified by either chemical liquid deposition using tetraethyl-orthosilicate or dealumination with steam. The modified catalysts were characterized by several techniques and tested for their catalytic activity in a continuous down-flow fixed bed reactor. Various operating conditions including WHSV’s of 5 to 20 h-1, reaction temperatures of 400 to 500 °C, and toluene-to-methanol molar ratios (T/M) of 1 to 4 were investigated for attaining possible highest p-xylene selectivity. As a result, the catalytic activity of parent HZSM-5 with temperature of 400 °C, T/M of 4 and WHSV of 24 h-1 showed 65.36% in p-xylene selectivity and 11.90% in toluene conversion as demonstrated for 4 h on stream.

Keywords: toluene methylaion, HZSM-5, silylation, dealumination

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846 Investigation of Flow Behavior inside the Single Channel Catalytic Combustor for Lean Mixture

Authors: Kumaresh Selvakumar, Man Young Kim

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Catalytic combustor substantially reduces emission entailing fuel-air premixing at very low equivalence ratios. The catalytic combustion of natural gas has the potential to become sufficiently active at light off temperature by the convection of heat from the catalyst surface. Only one channel is selected to investigate both the gas and surface reactions in the catalyst bed because of the honeycomb structure of the catalytic combustor. The objective of the present study is to find the methane catalytic combustion behavior inside the catalytic combustor, where the gas phase kinetics is employed by homogeneous methane combustion and surface chemistry is described with the heterogeneous catalysis of the oxidation of methane on a platinum catalyst. The reaction of the premixed mixture in the catalytic regime improves flame stability with complete combustion for lower operating flame temperature. An overview of the flow behavior is presented inside the single channel catalytic combustor including the operation of catalytic combustion with various F/A ratios and premixed inlet temperature.

Keywords: catalytic combustor, equivalence ratios, flame temperature, heterogeneous catalysis, homogeneous combustion

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845 Ammonia Cracking: Catalysts and Process Configurations for Enhanced Performance

Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

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844 The Catalytic Activity of CU2O Microparticles

Authors: Kanda Wongwailikhit

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Copper (I) oxide microparticles with the morphology of cubic and hollow sphere were synthesized with the assistance of a surfactant as the shape controller. Both particles were then subjected to a study of the catalytic activity and the results of shape effects of catalysts on rate of catalytic reaction was observed. The decolorizing reaction of crystal violet and sodium hydroxide was chosen and the decrease of reactant with respect to time was measured using a spectrophotometer. The result revealed that morphology of the crystal had no effect on the catalytic activity for the crystal violet reaction but contributed to total surface area predominantly.

Keywords: copper (I) oxide, catalytic activity, crystal violet

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843 Generation of Catalytic Films of Zeolite Y and ZSM-5 on FeCrAlloy Metal

Authors: Rana Th. A. Al-Rubaye, Arthur A. Garforth

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This work details the generation of thin films of structured zeolite catalysts (ZSM–5 and Y) onto the surface of a metal substrate (FeCrAlloy) using in-situ hydrothermal synthesis. In addition, the zeolite Y is post-synthetically modified by acidified ammonium ion exchange to generate US-Y. Finally the catalytic activity of the structured ZSM-5 catalyst films (Si/Al = 11, thickness 146 µm) and structured US–Y catalyst film (Si/Al = 8, thickness 23µm) were compared with the pelleted powder form of ZSM–5 and USY catalysts of similar Si/Al ratios. The structured catalyst films have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X–ray analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550°C). The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with an apparent activation energy of around 60 kJ mol-1. This paper demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.

Keywords: FeCrAlloy, structured catalyst, zeolite Y, zeolite ZSM-5

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842 Structure and Activity Research of Hydrocarbons Refining Catalysts Based on Wastes of Ferroalloy Production

Authors: Zhanat Shomanova, Ruslan Safarov, Yuri Nosenko, Zheneta Tashmuchambetova, Alima Zharmagambetova

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An effective way of utilization of ferroalloy production wastes is preparing hydrocarbon refining catalysts from them. It is possible due to accordable transition metals containing in the wastes. In the work, we are presenting the results on elemental analysis of sludge samples from Aksu ferroalloy plant (Aksu, Kazakhstan), method of catalysts preparing, results of physical-chemical analysis of obtained catalysts (X-ray analysis, electron microscopy, the BET method etc.), results of using the catalysts in some hydrocarbons refining processes such as hydrocracking of rubber waste, cracking of gasoil, oxidation of cyclohexane. The main results of catalytic activity research are: a) In hydrocracking of rubber waste 64.9% of liquid products were fuel fractions; b) In cracking of gasoil conversion was 51% and selectivity by liquid products was 99%; c) In oxidation of cyclohexane the maximal product yield 87.9% and selectivity by cyclohexanol 93.0% were achieved.

Keywords: catalyst, cyclohexane oxidation, ferroalloy production waste, gasoil cracking

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841 Three Dimensional Simulation of the Transient Modeling and Simulation of Different Gas Flows Velocity and Flow Distribution in Catalytic Converter with Porous Media

Authors: Amir Reza Radmanesh, Sina Farajzadeh Khosroshahi, Hani Sadr

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The transient catalytic converter performance is governed by complex interactions between exhaust gas flow and the monolithic structure of the catalytic converter. Stringent emission regulations around the world necessitate the use of highly-efficient catalytic converters in vehicle exhaust systems. Computational fluid dynamics (CFD) is a powerful tool for calculating the flow field inside the catalytic converter. Radial velocity profiles, obtained by a commercial CFD code, present very good agreement with respective experimental results published in the literature. However the applicability of CFD for transient simulations is limited by the high CPU demands. In the present work, Geometric modeling ceramic monolith substrate is done with square shaped channel type of Catalytic converter and it is coated platinum and palladium. This example illustrates the effect of flow distribution on thermal response of a catalytic converter and different gas flow velocities, during the critical phase of catalytic converter warm up.

Keywords: catalytic converter, computational fluid dynamic, porous media, velocity distribution

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840 A Probabilistic Study on Time to Cover Cracking Due to Corrosion

Authors: Chun-Qing Li, Hassan Baji, Wei Yang

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Corrosion of steel in reinforced concrete structures is a major problem worldwide. The volume expansion of corrosion products causes concrete cover cracking, which could lead to delamination of concrete cover. The time to cover cracking plays a key role to the assessment of serviceability of reinforced concrete structures subjected to corrosion. Many analytical, numerical, and empirical models have been developed to predict the time to cracking initiation due to corrosion. In this study, a numerical model based on finite element modeling of corrosion-induced cracking process is used. In order to predict the service life based on time to cover initiation, the numerical approach is coupled with a probabilistic procedure. In this procedure, all the influential factors affecting time to cover cracking are modeled as random variables. The results show that the time to cover cracking is highly variables. It is also shown that rust product expansion ratio and the size of more porous concrete zone around the rebar are the most influential factors in predicting service life of corrosion-affected structures.

Keywords: corrosion, crack width, probabilistic, service life

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839 Catalytic Degradation of Tetracycline in Aqueous Solution by Magnetic Ore Pyrite Nanoparticles

Authors: Allah Bakhsh Javid, Ali Mashayekh-Salehi, Fatemeh Davardoost

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This study presents the preparation, characterization and catalytic activity of a novel natural mineral-based catalyst for destructive adsorption of tetracycline (TTC) as water emerging compounds. Degradation potential of raw and calcined magnetite catalyst was evaluated at different experiments situations such as pH, catalyst dose, reaction time and pollutant concentration. Calcined magnetite attained greater catalytic potential than the raw ore in the degradation of tetracycline, around 69% versus 3% at reaction time of 30 min and TTC aqueous solution of 50 mg/L, respectively. Complete removal of TTC could be obtained using 2 g/L calcined nanoparticles at reaction time of 60 min. The removal of TTC increased with the increase in solution temperature. Accordingly, considering its abundance in nature together with its very high catalytic potential, calcined pyrite is a promising and reliable catalytic material for destructive decomposition for catalytic decomposition and mineralization of such pharmaceutical compounds as TTC in water and wastewater.

Keywords: catalytic degradation, tetracycline, pyrite, emerging pollutants

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838 Heterogeneous Catalytic Ozonation of Diethyl Phthalate

Authors: Chedly Tizaoui, Hussain Mohammed, Lobna Mansouri, Nidal Hilal, Latifa Bousselmi

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The degradation of diethyl phthalate (DEP) was studied using heterogeneous catalytic ozonation. Activated carbon was used as a catalyst. The degradation of DEP with ozone alone was slow while catalytic ozonation increased degradation rates. Second-order reaction kinetics was used to describe the experimental data, and the corresponding rate constant values were 1.19 and 3.94 M-1.s-1 for ozone and ozone/activated carbon respectively.

Keywords: ozone, heterogeneous catalytic ozonation, diethyl phthalate, endocrine disrupting chemicals

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837 Risk of Plastic Shrinkage Cracking in Recycled Aggregate Concrete

Authors: M. Eckert, M. Oliveira

Abstract:

The intensive use of natural aggregates, near cities and towns, associated to the increase of the global population, leads to its depletion and increases the transport distances. The uncontrolled deposition of construction and demolition waste in landfills and city outskirts, causes pollution and takes up space. The use of recycled aggregates in concrete preparation would contribute to mitigate the problem. However, it arises the problem that the high water absorption of recycled aggregate decreases the bleeding rate of concrete, and when this gets lower than the evaporation rate, plastic shrinkage cracking occurs. This phenomenon can be particularly problematic in hot and windy curing environments. Cracking facilitates the flow of liquid and gas into concrete which attacks the reinforcement and degrades the concrete. These factors reduce the durability of concrete structures and consequently the lifetime of buildings. A ring test was used, cured in a wind tunnel, to evaluate the plastic shrinkage cracking sensitivity of recycled aggregate concrete, in order to implement preventive means to control this phenomenon. The role of several aggregate properties on the concrete segregation and cracking mechanisms were also discussed.

Keywords: recycled aggregate, plastic shrinkage cracking, wind tunnel, durability

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836 Stress Corrosion Cracking, Parameters Affecting It, Problems Caused by It and Suggested Methods for Treatment: State of the Art

Authors: Adnan Zaid

Abstract:

Stress corrosion cracking (SCC) may be defined as a degradation of the mechanical properties of a material under the combined action of a tensile stress and corrosive environment of the susceptible material. It is a harmful phenomenon which might cause catastrophic fracture without a sign of prior warning. In this paper, the stress corrosion cracking, SCC, process, the parameters affecting it, and the different damages caused by it are given and discussed. Utilization of shot peening as a mean of enhancing the resistance of materials to SCC is given and discussed. Finally, a method for improving materials resistance to SCC by grain refining its structure by some refining elements prior to usage is suggested.

Keywords: stress corrosion cracking, parameters, damages, treatment methods

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835 Early-Age Cracking of Low Carbon Concrete Incorporating Ferronickel Slag as Supplementary Cementitious Material

Authors: Mohammad Khan, Arnaud Castel

Abstract:

Concrete viscoelastic properties such as shrinkage, creep, and associated relaxation are important in assessing the risk of cracking during the first few days after placement. This paper investigates the early-age mechanical and viscoelastic properties, restrained shrinkage-induced cracking and time to cracking of concrete incorporating ferronickel slag (FNS) as supplementary cementitious material. Compressive strength, indirect tensile strength and elastic modulus were measured. Tensile creep and drying shrinkage was measured on dog-bone shaped specimens. Restrained shrinkage induced stresses and concrete cracking age were assessed by using the ring test. Results revealed that early-age strength development of FNS blended concrete is lower than that of the corresponding ordinary Portland cement (OPC) concrete. FNS blended concrete showed significantly higher tensile creep. The risk of early-age cracking for the restrained specimens depends on the development of concrete tensile stress considering both restrained shrinkage and tensile creep and the development of the tensile strength. FNS blended concrete showed only 20% reduction in time to cracking compared to reference OPC concrete, and this reduction is significantly lower compared to fly ash and ground granulated blast furnace slag blended concretes at similar replacement level.

Keywords: ferronickel slag, restraint shrinkage, tensile creep, time to cracking

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834 Research on the Feasibility of Evaluating Low-Temperature Cracking Performance of Asphalt Mixture Using Fracture Energy

Authors: Tao Yang, Yongli Zhao

Abstract:

Low-temperature cracking is one of the major challenges for asphalt pavement in the cold region. Fracture energy could determine from various test methods, which is a commonly used parameter to evaluate the low-temperature cracking resistance of asphalt mixture. However, the feasibility of evaluating the low-temperature cracking performance of asphalt mixture using fracture energy is not investigated comprehensively. This paper aims to verify whether fracture energy is an appropriate parameter to evaluate the low-temperature cracking performance. To achieve this goal, this paper compared the test results of thermal stress restrained specimen test (TSRST) and semi-circular bending test (SCB) of asphalt mixture with different types of aggregate, TSRST and indirect tensile test (IDT) of asphalt mixture with different additives, and single-edge notched beam test (SENB) and TSRST of asphalt mixture with different asphalt. Finally, the correlation between in-suit cracking performance and fracture energy was surveyed. The experimental results showed the evaluation result of critical cracking temperature and fracture energy are not always consistent; the in-suit cracking performance is also not correlated well with fracture energy. These results indicated that it is not feasible to evaluate low-temperature performance by fracture energy. Then, the composition of fracture energy of TSRST, SCB, disk-shaped compact tension test (DCT), three-point bending test (3PB) and IDT was analyzed. The result showed: the area of thermal stress versus temperature curve is the multiple of fracture energy and could be used to represent fracture energy of TSRST, as the multiple is nearly equal among different asphalt mixtures for a specific specimen; the fracture energy, determined from TSRST, SCB, DCT, 3PB, SENB and IDT, is mainly the surface energy that forms the fracture face; fracture energy is inappropriate to evaluate the low-temperature cracking performance of asphalt mixture, as the relaxation/viscous performance is not considered; if the fracture energy was used, it is recommended to combine this parameter with an index characterizing the relaxation or creep performance of asphalt mixture.

Keywords: asphalt pavement, cold region, critical cracking temperature, fracture energy, low-temperature cracking

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