Dynamic Modeling and Simulation of Heavy Paraffin Dehydrogenation Reactor for Selective Olefin Production in Linear Alkyl Benzene Production Plant

Modeling of a heterogeneous industrial fixed bed reactor for selective dehydrogenation of heavy paraffin with Pt-Sn- Al2O3 catalyst has been the subject of current study. By applying mass balance, momentum balance for appropriate element of reactor and using pressure drop, rate and deactivation equations, a detailed model of the reactor has been obtained. Mass balance equations have been written for five different components. In order to estimate reactor production by the passage of time, the reactor model which is a set of partial differential equations, ordinary differential equations and algebraic equations has been solved numerically. Paraffins, olefins, dienes, aromatics and hydrogen mole percent as a function of time and reactor radius have been found by numerical solution of the model. Results of model have been compared with industrial reactor data at different operation times. The comparison successfully confirms validity of proposed model.

Adsorption of H2 and CO on Iron-based Catalysts for Fischer-Tropsch Synthesis

The adsorption properties of CO and H2 on iron-based catalyst with addition of Zr and Ni were investigated using temperature programmed desorption process. It was found that on the carburized iron-based catalysts, molecular state and dissociative state CO existed together. The addition of Zr was preferential for the molecular state adsorption of CO on iron-based catalyst and the presence of Ni was beneficial to the dissociative adsorption of CO. On H2 reduced catalysts, hydrogen mainly adsorbs on the surface iron sites and surface oxide sites. On CO reduced catalysts, hydrogen probably existed as the most stable CH and OH species. The addition of Zr was not benefit to the dissociative adsorption of hydrogen on iron-based catalyst and the presence of Ni was preferential for the dissociative adsorption of hydrogen.

Removal of Hydrogen Sulfide in Terms of Scrubbing Techniques using Silver Nano-Particles

Silver nano-particles have been used for antibacterial purpose and it is also believed to have removal of odorous compounds, oxidation capacity as a metal catalyst. In this study, silver nano-particles in nano sizes (5-30 nm) were prepared on the surface of NaHCO3, the supporting material, using a sputtering method that provided high silver content and minimized conglomerating problems observed in the common AgNO3 photo-deposition method. The silver nano-particles were dispersed by dissolving Ag-NaHCO3 into water, and the dispersed silver nano-particles in the aqueous phase were applied to remove inorganic odor compounds, H2S, in a scrubbing reactor. Hydrogen sulfide in the gas phase was rapidly removed by the silver nano-particles, and the concentration of sulfate (SO4 2-) ion increased with time due to the oxidation reaction by silver as a catalyst. Consequently, the experimental results demonstrated that the silver nano-particles in the aqueous solution can be successfully applied to remove odorous compounds without adding additional energy sources and producing any harmful byproducts

Simultaneous Treatment and Catalytic Gasification of Olive Mill Wastewater under Supercritical Conditions

Recently, a growing interest has emerged on the development of new and efficient energy sources, due to the inevitable extinction of the nonrenewable energy reserves. One of these alternative sources which has a great potential and sustainability to meet up the energy demand is biomass energy. This significant energy source can be utilized with various energy conversion technologies, one of which is biomass gasification in supercritical water. Water, being the most important solvent in nature, has very important characteristics as a reaction solvent under supercritical circumstances. At temperatures above its critical point (374.8oC and 22.1 MPa), water becomes more acidic and its diffusivity increases. Working with water at high temperatures increases the thermal reaction rate, which in consequence leads to a better dissolving of the organic matters and a fast reaction with oxygen. Hence, supercritical water offers a control mechanism depending on solubility, excellent transport properties based on its high diffusion ability and new reaction possibilities for hydrolysis or oxidation. In this study the gasification of a real biomass, namely olive mill wastewater (OMW), in supercritical water is investigated with the use of Pt/Al2O3 and Ni/Al2O3 catalysts. OMW is a by-product obtained during olive oil production, which has a complex nature characterized by a high content of organic compounds and polyphenols. These properties impose OMW a significant pollution potential, but at the same time, the high content of organics makes OMW a desirable biomass candidate for energy production. All of the catalytic gasification experiments were made with five different reaction temperatures (400, 450, 500, 550 and 600°C), under a constant pressure of 25 MPa. For the experiments conducted with Ni/Al2O3 catalyst, the effect of five reaction times (30, 60, 90, 120 and 150 s) was investigated. However, procuring that similar gasification efficiencies could be obtained at shorter times, the experiments were made by using different reaction times (10, 15, 20, 25 and 30 s) for the case of Pt/Al2O3 catalyst. Through these experiments, the effects of temperature, time and catalyst type on the gasification yields and treatment efficiencies were investigated.

HDS: Alumina- Boria Supported Catalysts

Hydrodesulfurization (HDS) of dibenzothiophene (DBT) in a high pressure batch reactor was done at 320 °C on CoMoS/Al2O3-B2O3 (4, 10, and 16 wt. % of Boria) using nhexadecane as solvent, dimethyldisulfide (DMDS) in tetradecane as sulfur agent, and stirring at 1000 rpm. The effects of boria were investigated by using X-ray diffraction (XRD), Temperature programmed desorption (TPD) of ammonia, and Brunauer-Emmet- Teller (BET) experiments. The results showed that the catalyst prepared with low boria content (4 wt. %) had HDS activity (in pseudo first order kinetic constant basis) value ~1.45 times higher to that of CoMoS/Al2O3 catalyst.

Kinetics of Palm Oil Cracking in Batch Reactor

The kinetics of palm oil catalytic cracking over aluminum containing mesoporous silica Al-MCM-41 (5% Al) was investigated in a batch autoclave reactor at the temperatures range of 573 – 673 K. The catalyst was prepared by using sol-gel technique and has been characterized by nitrogen adsorption and x-ray diffraction methods. Surface area of 1276 m2/g with average pore diameter of 2.54 nm and pore volume of 0.811 cm3/g was obtained. The experimental catalytic cracking runs were conducted using 50 g of oil and 1 g of catalyst. The reaction pressure was recorded at different time intervals and the data were analyzed using Levenberg- Marquardt (LM) algorithm using polymath software. The results show that the reaction order was found to be -1.5 and activation energy of 3200 J/gmol.

Aqueous Ranitidine Elimination in Photolytic Processes

The elimination of ranitidine (a pharmaceutical compound) has been carried out in the presence of UV-C radiation. After some preliminary experiments, it has been experienced the no influence of the gas nature (air or oxygen) bubbled in photolytic experiments. From simple photolysis experiments the quantum yield of this compound has been determined. Two photolytic approximation has been used, the linear source emission in parallel planes and the point source emission in spherical planes. The quantum yield obtained was in the proximity of 0.05 mol Einstein-1 regardless of the method used. Addition of free radical promoters (hydrogen peroxide) increases the ranitidine removal rate while the use of photocatalysts (TiO2) negatively affects the process.

Calcination Temperature of Nano MgO Effect on Base Transesterification of Palm Oil

Nano MgO has been synthesized by hydration and dehydration method by modifies the commercial MgO. The prepared MgO had been investigated as a heterogeneous base catalyst for transesterification process for biodiesel production using palm oil. TGA, FT-IR and XRD results obtained from this study lie each other and proved in the formation of nano MgO from decomposition of Mg(OH)2. This study proved that the prepared nano MgO was a better base transesterification catalyst compared to commercial MgO. The nano MgO calcined at 600ºC had gives the highest conversion of 51.3% of palm oil to biodiesel.

Influence of Taguchi Selected Parameters on Properties of CuO-ZrO2 Nanoparticles Produced via Sol-gel Method

The present paper discusses the selection of process parameters for obtaining optimal nanocrystallites size in the CuOZrO2 catalyst. There are some parameters changing the inorganic structure which have an influence on the role of hydrolysis and condensation reaction. A statistical design test method is implemented in order to optimize the experimental conditions of CuO-ZrO2 nanoparticles preparation. This method is applied for the experiments and L16 orthogonal array standard. The crystallites size is considered as an index. This index will be used for the analysis in the condition where the parameters vary. The effect of pH, H2O/ precursor molar ratio (R), time and temperature of calcination, chelating agent and alcohol volume are particularity investigated among all other parameters. In accordance with the results of Taguchi, it is found that temperature has the greatest impact on the particle size. The pH and H2O/ precursor molar ratio have low influences as compared with temperature. The alcohol volume as well as the time has almost no effect as compared with all other parameters. Temperature also has an influence on the morphology and amorphous structure of zirconia. The optimal conditions are determined by using Taguchi method. The nanocatalyst is studied by DTA-TG, XRD, EDS, SEM and TEM. The results of this research indicate that it is possible to vary the structure, morphology and properties of the sol-gel by controlling the above-mentioned parameters.

The Relationship between the Ramadan Bazaar and the Attraction and Dissemination of Information: A Case of International Tourists

Many people regard food events as part of gastronomic tourism and important in enhancing visitors’ experiences. Realizing the importance and contribution of food events to a country’s economy, the Malaysia government is undertaking greater efforts to promote such tourism activities to international tourists. Among other food events, the Ramadan bazaar is a unique food culture event, which receives significant attention from the Malaysia Ministry of Tourism. This study reports the empirical investigation into the international tourists’ perceptions, attraction towards the Ramadan bazaar and willingness in disseminating the information. Using the Ramadan bazaar at Kampung Baru, Kuala Lumpur as the data collection setting, results revealed that the Ramadan bazaar attributes (food and beverages, events and culture) significantly influenced the international tourist attraction to such a bazaar. Their high level of experience and satisfaction positively influenced their willingness to disseminate information. The positive response among the international tourists indicates that the Ramadan bazaar as gastronomic tourism can be used in addition to other tourism products as a catalyst to generate and boost the local economy. The related authorities that are closely associated with the tourism industry therefore should not ignore this indicator but continue to take proactive action in promoting the gastronomic event as one of the major tourist attractions.

Optimization of Reaction Rate Parameters in Modeling of Heavy Paraffins Dehydrogenation

In the present study, a procedure was developed to determine the optimum reaction rate constants in generalized Arrhenius form and optimized through the Nelder-Mead method. For this purpose, a comprehensive mathematical model of a fixed bed reactor for dehydrogenation of heavy paraffins over Pt–Sn/Al2O3 catalyst was developed. Utilizing appropriate kinetic rate expressions for the main dehydrogenation reaction as well as side reactions and catalyst deactivation, a detailed model for the radial flow reactor was obtained. The reactor model composed of a set of partial differential equations (PDE), ordinary differential equations (ODE) as well as algebraic equations all of which were solved numerically to determine variations in components- concentrations in term of mole percents as a function of time and reactor radius. It was demonstrated that most significant variations observed at the entrance of the bed and the initial olefin production obtained was rather high. The aforementioned method utilized a direct-search optimization algorithm along with the numerical solution of the governing differential equations. The usefulness and validity of the method was demonstrated by comparing the predicted values of the kinetic constants using the proposed method with a series of experimental values reported in the literature for different systems.

Wine Grape Residues Gasification in Supercritical Water

In this study, production possibilities of hydrogen and/or methane via SCWG from black grape residues have been investigated. For this aim, grape residues which remain as a byproduct of the wine making process have been used. Since utilization from grape residues is limited due to the high moisture content, supercritical water gasification is the most convenient method. The effect of the gasification temperature and type of catalyst on supercritical water gasification have been investigated. Gasification experiments were performed in a batch autoclave at four different temperatures 300, 400, 500 and 600°C. K2CO3 and Trona (NaHCO3.Na2CO3·2H2O) were used as catalyst. Real biomass types of black grape residues have been successfully gasified and the product gas (hydrogen, methane, carbon dioxide, carbon monoxide and a small amount of ethane and ethylene) were identified by using gas chromatography. A TOC analyzer was used to determine total organic carbon (TOC) content of aqueous phase. The amounts of carboxylic acids, aldehydes, ketones, furfurals and phenols present in the aqueous solutions were analyzed by high performance liquid chromatography. When the temperature increased from 300°C to 600°C, mol% of H2 in gas products increased. The presence of catalysts improves the hydrogen yield. Trona showed gasification activity to be similar to that of K2CO3. It may be concluded that the use of Trona instead of commercially produced catalysts, can be preferably used in the gasification of biomass in supercritical water.

Synthesis and Applications of Heteronanostructured ZnO Nanowires Array

ZnO heteronanostructured nanowires arrays have been fabricated by low temperature solution method. Various heterostructures were synthesized including CdS/ZnO, CdSe/CdS/ZnO nanowires and Co3O4/ZnO, ZnO/SiC nanowires. These multifunctional heterostructure nanowires showed important applications in photocatalysts, sensors, wettability control and solar energy conversion.

Oxidation of Carbon Monoxide in a Monolithic Reactor

Solution for the complete removal of carbon monoxide from the exhaust gases still poses a challenge to the researchers and this problem is still under development. Modeling for reduction of carbon monoxide is carried out using heterogeneous reaction using low cost non-noble metal based catalysts for the purpose of controlling emissions released to the atmosphere. A simple one-dimensional model was developed for the monolith using hopcalite catalyst. The converter is assumed to be an adiabatic monolith operating under warm-up conditions. The effect of inlet gas temperatures and catalyst loading on carbon monoxide reduction during cold start period in the converter is analysed.

Cloning and Expression of D-Threonine Aldolase from Ensifer arboris NBRC100383

D-erythro-cyclohexylserine (D chiral unnatural β-hydroxy amino acid expected for the synthesis of drug for AIDS treatment. To develop a continuous bioconversion system with whole cell biocatalyst of D-threonine aldolase (D genes for the D-erythro-CHS production, D-threonine aldolase gene was amplified from Ensifer arboris 100383 by direct PCR amplication using two degenerated oligonucleotide primers designed based on genomic sequence of Shinorhizobium meliloti Sequence analysis of the cloned DNA fragment revealed one open-reading frame of 1059 bp and 386 amino acids. This putative D-TA gene was cloned into NdeI and EcoRI (pEnsi His-tag sequence or BamHI (pEnsi-DTA[2]) sequence of the pET21(a) vector. The expression level of the cloned gene was extremely overexpressed by E. coli BL21(DE3) transformed with pEnsi-DTA[1] compared to E. coli BL21(DE3) transformed with pEnsi-DTA[2]. When the cells expressing the wild used for D-TA enzyme activity, 12 mM glycine was successfully detected in HPLC analysis. Moreover, the whole cells harbouring the recombinant D-TA was able to synthesize D-erythro of 0.6 mg/ml in a batch reaction.

Biodiesel Production from Waste Chicken Fatbased Sources

Chicken fat was employed as a feedstock for producing of biodiesel by trasesterification reaction with methanol and alkali catalyst (KOH). In this study chicken fat biodiesel with 1.4% free fatty acid, methanol and various amount of potassium hydroxide for 2 hour were studied. The progression of reaction and conversion of triglycerides to methyl ester were checked by IR spectrum method.

A Hybrid Approach to Fault Detection and Diagnosis in a Diesel Fuel Hydrotreatment Process

It is estimated that the total cost of abnormal conditions to US process industries is around $20 billion dollars in annual losses. The hydrotreatment (HDT) of diesel fuel in petroleum refineries is a conversion process that leads to high profitable economical returns. However, this is a difficult process to control because it is operated continuously, with high hydrogen pressures and it is also subject to disturbances in feed properties and catalyst performance. So, the automatic detection of fault and diagnosis plays an important role in this context. In this work, a hybrid approach based on neural networks together with a pos-processing classification algorithm is used to detect faults in a simulated HDT unit. Nine classes (8 faults and the normal operation) were correctly classified using the proposed approach in a maximum time of 5 minutes, based on on-line data process measurements.

Preparation of Porous Carbon Particles using a Spray-Drying Method with Colloidal Template

spherical porous carbon particles with controllable porosity with a mean size of 2.5m have been prepared using a spray drying method with organic particle colloidal template. As a precursor, a mixing solution of carbon nanopowder and polystyrene (PS) particles as a template was used. The result showed that the particles with a good porous structure could be obtained. The pore size and shape (spherical) were identical to the initial template, giving a potential way for further developments. The control of particle porosity was also possible and reported in this paper, in which this control could be achieved by means of PS concentration.

Palladium-Catalyzed Hydrodechlorination for Water Remediation: Catalyst Deactivation and Regeneration

Palladium-catalyzed hydrodechlorination is a promising alternative for the treatment of environmentally relevant water bodies, such as groundwater, contaminated with chlorinated organic compounds (COCs). In the aqueous phase hydrodechlorination of COCs, Pd-based catalysts were found to have a very high catalytic activity. However, the full utilization of the catalyst-s potential is impeded by the sensitivity of the catalyst to poisoning and deactivation induced by reduced sulfur compounds (e.g. sulfides). Several regenerants have been tested before to recover the performance of sulfide-fouled Pd catalyst. But these only delivered partial success with respect to re-establishment of the catalyst activity. In this study, the deactivation behaviour of Pd/Al2O3 in the presence of sulfide was investigated. Subsequent to total deactivation the catalyst was regenerated in the aqueous phase using potassium permanganate. Under neutral pH condition, oxidative regeneration with permanganate delivered a slow recovery of catalyst activity. However, changing the pH of the bulk solution to acidic resulted in the complete recovery of catalyst activity within a regeneration time of about half an hour. These findings suggest the superiority of permanganate as regenerant in re-activating Pd/Al2O3 by oxidizing Pd-bound sulfide.

Modeling Converters during the Warm-up Period for Hydrocarbon Oxidation

Catalytic converters are used for minimizing the release of pollutants to the atmosphere. It is during the warm-up period that hydrocarbons are seen to be released in appreciable quantities from these converters. In this paper the conversion of a fast oxidizing hydrocarbon propylene is analysed using two numerical methods. The quasi steady state method assumes the accumulation terms to be negligible in the gas phase mass and energy balance equations, however this term is present in the solid phase energy balance. The unsteady state model accounts for the accumulation term to be present in the gas phase mass and energy balance and in the solid phase energy balance. The results derived from the two models for gas concentration, gas temperature and solid temperature are compared.