H2 Permeation Properties of a Catalytic Membrane Reactor in Methane Steam Reforming Reaction

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.

A Comparative Study on Biochar from Slow Pyrolysis of Corn Cob and Cassava Wastes

Biomass such as corn and cassava wastes if left to decay will release significant quantities of greenhouse gases (GHG) including carbon dioxide and methane. The biomass wastes can be converted into biochar via thermochemical process such as slow pyrolysis. This approach can reduce the biomass wastes as well as preserve its carbon content. Biochar has the potential to be used as a carbon sequester and soil amendment. The aim of this study is to investigate the characteristics of the corn cob, cassava stem, and cassava rhizome in order to identify their potential as pyrolysis feedstocks for biochar production. This was achieved by using the proximate and elemental analyses as well as calorific value and lignocellulosic determination. The second objective is to investigate the effect of pyrolysis temperature on the biochar produced. A fixed bed slow pyrolysis reactor was used to pyrolyze the corn cob, cassava stem, and cassava rhizome. The pyrolysis temperatures were varied between 400 °C and 600 °C, while the heating rate and the holding time were fixed at 5 °C/min and 1 hour, respectively. Corn cob, cassava stem, and cassava rhizome were found to be suitable feedstocks for pyrolysis process because they contained a high percentage of volatile matter more than 80 mf wt.%. All the three feedstocks contained low nitrogen and sulphur content less than 1 mf wt.%. Therefore, during the pyrolysis process, the feedstocks give off very low rate of GHG such as nitrogen oxides and sulphur oxides. Independent of the types of biomass, the percentage of biochar yield is inversely proportional to the pyrolysis temperature. The highest biochar yield for each studied temperature is from slow pyrolysis of cassava rhizome as the feedstock contained the highest percentage of ash compared to the other two feedstocks. The percentage of fixed carbon in all the biochars increased as the pyrolysis temperature increased. The increment of pyrolysis temperature from 400 °C to 600 °C increased the fixed carbon of corn cob biochar, cassava stem biochar and cassava rhizome biochar by 26.35%, 10.98%, and 6.20% respectively. Irrespective of the pyrolysis temperature, all the biochars produced were found to contain more than 60 mf wt.% fixed carbon content, much higher than its feedstocks.

Investigation of Wood Chips as Internal Carbon Source Supporting Denitrification Process in Domestic Wastewater Treatment

Nitrogen removal from wastewater is accomplished by nitrification and denitrification processes. Successful denitrification requires carbon, therefore, if placed after biochemical oxygen demand (BOD) and nitrification process, a carbon source has to be re-introduced into the water. To avoid adding a carbon source, denitrification is usually placed before BOD and nitrification processes. This process however involves recycling the nitrified effluent. In this study wood chips were used as internal carbon source which enabled placement of denitrification after BOD and nitrification process without effluent recycling. To investigate the efficiency of a wood packed aerobic-anaerobic baffled reactor on carbon and nutrients removal from domestic wastewater, a three compartment baffled reactor was presented. Each of the three compartments was packed with 329 g wood chips 1x1cm acting as an internal carbon source for denitrification. The proposed mode of operation was aerobic-anoxic-anaerobic (OAA) with no effluent recycling. The operating temperature, hydraulic retention time (HRT), dissolved oxygen (DO) and pH were 24 ± 2 ℃, 24 h, less than 4 mg/L and 7 ± 1 respectively. The removal efficiencies of chemical oxygen demand (COD), ammonia nitrogen (NH4+-N) and total nitrogen (TN) attained was 99, 87 and 83% respectively. TN removal rate was limited by nitrification as 97% of ammonia converted into nitrate and nitrite was denitrified. These results show that application of wood chips in wastewater treatment processes is an efficient internal carbon source. 

Performance Comparison of Different Regression Methods for a Polymerization Process with Adaptive Sampling

Developing complete mechanistic models for polymerization reactors is not easy, because complex reactions occur simultaneously; there is a large number of kinetic parameters involved and sometimes the chemical and physical phenomena for mixtures involving polymers are poorly understood. To overcome these difficulties, empirical models based on sampled data can be used instead, namely regression methods typical of machine learning field. They have the ability to learn the trends of a process without any knowledge about its particular physical and chemical laws. Therefore, they are useful for modeling complex processes, such as the free radical polymerization of methyl methacrylate achieved in a batch bulk process. The goal is to generate accurate predictions of monomer conversion, numerical average molecular weight and gravimetrical average molecular weight. This process is associated with non-linear gel and glass effects. For this purpose, an adaptive sampling technique is presented, which can select more samples around the regions where the values have a higher variation. Several machine learning methods are used for the modeling and their performance is compared: support vector machines, k-nearest neighbor, k-nearest neighbor and random forest, as well as an original algorithm, large margin nearest neighbor regression. The suggested method provides very good results compared to the other well-known regression algorithms.

Modeling of Oxygen Supply Profiles in Stirred-Tank Aggregated Stem Cells Cultivation Process

This paper investigates a possible practical solution for reasonable oxygen supply during the pluripotent stem cells expansion processes, where the stem cells propagate as aggregates in stirred-suspension bioreactors. Low glucose and low oxygen concentrations are preferred for efficient proliferation of pluripotent stem cells. However, strong oxygen limitation, especially inside of cell aggregates, can lead to cell starvation and death. In this research, the oxygen concentration profile inside of stem cell aggregates in a stem cell expansion process was predicted using a modified oxygen diffusion model. This profile can be realized during the stem cells cultivation process by manipulating the oxygen concentration in inlet gas or inlet gas flow. The proposed approach is relatively simple and may be attractive for installation in a real pluripotent stem cell expansion processes.

Energy Efficiency Index Applied to Reactive Systems

This paper focuses on the development of an energy efficiency index that will be applied to reactive systems, which is based in the First and Second Law of Thermodynamics, by giving particular consideration to the concept of maximum entropy. Among the requirements of such energy efficiency index, the practical feasibility must be essential. To illustrate the performance of the proposed index, such an index was used as decisive factor of evaluation for the optimization process of an industrial reactor. The results allow the conclusion to be drawn that the energy efficiency index applied to the reactive system is consistent because it extracts the information expected of an efficient indicator, and that it is useful as an analytical tool besides being feasible from a practical standpoint. Furthermore, it has proved to be much simpler to use than tools based on traditional methodologies.

Optimization of Quercus cerris Bark Liquefaction

The liquefaction process of cork based tree barks has led to an increase of interest due to its potential innovation in the lumber and wood industries. In this particular study the bark of Quercus cerris (Turkish oak) is used due to its appreciable amount of cork tissue, although of inferior quality when compared to the cork provided by other Quercus trees. This study aims to optimize alkaline catalysis liquefaction conditions, regarding several parameters. To better comprehend the possible chemical characteristics of the bark of Quercus cerris, a complete chemical analysis was performed. The liquefaction process was performed in a double-jacket reactor heated with oil, using glycerol and a mixture of glycerol/ethylene glycol as solvents, potassium hydroxide as a catalyst, and varying the temperature, liquefaction time and granulometry. Due to low liquefaction efficiency resulting from the first experimental procedures a study was made regarding different washing techniques after the filtration process using methanol and methanol/water. The chemical analysis stated that the bark of Quercus cerris is mostly composed by suberin (ca. 30%) and lignin (ca. 24%) as well as insolvent hemicelluloses in hot water (ca. 23%). On the liquefaction stage, the results that led to higher yields were: using a mixture of methanol/ethylene glycol as reagents and a time and temperature of 120 minutes and 200 ºC, respectively. It is concluded that using a granulometry of

Investigation on Fischer-Tropsch Synthesis over Cobalt-Gadolinium Catalyst

Cobalt-gadolinium catalyst for Fischer-Tropsch synthesis was prepared by impregnation method with commercial silica gel, and its texture properties were characterized by BET, XRD, and TPR. The catalytic performance of the catalyst was tested in a fixed bed reactor. The results showed that the addition of gadolinium to the cobalt catalyst might decrease the size of cobalt particles, and increased the dispersion of catalytic active cobalt phases. The carbon number distributions for the catalysts was calculated by ASF equation.

The Use of Nuclear Generation to Provide Power System Stability

The decreasing use of fossil fuel power stations has a negative effect on the stability of the electricity systems in many countries. Nuclear power stations have traditionally provided minimal ancillary services to support the system but this must change in the future as they replace fossil fuel generators. This paper explains the development of the four most popular reactor types still in regular operation across the world which have formed the basis for most reactor development since their commercialisation in the 1950s. The use of nuclear power in four countries with varying levels of capacity provided by nuclear generators is investigated, using the primary frequency response provided by generators as a measure for the electricity networks stability, to assess the need for nuclear generators to provide additional support as their share of the generation capacity increases.

Optimization of Dissolution of Chevreul’s Salt in Ammonium Chloride Solutions

In this study, Chevreul’s salt was dissolved in ammonium chloride solutions. All experiments were performed in a batch reactor. The obtained results were optimized. Parameters used in the experiments were the reaction temperature, the ammonium chloride concentration, the reaction time and the solid-to-liquid ratio. The optimum conditions were determined by 24 factorial experimental design method. The best values of four parameters were determined as based on the experiment results. After the evaluation of experiment results, all parameters were found as effective in experiment conditions selected. The optimum conditions on the maximum Chevreul’s salt dissolution were the ammonium chloride concentration 4.5 M, the reaction time 13.2 min., the reaction temperature 25 oC, and the solid-to-liquid ratio 9/80 g.mL-1. The best dissolution yield in these conditions was 96.20%.

Alumina Supported Cu-Mn-La Catalysts for CO and VOCs Oxidation

Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al2O3 supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH3OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La2O3, MnO2 and Cu1.5Mn1.5O4. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.

Thermodynamic Attainable Region for Direct Synthesis of Dimethyl Ether from Synthesis Gas

This paper demonstrates the use of a method of synthesizing process flowsheets using a graphical tool called the GH-plot and in particular, to look at how it can be used to compare the reactions of a combined simultaneous process with regard to their thermodynamics. The technique uses fundamental thermodynamic principles to allow the mass, energy and work balances locate the attainable region for chemical processes in a reactor. This provides guidance on what design decisions would be best suited to developing new processes that are more effective and make lower demands on raw material and energy usage.

Effects of Turbulence Penetration on Valve Leakage in Nuclear Reactor Coolant System

Thermal stratification has drawn much attention because of the malfunctions at various nuclear plants in U.S.A that raised significant safety concerns. The concerns due to this phenomenon relate to thermal stresses in branch pipes connected to the reactor coolant system piping. This stress limits the lifetime of the piping system, and even leading to penetrating cracks. To assess origin of valve damage in the pipeline, it is essential to determine the effect of turbulence penetration on valve leakage; since stratified flow is generally generated by turbulent penetration or valve leakage. As a result, we concluded with the help of coupled fluent-structural analysis that the pipe with less turbulence has less chance of failure there by requiring less maintenance.

Heat Transfer Analysis of a Multiphase Oxygen Reactor Heated by a Helical Tube in the Cu-Cl Cycle of a Hydrogen Production

In the thermochemical water splitting process by Cu-Cl cycle, oxygen gas is produced by an endothermic thermolysis process at a temperature of 530oC. Oxygen production reactor is a three-phase reactor involving cuprous chloride molten salt, copper oxychloride solid reactant and oxygen gas. To perform optimal performance, the oxygen reactor requires accurate control of heat transfer to the molten salt and decomposing solid particles within the thermolysis reactor. In this paper, the scale up analysis of the oxygen reactor that is heated by an internal helical tube is performed from the perspective of heat transfer. A heat balance of the oxygen reactor is investigated to analyze the size of the reactor that provides the required heat input for different rates of hydrogen production. It is found that the helical tube wall and the service side constitute the largest thermal resistances of the oxygen reactor system. In the analysis of this paper, the Cu-Cl cycle is assumed to be heated by two types of nuclear reactor, which are HTGR and CANDU SCWR. It is concluded that using CANDU SCWR requires more heat transfer rate by 3-4 times than that when using HTGR. The effect of the reactor aspect ratio is also studied and it is found that increasing the aspect ratio decreases the number of reactors and the rate of decrease in the number of reactors decreases by increasing the aspect ratio. Comparisons between the results of this study and pervious results of material balances in the oxygen reactor show that the size of the oxygen reactor is dominated by the heat balance rather than the material balance.

Online Measurement of Fuel Stack Elongation

The performances of nuclear fuels and materials are qualified at an irradiation system in research reactors operating under the commercial nuclear power plant conditions. Fuel centerline temperature, coolant temperature, neutron flux, deformations of fuel stack and swelling are important parameters needed to analyze the nuclear fuel performances. The dimensional stability of nuclear fuels is a key parameter measuring the fuel densification and swelling. In this study, the fuel stack elongation is measured using a LVDT. A mockup LVDT instrumented fuel rod is developed. The performances of mockup LVDT instrumented fuel rod is evaluated by experiments.

Prediction of the Thermal Parameters of a High-Temperature Metallurgical Reactor Using Inverse Heat Transfer

This study presents an inverse analysis for predicting the thermal conductivities and the heat flux of a high-temperature metallurgical reactor simultaneously. Once these thermal parameters are predicted, the time-varying thickness of the protective phase-change bank that covers the inside surface of the brick walls of a metallurgical reactor can be calculated. The enthalpy method is used to solve the melting/solidification process of the protective bank. The inverse model rests on the Levenberg-Marquardt Method (LMM) combined with the Broyden method (BM). A statistical analysis for the thermal parameter estimation is carried out. The effect of the position of the temperature sensors, total number of measurements and measurement noise on the accuracy of inverse predictions is investigated. Recommendations are made concerning the location of temperature sensors.

Similitude for Thermal Scale-up of a Multiphase Thermolysis Reactor in the Cu-Cl Cycle of a Hydrogen Production

The thermochemical copper-chlorine (Cu-Cl) cycle is considered as a sustainable and efficient technology for a hydrogen production, when linked with clean-energy systems such as nuclear reactors or solar thermal plants. In the Cu-Cl cycle, water is decomposed thermally into hydrogen and oxygen through a series of intermediate reactions. This paper investigates the thermal scale up analysis of the three phase oxygen production reactor in the Cu-Cl cycle, where the reaction is endothermic and the temperature is about 530 oC. The paper focuses on examining the size and number of oxygen reactors required to provide enough heat input for different rates of hydrogen production. The type of the multiphase reactor used in this paper is the continuous stirred tank reactor (CSTR) that is heated by a half pipe jacket. The thermal resistance of each section in the jacketed reactor system is studied to examine its effect on the heat balance of the reactor. It is found that the dominant contribution to the system thermal resistance is from the reactor wall. In the analysis, the Cu-Cl cycle is assumed to be driven by a nuclear reactor where two types of nuclear reactors are examined as the heat source to the oxygen reactor. These types are the CANDU Super Critical Water Reactor (CANDU-SCWR) and High Temperature Gas Reactor (HTGR). It is concluded that a better heat transfer rate has to be provided for CANDU-SCWR by 3-4 times than HTGR. The effect of the reactor aspect ratio is also examined in this paper and is found that increasing the aspect ratio decreases the number of reactors and the rate of decrease in the number of reactors decreases by increasing the aspect ratio. Finally, a comparison between the results of heat balance and existing results of mass balance is performed and is found that the size of the oxygen reactor is dominated by the heat balance rather than the material balance.

Statistical Analysis and Optimization of a Process for CO2 Capture

CO2 capture and storage technologies play a significant role in contributing to the control of climate change through the reduction of carbon dioxide emissions into the atmosphere. The present study evaluates and optimizes CO2 capture through a process, where carbon dioxide is passed into pH adjusted high salinity water and reacted with sodium chloride to form a precipitate of sodium bicarbonate. This process is based on a modified Solvay process with higher CO2 capture efficiency, higher sodium removal, and higher pH level without the use of ammonia. The process was tested in a bubble column semi-batch reactor and was optimized using response surface methodology (RSM). CO2 capture efficiency and sodium removal were optimized in terms of major operating parameters based on four levels and variables in Central Composite Design (CCD). The operating parameters were gas flow rate (0.5–1.5 L/min), reactor temperature (10 to 50 oC), buffer concentration (0.2-2.6%) and water salinity (25-197 g NaCl/L). The experimental data were fitted to a second-order polynomial using multiple regression and analyzed using analysis of variance (ANOVA). The optimum values of the selected variables were obtained using response optimizer. The optimum conditions were tested experimentally using desalination reject brine with salinity ranging from 65,000 to 75,000 mg/L. The CO2 capture efficiency in 180 min was 99% and the maximum sodium removal was 35%. The experimental and predicted values were within 95% confidence interval, which demonstrates that the developed model can successfully predict the capture efficiency and sodium removal using the modified Solvay method.

Renewable Energy Potential of Diluted Poultry Manure during Ambient Anaerobic Stabilisation

In this study, the anaerobic treatability of chicken manure diluted with tap water (with an influent feed ratio of 1 kg of fresh chicken manure to 6 liter of tap water) was investigated in a lab-scale anaerobic sludge bed (ASB) reactor inoculated with the granular sludge already adapted to chicken manure. The raw waste digested in this study was the manure from laying-hens having average total solids (TS) of about 30% with ca. 60% volatile content. The ASB reactor was fed semi-continuously at ambient operating temperature range (17-23◦C) at a HRT of 13 and 26 days for about 6 months, respectively. The respective average total and soluble chemical oxygen demand (COD) removals were ca. 90% and 75%, whereas average biomethane production rate was calculated ca. 180 lt per kg of CODremoved from the ASB reactor at an average HRT of 13 days. Moreover, total suspended solids (TSS) and volatile suspended solids (VSS) in the influent were reduced more than 97%. Hence, high removals of the organic compounds with respective biogas production made anaerobic stabilization of the diluted chicken manure by ASB reactor at ambient operating temperatures viable. By this way, external heating up to 35◦C (i.e. anaerobic processes have been traditionally operated at mesophilic conditions) could be avoided in the scope of this study.

Effect of Pulp Density on Biodesulfurization of Mongolian Lignite Coal

Biological processes based on oxidation of sulfur compounds by chemolithotrophic microorganisms are emerging as an efficient and eco-friendly technique for removal of sulfur from the coal. In the present article, study was carried out to investigate the potential of biodesulfurization process in removing the sulfur from lignite coal sample collected from a Mongolian coal mine. The batch biodesulfurization experiments were conducted in 2.5 L borosilicate baffle type reactors at 35 ºC using Acidithiobacillus ferrooxidans. The effect of pulp density on efficiency of biodesulfurization was investigated at different solids concentration (1-10%) of coal. The results of the present study suggested that the rate of desulfurization was retarded at higher coal pulp density. The optimum pulp density found 5% at which about 48% of the total sulfur was removed from the coal.