Search results for: gasification kinetics

Authors: Yong Ren, Yaping Zhang

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A numerical model has been developed to investigate the thermally triggered release kinetics for drug delivery using phase change material as shell of microcapsules. Biocompatible material n-Eicosane is used as demonstration. PCM shell of microcapsule will remain in solid form after the drug is taken, so the drug will be encapsulated by the shell, and will not be released until the target body part of lesion is exposed to external heat source, which will thermally trigger the release kinetics, leading to solid-to-liquid phase change. The findings can lead to better understanding on the key effects influencing the phase change process for drug delivery applications. The facile approach to release drug from core/shell structure of microcapsule can be well integrated with organic solvent free fabrication of microcapsules, using double emulsion as template in microfluidic aqueous two phase system.

Keywords: phase change material, drug release kinetics, double emulsion, microfluidics

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Authors: Yousaf Ayub

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A co-gasification process, which involves the utilization of both biomass and plastic waste, has been developed to enable the production of blue and green hydrogen. To support this endeavor, an Aspen Plus simulation model has been meticulously created, and sustainability analysis is being conducted, focusing on economic viability, energy efficiency, advanced exergy considerations, and exergoeconomics evaluations. In terms of economic analysis, the process has demonstrated strong economic sustainability, as evidenced by an internal rate of return (IRR) of 8% at a process efficiency level of 70%. At present, the process has the potential to generate approximately 1100 kWh of electric power, with any excess electricity, beyond meeting the process requirements, capable of being harnessed for green hydrogen production via an alkaline electrolysis cell (AEC). This surplus electricity translates to a potential daily hydrogen production of around 200 kg. The exergy analysis of the model highlights that the gasifier component exhibits the lowest exergy efficiency, resulting in the highest energy losses, amounting to approximately 40%. Additionally, advanced exergy analysis findings pinpoint the gasifier as the primary source of exergy destruction, totaling around 9000 kW, with associated exergoeconomics costs amounting to 6500 $/h. Consequently, improving the gasifier's performance is a critical focal point for enhancing the overall sustainability of the process, encompassing energy, exergy, and economic considerations.

Keywords: blue hydrogen, green hydrogen, co-gasification, waste valorization, exergy analysis

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Authors: A. Ribeiro, N. Pacheco, M. Soares, N. Valério, L. Nascimento, A. Silva, C. Vilarinho, J. Carvalho

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Hydrogen will play a key role in changing the current global energy paradigm, associated with the high use of fossil fuels and the release of greenhouse gases. This work intended to identify and quantify the potential of Solid Recovered Fuels (SFR) existing in Portugal and project the cost of hydrogen, produced through its steam gasification in different scenarios, associated with the size or capacity of the plant and the existence of carbon capture and storage (CCS) systems. Therefore, it was performed a techno-economic analysis simulation using an ASPEN base model, the H2A Hydrogen Production Model Version 3.2018. Regarding the production of SRF, it was possible to verify the annual production of more than 200 thousand tons of SRF in Portugal in 2019. The results of the techno-economic analysis simulations showed that in the scenarios containing a high (200,000 tons/year) and medium (40,000 tons/year) amount of SFR, the cost of hydrogen production was competitive concerning the current prices of hydrogen. The results indicate that scenarios 1 and 2, which use 200,000 tons of SRF per year, have lower hydrogen production values, 1.22 USD/kg H2 and 1.63 USD/kg H2, respectively. The cost of producing hydrogen without carbon capture and storage (CCS) systems in an average amount of SFR (40,000 tons/year) was 1.70 USD/kg H2. In turn, scenarios 5 (without CCS) and 6 (with CCS), which use only 683 tons of SFR from urban sources, have the highest costs, 6.54 USD/kg H2 and 908.97 USD/kg H2, respectively. Therefore, it was possible to conclude that there is a huge potential for the use of SRF for the production of hydrogen through steam gasification in Portugal.

Keywords: gasification, hydrogen, solid recovered fuels, techno-economic analysis, waste-to-energy

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Authors: Grâce Chidikofan, François Pinta, A. Benoist, G. Volle, J. Valette

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Statement of the Problem: biomass gasification systems may be relevant for decentralized power generation from recoverable agricultural and wood residues available in rural areas. In recent years, many systems have been implemented in all over the world as especially in Cambodgia, India. Although they have many positive effects, these systems can also affect the environment and human health. Indeed, during the process of biomass gasification, black wastewater containing tars are produced and generally discharged in the local environment either into the rivers or on soil. However, in most environmental assessment studies of biomass gasification systems, the impact of these releases are underestimated, due to the difficulty of identification of their chemical substances. This work deal with the analysis of the environmental impacts of tars from wood gasification in terms of human toxicity cancer effect, human toxicity non-cancer effect, and freshwater ecotoxicity. Methodology: A Life Cycle Assessment (LCA) approach was adopted. The inventory of tars chemicals substances was based on experimental data from a downdraft gasification system. The composition of six samples from two batches of raw materials: one batch made of tree wood species (oak+ plane tree +pine) at 25 % moisture content and the second batch made of oak at 11% moisture content. The tests were carried out for different gasifier load rates, respectively in the range 50-75% and 50-100%. To choose the environmental impacts assessment method, we compared the methods available in SIMAPRO tool (8.2.0) which are taking into account most of the chemical substances. The environmental impacts for 1kg of tars discharged were characterized by ILCD 2011+ method (V.1.08). Findings Experimental results revealed 38 important chemical substances in varying proportion from one test to another. Only 30 are characterized by ILCD 2011+ method, which is one of the best performing methods. The results show that wood species or moisture content have no significant impact on human toxicity noncancer effect (HTNCE) and freshwater ecotoxicity (FWE) for water release. For human toxicity cancer effect (HTCE), a small gap is observed between impact factors of the two batches, either 3.08E-7 CTUh/kg against 6.58E-7 CTUh/kg. On the other hand, it was found that the risk of negative effects is higher in case of tar release into water than on soil for all impact categories. Indeed, considering the set of samples, the average impact factor obtained for HTNCE varies respectively from 1.64 E-7 to 1.60E-8 CTUh/kg. For HTCE, the impact factor varies between 4.83E-07 CTUh/kg and 2.43E-08 CTUh/kg. The variability of those impact factors is relatively low for these two impact categories. Concerning FWE, the variability of impact factor is very high. It is 1.3E+03 CTUe/kg for tars release into water against 2.01E+01 CTUe/kg for tars release on soil. Statement concluding: The results of this study show that the environmental impacts of tars emission of biomass gasification systems can be consequent and it is important to investigate the ways to reduce them. For environmental research, these results represent an important step of a global environmental assessment of the studied systems. It could be used to better manage the wastewater containing tars to reduce as possible the impacts of numerous still running systems all over the world.

Keywords: biomass gasification, life cycle analysis, LCA, environmental impact, tars

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Authors: Dharminder Singh, Sanjeev Yadav, Pravakar Mohanty

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In this work, study of temperature profile in a pilot scale air bubbling fluidized bed (ABFB) gasifier for rice husk gasification was carried out. Effects of different factors such as multiple cyclones, gas cooling system, ventilate gas pipe length, and catalyst on temperature profile was examined. ABFB gasifier used in this study had two sections, one is bed section and the other is freeboard section. River sand was used as bed material with air as gasification agent, and conventional charcoal as start-up heating medium in this gasifier. Temperature of different point in both sections of ABFB gasifier was recorded at different ER value and ER value was changed by changing the feed rate of biomass (rice husk) and by keeping the air flow rate constant for long durational of gasifier operation. ABFB with double cyclone with gas coolant system and with short length ventilate gas pipe was found out to be optimal gasifier design to give temperature profile required for high gasification performance in long duration operation. This optimal design was tested with different ER values and it was found that ER of 0.33 was most favourable for long duration operation (8 hr continuous operation), giving highest carbon conversion efficiency. At optimal ER of 0.33, bed temperature was found to be stable at 700 °C, above bed temperature was found to be at 628.63 °C, bottom of freeboard temperature was found to be at 600 °C, top of freeboard temperature was found to be at 517.5 °C, gas temperature was found to be at 195 °C, and flame temperature was found to be 676 °C. Temperature at all the points showed fluctuations of 10 – 20 °C. Effect of catalyst i.e. dolomite (20% with sand bed) was also examined on temperature profile, and it was found that at optimal ER of 0.33, the bed temperature got increased to 795 °C, above bed temperature got decreased to 523 °C, bottom of freeboard temperature got decreased to 548 °C, top of freeboard got decreased to 475 °C, gas temperature got decreased to 220 °C, and flame temperature got increased to 703 °C. Increase in bed temperature leads to higher flame temperature due to presence of more hydrocarbons generated from more tar cracking at higher temperature. It was also found that the use of dolomite with sand bed eliminated the agglomeration in the reactor at such high bed temperature (795 °C).

Keywords: air bubbling fluidized bed gasifier, bed temperature, charcoal heating, dolomite, flame temperature, rice husk

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Authors: Daniel Fozer

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Limiting global warming to 1.5°C to the pre-industrial levels urges the application of efficient and sustainable carbon dioxide removal (CDR) technologies. Microalgae based biorefineries offer scalable solutions for the biofixation of CO2, where the produced biomass can be transformed into value added products by applying thermochemical processes. In this paper we report on the utilization of hydrochar as a blending component in hydrothermal gasification (HTG) process. The effects of blending ratio and hydrochar quality were investigated on the biogas yield and and composition. It is found that co-gasifying the hydrochar and the algae biomass can increase significantly the total gas yield and influence the biogas (H2, CH4, CO2, CO, C2H4, C2H6) composition. It is determined that the carbon conversion ratio, hydrogen and methane selectivity can be increased by influencing the fuel ratio of hydrochar via hydrothermal carbonization. In conclusion, it is found that increasing the synergy between hydrothermal technologies result in elevated conversion efficiency.

Keywords: biogas, CDR, Co-HTG, hydrochar, microalgae

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Authors: M. Fatmi, T. Chihi, M. A. Ghebouli, B. Ghebouli

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This work presents the experimental results of the differential scanning calorimetry (DSC), hardness measurements (Hv) and XRD analysis, for order to investigate the kinetics of precipitation phenomena in Al-7%wt. Mg alloy. In the XRD and DSC curves indicates the formation of the intermediate precipitation of β-(Al3Mg2) phase respectively. The activation energies associated with the processes have been determined according to the three models proposed by Kissinger, Ozawa, and Boswell. Consequently, the nucleation mechanism of the precipitates can be explained. These phases are confirmed by XRD analysis.

Keywords: discontinuous precipitation, hardening, Al–Mg alloys, mechanical and mechatronics engineering

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Authors: K. Radha Krishnan, Mirajul Alom

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Dehydrated powder prepared from fresh radish (Raphanus sativus) leaves were investigated for the color stability by different drying methods (tray, sun and solar). The effect of blanching conditions, drying methods as well as drying temperatures (50 – 90°C) were considered for studying the color degradation kinetics of chlorophyll in the dehydrated powder. The hunter color parameters (L*, a*, b*) and total color difference (TCD) were determined in order to investigate the color degradation kinetics of chlorophyll. Blanching conditions, drying method and drying temperature influenced the changes in L*, a*, b* and TCD values. The changes in color values during processing were described by a first order kinetic model. The temperature dependence of chlorophyll degradation was adequately modeled by Arrhenius equation. To predict the losses in green color, a mathematical model was developed from the steady state kinetic parameters. The results from this study indicated the protective effect of blanching conditions on the color stability of dehydrated radish powder.

Keywords: chlorophyll, color stability, degradation kinetics, drying

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Authors: F. R. M. Nascimento, E. E. S. Lora, J. C. E. Palácio

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A mathematical model to investigate the performance of a two stage fixed bed downdraft gasifier operating with air, steam and oxygen mixtures as the gasifying fluid has been developed. The various conditions of mixtures for a double stage fluid entry, have been performed. The model has been validated through a series of experimental tests performed by NEST – The Excellence Group in Thermal and Distributed Generation of the Federal University of Itajubá. Influence of mixtures are analyzed through the Steam to Biomass (SB), Equivalence Ratio (ER) and the Oxygen Concentration (OP) parameters in order to predict the best operating conditions to obtain adequate output gas quality, once is a key parameter for subsequent gas processing in the synthesis of biofuels, heat and electricity generation. Results show that there is an optimal combination in the steam and oxygen content of the gasifying fluid which allows the user find the best conditions to design and operate the equipment according to the desired application.

Keywords: air, equilibrium, downdraft, fixed bed gasification, mathematical modeling, mixtures, oxygen steam

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Authors: Prangya P. Sahoo, B. S. Murty

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The present study deals with phase evolution of oxide dispersed CoCrFeMnNi high entropy alloy as a function of amount of added Y2O3 during mechanical alloying and analysis of grain growth kinetics of CoCrFeMnNi high entropy alloy without and with oxide dispersion. Mechanical alloying of CoCrFeMnNi resulted in a single FCC phase. However, evolution of chromium carbide was observed after heat treatment between 1073 and 1473 K. Comparison of grain growth time exponents and activation energy barrier is also reported. Micro structural investigations, using electron microscopy and EBSD techniques, were carried out to confirm the enhanced grain growth resistance which is attributed to the presence oxide dispersoids.

Keywords: grain growth kinetics, mechanical alloying, oxide dispersion, phase evolution

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Authors: Young Nam Chun, Mun Sup Lim, Byeo Ri Jeong

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Sewage sludge is regarded as the residue produced by the waste water treatment process, during which liquids and solids are being separated. Thermal treatments are interesting techniques to stabilize the sewage sludge for disposal. Among the thermal treatments, pyrolysis and/or gasification has been being applied to the sewage sludge. The final goal of our NRF research is to develop a microwave In-line Drying-Pyrolysis-Gasification (IDPG) technology for the dewatered sewage sludge for the bio-waste to energy conversion. As a first step, the pyrolysis characteristics in a bench scale electric furnace was investigated at 800℃ for the dewatered sludge and dried sludge samples of which moisture contents are almost 80% and 0%, respectively. Main components of producer gas are hydrogen and carbon dioxide. Particularly, higher hydrogen for the dewatered sludge is shown as 75%. The hydrogen production for the dewatered sludge and dried sludge are 56% and 32%, respectively. However, the pyrolysis for the dried sludge produces higher carbon dioxide and other gases, while higher methane and carbon dioxide are given to 74% and 53%, respectively. Tar also generates during the pyrolysis process, showing lower value for case of the dewatered sludge. Gravimetric tar is 195 g/m3, and selected light tar like benzene, naphthalene, anthracene, pyrene are 9.4 g/m3, 2.1 g/m3, 0.5 g/m3, 0.3 g/m3, respectively. After the pyrolysis process, residual char for the dewatered sludge and dried sludge remain 1g and 1.3g, showing weight reduction rate of 93% and 57%, respectively. Through the results, this could be known that the dewatered sludge can be used to produce a clean hydrogen-rich gas fuel without the drying process. Therefore, the IDPG technology can be applied effectively to the energy conversion for dewater sludge waste without a drying pretreatment. Acknowledgment: This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government(MSIP) (No. 2015R1A2A2A03003044).

Keywords: pyrolysis, gasification, sewage sludge, tar generation, producer gas, sludge char, biomass energy

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Authors: Chandrashekar, R. T. Radhika, B. M. Venkatesha, S. Ananda, Shivalingegowda, T. S. Shashikumar, H. Ramachandra

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The kinetics of the oxidation of amitriptyline (AT) by sodium N-bromotoluene sulphonamide (C₆H₅SO₂NBrNa) has been studied in an acidic buffer medium of pH 1.2 at 303 K. The oxidation reaction of AT was followed spectrophotometrically at maximum wavelength, 410 nm. The reaction rate shows a first order dependence each on concentration of AT and concentration of sodium N-bromotoluene sulphonamide. The reaction also shows an inverse fractional order dependence at low or high concentration of HCl. The dielectric constant of the solvent shows negative effect on the rate of reaction. The addition of halide ions and the reduction product of BAT have no significant effect on the rate. The rate is unchanged with the variation in the ionic strength (NaClO₄) of the medium. Addition of reaction mixtures to be aqueous acrylamide solution did not initiate polymerization, indicating the absence of free radical species. The stoichiometry of the reaction was found to be 1:1 and oxidation product of AT is identified. The Michaelis-Menton type of kinetics has been proposed. The CH₃C₆H₅SO₂NHBr has been assumed to be the reactive oxidizing species. Thermodynamical parameters were computed by studying the reactions at different temperatures. A mechanism consistent with observed kinetics is presented.

Keywords: amitriptyline, bromamine-T, kinetics, oxidation

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Authors: Betül Özgenç, Soner Kuşlu, Sabri Çolak, Turan Çalban

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The aim of this study was investigate the leaching kinetics of ulexite in disodium hydrogen phosphate solutions in a mechanical agitation system. Reaction temperature, concentration of disodium hydrogen phosphate solutions, stirring speed, solid/liquid ratio and ulexite particle size were selected as parameters. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase the dissolution rate of ulexite. The activation energy was found to be 63.4 kJ/mol. The leaching of ulexite was controlled by chemical reaction.

Keywords: ulexite, disodium hydrogen phosphate, leaching kinetics

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Authors: Azade Ghorbani-HasanSaraei, Seyed-Ahmad Shahidi, Sakineh Alizadeh, Adeleh Maghsoudlou

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Improvement of color, as a quality attribute of Plum Concentrate, has been made possible by the increase in knowledge of kinetic of color change. Three different heating/evaporation processes were employed for the production of pPlum juice concentrate. The Plum juice was concentrated to a final 55 °Bx from an initial °Bx of 15 by microwave heating, rotary vacuum evaporator and evaporating at atmospheric pressure. The final Plum juice concentration of 55 °Bx was achieved in 17, 24 and 57 min by using the microwave, rotary vacuum and atmospheric heating processes, respectively. The colour change during concentration processes was investigated. Total colour differences, Hunter L, a and b parameters were used to estimate the extent of colour loss. All Hunter colour parameters decreased with time. The zero-order, first-order and a combined kinetics model were applied to the changes in colour parameters. Results indicated that variation in TCD followed both first-order and combined kinetics models, and parameters L, a and b followed only combined model. This model implied that the colour formation and pigment destruction occurred during concentration processes of plum juice.

Keywords: colour, kinetics, concentration, plum juice

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Authors: Juan C. Domínguez, Belén Del Saz-Orozco, María V. Alonso, Mercedes Oliet, Francisco Rodríguez

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In the present study, the kinetics of thermal degradation of a phenolic and lignin reinforced phenolic foams, and the lignin used as reinforcement were studied and the activation energies of their degradation processes were obtained by a DAEM model. The average values for five heating rates of the mean activation energies obtained were: 99.1, 128.2, and 144.0 kJ.mol-1 for the phenolic foam, 109.5, 113.3, and 153.0 kJ.mol-1 for the lignin reinforcement, and 82.1, 106.9, and 124.4 kJ. mol-1 for the lignin reinforced phenolic foam. The standard deviation ranges calculated for each sample were 1.27-8.85, 2.22-12.82, and 3.17-8.11 kJ.mol-1 for the phenolic foam, lignin and the reinforced foam, respectively. The DAEM model showed low mean square errors (< 1x10-5), proving that is a suitable model to study the kinetics of thermal degradation of the foams and the reinforcement.

Keywords: kinetics, lignin, phenolic foam, thermal degradation

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Authors: Ibrahim Laro ABUBAKAR

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The study examined the Availability and Utilization of E-Learning Technologies in Teaching of Human Kinetics and Health Education courses in Nigerian Universities, specifically, Universities in Kwara State. Two purposes were formulated to guide the study from which two research questions and two hypotheses were raised. The descriptive research design was used in the research. Three Hundred respondents (100 Lecturers and 200 Students) made up the population for the study. There was no sampling, as the population of the study was not much. A structured questionnaire tagged ‘Availability and Utilization of E-Learning Technologies in Teaching and Learning Questionnaire’ (AUETTLQ) was used for data collection. The questionnaire was subjected to face and content validation, and it was equally pilot tested. The validation yielded a reliability coefficient of 0.78. The data collected from the study were statistically analyzed using frequencies and percentage count for personal data of the respondents, mean and standard deviation to answer the research questions. The null hypotheses were tested at 0.05 level of significance using the independent t-test. One among other findings of this study showed that lecturers and Student are aware of synchronous e-learning technologies in teaching and learning of Human Kinetics and Health Education but often utilize the synchronous e-learning technologies. It was recommended among others that lecturers and Students should be sensitized through seminars and workshops on the need to maximally utilize available e-learning technologies in teaching and learning of Human Kinetics and Health Education courses in Universities.

Keywords: awareness, utilization, E-Learning, technologies, human kinetics synchronous

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Authors: Abeer S. Elsherbiny, Ali H. Gemeay

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In this study, graphene oxide (GO) nanosheets have been synthesized and characterized using different spectroscopic tools such as X-ray diffraction spectroscopy, infrared Fourier transform (FT-IR) spectroscopy, BET specific surface area and Transmission Electronic Microscope (TEM). The prepared GO was investigated for the removal of malachite green, a cationic dye from aqueous solution. The removal methods of malachite green has been proceeded via adsorption process. GO nanosheets can be predicted as a good adsorbent material for the adsorption of cationic species. The adsorption of the malachite green onto the GO nanosheets has been carried out at different experimental conditions such as adsorption kinetics, concentration of adsorbate, pH, and temperature. The kinetics of the adsorption data were analyzed using four kinetic models such as the pseudo first-order model, pseudo second-order model, intraparticle diffusion, and the Boyd model to understand the adsorption behavior of malachite green onto the GO nanosheets and the mechanism of adsorption. The adsorption isotherm of adsorption of the malachite green onto the GO nanosheets has been investigated at 25, 35 and 45 °C. The equilibrium data were fitted well to the Langmuir model. Various thermodynamic parameters such as the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) change were also evaluated. The interaction of malachite green onto the GO nanosheets has been investigated by infrared Fourier transform (FT-IR) spectroscopy.

Keywords: adsorption, graphene oxide, kinetics, malachite green

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Authors: Young Nam Chun, Mun Sup Lim

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Carbon dioxide and methane, the major components of biomass pyrolysis/gasification gas and biogas, top the list of substances that cause climate change, but they are also among the most important renewable energy sources in modern society. The purpose of this study is to convert carbon dioxide and methane into high-quality energy using char and commercial activated carbon obtained from biomass pyrolysis as a microwave receptor. The methane reforming process produces hydrogen and carbon. This carbon is deposited in the pores of the microwave receptor and lowers catalytic activity, thereby reducing the methane conversion rate. The deposited carbon was removed by carbon gasification due to the supply of carbon dioxide, which solved the problem of microwave receptor inactivity. In particular, the conversion rate remained stable at over 90% when the ratio of carbon dioxide to methane was 1:1. When the reforming results of carbon dioxide and methane were compared after fabricating nickel and iron catalysts using commercial activated carbon as a carrier, the conversion rate was higher in the iron catalyst than in the nickel catalyst and when no catalyst was used. 

Keywords: microwave, gas reforming, greenhouse gas, microwave receptor, catalyst

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Authors: Wei-Jing Li, Ren-Xuan Yang, Kui-Hao Chuang, Ming-Yen Wey

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Nowadays, plastic product and utilization are extensive and have greatly improved our life. Yet, plastic wastes are stable and non-biodegradable challenging issues to the environment. Waste-to-energy strategies emerge a promising way for waste management. This work investigated the co-production of hydrogen and carbon nanotubes from the syngas which was from the gasification of polypropylene. A nickel-silica core-shell catalyst was applied for syngas reaction from plastic waste gasification in a fixed-bed reactor. SiO2 were prepared through various synthesis solvents by Stöber process. Ni plays a role as modified SiO2 support, which were synthesized by deposition-precipitation method. Core-shell catalysts have strong interaction between active phase and support, in order to avoid catalyst sintering. Moreover, Fe or Co metal acts as promoter to enhance catalytic activity. The effects of calcined atmosphere, second metal addition, and reaction temperature on hydrogen production and carbon yield were examined. In this study, the catalytic activity and carbon yield results revealed that the Ni/SiO2 catalyst calcined under H2 atmosphere exhibited the best performance. Furthermore, Co promoted Ni/SiO2 catalyst produced 3 times more than Ni/SiO2 on carbon yield at long-term operation. The structure and morphological nature of the calcined and spent catalysts were examined using different characterization techniques including scanning electron microscopy, transmission electron microscopy, X-ray diffraction. In addition, the quality and thermal stability of the nano-carbon materials were also evaluated by Raman spectroscopy and thermogravimetric analysis.

Keywords: plastic wastes, hydrogen, carbon nanotube, core-shell catalysts

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Authors: Shrawan Baghel, Helen Cathcart, Biall J. O'Reilly

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Amorphous drug formulations have great potential to enhance solubility and thus bioavailability of BCS class II drugs. However, the higher free energy and molecular mobility of the amorphous form lowers the activation energy barrier for crystallization and thermodynamically drives it towards the crystalline state which makes them unstable. Accurate determination of the crystallization tendency/kinetics is the key to the successful design and development of such systems. In this study, dipyridamole (DPM) and cinnarizine (CNZ) has been selected as model compounds. Thermodynamic fragility (m_T) is measured from the heat capacity change at the glass transition temperature (Tg) whereas dynamic fragility (m_D) is evaluated using methods based on extrapolation of configurational entropy to zero 〖(m〗_(D_CE )), and heating rate dependence of Tg 〖(m〗_(D_Tg)). The mean relaxation time of amorphous drugs was calculated from Vogel-Tammann-Fulcher (VTF) equation. Furthermore, the correlation between fragility and glass forming ability (GFA) of model drugs has been established and the relevance of these parameters to crystallization of amorphous drugs is also assessed. Moreover, the crystallization kinetics of model drugs under isothermal conditions has been studied using Johnson-Mehl-Avrami (JMA) approach to determine the Avrami constant ‘n’ which provides an insight into the mechanism of crystallization. To further probe into the crystallization mechanism, the non-isothermal crystallization kinetics of model systems was also analysed by statistically fitting the crystallization data to 15 different kinetic models and the relevance of model-free kinetic approach has been established. In addition, the crystallization mechanism for DPM and CNZ at each extent of transformation has been predicted. The calculated fragility, glass forming ability (GFA) and crystallization kinetics is found to be in good correlation with the stability prediction of amorphous solid dispersions. Thus, this research work involves a multidisciplinary approach to establish fragility, GFA and crystallization kinetics as stability predictors for amorphous drug formulations.

Keywords: amorphous, fragility, glass forming ability, molecular mobility, mean relaxation time, crystallization kinetics, stability

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Authors: Emine Teke, Soner Kuşlu, Sabri Çolak, Turan Çalban

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The aim of the present study was to investigate the dissolution kinetics of ulexite in sodium dihydrogen phosphate in a mechanical agitation system and also to declare an alternative reactant to produce the boric acid. Reaction temperature, concentration of sodium dihydrogen phosphate, stirring speed, solid-liquid ratio, and ulexite particle size were selected as parameters. The experimental results were successfully correlated by using linear regression and a statistical program. Dissolution curves were evaluated in order to test the shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase in the dissolution rate of ulexite. The activation energy was found to be 36.4 kJ/mol. The leaching of ulexite was controlled by diffusion through the ash (or product) layer.

Keywords: ulexite, sodium dihydrogen phosphate, leaching kinetics, boron

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Authors: Z. V. P. Murthy, Preeti Arunachalam, Sangeeta Balram

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Removal of metal ions from different wastewaters has become important due to their effects on living beings. Cadmium is one of the heavy metals found in different industrial wastewaters. There are many conventional methods available to remove heavy metals from wastewaters like adsorption, membrane separations, precipitation, electrolytic methods, etc. and all of them have their own advantages and disadvantages. The present work deals with the use of natural biosorbents (chitin and chitosan) to separate cadmium ions from aqueous solutions. The adsorption data were fitted with different isotherms and kinetics models. Amongst different adsorption isotherms used to fit the adsorption data, the Freundlich isotherm showed better fits for both the biosorbents. The kinetics data of adsorption of cadmium showed better fit with pseudo-second order model for both the biosorbents. Chitosan, the derivative from chitin, showed better performance than chitin. The separation results are encouraging.

Keywords: chitin, chitosan, cadmium, isotherm, kinetics

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Authors: P. A. Broodryk, A. F. Van Der Merwe, H. W. J. P. Neomagus

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The production of the clear liquid fertilizer ammonium polyphosphate (APP) is best achieved by the pyrolysis of urea phosphate, as it produces a product that is free from any of the impurities present in the raw phosphoric acid it was made from. This is a multiphase, multi-step reaction that produces carbon dioxide and ammonia as gasses and ammonium polyphosphate as liquid products. The polyphosphate chain length affects the solubility and thus the applicability of the product as liquid fertiliser, thus proper control of the reaction conditions is thus required for the use of this reaction in the production of fertilisers. This study investigates the reaction kinetics of the aforementioned reaction, describing a mathematical model for the kinetics of the reaction along with the accompanying rate constants. The reaction is initially exothermic, producing only carbon dioxide as a gas product and ammonium diphosphate, at higher temperatures the reaction becomes endothermic, producing ammonia gas as an additional by-product and longer chain polyphosphates, which when condensed too far becomes highly water insoluble. The aim of this study was to (i) characterise the pyrolysis reaction of urea phosphate by determining the mechanisms and the associated kinetic constants, and (ii) to determine the optimum conditions for ammonium diphosphate production. A qualitative investigation was also done to find the rate of hydrolysis of APP as this provides an estimate of the shelf life of an APP clear liquid fertiliser solution.

Keywords: ammonium polyphosphate, kinetics, pyrolysis, urea phosphate

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

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

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

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Authors: A.D. Susanti, W. B. Sediawan, S.K. Wirawan, Budhijanto, Ritmaleni

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Oryzanol content in rice bran oil (RBO) naturally has high antioxidant activity. Its reviewed has several health properties and high interested in pharmacy, cosmetics, and nutrition’s. Because of the low concentration of oryzanol in crude RBO (0.9-2.9%) then its need to be further processed for practical usage, such as via adsorption process. In this study, investigation and adjustment of adsorption equilibrium models were conducted through the kinetic data approachments. Mathematical modeling on kinetics of batch adsorption of oryzanol separation from RBO has been set-up and then applied for equilibrium results. The size of adsorbent particles used in this case are usually relatively small then the concentration in the adsorbent is assumed to be not different. Hence, the adsorption rate is controlled by the rate of oryzanol mass transfer from the bulk fluid of RBO to the surface of silica gel. In this approachments, the rate of mass transfer is assumed to be proportional to the concentration deviation from the equilibrium state. The equilibrium models applied were Langmuir, coefficient distribution, and Freundlich with the values of the parameters obtained from equilibrium results. It turned out that the models set-up can quantitatively describe the experimental kinetics data and the adjustment of the values of equilibrium isotherm parameters significantly improves the accuracy of the model. And then the value of mass transfer coefficient per unit adsorbent mass (kca) is obtained by curve fitting.

Keywords: adsorption equilibrium, adsorption kinetics, oryzanol, rice bran oil

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Authors: Karen E. Supan

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Thermal degradation kinetics of switchgrass (Panicum virgatum) from the field, as well as in a pellet form, are presented. Thermogravimetric analysis tests were performed at heating rates of 10-40 K min⁻¹ in an inert atmosphere. The activation energy and the pre-exponential factor were calculated using the Ozawa/Flynn/Wall method as suggested by the ASTM Standard Test Method for Decomposition Kinetics by Thermogravimetry. Four stages were seen in the degradation: dehydration, active pyrolysis of hemicellulose, active pyrolysis of cellulose, and passive pyrolysis. The derivative mass loss peak for active pyrolysis of cellulose in the field-dried sample was much higher than the pelletized. The range of activation energy in the 0.15 – 0.70 conversion interval was 191 – 242 kJ mol⁻¹ for the field-dried and 130-192 kJ mol⁻¹ for the pellets. The highest activation energies were achieved at 0.50 conversion and were 242 kJ mol⁻¹ and 192 kJ mol⁻¹ for the field-dried and pellets, respectively. The thermal degradation and activation energies were comparable to switchgrass and other biomass reported in the literature.

Keywords: biomass, switchgrass, thermal degradation, thermogravimetric analysis

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Authors: Andi Ismanto

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Indonesia is the largest palm oil producer in the world. The increasing number of palm oil extensification in Indonesia started on 2000-2011. Based on preliminary figures from the Directorate General of Plantation, palm oil area in Indonesia until 2011 is about 8.91 million hectares.On 2011 production of palm oil CPO reaches 22.51 million tons. In the other hands, the increasing palm oil production has impact to environment. The Empty Bunch of Palm Oil (EBPO)waste was increased to 20 million tons in 2009. Utilization of waste EBPO currently only used as an organic fertilizer for plants. But, it was not a good solution, because TKKS that used as organic compost has high content of carbon and hydrogen compound. The EBPO waste has potential used as fuel by gasification because it has short time of decomposition. So, the process will be more efficient in time. Utilization of urban wastehas been created using an incinerator used as a source of electrical energy for household.Usually, waste burning process by incinerator is using diesel fuel and kerosene. It is certainly less effective and not environment friendly, considering the waste incineration process using Incinerator tools are continuously. Considering biomass is a renewable source of energy and the world's energy system must be switch from an energy based on fossil resources into the energy based on renewable resources, the "Gurza Incinerator": Design Build Powerful Biomass Incinerator Empty Bunch of Palm Oil (EBPO) as Elecrical Biomass Base Development, a renewable future technology. The tools is using EBPO waste as source of burning to burn garbage inside the Incinerator hopper. EBPO waste will be processed by means of gasification. Gasification isa process to produce gases that can be used as fuel for electrical power. Hopefully, this technology could be a renewable future energy and also as starting point of electrical biomass base development.

Keywords: incinerator, biomass, empty bunch palm oil, electrical energy

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Authors: C. C. Lin, S. C. Kan, C. W. Yeh, C. I Chen, C. J. Shieh, Y. C. Liu

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In this study, lipid-deprived residuals of microalgae were hydrolyzed for the production of reducing sugars by using the recombinant Bacillus cellulosome, carrying eight genes from the Clostridium thermocellum ATCC27405. The obtained cellulosome was found to exist mostly in the broth supernatant with a cellulosome activity of 2.4 U/mL. Furthermore, the Michaelis-Menten constant (Km) and Vmax of cellulosome were found to be 14.832 g/L and 3.522 U/mL. The activation energy of the cellulosome to hydrolyze microalgae LDRs was calculated as 32.804 kJ/mol.

Keywords: lipid-deprived residuals of microalgae, cellulosome, cellulose, reducing sugars, kinetics

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Authors: V. E. Messerle, O. A. Lavrichshev, A. B. Ustimenko

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Currently and in the foreseeable future (up to 2100), the global economy is oriented to the use of organic fuel, mostly, solid fuels, the share of which constitutes 40% in the generation of electric power. Therefore, the development of technologies for their effective and environmentally friendly application represents a priority problem nowadays. This work presents the results of thermodynamic and experimental investigations of plasma technology for processing of low-grade coals. The use of this technology for producing target products (synthesis gas, hydrogen, technical carbon, and valuable components of mineral mass of coals) meets the modern environmental and economic requirements applied to basic industrial sectors. The plasma technology of coal processing for the production of synthesis gas from the coal organic mass (COM) and valuable components from coal mineral mass (CMM) is highly promising. Its essence is heating the coal dust by reducing electric arc plasma to the complete gasification temperature, when the COM converts into synthesis gas, free from particles of ash, nitrogen oxides and sulfur. At the same time, oxides of the CMM are reduced by the carbon residue, producing valuable components, such as technical silicon, ferrosilicon, aluminum and carbon silicon, as well as microelements of rare metals, such as uranium, molybdenum, vanadium, titanium. Thermodynamic analysis of the process was made using a versatile computation program TERRA. Calculations were carried out in the temperature range 300 - 4000 K and a pressure of 0.1 MPa. Bituminous coal with the ash content of 40% and the heating value 16,632 kJ/kg was taken for the investigation. The gaseous phase of coal processing products includes, basically, a synthesis gas with a concentration of up to 99 vol.% at 1500 K. CMM components completely converts from the condensed phase into the gaseous phase at a temperature above 2600 K. At temperatures above 3000 K, the gaseous phase includes, basically, Si, Al, Ca, Fe, Na, and compounds of SiO, SiH, AlH, and SiS. The latter compounds dissociate into relevant elements with increasing temperature. Complex coal conversion for the production of synthesis gas from COM and valuable components from CMM was investigated using a versatile experimental plant the main element of which was plug and flow plasma reactor. The material and thermal balances helped to find the integral indicators for the process. Plasma-steam gasification of the low-grade coal with CMM processing gave the synthesis gas yield 95.2%, the carbon gasification 92.3%, and coal desulfurization 95.2%. The reduced material of the CMM was found in the slag in the form of ferrosilicon as well as silicon and iron carbides. The maximum reduction of the CMM oxides was observed in the slag from the walls of the plasma reactor in the areas with maximum temperatures, reaching 47%. The thusly produced synthesis gas can be used for synthesis of methanol, or as a high-calorific reducing gas instead of blast-furnace coke as well as power gas for thermal power plants. Reduced material of CMM can be used in metallurgy.

Keywords: gasification, mineral mass, organic mass, plasma, processing, solid fuel, synthesis gas, valuable components

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Authors: Olushola S. Ayanda, Olalekan S. Fatoki, Folahan A. Adekola, Bhekumusa J. Ximba, Cecilia O. Akintayo

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In the present study, the kinetics, equilibrium and thermodynamics of the adsorption of triphenyltin (TPT) from TPT-contaminated water onto nanoSiO2/fly ash/activated carbon composite was investigated in batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D-R) isotherm models. Pseudo first- and second-order, Elovich and fractional power models were applied to test the kinetic data and in order to understand the mechanism of adsorption, thermodynamic parameters such as ΔG°, ΔSo and ΔH° were also calculated. The results showed a very good compliance with pseudo second-order equation while the Freundlich and D-R models fit the experiment data. Approximately 99.999 % TPT was removed from the initial concentration of 100 mg/L TPT at 80oC, contact time of 60 min, pH 8 and a stirring speed of 200 rpm. Thus, nanoSiO2/fly ash/activated carbon composite could be used as effective adsorbent for the removal of TPT from contaminated water and wastewater.

Keywords: isotherm, kinetics, nanoSiO₂/fly ash/activated carbon composite, tributyltin

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