Thermodynamic Analysis of Glycerol Conversion to Olefins

AbstractThermodynamic equilibrium analysis of glycerol steam reforming to light olefins has been investigated based on the total Gibbs free energy minimization method. Equilibrium product compositions for glycerol steam reforming were determined according to the following range: temperature, 573–1273K; GWR (glycerol/water ratio), 1:12 - 2:1 and pressure, 1-12 bars. Analysis of the feasible reactions revealed hydrogen as the main product followed by carbon monoxide, methane and ethane. The equilibrium analysis indicated light olefins formation was not spontaneous. The amount of ethylene produced was very small, but improved at higher pressure and temperature between 873-1023K. Coking was also dependent on GWR and temperature. From Gibbs analysis, light olefin formation at equilibrium is thermodynamically not feasible, but experimental work involving catalyst proved that ethylene selectivity could be improved in a heterogeneous reaction

A Two-Step SO3H/ICG Catalyst Synthesis for Biodiesel Production: Optimization of Sulfonation Step via Microwave Irradiation

Conventional heating, a common method used for heterogeneous solid acid catalyst synthesis unknowingly consumes massive time and energy. In this study, acid catalyst was prepared through sulfonation process of incomplete carbonized glucose (ICG) via microwave-assisted technique to shorten the heating time and energy consumption. Optimization of the sulfonation process of ICG via microwave-assisted was carried out. Four-factor-three-level central composite design (CCD) was used to develop the design of experiments (DOE). Interaction between two factors was evaluated to determine the optimum process conditions. A quadratic model was proposed for prediction of biodiesel yield (Y) from palm fatty acid distillate (PFAD) and its conversion (C). The application of DOE successfully optimized the operating conditions for the two-step SO3H/ICG catalyst synthesis to be used for the esterification process. The optimized conditions of the best performing SO3H/ICG with maximum Y and C were at 7.5 minutes of reaction time, 159.5 mL of H2SO4 used, 671 rpm of stirring rate as well as 413.64 watt of power level. At these optimum conditions the predicted yield percentage and conversion percentage were 94.01% and 91.89%, respectively, which experimentally verified the accuracy of the model. The utilization of sulfonated glucose solid acid catalyst via microwave-assisted in biodiesel production has great potential towards sustainable and green method of synthesizing catalyst for biodiesel. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Development of Microwave-Assisted Sulfonated Glucose Catalyst for Biodiesel Production from Palm Fatty Acid Distillate (PFAD)

Microwave-heating method for catalyst preparation has been utilized recently due to its shorter operation time compared to the conventional method. Glucose, a renewable carbon source can be partially carbonized and sulfonated via microwave heating which could result in highly potential heterogeneous carbon-based acid catalyst. In this study, the impacts of the carbonization and sulfonation parameters during the catalyst preparation were investigated. Catalysts prepared were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), X-Ray Diffraction (XRD), Brunauer-Emmet-Teller (BET), and Temperature Programmed Desorption–Ammonia (TPD-NH3). Analysis of the carbonization screening process discovered that the best incomplete carbonized glucose (ICG) prepared was at 20 minutes, 20 g of D(+)-glucose with medium microwave power level (400W) which exhibited the highest percentage yield (91.41%) of fatty acid methyl ester (FAME). The total surface area and acid site density obtained were 16.94 m2/g and 25.65 mmol/g, respectively. Regeneration test was further carried out and succeeded to achieve 6 cycles. The highest turnover frequency (TOF) of the sulfonated catalyst was methyl palmitate, 25.214´10−3 s−1 compared to other component of the methyl ester. Kinetic study was developed throughout the esterification process and activation energy from the forward and reverse reaction was 3.36 kJ/mol and 11.96 kJ/mol, respectively. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Assessing USECHH regulation 2000 implementation on chemical laboratories: a case study of Universiti Teknologi Malaysia

Chemical laboratories safety has become an important issue in Universiti Teknologi Malaysia (UTM), as many accidents occurred in the laboratory such as spillage and explosion. By using USECHH Regulation 2000 as the baseline study, this research was conducted on 18 chemical testing laboratories in UTM which are divided into Service Lab, Teaching and Learning Lab and also Research Lab. The enforcement of USECHH Regulation 2000 commonly took place in the industry, however the implementation of it in universities are still not widely accepted. The study was conducted by using audit checklist, questionnaire, on-site observation and interview based on seventeen requirements listed in USECHH Regulation 2000. The methodology was divided into four phases; (1) the quality control; pre-test survey phase, (2) the on-site data gathering information phase, (3) data evaluation phase, and (4) safety plan proposal phase. Among the three types of laboratory, Service Laboratory shows the best result. However one way ANOVA statistical test proved that there are no significant differences between each type of laboratory. The questionnaire results revealed that training, awareness and knowledge, and management support are the critical reasons that contributed to the compliance status of the laboratories. Involvement of students and lecturers, website and system development, and control of procurement are among the critical success factors to improve the enforcement of USECHH Regulation 2000 in the campus

Challenges & Opportunities on Catalytic Conversion of Glycerol to Value Added Chemicals

With the rapid expansion of biodiesel industry, its main by-product, crude glycerol, is anticipated to reach a global production of 6 million tons in 2025. It is actually a worrying phenomenon as glycerol could potentially emerge as an excessive product with little value. Glycerol, an alcohol and oxygenated chemical from biodiesel production, has essentially enormous potential to be converted into higher value-added chemicals. Using glycerol as a starting material for value-added chemical production will create a new demand on the glycerol market such as lactic acid, propylene glycol, alkyl lactatehydrogen, olefins and others. This paper briefly reviews the recent development on value-added chemicals derived from glycerol through catalytic conversion of refined and crude glycerol that have been proven to be promising in research stage with commercialization potential, or have been put in a corporate marketable production. Despite of the huge potential of products that can be transformed from glycerol, there are still numerous challenges to be addressed and discussed that include catalyst design and robustness; focus on crude or refined glycerol; reactor technology, reaction mechanism and thermodynamic analysis; and overall process commercial viability. The discussion will hopefully provide new insights on justified direction to focus on for glycerol transformation technology. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Preparation of Ti-SO3H/ICG using microwave-assisted for esterification of palm fatty acid distillate to methyl ester

The utilisation of low-cost yet valuable feedstock such as palm fatty acid distillate (PFAD) in the replacement of edible oils have a great potential in solving high-cost problem in biodiesel industries. Heterogeneous solid acid catalyst is the most proficient to esterify the feedstock containing high free fatty acid (FFA). Most of the prepared catalysts from the previous studies were produced using a conventional heating method which is basically time and energy consuming. The development of heterogeneous solid acid catalyst from sulfonated glucose and impregnation with titanium (Ti-SO3H/ICG) was prepared by using a microwave-assisted heating method with various heating time during the sulfonation process. The heating times taken were 3, 5, 7 and 9 min for acid treatment using H2SO4. The catalysts showed an outstanding result in reducing the catalyst separation problem and efficiently producing high percentage yield of biodiesel. The physical and chemical properties of the modified catalyst were analysed by using Temperature Programmed Desorption-Ammonia (TPD-NH3) and Brunauer-Emmett-Teller (BET). 7 min Ti-SO3/ICG showed the best performance catalyst due to its high surface area and acid site density, which were 78.37 m2/g and 15.16 mmol/g. The catalyst showed highest percentage yield and conversion of 98.92 % and 80.24 % at 70 °C, with a molar ratio of methanol to PFAD of 10: 1, 2.5 wt% of catalyst loading and 90 min of reaction time. A kinetic model was studied and the activation energy (Ea) obtained was 13.43 kJ/mol.K, the lowest value recorded as compared with the activation energy from previous studies in related field

Integration of roundtable on sustainable palm oil - environmental sustainability index for the development of quantitative environmental sustainability index

The Roundtable on Sustainable Palm Oil (RSPO) was founded in 2004 to promote the expansion and use of sustainable oil palm products through credible global standards and multistakeholder governance. Though RSPO was widely accepted as a reliable standard, it still lacks into certain extent quantification element to enable proper and smoother standardized measurement. To eliminate this problem, a new indexing method called Environmental Sustainability Index (ESI) was designed and proposed. The paper presents a case study to demonstrate the real-life application of the ESI-RSPO Integrated Environmental Sustainability Index Framework. The framework designed by the fusion of the key features of the ESI of measuring the overall progress towards environmental sustainability and RSPO of encouraging the growth and use of sustainable oil palm products, exhibits an organized, procedural and scientific pathway of measuring the environmental performance of palm oil manufacturing entities. Quantitative approach from ESI coupled with qualitative valuation from RSPO brings about tremendous advantages in the environmental sustainability context in particular by clearly showing where an entity is positioned in relation to the desired target. The results of this case study clearly pinpoint the environmental parameter outlier and prove that integration of ESI and RSPO will not only promote objectivity but also consistency of results across different production units. Both qualitative and quantitative measurement, operating in conjunction, is very much needed in a system as critical and dynamic with complex inter-relationship and linkages between various subsystems such as environmental sustainability

Fractional freezing of ethanol and water mixture

Fractional freezing was introduced to separate a mixture that contains a volatile organic compound in this case; ethanol and water. The mixture was separated by using freezing process since both ethanol and water have different freezing points. This method is an alternative method for fractional distillation as it does not consume high amount of energy to supply heat for vaporization purpose. Besides, this method is safer to our environment as it does not liberate any harmful vapor or gases since there is no heating process involved. In this study, the performance of the process in producing high purity ethanol was evaluated based on two parameters which are stirring rate and coolant temperature. It was found that the concentration of ethanol in liquid phase increased as the stirring rate increased. The ethanol concentration has increased by 52.2% when the stirring rate was at the highest rotating speed which is 500 rpm. When the coolant temperature was decreased to -14°C, the ethanol concentration in liquid phase increased the most by 56.5%. Thus it can be concluded that the concentration of ethanol in liquid phase increased as the coolant temperature decrease

Production of eco-friendly soap from glycerine pitch and blend oil

Glycerine or glycerol is an alcohol with three hydroxyl (-OH) groups. It is a colourless, odourless, viscous and water-soluble liquid. Being a by-product from the production of biodiesel, glycerine is presently abundantly available. This situation is alarming since the surplus of glycerine could not be coped and part of the effort to reduce it is by incineration, which leads to environmental concern. On the other hand, glycerine pitch is an unwanted residue from oleo-chemical plant. Hence, there is an urgent need to utilize the abundantly available and cheap glycerine and the unwanted glycerine pitch. On the bright side, from previous research and application, glycerine can be transformed to other higher value-added products. Due to its moisturising properties, one of the main uses of glycerine is in the blending of eco-friendly soap. This study was aimed to investigate the blending process and properties of liquid soap. The starting materials used were lab grade glycerine and glycerine pitch waste. Both glycerines were mixed with sulphuric acid; underwent activated carbon treatment and evaporation for purification. Combination of glycerine and glycerine pitch obtained demonstrated very little absence of soap. Final observation showed good indicator of the utilization of glycerine pitch. This was proven from soap B with pH 8.3 that took 5.9 hours before the disappearance of soap

Process development of oil palm empty fruit bunch gasification by using fluidised bed reactor for hydrogen gas production

Hydrogen can store and deliver usable energy, but it does not typically exist by itself in nature and must be produced from compounds that contain it such as biomass. Hydrogen can be used as fuel which produce from gasification process that used renewable sources as feedstock. Large amount of empty fruit bunch (EFB) has been produced in Malaysia and yet has no specific used in large quantity and it is being incinerated or used as landfill material dumped in the plantation. These situations have led to increased CO2 and other greenhouse gas (GHG) emissions in the atmosphere. During preliminary study, it shows that there are very limited studies being done in the process design development of the hydrogen production by using EFB from oil palm. Despite of tremendous experimental studies done on the effectiveness of using EFB for production of hydrogen, the process implementation in industry is still discouraging. This is due to lack of proven technology and high capital cost of investment. In this study, the drying, gasification and purification unit operations were modelled in Aspen Plus simulator for production of pure hydrogen gas and char was removed significantly after several gas cleaning processes. The final product for purified hydrogen gas is 12.3 t/h which is 16.3 % of hydrogen gas produced from the total EFB feedstock. Based on the result, the optimum temperature and pressure for gasification process is 850 °C and 1 atm respectively. Since, there is not much research have been carried out on process design of hydrogen production process by using EFB as feedstock, the understanding towards this topic can be prolonged