Stabilization of Empty Fruit Bunch (EFB) Derived Bio-oil

Bio-oil is a promising alternative source of energy which can be produced from empty fruit bunch (EFB). Bio-oil comprises a mixture of highly oxygenated compounds, carboxylic acids and trace water. Bio-oil can be used as a substitute for conventional fuels after it is upgraded. However, bio-oil can react through many chemical reactions such as polymerization and this will lead to the increase in viscosity of bio-oil during storage. Thus, this research project will explore on the stabilization of empty fruit bunch derived bio-oil. The bio-oil that will be used in this research is produce from the catalytic pyrolysis of EFB. The optimum reaction condition used is catalytic pyrolysis of EFB using 5 wt% of H-Y catalyst at reaction temperature of 500 °C and nitrogen flow rate of 100 ml/min. This operating condition is able to obtain the maximum yield. There are 2 type of methods will be used in this research to improve the stability of the bio-oil: addition of anti-oxidants and addition of solvents. For the addition of anti-oxidants, three kinds of anti-oxidants which are propyl gallate (PG), tert-butyl hydroquinone (TBHQ), butylatedhydroxyanisole (BHA) and calcium chloride salts (CaCl2) are added to bio-oil in the amount of 1000 ppm. On the other hand, the second methods will use 10 wt% of solvents including acetone, ethanol 95 %, and ethyl acetate to increase the bio-oil’s stability. All the test samples are subjected to accelerated aging involving exposure to high temperature of 80 oC for 7 days. The properties of samples which are chosen as the indicator of the aging are viscosity, water content and acidity. This progress report contains 6 chapters. Chapter 1 will discuss the introduction on the background, problem statement, objective and the scope of study for the project, relevancy of the project and feasibility of the project within the scope and time frame. A detailed literature review will be discussed in chapter 2. Besides, chapter 3 will focus on the research methodology and also the key milestones for the project in order to give a detail overview of the whole research project. Chapter 4 will be the results and discussion for the research project. Chapter 5 and 6 are the conclusion and references respectively

A Molecular Simulation Study of Silica/Polysulfone Mixed Matrix Membrane for Mixed Gas Separation

Polysulfone-based mixed matrix membranes (MMMs) incorporated with silica nanoparticles are a new generation material under ongoing research and development for gas separation. However, the attributes of a better-performing MMM cannot be precisely studied under experimental conditions. Thus, it requires an atomistic scale study to elucidate the separation performance of silica/polysulfone MMMs. As most of the research work and empirical models for gas transport properties have been limited to pure gas, a computational framework for molecular simulation is required to study the mixed gas transport properties in silica/polysulfone MMMs to reflect real membrane separation. In this work, Monte Carlo (MC) and molecular dynamics (MD) simulations were employed to study the solubility and diffusivity of CO2/CH4 with varying gas concentrations (i.e., 30% CO2/CH4, 50% CO2/CH4, and 70% CO2/CH4) and silica content (i.e., 15–30 wt.%). The accuracy of the simulated structures was validated with published literature, followed by the study of the gas transport properties at 308.15 K and 1 atm. Simulation results concluded an increase in the free volume with an increasing weight percentage of silica. It was also found that pure gas consistently exhibited higher gas transport properties when compared to mixed gas conditions. The results also showed a competitive gas transport performance for mixed gases, which is more apparent when CO2 increases. In this context, an increment in the permeation was observed for mixed gas with increasing gas concentrations (i.e., 70% CO2/CH4 > 50% CO2/CH4 > 30% CO2/CH4). The diffusivity, solubility, and permeability of the mixed gases were consistently increasing until 25 wt.%, followed by a decrease for 30 wt.% of silica. An empirical model based on a parallel resistance approach was developed by incorporating mathematical formulations for solubility and permeability. The model results were compared with simulation results to quantify the effect of mixed gas transport, which showed an 18% and 15% percentage error for the permeability and solubility, respectively, in comparison to the simulation data. This study provides a basis for future understanding of MMMs using molecular simulations and modeling techniques for mixed gas conditions that demonstrate real membrane separation

REPRODUCIBILITY OF NATURAL RESOURCES FOR THE SYNTHESIS OF LOW TRANSITION TEMPERATURE MIXTURES (LTTMS)

LTTMs are combinationsof hydrogen bond donors(HBDs) and hydrogen bond acceptors(HBAs) as a new class of green solvents which aim to overcome the limitation of ionic liquids while sharingsome of theiradvantages. The materialsused as HBDsweremalic acidsextracted from cactus, papaya, and luffa cylindricawhile HBAs were L-proline, L-histidine, glycine, and choline chloride, all of which existednaturally in living organismsor plants. Compatibilityof different combinations of HBD and HBA to form LTTMsand varying their molar ratio were the subjectsof interest in this project. A biopolymer solubility test was carried out on all LTTMs to identify the best performed LTTM and utilize it in oil palm empty fruit bunch biomass pretreatment. For LTTMssynthesis, onlyhistidine was incompatible with malic acid. The solubility screening test showed that combination of cactus and proline with a molarratio of 1:1 (CP 1:1) is the most effective LTTM in dissolving lignin (12.87 wt%), followed by luffa cylindrica :proline 1:1 (11.53 wt%). FTIR analysis was carried out and proved the existence and formation of a hydrogen bond within the solvent structure. The most critical disadvantage of LTTMs was the thermal instability due to its weak hydrogen bonding. CP 1:1 showedthe similarresult in biomass pretreatment to the biopolymerssolubility screening test, which is around 12 wt% of lignin solubility. This work provides an alternativemethod of biomass pretreatment for lignin extraction

Delignification of Empty Fruit Bunch (EFB) using Low Transition Temperature Mixtures (LTTMs) : A Review

Biomass processing using low transition temperature mixtures (LTTMs) has the potential to become a sustainable alternative resource for production of raw materials and fuels with a neutral carbon dioxide balance. The state of art for customizing the physicochemical behaviour of these new green solvents by a prudent selection of the constituents’ nature and ratio through microwave irradiation is presented in this work. The impact of the following parameters, namely type of malic acid, molar ratio of malic acid to natural salt, water content and temperature of treatment are related to the solvation behaviour of LTTMs. An overview of the conditions for the highest efficiency in the delignification of empty fruit bunch (EFB) are described

Stabilization of Empty Fruit Bunch derived Bio-oil using Solvents

The intention of this research was to select the ideal condition for accelerated aging of bio-oil and the consequences of additive in stabilizing the bio-oil. The bio-oil was produced from the catalytic pyrolysis of empty fruit bunch. The optimum reaction conditions applied to obtain the utmost bio-oil yield were 5 wt% of H-Y catalyst at reaction temperature of 500 °C and nitrogen flow rate of 100 ml/min. A 10 wt% of solvents including acetone, ethanol, and ethyl acetate were used to study the bio-oil’s stability. All the test samples were subjected to accelerated aging at temperature of 80 °C for 7 days. The properties of samples used as the indicator of aging were viscosity and water content. The effectiveness of solvents increased in the following order: acetone, ethyl acetate, and 95 vol% ethanol. Based on the result of Gas Chromatography-Mass Spectrometry (GC-MS), it could impede the chain of polymerization by converting the active units in the oligomer chain to inactive units. The solvent reacted to form low molecular weight products which resulted in lower viscosity and lessen the water content in bio-oil. Addition of 95 vol% ethanol also inhibited phase separation

Determination of Optimum Condition for the Production of Rice Husk‐Derived Bio‐oil by Slow Pyrolysis Process

Recently, studies on bio‐oil have captured international interest in developing it as an alternative energy option. Bio‐oil which is also known as pyrolysis oil or bio‐fuel oil was produced by pyrolysis process without any additional oxygen. Biomass pyrolysis essentially converts 80–95% of the feed material to gases and bio‐oil. This chapter provides an overview of how to produce bio‐oil through slow pyrolysis of rice husk (RH) at different heating rates in order to determine the optimum reaction condition that will give maximum liquid yield. The characteristics of bio‐oil produced at different heating rates are then analyzed. The chemical compound of bio‐oil product was analyzed by using gas chromatography‐mass spectroscopy (GC‐MS). The bio‐oil produced at different heating rates is analyzed for its chemical composition. The higher number of phenol and acid compounds contributes to the higher pH number of bio‐oil that was produced at a heating rate of 20°C/min

Physicochemical Properties of Low Transition Temperature Mixtures in Water

A new generation of designer solvents, low transition temperature mixtures (LTTMs) could be the ideal solvent for the separation of the main biopolymers in lignocellulosic biomass such as lignin, cellulose and hemicellulose. The separated biopolymers have prospective to be converted into high valuable products. LTTMs can be synthesized from two natural high melting point materials through hydrogen bonding interactions. The objective of this research was to study the effects of water in the physicochemical properties of LTTMs such as hydrogen bonding, thermal stability and lignin solubility. LTTMs were prepared in the presence and absence of distilled water with malic acid as the hydrogen bond donor (HBD) and sucrose as hydrogen bond acceptor (HBA). The molar ratio of malic acid to sucrose was fixed at 1:1. Based on the fourier transform infrared spectroscopy (FTIR) analysis, the FT-IR spectra of all the LTTMs shown representative peak of carboxylic acid group of malic acid turned broader at 1,710 cm-1 for the C=O group. Nevertheless, the peaks involved in the H-bonding due to the formation of LTTMs shifted and became broader within 2,500 - 3,600 cm-1 for the OH groups of carboxylic acid and alcohols in the presence of water. The degradation temperature of LTTM was not affected by the addition of water which remained at 400 K. In addition, the LTTM with water had increased the lignin solubility from 6.22 to 6.38 wt% without affecting the thermal behaviour of LTTMs

Techno-economic and life-cycle assessment of volatile oil extracted from Aquilaria sinensis using supercritical carbon dioxide

Extracts of Aquilaria sinensis possess pharmacological activity that has been widely used in traditional medicines since ancient times. In this study, techno-economic assessment was conducted for extraction of volatile oil from abundant biomass (lignified ring) and resin of A. sinensis to evaluate their respective economic feasibility using supercritical carbon dioxide (SC-CO2) extraction in Malaysia. The assessment revealed that for a production capacity of 5280 kg/y volatile oil, the total capital investment (TCI) was $7.11 million from summation of fixed capital cost and working capital. In terms of operating expenditure (OPEX), the volatile oil extracted from resin and lignified ring of A. sinensis required$ 81.96 million and $52.39 million, respectively. The selling price of volatile oil from resin and lignified ring were estimated to be$ 0.025 million/kg and $ 0.0125 million/kg, respectively. Both volatile oil extracted from resin and lignified ring showed a positive net profit which indicated their profitability. In addition, a cradle-to-gate analysis of life-cycle assessment (LCA) was performed, whereby the extraction process contributed the highest impact towards the environment due to its high energy consumption. Nevertheless, this study estimated that the process might reduce the environmental impacts by approximately 90% when the technology readiness levels (TRLs) reach the level of 9–10. These findings are beneficial in providing preliminary insights in terms of economic and environmental aspects for volatile oil extraction using SC-CO2 technology

Physicochemical and structural characterisation of oil palm trunks (OPT) hydrochar made via wet torrefaction

This study evaluates the effect of wet torrefaction of OPT under autogenous pressures at 3 different relatively low temperatures (i.e. 180, 200, and 220 oC) and extended residence times (i.e. 3, 6, 9, 12, 18, 24, 48, and 72 h) on the hydrochar's physical, chemical, and structural properties. Logarithmic-like increase of HHV profile was observed at the highest temperature of 220 oC, in which a plateau was reached at 24 h. Between temperature and residence time, temperature gave a more significant influence on the characteristics of the produced biochar. The HHV of the biomass sample increases from 16.4 MJ kg−1 in raw OPT to the highest HHV of 26.9 MJ kg−1 when torrefied at 220 oC for 72 h. Van Krevelen analysis shows dehydration was the primary reaction pathway that occurred during wet torrefaction of OPT at 180 oC for 24 h, 200 oC for 24 h, 220 oC for 6 h, and 220 oC for 12 h. Decarboxylation dominates the reaction when temperature and residence time was increased to 220 oC for 24 h, respectively. Further increasing the residence time to 48 and 72 h at 220 oC promotes demethylation as the dominant reaction. FTIR analysis reveals that most hemicellulose and parts of cellulose decomposed when OPT was subjected to lower temperature and/or residence time (i.e. 180 oC for 24 h, 200 oC for 24 h, 220 oC for 6 h, and 220 oC for 12 h). However, increasing temperature to 220 oC and beyond 24 h resulted in carbon-rich and lignin-dense hydrochar, which was observed in powder XRD results where graphite nitrate peak at 2θ of 7.4o appears. Morphology analysis reveals that most of the hemicellulose and cellulose-rich parenchyma was removed when subjected to wet torrefaction at 220 oC for 24 h. The formation of microspheres from the repolymerisation of 5-HMF was observed in large quantities in OPT hydrochar treated at 220 oC for 72 h. Inorganic elemental analysis shows that wet torrefaction of OPT effectively removes K and Cl from the biomass. The removal of K increased with increased temperature, which may partially resolve the corrosion problems in combustion reactions related to silicate deposition. OPT hydrochar from WT under autogenous condition and relatively low temperature exhibits much more improved fuel properties compared to raw OPT

Stabilization of Empty Fruit Bunch derived Bio-oil using Solvents

The intention of this research was to select the ideal condition for accelerated aging of bio-oil and the consequences of additive in stabilizing the bio-oil. The bio-oil was produced from the catalytic pyrolysis of empty fruit bunch. The optimum reaction conditions applied to obtain the utmost bio-oil yield were 5 wt% of H-Y catalyst at reaction temperature of 500 °C and nitrogen flow rate of 100 ml/min. A 10 wt% of solvents including acetone, ethanol, and ethyl acetate were used to study the bio-oil’s stability. All the test samples were subjected to accelerated aging at temperature of 80 °C for 7 days. The properties of samples used as the indicator of aging were viscosity and water content. The effectiveness of solvents increased in the following order: acetone, ethyl acetate, and 95 vol% ethanol. Based on the result of Gas Chromatography-Mass Spectrometry (GC-MS), it could impede the chain of polymerization by converting the active units in the oligomer chain to inactive units. The solvent reacted to form low molecular weight products which resulted in lower viscosity and lessen the water content in bio-oil. Addition of 95 vol% ethanol also inhibited phase separation