A project thesis submitted to the Chemical Engineering Program Universiti Teknologi PETRONAS in partial fulfillment of the requirement for the. The solvolysis reaction was followed by a typical dry leaf liquefaction reaction system using a sulfuric acid catalyst at elevated temperature (80–200 °C) and reaction time (60–200 minutes). The breakdown and decomposition of cellulose is evidenced in FTIR, where the hemicellulose peak decreases while the carboxylic acid peak increases.
The density and viscosity have been measured and the results are the same as the actual bio oil in the literature review. I would like to thank everyone who contributed to a successful dry leaf liquefaction project. Thanabalan who helps in providing relevant data and information related to the project by guiding the liquefaction study process.
A brief schematic of the separation method and product analysis Figure 4.1: Effect of reaction temperature on percent yield. Mechanism of cellulose degradation and decomposition during the solvolysis reaction and analysis of the solvolized product.
INTRODUCTION
- Background Study
- Problem Statement
- Malaysia's Biomass Energy Outlook
- Objectives and Scope of Study
Unlike other renewable energy sources that require costly technology, biomass can generate electricity with the same type of equipment and power plants that now burn fossil fuels (Y an et a!, 1997). There are currently not many government policies regarding the development and use of biomass resources for power generation and combined heat and power (CHP). It includes renewable energy as the fifth fuel and under this policy it was intended that renewable energy supply 5% of the national electricity demand by 2005 (Mohamed and Lee, 2006).
Despite this development and the potential of biomass energy, there are several obstacles that limit its commercialization and industrial application. Financially, since biomass energy projects are capital intensive, it is difficult to get loans from banks as there is no track record to back them up. The overall utilization of biomass energy is still in its infancy in Malaysia, although there are abundant potential resources in the country, as shown in Table I .
There are few objectives that have been identified and are related to the start of this project. To study the effect of the solvent used in the process that gives a high conversion of biomass to bio-oil.
CHAPTER2 LITERATURE REVIEW
- An Overview of Biomass
- An overview of Bio-Oil
- Characteristics of Bio-oil
- Direct Liquefaction
- Mechanism of liquefaction
- Review From Journal
It is known to be the primary reason for the large differences between bio-oils and petroleum fuels. The water content of bio-oils usually varies in the range of 15-30 wt"/o, depending on the initial moisture in raw materials and pyrolysis conditions. The presence of water has both negative and positive effects on the storage and utilization of bio-oils. oils.
On the one hand, it reduces heating values and can cause phase separation of bio-oils. Therefore, the volumetric energy density of bio-oils can reach 50-60% of that of petroleum fuels. Bio-oils contain more or less solids, mainly carbonized particles and other materials such as fluidized bed materials used in the pyrolysis process.
Corrosion rates would increase at elevated temperatures or with an increase in the water content of bio-oils. Lignin is a macromolecule that consists of alkylphenols and has a complex three-dimensional structure. Decomposition of biomass into smaller products takes place primarily through depolymerization and deoxygenation.
CHAPTER3 METHODOLOGY
Experimental Work
- Collection and Preparation of Raw Materials
Experiment Procedure
- Measurement of Residue Content
- Separation Process
Characterization of Products .1 Liquid Products
- Density Determination
- Viscosity Determination
- Gas Chromatography-Mass Spectrometry
- Fourier Transform Infra-Red (FTIR) Spectra
CHAPTER4
RESULTS AND DISCUSSION
Degree of Extent of Liquefaction
- Effect of Reaction Temperature and Solvent
In order to investigate the effect of reaction temperature on heavy oil yield, experimental measurements were carried out at five different temperatures. The results of the experiment for the dependence of the yield of heavy oil on the reaction temperature are shown in Figure 4.1. From Figure 4.1, the heavy oil yield strongly depends on the reaction temperature at 140 °C for ethylene carbonate (EC) and at 160 °C for ethylene glycol (EG).
It can be seen that the heavy oil yield first increases with increasing reaction temperature and then is followed by decrease with further increasing reaction temperature. This is due to the competition of two reactions involved in the liquefaction, that is, hydrolysis and repolymerization. It can also be seen that EC gives higher yield compared to EO in the experiment.
EC has been used as effective solvents in electrical engineering due to high permittivity value of 89.9 (40 °C) (Riddick et al., 1986). It has been known that the acid potential of an acid-catalyzed reaction in non-aqueous solvent depends on the gravity of the solvent. Considering this concept, the meltwater of cellulose using EC in the presence of acid catalyst, acid-catalyzed decomposition of cellulose would be satisfactory due to its high gravity and could lead to complete liquefaction in a short time.
It is known that EC is converted to EG with release of carbon dioxide at elevated temperature in the presence of acid catalysts, as shown in Scheme 1 (Peppel, 1958). The significant bubbles observed in the flask were likely due to the formation of carbon dioxide. In the case of ethylene glycol (EG), the liquefaction is so slow that only 27% of the yield is achieved after 120 minutes.
On the other hand, cellulose was liquefied very quickly and almost completely in 200 min when ethylene carbonate was used. There the values of the rate constants were calculated from the slope of the line at the early stage of liquefaction as shown in Appendix A. It is implied from the figure that cellulose liquefaction follows the pseudo-order reaction during the early stage.
Liquid Product Analysis .1 Density Determination
- Viscosity Determination
- GC-MS Analysis
From table 4.4 we can see that EC gives approximately 2 times faster densification speed than EG. In the presence of a strong acid, such as sulfuric acid, the bond between glycosidic units of cellulose compounds is subjected to hydrolytic cleavage. Furthermore, synergies between basic components of dry leaves are difficult to account for during the densification reaction.
Samples of microcrystalline cellulose were liquefied in ethylene glycol and ethylene carbonate acidified with H2SO4, in the experimental conditions described above for dry leaves. The yield in liquid cellulose increases, while the acidity of the solvent medium drops drastically to an almost zero value. This leads to the conclusion that acid donates more for H+ ion in the presence of ethylene carbonate leading to a high fluidity yield percentage.
It can be seen that the product categories and abundance were greatly influenced by the solvent type. According to literature review (BREW Project, 2008), the hydrolysis conversion products will be as in figure 4.4. 75 min identified as butyric acid, gluconic acid and glycolic acid respectively and these compounds accounted for about 95.2% of total peak area.
Butyric acid, gluconic acid, and gluconic acid are the hydrolysis conversion products from the literature review. Traces of this compound suggest that the dried leaves can be converted into bio-oil. Butyric acid and succinic acid are also products of hydrolysis conversion from literature review.
From both GC-MS analyses, 95.2% of the total area from the ethylene carbonate liquefaction products is from the literature review while only 1.63% is the total area from the ethylene glycol liquefaction product from the literature review. It is also worth noting that fewer compounds with nitrogen and sulfur atoms were detected in the oils obtained in this study. The lower content of heteroatoms can be related to the optimal temperature which caused complete decomposition containing polymer (eg protein) and elimination of hero atoms such as nitrogen, sulfur etc.
Residue Content Analysis
- Fourier Transform Infra-Red (FTIR) Spectra ETHYLNE CARBONATE
The band at 1630 cm·1 decreases and band at 1020 cm·1 has almost disappeared as the retention time of liquefaction increases. The IR spectrum of the residue at the initial stage (liquefaction at 60 minutes) is similar to that of raw material, while the spectrum of residues at 120 minutes, 180 minutes and 200 minutes differs from the raw material. Previous studies suggest that the band at about 1400 cm-1 may represent both the overlap of symmetric carboxyl stretching vibrations of non-ionized carboxylates and C-0-C stretching vibrations of esters.
It has been reported that delignification of dry leaves is more difficult than wood in organic acid cooking due to the condensation reaction of lignin. This mechanism can be interpreted that the liquefaction of dry leaves is not so complete. From Figure 4.7, the broad intense band between 3370 cm-1 and 3410 cm-1 indicates the presence of OH groups in large amounts in dry leaves.
It can also be seen that the band at 1620 cm-1 shows that the residue obtained after 60 minutes still has cellulose and lignin. It can be seen that the four types of residues from different reaction times have the same functional groups. From Figure 4.7, those between 930 cm-1 and 684 cm-1 respectively indicate the presence of the aromatic double bond.
These bands in the spectrum of liquid dry leaves indicate the presence of the aromatic lignin-based components. Comparing the FTIR spectrum between ethylene glycol and ethylene carbonate, it can be seen that the band at 1630 cm-1 decreases sharply and the band at 1020 cm-1 in ethylene carbonate. It can also be seen from Figures 4.6 and 4.7 that there is a very strong band at 1400 cm·1, indicating carboxylic acid in ethylene carbonate compared to ethylene glycol.
In the literature review, the conversion product of liquid ethylene carbonate and ethylene glycol is levulinic acid. We previously reported that when EG was used as a solvolysis reagent, cellulose was degraded and produced a significant amount of EG glucosides at the early stage of the reaction; then the glucosides are broken down into a large amount of levulinates. The glucose content was measured by hydrolysis treatment of the liquid product and was defined as the glucoside content of the solvolysed products.
CHAPTERS
CONCLUSION
CHAPTER6
RECOMMENDATION
Academic syllabus
Effect of solvent on liquefaction: solubilization profiles of Canadian prototype wood populus deltoides in the presence of different solvents. 1988) "Liquification of Lignocellulose in Model Solvents: Creosote Oil and Ethylene Glycol", Canadian Journal of Chemical Engineering, Vol. 2005) 'Effects of Solid Acid and Alkaline Catalysts on Catalytic Cracking of Biomass Tar', Journal of Zhejiang University (Engineering Science), Vol.
APPENDIX A MEffiODOLOGY
Preparation of Raw Material
Liquefaction Process
APPENDIXB
APPENDIXC
ETHYLENE CARBONATE
Density Measurements
Viscosity Measurements
APPENDIXE
Molecular Formula and Relative Content in Bio-Oil
