This project is to discuss the potential of green bio-oil to be use in petroleum industry which acts as a demulsifier to the crude oil. Every crude oil in the world has water content in it. So, green bio-oil will separate the mixture of crude oil and water. Bio-oil consists of green product which comes from an Empty Fruit Bunch (EFB) in palm oil. It does not content any chemical substances which bring effect to the environment. The project will help on providing an alternative source that has a similar chemical formula with furfural. In this project, the focus will be on finding the best quantity and measurement of bio-furfural to extract water content based on similarity of furfural.
The advantage of using bio-oil from empty fruit bunch it is a green technology, which is cheap source of energy and environment friendly. Green bio-oil is significantly developed to replace other chemical solvent in petroleum industry which is more expensive and causes pollution to the environment such as air
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pollution and water pollution. Basically bio-oil can be produced from pyrolysis process, which involves high heat at atmospheric pressure.
Global warming has become a threat to the world since then, which depletion of ozone become worse. The petroleum product has increased based on high demand on the other sector such as transportation, pharmaceutical industry and others. This bring more effect to the environment as production of petroleum increased, the chemical usage also increased. As for alternative source of replacing the usage of chemical in petrochemical field, green demulsifier will be used which consist of bio-oil from empty fruit bunch in palm oil produced from liquid-liquid extraction process. The dehydration process, which eliminates water using bio-liquid descendant is one of the regeneration process based on retention time. The pyrolysis process is a process of producing bio-oil from empty fruit bunch from oil palm which reacts at high temperature.
With the abundance of palm oil field in Malaysia, peoples should make use of it and not throwing away the palm oil waste. The palm oil waste has a high potential in Malaysia in the long run. The pyrolysis process is a heating process which involves the combustion of empty fruit bunch and kernel of oil palm.
This project was prepared to achieve a few objectives which are:
Determine the alternative source to replace chemical usage in dehydration process in petroleum industry.
Determine the quantity and measurement of bio-furfural that will be used to extract water that can be applied in dehydration process.
Determine the properties of bio furfural that lead to instability of water-oil emulsion
Determine the variables that bring effect the water-oil emulsion.
1.4 Scope of Work
The scope of the project consists of 3 scopes, which is:
Bio-oil produced from pyrolysis process from empty fruit bunch of palm oil.
Using bio-oil that has similar chemical properties with furfural.
Investigation is to be done in a biotransformation lab.
Using crude oil from Terengganu Crude Oil Terminal(TCOT)
Study the effect of temperature on water-oil emulsion
Study the effect of concentration of bio-furfural on water-oil emulsion.
1.5 Significant of Study
This study will focus on seeking other alternative source to replace chemical usage in dehydration process. The amount of water content been removed based on amount of bio-oil been applied. To get a good amount of water content, the study need to have an experimental test as much as possible to determine amount of water that can be removed in experimental scale before going into larger scale.
1.6 Organization of Thesis
This thesis is divided into five sections: Chapter 1: Introduction, Chapter 2: Literature Review, Chapter 3: Methodology, Chapter 4: Result and discussion and Chapter 5: Conclusions and recommendation. Chapter 1 explains about the background of this research, its scopes and objectives. Chapter 2 reviews the theories behind the synthesis of bio-oil form empty fruit bunches and characterization of bio-oil that act as a demulsifier. Furthermore, Chapter 3 gives details on the apparatus, chemicals and experimental procedure that are applied to carry out this research. Meanwhile, Chapter 4 explains on the results that were obtained of this research and make reasonable justification about them. Finally, Chapter 5 is about the conclusions that will summarize from the study and recommendation for further study on this research.
2.1 General principles
2.1.1 Empty Fruit Bunch
Always on Time
Marked to Standard
Empty fruit bunches is a waste by-product of palm oil. In southern-east region such as Indonesia and Malaysia, these two countries contributed about 86% of the global palm oil production. Also, rate of deforestation also increase with the increasing demand of palm oil. Empty fruit bunches (EFB), wastes which are abundant, commercially used to produce steam and power, and the remaining ashes from the combustion are used as fertilizers. However, EFBs usually applied as organic fertilizer where 0.07 tons of palm shell, 0.103 tons of palm fibre and 0.012 tons of kernels been produced as solid wastes for every ton of oil palm. (Pansamut et al., 2003).
2.1.2 Pyrolysis Process
Pyrolysis is a technology of thermo-chemical conversion for the production of pyrolyzed liquid oil (Bridgwater and Bridge, 1991). Pyrolysis processes categorized into two parts, conventional or slow pyrolysis and fast pyrolysis, depending on the operating conditions that are used (Jakab et al. 2000). The pyrolysis tests were conducted in a fixed-bed pyrolyser, as shown in Fig. 2.1(a). The pyrolyser, an operating machine consisted of a stainless steel reactor with 125 mm in diameter and 500 mm in height. It was fixed in an electrically heated furnace. The reactor was connected to two water-cooled condensers with liquid traps through an insulated stainless steel pipe. Another furnace was attached to nitrogen stream which pre-heat at the bottom of the reactor.
Fast pyrolysis represents a crucial potential route to upgrade the EFB waste to value added product which are fuels and renewable chemicals. For woody feedstock, temperatures of 500 °C together with short vapour residence times are used to obtain 70% of bio-oil yields, along with 15% of char and gas yields. Samples obtained in the form of whole bunch and chopped into smaller sizes. Then, a Fritsch grinder with a screen size of 500 µm was used to reduce the size of the feedstock to less than 500 µm. Finally, the particle sizes of interest for this study are between 250 and 355 µm as the feedstock of this size range can easily be fed into the feeder.
Figure 2.1: Pyrolyzer
Two of the experiments, for particles sized less than 150 µm and an average of 150-250 µm can only obtained as close as 90% due to feeding difficulties, while all other experiments had closures above 95%. Furthermore, the low organic yield obtained produced the highest ash content of particle size range less than150 µm, is nevertheless impure. All other yields were higher than compared to the size range of 300-355 µm, with more than ten percent lower of the organic yield. It is also noted that ash content is not the only valuable variable that is impacted by the particle size ranges. Pyrolysis yields may bring effect to particle size itself, especially for small particles.
The pyrolysis liquids that been produced separated into two phases; a phase of tarry organic compounds and an aqueous phase. The relative shares of the total liquid product yield of the two phases are approximately 60% for the former and 40% for the latter. The value for sulphur was unidentified, as there is very small proportion of sulphur in the EFB itself. Higher heating value of the aqueous phase was not measured due to high water content.
2.2 Composition of Bio-oil
Bio -oil is a liquid which produced through the process of pyrolysis from Empty Fruit Bunch (EFB). There are six main components inside bio -oil which are phenol, 2-methoxyphenol (guaiacol), 2,6-Dimethoxyphenol, 2-methylphenol(o-Cresol), 2-Furancarboxaldehyde (Furfural) and 2-Methoxy-4-methylphenol. Each of these components have its own properties of water solubility. Phenol has water solubility of 8 g/100 ml whereas 2-methoxyphenol has 17 g/1000 ml of water solubility. Meanwhile, 2,6-Dimethoxyphenol has water solubility of 20 g/1000 ml at 13 °C. o-Cresol has 31g/1000ml of water solubility at 40°C while Furfural has 83 g/1000 ml. Table 2.1 shows chemical composition of bio-oil that has been done by pyrolysis process.
Table 2.1: Chemical composition of Bio-oil
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2.3 Dehydration Process in Petrochemical Refinery
The production of oil from underground reservoirs results in crude oil containing varying amounts of water generally in the form of a water-in-oil emulsion. It is general practice to dehydrate the crude oil by allowing it to stand but often times when the dehydration is enhanced by the addition of a demulsifier to break the emulsion facilitating physical separation of the crude oil from the water. Following this dehydration step, the crude oil is transported to the refinery where it may undergo an initial dewatering procedure and/or subjected to the process of desalting, which is the removal of salts from hydrocarbon crude oil.
The most widely used extraction solvents in dehydration process are phenol, furfural, and cresylic acid. Furfural is a heavy, straw-colored liquid that boils at 162°C (323°F). The process is carried out in the same manner as phenol treatment, but the raffinate or treated oil has so little furfural dissolved in it that distillation is not used to remove it.
Demulsifiers are surface-active agents which have properties which make them effective in disrupting the effect of the natural emulsifiers present in the oil. Their initial action is at the water-oil interface. The layer surrounding the tiny water droplets in the emulsion prevent the water droplets from uniting and result in a stable emulsion. Once the demulsifier is at the water-oil interface, it is able to carry out its primary action of flocculation. The demulsifier acts at the interface of the water and oil to provoke coalescence of the water drops dispersed throughout the continuous oil phase of the water-in-oil emulsion.
A good demulsifier that concentrated at the surface of a water droplet has a strong attraction for other droplets in the same condition. By this mechanism, takes on a very bright appearance since the small water droplets are no longer dispersed throughout the oil to diffuse the light. The characteristic of the demulsifier to produce the joining of droplet does not disrupt the continuity of the emulsifier film but just adds to it. If the emulsifier has certain weaknesses, this flocculation force may be sufficient to cause complete resolution of the emulsion.
However, in most cases further action is necessary for the water droplets to bond and become large enough and free enough to settle out. A good demulsifier most not be able to flocculate the water particles, but also it must be able to disrupt the films surrounding them and allow them to unite.
2.5 Furfural as a Hydrophilic Demulsifier
Furfural is a one of the most crucial and the key ingredient to a derivative of renewable energy of biomass and agricultural, for the massive production of non-petroleum-derived chemicals, along with crude oil. On the other hand, the usage of furfural is increasing in different fields, such as pharmaceutical, oil refining, plastics, and agrochemical industries. Furfural been produced from waste material producing pentosan polymers (e.g., xylan present in corncobs, bagasse, wood chips, empty fruit bunches etc.) by acidic degradation. Then, the reaction involves hydrolysis of pentosan into pentoses such as xylose followed by slow dehydration to form furfural. The reaction showed in figure 2.2. These sequential reactions are catalyzed by acids. Moreover, the reaction mechanism for the dehydration of xylose to furfural involves an irreversible reaction through formation of enediol intermediates.
Figure 2.2: Simplified reaction mechanism of acidic degradation of pentosan
The research methodology is a vital part of the study based on the scope and the objectives. Since the study divided into three categories which are the sample preparation, chemical characterization and chemical testing; the experimental technique need to be arranged properly. The emulsion and demulsifier is prepared by in-situ experimental method, analysis method and comparison method that are all about to explain in the next section. Among the three methods, the amount of water that been separated is measured.
3.2 Research Design
This chapter will summarize the physical and chemical properties of bio-furfural to be used in extraction of water. Besides, the experimental as well as the
method and analysis used will be discussed to test the effectiveness of bio-furfural. Figure 3.2 shows the research design of this study.
Preparation of Emulsion:
Synthetic Brine water
Selection of the Demulsifier:
Mixture of Emulsion-Demulsifier formation
Emulsion-Demulsifier Separation Testing
Determination of emulsification of water-oil and hydrophilic properties of bio-furfural
Figure 3.2: Research Design
3.3.1 Preparation of Crude oil
Two samples of crude oil are obtained straight from Terengganu Crude Oil Terminal (TCOT) which is ex-desalting and desalting crude oil. The crude oil is prepared for about 100 ml into a 500 ml beaker.
3.3.2 Preparation of Synthetic Brine Water
Water which is distilled water is prepared for 100 ml. Then, Sodium Hydroxide (NaCl) mixed together with Chrome Lignosulfonate. Next, the mixture need to stir on hotplate magnetic stirrer. Refer to appendix A to determine amount of NaCl needed to prepare synthetic brine water.
3.4.1 Preparation of Bio-Furfural
Three samples of bio-furfural are prepared according to each concentration. Refer to appendix B to determine volume needed to each concentration of bio-furfural. After that, all three samples is mixed in 1000 ml water to prepare 1500 ppm, 2000 ppm and 3000 ppm of solution. Stir the solution for about 2 hours until all the solution mix with each other.
A set of water bath is prepared in the lab. Other equipments in the lab are:
Hotplate magnetic stirrer
500 ml beaker
2000 ml beaker
50 ml beaker
Table 3.5: Volume data for the prepared and numbered sample tubes
Concentration of bio-furfural (ppm)
Volume of crude oil (ml)
Volume of distilled water (ml)
3.6 Experimental procedure
First of all, synthetic brine water need to be prepared by preparing 100 ml of distilled water inside 1000 ml beaker. Next, prepare 11.6722 g of NaCl and 1.2 g of Chrome Lignosulfonate. Mix both distilled water and NaCl and stir onto hotplate magnetic stirrer. After that, add 1.2 g of Chrome Lignosulfonate and let the temperature at 50 ËšC for 30 minutes. After 30 minutes, the mixture between distilled water and NaCl called synthetic brine water becoming soluble. Add 100 ml of crude oil and stir for 3 hours.
On the other hand, samples of crude oil-bio-furfural are prepared into several sample of tubes according to table 3.5. First thing, prepare 1000 ml of distilled water. Calculate the concentration of bio-furfural by determine its density. Prepare 1500 ppm of bio-furfural by measuring 1.293 ml of bio-furfural. After that, prepare sample 1,2 and 3 by having 10 ml of crude oil that has been mixed with synthetic brine water and 10 ml of bio-furfural. Shake the samples until it dissolve towards each other. Set the temperature of each sample starting from 27ËšC, 60 ËšC and 80ËšC. Place the samples inside water bath for about 2 hours each regarding on each samples. The temperature of the water bath should start at room temperature of 25 °C and should not above 85°C. The bulb of digital thermometer must be immersed on the surface of water bath before it is switched on. The heater-stirrer will be turned on to increase the temperature of water bath. Several sample tubes will be placed on a plastic rack which will then be immersed in the water bath. The water level should be near or at the bottom of the tube caps. If the water level is not sufficient, more water will be added to the water bath. Then the water bath been switched on and the temperature been recorded. The temperature should start from 27ËšC, 60ËšC and 80ËšC. Initially, each of the tubes will show two phases region of crude oil and bio-furfural after going through heating and mixing.
Figure 3.3: Synthetic Brine Water
Figure 3.4: Crude Oil
Figure 3.5: Water bath
As the sample tubes become warm, their caps may loosen due to contraction. The caps of sample tubes need to be tightened once or twice during experiment to prevent mixture of crude oil and bio furfural from leaking out from sample tubes. A replacement sample tube need to be prepared in case the cap cannot be tightened sufficiently or leakage occurs. To do so require a similar volume of crude oil and bio-furfural need to be measured and put it into a new sample tube. A sample number will then be written on its cap. As each of the temperature reached, placed out the sample from water bath and the volume of water separated are measured by using pipette.
Figure 3.6: Pipette
The experiment continues with preparation of 2000 ppm and 3000 ppm of bio-furfural that need to be dissolve in 1000 ml of distilled water. After that, prepare sample 4, 5, 6, 7, 8, 9 by having 10 ml of crude oil that mixed with synthetic brine water and 10 ml of bio-furfural. As the time goes by, the temperature of the water bath will be increased gradually and the sample tubes will approach miscibility. After a while, cloudiness in the tube or blurring of the phase boundary will appear. A test-tube holder will be used to immerse each of the tube completely one at a time. The tubes will then be shaken to stir the contents. For caution, the tube cap must be sealed tightly at this point. The rack of tubes will be removed from the water bath after reaching the emulsion temperature. The tubes will then be placed securely in a container.
RESULTS AND DISCUSSION
In this chapter, investigation is to be done regarding on different concentration of demulsifier and varies in temperature that act towards the stability of water-oil emulsion. In addition, the experimental results are successfully been analyzed and discussed. The main focus of this study is to find the most effective concentration of demulsifier and the suitable temperature that influence the stability of water-oil emulsion.
4.2. Experimental Results
4.2.1 Volume of water separated (See Appendix C)
4.3 Effect of Emulsion
It is noted that the crude oil and synthetic brine water inside beaker is separated after going through heating and mixing. From the observation, it shows that emulsion consists of water droplet in crude oil and formed water-oil emulsion. In this experiment, the stability of emulsion is evaluated based on percentage of water been separated by using the equation:
Volume of water separated,% = x 100%
The stability of emulsion is depends on factors like physical nature of interfacial film where emulsion of water-oil are stabilized by the presence of interface films surrounding the dispersed water droplet. These interfacial films are known as solid condensed type, which have very strong intermolecular forces with respect to interfacial films, and water droplet is prevented by its mechanical strength.
Other than that, size distribution of droplet also plays its role where more stable emulsion can be achieved by having small ranges of size of droplet. Unlike larger particle, they have less interfacial surface per unit volume as they are thermodynamically less stable than smaller droplet and tend to expend at the load of the smaller ones. However, the interfacial film will expand further and its capability to surround droplet will decrease if the volume of dispersed phase in macro emulsion increases. This can lead to emulsion instability.
Figure 4.3: Two phase region of crude oil and synthetic brine water
4.4 Effect of Concentration
Figure 4.4: Graph of Volume of water separated (%) against temperature (ËšC) at (a) 1500 ppm, (b) 2000 ppm and (c) 3000 ppm
The graph shows volume of water separated against temperature of samples at certain concentration. At 1500 ppm, volume of water separated is 8% at 27ËšC, 38% at 60ËšC and 48% at 80ËšC.Then, at 2000 ppm, volume of water separated is 14% at 27ËšC, 40% at 60ËšC and 50% at 80ËšC. Meanwhile, at 3000 ppm, volume of water separated is 18% at 27ËšC, 44% at 60ËšC and 54% at 80ËšC.
From the graph shows an increasing volume of water separated as concentration of bio-furfural is also increased. Obviously, bio-furfural with concentration of 3000 ppm is giving the highest value of volume of water been separated followed by 2000 ppm and 1500 ppm. The amount of demulsifier is crucial as it gives impact on the amount volume of water been separated. If the amount is insufficient, the emulsion will not resolve and the amount of demulsifier is overdose, the process is halted.
The minimum amount of bio-furfural concentration gives a lowest volume of water separated and conclusion can be made that maximum amount of concentration gives a higher percentage of water separated.
4.5 Effect of Temperature
Figure 4.5: Graph of volume of water separated (%) against concentration of bio-furfural (ppm)
The graph shows volume of water separated against concentration of bio-furfural after going through heating and mixing. At temperature of 27ËšC, the volume of water separated is 0.9 ml in 1500 ppm, 1.2 ml in 2000 ppm and 1.4 ml in 3000 ppm. At temperature of 60ËšC, volume of water separated is 2.4 ml in 1500 ppm, 2.5 ml in 2000 ppm and 2.7 ml in 3000 ppm. Meanwhile, at temperature of 80ËšC, volume of water separated is 2.9 ml in 1500 ppm, 3.0 ml in 2000 ppm and 3.2 ml in 3000 ppm.
From the observation, it shows that as the temperature increase, the stability of emulsion of crude oil decrease. This is due to the action temperature as disturbance that affects the physical properties of both oil and water, and also the interfacial films. The temperature also plays its role on the viscosity of emulsion as it decreases when temperature increases. This is due to decrease in oil viscosity that the temperature increase the thermal energy of the droplet and enhance the frequency of drop collision. Other than that, it also reduces the interfacial viscosity and result in higher drop coalescence. However, a kinetic barrier of drop coalescence still appears even at high temperature. But still, temperature itself cannot resolve emulsion even at higher temperature unless demulsifier are added in order to have an effective action in breaking the emulsion.
As the temperature increase, it causes rigid films to be unstable due to reduction in interfacial viscosity. Heat is indeed a factor that related to separation of two phase region where breaking of emulsion is required. This is due to decrease in surface tension as bonding between molecules of water is broken. Heat is also act as viscosity disturbance and result in increasing unstable emulsion. .
CONCLUSIONS AND RECOMMENDATIONS
5.1 Overall conclusion
In conclusion, it is clear that bio -furfural can act as a demulsifier as it successfully separate water molecules from oil-water emulsion. Furthermore, the temperature plays a vital role in determining the amount of volume of water separated as well as the concentration. However, temperature would not be effective without presence of demulsifier as it enhance the mechanism of water extraction that act at its interfacial film. As more concentration been used, the emulsion of water-oil will be unstable. From the result, the concentration of 3000 ppm and temperature of 80ËšC is the suitable application for this study.
For the further study, there are few recommendations are suggested below. The following suggestions can be considered to get better finding and to find the best optimum condition:
Other surfactant should be added in order to have a good demulsifier of bio-furfural such as toluene and xylene.
. Bottle testing is one of the method that can be considered to test on bio-degradable product as to find out the most economical and effective demulsifier.
Turbidity meter can also be used as to determine turbidiness of emulsion itself.