Bio Furfural As Green Demulsifier Agent Biology Essay

Published: Last Edited:

This essay has been submitted by a student. This is not an example of the work written by our professional essay writers.

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

pollution and water pollution. Basically bio-oil can be produced from pyrolysis process, which involves high heat at atmospheric pressure.

Problem Statement

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.

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.

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

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

Retention Time


Utm Bio-oil

(Area %)





2-methyl phenol



4-methyl phenol



2-methoxy phenol



2-Methoxy-4-methyl phenol



2,6-dimethoxy phenol



2-methoxy-4-(2-propenyl) phenol





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.

2.4 Demulsifier

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

to furfural.



3.1 Preface

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 is to be arranged properly. The catalyst will be 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, only the amount of water that been separated will be different.

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 or analysis used will be discussed to test the effectiveness of bio-furfural. Figure 3.2 shows the research design of this study.


Parameter involved

Preparation of water sample:

De-ionised water

Selection of the catalyst:

Bio-oil (furfural)

Mixture of water-bio-furfural formation

Water-bio-furfural Separation Testing

Determination of solubility and permeability

Figure 3.2: Research Design

3.3 Chemical

3.3.1 Preparation of Water

Water which is de-ionised water will be prepared constantly. Each of the water samples will be divided into five sections of tube sample which consist the de-ionised water itself. Each of the tube samples will be filled with 10 ml of de-ionised water.

3.4 Preparation of Catalysts

3.4.1 Preparation of Bio-Furfural

Bio-furfural that has been prepared then mixed with water sample with a quantity regarding on each of the tube sample starting from blank sample, 20 mole percent, 40 mole percent, 60 mole percent and 80 mole percent by volume of bio-furfural.

3.5 Apparatus

A set of water bath is prepared in the lab. Other equipments in the lab are:

A digital thermometer

PTFE tape for sealing tube sample

Electronic rheometer

Table 3.5: Volume data for the prepared and numbered sample tubes

Sample tube

Furfural in mole percent (%)

De-ionised water (ml)
















3.6 Calibration of water

Firstly, 0, 20, 40, 60 and 80 mol percent of water will be prepared in a different set of tube sample. Next, all five samples will be mixed with 10 ml of bio-furfural and heated starting with 30ËšC, 40ËšC, 50ËšC, 60ËšC, 70ËšC and 80ËšC. Then, the mixture is shaken until it boundary layer of two region appeared. All five samples been tested at boundary phase of two region for its viscosity that been recorded by using electronic rheometer. The graph of viscosity reading against water sample is plotted.

3.7 Experimental procedure

First of all, an emulsion of water-bio-furfural will be prepared into several sample tubes according to table 3.5. 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 30ËšC, 40ËšC, 50ËšC, 60ËšC, 70ËšC and 80ËšC. Initially, each of the tubes will show two phases region of water and bio-furfural.

D:\picS\PSM_picture\New folder\P3140004.JPG

Figure 3.4: Tube samples

D:\picS\PSM_picture\New folder\P3140005.JPG

Figure 3.5: Water bath


Figure 3.5: Electronic rheometer

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 furfural and benzyl chromium chloride 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 bio-furfural and need to be measured and put it into a new sample tube of crude oil and its threads will be wrapped twice with PTFE tape. 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 viscosity reading of bio-furfural will be recorded each by using electronic rheometer.

The temperature of the water bath will be increased gradually. As the temperature rises, 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 temperature will then be recorded at which the two liquid phases mix. In order to check an emulsion temperature point, the bath's temperature may be lowered. The rack of tubes will be removed from the water bath after recording the emulsion temperature. The tubes will then be placed securely in a container in the refrigerator.



4.1 Introduction

In this chapter, results from the experiment will be analyzed. This includes the proportion of water content that can be miscible with furfural based on observation.

4.1.1 Effect of water

It is noted that the sample containing deionised water and bio-furfural inside tube sample will have boundary layer of region which consists of deionised water and furfural. This shows that water and bio-furfural can solute at certain miscibility point where boundary layer of two phases is mixed that can be seen after going through heating and mixing process.


30ËšC 40ËšCD:\picS\PSM_picture\2\30.JPG



50ËšC 60ËšC


70ËšC 80ËšCD:\picS\PSM_picture\2\70.JPG

Figure : 20 mol percent of bio-furfural at 30ËšC,40ËšC, 50ËšC, 60ËšC, 70ËšC and 80ËšC


30ËšC 40ËšCD:\picS\PSM_picture\4\30.JPG


50ËšC 60ËšCD:\picS\PSM_picture\4\50.JPG


70ËšC 80ËšCD:\picS\PSM_picture\4\70.JPG

Figure : 40 mol percent of bio-furfural at 30ËšC, 40ËšC, 50ËšC, 60ËšC, 70ËšC and 80ËšC

D:\picS\PSM_picture\6\30.JPG D:\picS\PSM_picture\6\40.JPG

30ËšC 40ËšC


50ËšC 60ËšCD:\picS\PSM_picture\6\50.JPG


70ËšC 80ËšCD:\picS\PSM_picture\6\70.JPG

Figure : 60 mol percent of bio-furfural at 30ËšC,40ËšC,50ËšC,60ËšC,70ËšC and 80ËšC



30ËšC 40ËšC


50ËšC 60ËšCD:\picS\PSM_picture\8\50.JPG


70ËšC 80ËšCD:\picS\PSM_picture\8\70.JPG

Figure : 80 mol percent of bio-furfural at 30ËšC,40ËšC,50ËšC,60ËšC,70ËšC and 80ËšC

4.1.2 Effect on miscibility

From the experiment, it shows that bio-furfural does not dissolve completely in deionised water. However, they do have miscibility point at boundary layer of two regions where in this layer, both bio-furfural and deionised water have a cloudiness area that shows they miscible towards each other in a small portion. The miscibility occurs due to the temperature that took place in the experiment that act as a starter.

4.1.3 Effect on Composition

Figure : Graph of viscosity reading against mol percent of bio-furfural and water

The graph shows viscosity reading against the mol percentage of bio-furfural and water when both substances mixed together inside tube sample. The viscosity reading is taken at phase of bio-furfural and boundary layer of two regions between water and bio-furfural. When the viscosity reading is plotted at 4, the mol % of water is 19 while the mol % of bio-furfural is 17.5. When the viscosity reading is plotted at 8, the mol % of water is 41.2 while the mol % of bio-furfural is 39.4. When the viscosity reading is plotted at 12, the mol % of water is 62.1 and mol % of bio-furfural is 58.4. When the viscosity reading is plotted at 14, the mol % of water is 77 while mol % of bio-furfural is 70.3. It shows that bio-furfural does extract water at certain composition when temperatures take into places. This can be stated that the amount of bio-furfural plays a vital role in determining the amount of water that been extracted based on the miscibility point. However, the bio-furfural and water does not dissolve completely because of different density.

4.1.4 Effect on temperature

Figure : Graph of viscosity reading of temperature against mol percent of water mix with bio-furfural.

The graph shows the result of viscosity reading when temperature against the mol percentage of bio-furfural and water when both substances mixed together inside tube sample. When the temperature is at 30ËšC, there is a series of numbers which are 0.21 at 20 mol %, 0.27 at 40 mol %, 0.53 at 60 mol % and 0.84 at 80 mol % of water-bio-furfural emulsion. When the temperature is at 40ËšC, the viscosity readings are 2.22 at 20 mol %, 3.73 at 40 mol %, 3.94 at 60 mol % and 4.08 at 80 mol % of water-bio-furfural emulsion. When the temperature is at 50ËšC, the viscosity readings are 2.26 at 20 mol %, 4.36 at 40 mol %, 3.92 at 60 mol % and 5.81 at 80 mol % of water-bio-furfural emulsion. When the temperature is at 60ËšC, the viscosity readings are 3.90 at 20 mol %, 6.33 at 40 mol %, 8.02 at 60 mol % and 8.46 at 80 mol % of water-bio-furfural emulsion. When the temperature is at 70ËšC, the viscosity readings are 4.19 at 20 mol %, 6.30 at 40 mol %, 9.75 at 60 mol % and 11.12 at 80 mol % of water-bio-furfural emulsion. When the temperature is at 80ËšC, the viscosity readings are 5.66 at 20 mol %, 8.37 at 40 mol %, 12.54 at 60 mol % and 16.23 at 80 mol % of water-bio-furfural emulsion. There is no mixture of water and bio-oil that appeared inside the tube sample until miscibility point appeared as the temperature reaches 80 ËšC. There become two layer of boundary which some composition of water and furfural are miscible. When the temperature increases, the amount of water been extracted is also increased. On top of that, the composition of water is obviously changed as the water mixed with furfural at high temperature.



5.1 Overall conclusion

In conclusion, it is noted that a mixture of water and furfural will become two layers when the temperature been put into action. Each of the mixture has the miscibility point at certain temperature depending on each composition. Water and bio-furfural does miscible but bio-furfural does not dissolve completely in water. When the composition of furfural increase, miscibility point will clearly appear when temperature is increase until maximum temperature.

5.2 Recommendation

For the further study, there are few recommendations are suggested below. The following suggestions can be considered to get better miscibility and to find the best optimum condition:

Other catalyst should be considered in order to have a good solubility between water and furfural such as benzyl chromium chloride and xylene.

Turbidity meter can also be used as to determine turbidiness of both bio-furfural and water

Crude oil also can be use as a sample itself to determine the amount of water that can be extracting in the experiment.

The concentration level of bio-furfural and water inside tube sample should be determined by using measurement test.