biodiesel prod cut ion

Muhamad Hazim Bin Azemi [11605]

Universiti Teknologi PETRONAS

Internship Final Report [Dec 2009-July 2010]

1.0 INTRODUCTION

1.1 National Science and Technology Development Agency (NSTDA)

Thailand's National Science and Technology Development Agency (NSTDA) were

created by the Science and Technology Development Act of 1991 and officially

commenced its operations in 1992. It vision is to perform research and development

to strengthen Thailand's sustainable competitiveness, complemented by technology

transfer and the development of human resources and science and technology

infrastructure, with outcomes that have positive impacts on society and the economy.

The agency initially brought together three national technology centers which is the

National Center for Genetic Engineering and Biotechnology (BIOTEC), formed in

1983, the National Metal and Materials Technology Center (MTEC) and the National

Electronics and Computer Technology Center (NECTEC), both formed in 1986. In

2003 NSTDA established the National Nanotechnology Center (NANOTEC), and in

2005 the Technology Management Center (TMC) was established as the fifth center

under the NSTDA umbrella. NSTDA was founded with the explicit aim to conduct,

support, coordinate, and promote efforts in scientific and technological development

between the public and the private sectors towards maximizing benefit for national

development. NSTDA has served as a major base where leading scientists and

experts can meet and work on scientific and technological issues of immediate

concern to both the national and international communities. NSTDA is located at the

world-class research facilities at the Thailand Science Park just north of Bangkok.

Figure 1: Technology Center in NSTDA




1.2 National Metal and Materials Technology Center (MTEC)

In order to attain sustainable development in materials engineering research and

education in Thailand, the National Metal and Materials Technology Center (MTEC)

has been established under the Ministry of science and Technology on September

19th

, 1986. It mission is to support research and development in metals and

materials, which are instrumental in the growth of the industrial sector and the

overall development of Thailand. MTEC was merged into the National Science and

Technology Development Agency (NSTDA) on December 29th

, 1991 in the Ministry

of Science and Technology. It is one of the new public establishments set up with a

view to providing flexibility in operation. MTEC has set its operational plan for the

fiscal period 2006-2010 to correspond with the NSTDA’s strategic plan. MTEC

consist of many division and research unit. Each of any one of them play different

role in order to achieve MTEC vision.

Figure 2: Division and Research Unit in MTEC

• Research Development Division

• HRD & Infrastructure Development for Material Technology Division

• Internal Infrastructure Management Division

• General Administration Management Division

• Organization Strategy Division

• Computer-Aded Technology Research Unit

• Design and Engineering Research Unit

• Ceramic Technology Research Unit

• Polymers Research Unit

• Biomedical Engineeering Research Unit

• Materials for Energy Research Unit

• Materials Reliability Research Unit

• Environment Research Unit

• Analytical and Testing Research Unit




Figure 3: Materials for Energy Research Unit Laboratory

1.3 Bioenergy Laboratory

There are two main laboratories that attach to Material for Energy Research Unit at

MTEC which is Electrochemical Materials and System Laboratory and Bioenergy

Laboratory. Electrochemical Materials and System Laboratory mainly focus on the

development of materials and systems related to electrochemical energy. Solid Oxide

Fuel Cells and Proton Exchange Membrane Fuel Cell are presently under

development. Bioenergy Laboratory mainly focuses on renewable source of fuels

such as biodiesel and bio oil. Under Bioenergy Laboratory, it has another two sub

laboratories which is Automotive and Alternative Fuel Laboratory and Biofuel

Testing Laboratory. Automotive and Alternative Fuel Laboratory conduct research

and development of alternative fuels for automobiles. The lab specializes in a wide

range of areas, including the effects of biofuels on engine performance, fuel

combustions, emissions, degradation of engine parts, and lubricant properties of

additives. Furthermore, the lab also offers technical consulting, testing and analysing

services. The Biofuels Testing Laboratories offers several aspects of technical

assistance and problem solving for both government and private sectors. It also

provides a complete-cycle service for biofuels testing and analysis including

determination of physical and chemical properties, efficiency and engine impact.

Materials for Energy Research

Unit

Bioenergy Laboratory

Biofuels Testing Laboratory

Automotive and Alternative Fuel

Laboratory

Electrochemical Materials and

System Laboratory




1.4 Objective of the Industrial Internship Programme

Apart from UTP course outline requirement, the main purpose of the industrial

internship is to give opportunity for UTP students to experience the real working

environment beside to apply all theoretical skills in industrial level. During the

period of internship programme, the students will also develop skills in safety

practices, work ethics, communication, management and discipline. Furthermore,

with internship programme, this will open a new gateway not just UTP students but

for UTP as well to establish a good relationship between industries. The industrial

internship programme will provide opportunity to UTP’s students to build a solid

understanding of the fundamentals of business and organization performance such as

economic models of business, competitive positioning and strategy execution. The

32 weeks Industrial Internship programme is aligned with the university’s objective

to produce well-rounded graduates who are technically competent, have good

interpersonal skills, lifetime learning capability, an entrepreneur spirit, critical

thinking capability, practical aptitude and the ability to synthesize solutions.

Among the main objectives of internship programme are:

o To further improve basic skills such as communication, team work and

management.

o To apply theoretical knowledge in real working environment.

o To train students to become more responsible with the task and assignment

that being assign to them as part of internship programme.

o To give opportunity to students to work with industrial expertise by

understanding their role in the industry.




1.5 Scope of Work, Task and Project

The actual scope of work during the author’s internship period is mainly focuses on

fractionation and stabilization of biooil in order to enhance its storage stability. But,

due to unavoidable circumstances, the task cannot be done and a new scope of work

had been given to the author from his supervisor. The new scope of work mainly

focuses on biodiesel production. During internship period, there are several tasks that

the author supervisor had assigned to him. Some of the task that the author has done

is literature survey in biodiesel production. He also had been given a task to

measured physical properties of biodiesel and bio oil according to American

Standard Testing Method (ASTM). With this task, the author have the opportunity to

learn and to use some equipment in order to determine properties of bio oil and

biodiesel such as viscometer, oil test centrifuge, oxidation stability, Karl Fisher

Coulometer, automatic titration, bomb calorimeter and density meter. Although the

new task is quite different from the original task, but the author manage to learn and

to complete the entire task that being assigned to me without any major problems.

In term of project, he has been given a project which is to study and to compare

biodiesel production of biodiesel using homogeneous and heterogeneous catalyst.

The objective of this project is to determine which catalyst is better to use for

biodiesel production in term of cost, materials and energy factor. In this project, the

author also has to design equipments use in biodiesel production such as evaporator,

batch reactor and mixer.




2.0 MAIN ACTIVITIES

Basically, there are several activities that the author has done during his internship at

MTEC. All of these activities play important role because it can act as a basic

knowledge before going further into main project. Below are some of activities that

he has done during his internship at MTEC:

No Activities

1 Literature Review

2 Equipment Analysis

3 Weekly Meeting

Table 1: List of Activities

2.1 Literature Review

One of the important part in conducting a research or study is to do literature review.

A literature review is designed to identify related research, to set the current research

project within a conceptual and theoretical context. Literature reviews can be either

a part of a larger report of a research project, a thesis or a bibliographic essay that is

published separately in a scholarly journal. The reason for doing so is that to

demonstrate how much you can understand regarding the topic that you wish to

study.

In my literature review, the author was assigned to find papers that explain overview

of biodiesel. Basically this activity is to give a basic knowledge regarding biodiesel.

Below are the summary of his literature review regarding overview of biodiesel.




2.1.1 Overview of Biodiesel

Biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from

renewable lipid sources. Biodiesel is widely recognized in the alternative fuels

industry as well as by the Department of Energy (DOE), the Environmental

Protection Agency (EPA) and the American Society of Testing and Materials

(ASTM). This definition has been the topic of some discussion, however, as other

materials (tree oil derivatives, other woody products, or even biological slurries)

have sometimes been referred to as “biodiesel.” Although these other materials are

biological in nature, and are a substitute for diesel fuel, they are not deemed biodiesel

as accepted by the NBB, DOE, ASTM, or diesel engine manufacturers. Biodiesel is

typically produced through the reaction of a vegetable oil or animal fat with

methanol in the presence of a catalyst to yield glycerine and methyl esters. Virtually

all of the biodiesel used and produced has been made by this process.

Figure 4: Equation for Biodiesel Production

Biodiesel has many advantages compare to fossil fuel. The main advantage is that by

using biodiesel, it can help to reduce greenhouse gas emission. Besides that, it can

also reduce the dependence on foreign petroleum as well. The interesting part is that

one gallon of biodiesel provides the same benefits used neat (100%) or used in

blends, such as B20 (20% biodiesel with 80% diesel fuel). It also non-toxic and

biodegradable fuels which is very environment friendly.

Triglyceride

(oil or fat)

Methanol Glycerol FAME

(Biodiesel)

1, 2, 3




2.2 Equipment Analysis

Equipment analysis is basically to learn how to operate the equipment that available

in the laboratory. All of this equipment is use to obtain physical properties of a liquid

substance such as biodiesel, bio oil, crude palm oil and many more. Some of this

equipment use standard method and compare the result using American Society for

Testing and Materials (ASTM). All of this equipment has their own specification

and accuracy to determine the properties that we want to measure. Below are some

lists of equipment that the author manage to learn during his internship at MTEC.

a) Viscometer

Viscometer is use to measure viscosity of a liquid. For high viscous liquid,

viscometer tube number 250 is use and for low viscous liquid, viscometer tube

number 250 is use. Silicon oil is use as a heating medium to the liquid sample. Water

is not suitable for heating medium because water can easily evaporate. Here,

viscometer uses a standard ASTM method which is ASTM D445.

b) Oil Test Centrifuge

The main purpose of this equipment is to separate all the sediment contain in the

sample. It also can be use to separate water layer (soluble and insoluble). The result

from this equipment that can be observed is that all the sediment will settle at the

bottom of the tube we call cone tube. This equipment use ASTM D2709, which

require no heating to the sample. Usually, the experiment is run using speed below

1500rpm.

g) Density Meter

Density meter is use to measure density of the sample. The equipment can also

calculate the specific gravity of the sample. It can measure many types of liquid

density. It usually operates at temperature 2 C.




c) Oxidation Stability

The main purpose of this equipment is to measure conductivity of the sample such as

vegetable oil or bio diesel because both of them has ester group, contains oxygen. In

this method, the sample is allowed to oxide using air that is bubbled through the

sample. Then the sample will evaporate and the evaporate gas is then will be channel

to deionised water. This type of water has no ion in it and temperature is high in

order to reduce time taken for maximum oxidation occurs. The evaporate gas is then

will enter to deionised water and then it will be transfer to electrode. Electrode then

will detect the evaporate gas and then the conductivity of the sample can be

determine using computer that are connected to the equipment.

e) Automatic Titration

The main purpose of this equipment is to determine acid value of the sample. Small

amount of sample size is use if the acidity of the sample is high. Higher sample size

is use for sample that has low water content. Potassium hydroxide is use to determine

acid value of the sample. Solution of phenolphthalein can be use to check the result

of the equipment.

f) Bomb Calorimeter

Bomb calorimeter is use to estimate heating value of the sample. In this equipment,

the sample will be burn. The equipment will be added with excess of oxygen to help

the combustion of the sample. The heat produce from the combustion of the sample

will be transfer to the deionise water as a medium. Then the temperature sensor will

sense the temperature change and calculate the heat produce from the combustions of

the sample.

d) Karl Fisher Coulometer

The purpose of using this equipment is to know water content of the sample. Karl

Fisher Coulometer is use for sample that has low amount of water and Karl Fisher

Volumetric is use for sample that has high water contain. Karl Fisher solution is use

as a medium to determine the water content of the sample. Karl Fisher solution

contains iodide which letter will be converted to iodine. Then iodine will react with

water to produce complex compound.




2.3 Weekly Meeting

During internship at MTEC, the author and his supervisor will sit down once a week

to discuss regarding the progress of task and the project that had been given to him.

During this activity, the author will explain the progress that he has done so far and

his supervisor will comment and point out some error or recommendation regarding

the task that he has done.

3.0 MAIN PROJECTS

The main project that the author had done during his internship is basically to

analysis production of biodiesel. In order to do the analysis, a suitable method for

biodiesel production is selected and some factors are taking into account for the

analysis. The diagram below shows sequences of task that need to be done in order to

obtain result of analysis.

Figure 5: Task Sequence in Main Project

3.1 Preferred Method to Produce Biodiesel

In this task, the author has to do a literature review on how biodiesel is produce.

Basically there are many ways to produce biodiesel. This task is important because

later on the author need to select the suitable method to apply in the main project.

Prefered MethodFactors to Analyze

Process Diagram

Equipment Modeling

Project Result

& Discussion

Project Recommendation




i) Production of Biodiesel using Supercritical Methanol

Transesterification process of vegetable oil using supercritical methanol are carry out

without using catalyst. Methyl ester of vegetable oil or biodiesel has several

outstanding advantages among other new-renewable engine fuel and can be use in

any diesel engine without any modification. Supercritical methanol has a high

potential for both transesterification process of triglycerides and methyl esterification

of free fatty acids to methyl ester for diesel fuel substitute. By using supercritical

methanol, it can achieve 95% conversion of vegetable oil in 10 minutes and reduce

viscosity as well as flash point of biodiesel. It also can increase density of biodiesel

up to 885kg/m3, which meets ASTM standard value.

ii) Production of Biodiesel using Pyrolysis Process

Pyrolysis or thermal cracking of triglyceride materials can act as an alternative

method to produce biodiesel and other substance for chemical application. This

option is especially promising in areas where the hydroprocessing industry is well

established because the technology is very similar to that of conventional petroleum

refining. There are significant advantages of this type of technology over

transesterification including lower processing costs, compatibility with infrastructure,

engines and fuel standards, and feed stock flexibility. More importantly, the final

products are similar to diesel fuel in composition. The pyrolysis process of

triglycerides can be divided into two category process which is catalytic and non-

catalytic processes.

iii) Production of Biodiesel using Catalyzed Transesterification

In catalyzed transesterification, sodium hydroxide and potassium hydroxide are

commonly employed as homogenous catalysts. For heterogeneous catalyst, calcium

oxide is use. Using catalyst is the most popular process for biodiesel production, but

it requires strict feedstock specification. Only highly refined vegetable oils should be

used as feedstock to produce biodiesel by this method.

4

5

6




Furthermore, the water and free fatty acid (FFA) contents in the reaction system

should be less than 0.1 and 0.5%, respectively. At high water contents, hydrolysis

will become the dominant reaction and leads to a decline in biodiesel yields. In

addition, the use of oils with higher FFA contents in alkalicatalyzed

transesterification results in the formation of soaps and causes difficulties in the

purification of biodiesel, thereby increasing the overall production cost.

iv) Production of Biodiesel using Enzyme/Acid Catalyzed Hybrid Process

As we know, besides using vegetable oil such as crude palm oil to produce biodiesel,

we also can use waste cooking oil. This is because using crude palm oil will be costly

due price and quantity of crude palm oil needed as a feedstock. But with waste

cooking oil, not only it is cheap but it is also easy to obtain. There are several

setbacks when using waste cooking oil as our feedstock. The main setback is due to

high acid number of waste cooking oil. But recent study shows that even with high

acid value, waste cooking oil can produce good quality biodiesel using Enzyme/Acid

Catalyzed Hybrid Process. This process can be applied with oils that have high Free

Fatty Acids (FFA) contents. Therefore, unrefined oils with high FFA contents can be

used as feedstock to produce biodiesel. Also, the enzymatic/acidcatalyzed hybrid

process uses milder reaction conditions. Finally, the enzymatic/acid catalyzed hybrid

process can avoid inactivation of the immobilized enzyme by polar compounds and

increase biodiesel yields.

After analysing all the four methods, the author decided to select biodiesel

production using catalyzed transesterification due to the reason that:

- Production of biodiesel using catalyst is much more convenient because it can

be conduct in laboratory and don’t need additional equipment such as

compressor or reactor.

- Catalyst can be divided into two types which is homogeneous and

heterogeneous catalyst. Both catalyst can be use to produce biodiesel and

both have their own advantages.

7




- The substance use for this process is easy to get and cheap. For example

potassium hydroxide for homogeneous catalyst and calcium oxide for

heterogeneous catalyst is quite cheap compare to other process.

- The process using catalyst is much easier and less equipment is needed.

Since catalyst can be divided into two types which is homogeneous and

heterogeneous catalyst, it is important to analyse both of them since both can be use

to produce biodiesel. By analysing both of catalysts, comparison of homogeneous

and heterogeneous catalyst can be made. The result of this project also can determine

which catalyst is better to use for biodiesel production under certain condition.

3.2 Factors to Analyze

Three factors have been selected in this project which is cost, energy and materials.

The reasons why these factors are selected are because:

- They contribute the most in determining which catalyst is the best. This is

because if process A require less heat consumption, low total cost production

and produce high quality of biodiesel compare to process B, then process A is

much better than process B. Same goes if process B is better in all the factors.

These factors not just determine which catalyst is better but they also can act

as a reference in term of business and economic point of view.

- All factors can be related to each other. For example high energy

consumption of biodiesel process would cause increase in cost of biodiesel

production. This is because high energy consumption will leads to high use of

electricity.

- Some of the factor will change with time for example price of crude palm oil.

The price for crude palm oil varies with time depends on stock market.

- Energy and materials affect towards environment. According to law of

energy, energy cannot be destroyed or created. When a system receives

energy, some of energy will be rejected to environment. This rejected energy

is important to analyze because it can increase surrounding temperature.

Same goes with materials. Unwanted materials must be treated first before it

can be release to environment.




3.3 Process Diagram

In order to produce biodiesel, several processes are needed to convert vegetable oil to

quality biodiesel. The process for biodiesel production is quite different when using

homogeneous and heterogeneous catalyst. Process diagram for biodiesel production

using homogeneous and heterogeneous catalyst are describe in the next section.

3.3.1 Biodiesel Production Using Homogeneous Catalyst

Figure 6: Biodiesel production Process Using Homogeneous Catalyst

Figure above show the process diagram for biodiesel production using homogeneous

catalyst. This process is based on small scale batch process. In this process, treated

palm oil is use as feedstock of the system. Treated palm oil is use because it has low

water content. This can reduce production of soap due to saponification reaction in

tranesterification process. First the treated palm oil is heated up until 0 C. This

process is called preheating process and purpose of this process is to heat up the

feedstock. When feedstock is at high temperature, it can easily react and produce

high reaction rate. After preheating process takes place, mixing process is next. The

purpose of mixing process is to mix methanol and potassium hydroxide according to

specific ratio. The ratio of methanol use is 6:1 mol ratio of feedstock use while ratio

of potassium hydroxide use is 1 100 g ratio of feedstock use. Potassium hydroxide is

use as homogeneous catalyst. In the mixing process methanol is allowed to mix with

potassium hydroxide for 30 minutes and maintain the operating temperature at 0 C.




After 30 minutes had pass, solution of methoxide is produce and being channel to

transesterification process. This is the most important process because it converts

feedstock to FAME (biodiesel) and glycerol. In this process, feedstock which is

treated palm oil is allowed to react with potassium methoxide for 1 hour at constant

operating temperature which is at 0 C. The reason for using operating temperature

at 0 C and duration of 1 hr is because this parameter is the optimal parameter for

transesterification process . The outputs of this process are FAME, glycerol,

excess methanol and excess potassium hydroxide. Next is the separation process.

This process allowed the substances to settle using gravitational force and the main

function of this process is to remove glycerol. After that methanol removal process

takes place. This process will remove methanol and the remove methanol will be

recycle to mixing process. In this process the mixture is heated up to 0 C and will

cause methanol to evaporate from the mixture. The remaining mixture is then sent to

purification process. In this process, water is use to remove remaining potassium

hydroxide from transesterification process. Potassium hydroxide has higher tendency

to dissolve in water rather than in FAME. The last process is drying process. When

water is use to remove potassium hydroxide, some of water dissolve in FAME.

Although amount of water dissolve in FAME is not significant, but it is important to

remove it in order to produce high quality biodiesel.

8




3.3.2 Biodiesel Production Using Heterogeneous Catalyst

Figure 7: Biodiesel Production Using Heterogeneous Catalyst

Basically, the processes that involve using heterogeneous catalyst are quite the same

with homogeneous catalyst. Calcium oxide is use as heterogeneous catalyst. The

different is that with heterogeneous catalyst, there is no purification and drying

process but additional process is added to the system which is filtration and

decomposes process. The ratio of catalyst use is the same but ratio of methanol use is

different. The ratio of methanol use is 15:1 mol ratio of feedstock use while ratio of

potassium hydroxide use is 10:100 g ratio of feedstock use. When transesterification

process is done in heterogeneous catalyst, instead of channel the mixture to

separation process, the mixture is first been filtered. The filtration process is use to

remove all excess calcium oxide. The filtered calcium oxide is then sent to mixing

process. Another difference in heterogeneous catalyst is the decompose process.

Decompose process is use to convert calcium carbonate to calcium oxide. This

process operates at 00 C for 3 hour.




3.4 Equipment Modelling

In order to analysis in term of cost, materials and energy, equipment modelling need

to be done for each of the process involve. Some equipment can be applied for both

catalysts. Assumptions are made in each of equipment to simplify the calculation.

Below are the equipment that is use to represent each process. The filtration process

will not be consider in the equipment modelling because this process doesn’t involve

any heat needed or wasted to the system and amount of calcium oxide coming in this

process is the same with amount of calcium oxide been filtered.

Process Equipment

Preheating Heating Tank

Decompose Oven

Mixing Mixer Tank

Transesterification Batch Reactor

Glycerol Separation Gravity Settler

Methanol Removal Heating Tank

Purification Purification Tank

Drying Dryer

Table 2: Equipment Use in Each Process

There are several term that will be use in equipment modelling. Thus it is important

to describe this term before going further in the equipment modelling. The term that

will mostly use in the equipment modelling is energy and symbol term. All of this

term can be repetition.




Symbol Term

Q required total is total heat required for system or equipment (J)

Q wasted total is total heat release from the system or equipment (J)

m is amount of mass of substances. (Kg)

k is thermal conductivity of the oven (0.03 W/m K)

h air is heat transfer coefficient of air (50 W/m2 K)

T air is the ambient temperature (3 C)

T equipment is the temperature of operating temperature C)

T i is initial temperature of substance in equipment C)

T f is final temperature operating temperature C)

A is area of the equipment (m2)

n is number of moles of substances present

Cp is the specific heat capacity substances (J/mol K)

o

CfH 25@ is heat of formation of substance at 2 C (J/mol)

o

ToutfH @ is heat of formation of substances at operating

temperature (J/mol K)

Total time is the time for a process (minutes or hour)




Type of Heat Involve

Heat to raise temperature (Q raise)

This heat is required to increase temperature of the system to operating temperature

and is define as

In mass basics

)( ifipiraise TTCmQ

In mole basic

)( ifipiraise TTCnQ

Heat Released by conduction or by convection (Q out conduction / Q out convection)

This heat occurs when there is temperature different between equipment and

surrounding.

)( airequipmentequipmentairconvectionout TTAhQ

])(

)([

21 xx

TTAkQ

airequipment

equipmentequipmentconductionout

Heat Release by temperature drop (Q drop)

This heat is due to cooling down substance before going to next process.

In mass basics

)( ifipidrop TTCmQ

In mole basic

)( ifipidrop TTCnQ




Heat of reaction (Q reaction)

This heat occurs due to chemical reaction from two or more substances. There are

two type heat of reaction which is exothermic and endothermic heat of reaction.

Exothermic heat of reaction will release heat from the system to environment and for

endothermic reaction will require heat for reaction to take place.

outT

o

Cf HHQrxn @25@

treac

o

fiproduct

o

fi

o

Cf iiHnHnH tan25@ )()(

)()()()( 25@tan25@@ CtreacpiiCprodpiiT TTCnTTCnHout

Heat to maintain temperature (Q maintains)

This heat is required for the system to maintain its operating temperature for period

of time until the process is done.

For exothermic reaction

rxnconvectionoutainma QQQ int

For endothermic reaction

rxnconvectionoutainma QQQ int




i) Heating Tank

The main function of heating tank is to heat feedstock which in this case is treated

palm oil up to 0 C. The reason by doing this is because at high temperature,

molecule substance has higher kinetic energy thus can result a high reaction rate. The

model and process diagram for heating tank is describe as below.

Vegetable

Oil

Heat

In

Feed in

Temp

Inital

Q

Temp

final

Input Output

Feed

out

Figure 8: Process and Model Diagram for Heating Tank

Direct heating methods is applied in this equipment. Only heat required to raise

temperature (Q raise) of the feedstock is needed for the process to take place. Below

are the assumptions that were use to design this equipment.

Assumption:

- There is no heat loss from the system to surrounding when heating process

take place.

- No substance will be evaporating in this process.

- Duration for the process doesn’t take into account in order to calculating heat

required.

- Total amount of vegetable oil is the same at initial and final process.




Calculation of Total Heat Required for the Equipment (Heating Tank)

raisetotalrequired QQ

)( ifoilvegpoilvegtotalrequired TTCmQ

ii) Oven

ven is use to convert calcium carbonate to calcium oxide. ere there are 2 process

involve which is decompose and cooling process. Cooling process take place when

decompose process is complete. hen calcium carbonate decomposes at 00 C for 3

hour, carbon dioxide and calcium oxide are produce.

23 COCaOCaCO Heat

The process and model diagram for oven can be describe as figure below.

Heat to

raise

temperature

3CaCO

Heat Release

by Conduction

Qrxn

Heat to

maintain

temperature

Heat Release

by temperature

drop

Figure 9: Process Diagram for Oven

Calcium

carbonat

e

Calcium

Oxide

Carbon

dioxide




Operating temperature

Outside temperature

Area Oven

Thermal Conductivity Oven

Heating Time

Thickness Oven’s Wall

Amount CaO recover

Total CaO needed Remaining

CaO

needed

Qrxn

CO2 produce

CaCO3 need

Qneeded

Figure 10: Model Diagram for Oven

Assumption use in this equipment modelling is:

- Heat loss from the system occurs by conduction only.

- Oven thickness is the same for all side.

- 100% conversion of Calcium carbonate to Calcium oxide.

- eat release by convection takes place when the system heat 00 C for 3 hr.

- Heat release by reaction can be use to maintain operating temperature system.

- Calculation of heat loss from conduction mode is multiply with 6 because

oven has 6 surfaces.

- Calcium oxide produce must be cooled down from 00 C to 3 C before

feeding it back to mixer.

Calculation of Total Heat Required for the Equipment (Oven)

reactionconductionoutraisetotalrequired QQQQ

)(

]6))(

)([()]([

@25@

2133

out

CaCO

T

o

Cf

airovenovenovenifPCaCOtotalrequired

HH

timetotalxx

TTAkTTCnQ




Calculation of Total Heat Wasted from the Equipment (Oven)

dropconductionouttotalwasted QtimetotalQQ )(

iii) Mixer tank

Mixer tank is use to mix methanol and catalyst and produce methoxide solutions. In

mixing process, the temperature is maintained at 0 C for 30 minutes. The catalyst

and methanol are reacting according to the chemical equation below

Homogeneous catalyst chemical reaction (endothermic)

Heterogeneous catalyst chemical reaction (exothermic)

Potassium

Hydroxide

Methanol Potassium

Methoxide

Water

Calcium

Oxide Methanol Calcium

Hydroxide

Calcium

Methoxide

)(]6)(

)([

21

ifpCaOairoven

ovenoventotalwasted TTCntimetotalxx

TTAkQ

CaO




Figure 11: Process Diagram for Mixer Tank

Mass Veg Oil In

Temp In

Temp Out

Area

Mass MeOH Need

Mass KOH/CaO Need

Heat of Mixing

Q rxn

Qout by convection

Q in

Figure 12: Model Diagram for Mixer Tank

Assumptions that being used in mixer tank are:

- Heat loss from the equipment occurs by convection only.

- There is no enthalpy of mixing or enthalpy of solution when mixing

potassium hydroxide or calcium oxide in methanol (ideal mixing).

- Heat release by convection takes place when the mixture is at 0 C.

- Heat release by reaction can be use to maintain operating temperature.

- The tank is assumed to be in cylindrical shape.




Calculation of Total Heat Wasted from the Equipment (Mixer Tank) for

Homogeneous and Heterogeneous Catalyst.

Calculation of Total Heat Required for Equipment (Mixer Tank) using

Homogeneous Catalyst.

Since the reaction of methanol and potassium hydroxide is endothermic, heat of

reaction must be included in the total heat required for the equipment.

ainmaraisetotalrequired QQQ int

reactionconvectionoutraisetotalrequired QQQQ

)(

)]([)]([

@25@

33

out

OHCH

T

o

Cf

airmixermixerairifKOHPKOHPOHCHtotalrequired

HH

timeTTAhTTCnCnQ

Calculation of Total Heat Required for Equipment (Mixer Tank) using

Heterogeneous Catalyst.

Since the reaction of methanol and calcium oxide is exothermic, the heat release by

the reaction process can be use as heat to maintain system temperature.

ainmaraisetotalrequired QQQ int

timetotalTTAhQ airmixermixerairtotalwasted )]([




reactionconvectionoutraisetotalrequired QQQQ

)(

)]([)]([

@25@

33

out

OHCH

T

o

Cf

airmixermixerairifCaOPCaOPOHCHtotalrequired

HH

timeTTAhTTCnCnQ

iv) Batch Reactor

A batch reactor is use for transesterification process. This is the “heart” of the overall

process since FAME is produce during tranesterification process. The purpose of

batch reactor is to convert vegetable oil and liquid methoxide to FAME and glycerol.

The reactants are allowed to stay in the reactor for approximate 1 hr to complete the

reaction. The temperature of reactants enter to reactor is 0 C.

Chemical equation in batch reactor for homogeneous catalyst (exothermic)

Chemical equation in batch reactor for homogeneous catalyst (exothermic)

Feedstock

Methanol

Biodiesel Excess

Methanol

Feedstock Biodiesel Excess

Methanol




Figure 13: Process Diagram for Batch Reactor

Figure 14: Model Diagram for Batch Reactor

Assumptions that being used in batch reactor are:

- Heat loss from the system occurs by convection only.

- There is no enthalpy of mixing potassium methoxide or calcium methoxide

with vegetable oil (ideal mixing).

- Heat release by reaction can be use to maintain temperature of the system at

0 C.




- 100% conversion is achieved.

- The tank is assumed to be in cylindrical shape.

- Ambient temperature air is taken as 3 C

- 60% methanol goes in FAME, 40% methanol goes in glycerol.

Calculation of Total Heat Wasted from Equipment (Reactor Tank) for


Heat release from reactor using homogeneous and heterogeneous is the same using

convection mode.

timetotalTTAhQ airreactorreactorairtotalwasted )]([

Calculation of Total Heat Required for Equipment (Reactor Tank) using


Since the reaction for potassium and calcium methoxide with vegetable oil is

exothermic, thus calculation of heat required total is defined as:

ainmatotalrequired QQ int

reactionconvectionouttotalrequired QQQ

][)( @25@ outT

o

Cfairreactorreactorairtotalrequired HHtimetotalTTAhQ

v) Gravity Settler

Gravity settler is use in separation process. The purpose of gravity settler is to

remove glycerol from FAME. In this process, the product will enter gravity setter

and let it settle for a period of time. Glycerol will be separated by using gravitational

force since it is denser. There also a fraction of methanol in FAME and in glycerol

due to transesterification process.




Figure 15: Process diagram for Gravity Settler

Figure 16: Model Diagram for Gravity Settler

Homogeneous Catalyst Heterogeneous Catalyst

Homogeneous Catalyst

Heterogeneous Catalyst




As the process diagram shows that the only heat involve in this system is heat loss

due to cooling down the substance.

The assumption that is use in this model is:

- Heat loss from the system to environment.

- The mode of heat loss to environment is not taking into account.

- Heat loss from the system will be calculated using direct heat loss method.

- 100% glycerol separation is achieved.

Calculation of Total Heat Wasted from Equipment (Gravity Settler) for


For Homogeneous Catalyst

cesubsdroptotalwasted QQ tan

KOHGlycerolFAMEMeOHtotalwasted QQQQQ

)()()()()( ifKOHpKOHglypglyFAMEpFAMEMeOHpMeOHtotalwasted TTCnCnCnCnQ

For Heterogeneous Catalyst

cesubsdroptotalwasted QQ tan

GlycerolFAMEMeOHtotalwasted QQQQ

)()()()( ifglypglyFAMEpFAMEMeOHpMeOHtotalwasted TTCnCnCnQ




vi) Heating Tank (Methanol Removal Process)

In order to remove methanol that contain in FA E heating tank is use. It same like

tank use in preheating process but instead of heating to 0 C, the mixture will be

heat until 0 C. The reason for doing this is because to evaporate methanol in the

mixture (highly volatile substance). We can see that model and process diagram is

different due to present of potassium hydroxide.

Figure 17: Process and Model Diagram for Homogeneous Catalyst in Heating Tank

Equipment

Figure 18: Process and Model Diagram for Heterogeneous Catalyst in Heating Tank

Equipment




Direct heating methods is applied in this equipment. Only heat required to raise

temperature of the mixture is needed for the process to take place. Below are the

assumptions that were use to design this equipment:

- Use direct heat method to evaporate methanol.

- No others substance will be evaporate except methanol.

- Assume 100% methanol evaporation.

- No heat loss occurs during evaporation process.

Calculation of Total Heat Required for Equipment (Heating Tank) using


The energy calculation in this process is divided into three types. The first Q1 is

energy to increase temperature of the mixture to boiling point of methanol. Second is

Q2 and it is vaporization enthalpy of methanol. The last one which is Q3 is energy to

increase temperature of mixture to operating temperature.

Figure 19: Profile Diagram for Heat Required

31 raisemethanolonvaporizatiraisetotalrequired QQQQ

)()( ifpMeOHonvaporizatiMeOHifpMeOHtotalrequired TTCnHnTTCnQMeOHMeOH




vii) Purification Tank

Purification tank only apply for biodiesel production using homogeneous catalyst.

This is due to present of potassium hydroxide. The purpose of using purification

process is to remove KOH from FAME. Water is use as medium to remove KOH.

KOH will tense to dissolve in water rather than in FAME when water is added to the

mixture.

Figure 20: Process Diagram for Purification Tank

Figure 21: Model Diagram for Purification Tank




Assumption that is use in this model is:

- No heat loss from the system to environment.

- Amount of potassium hydroxide that enters in reactor will be the same

entering methanol removal process.

- 99% of water will be use to dissolve potassium hydroxide.

- 1 % of water will be dissolve in FAME.

- Amount of heat transfer from FAME will be the same for heat absorb from

water.

- Final temperature of product is calculated when the system reach thermal

equilibrium.

- Specific heat of mixture is use since the mixture is miscible (KOH and

FAME).

There is no energy calculation involve since the assumption that is use stated that all

heat release from the mixture is absorb by water. The only calculation that involve in

this process is to determine final temperature of the product, which is define as:

)()(222 fmiximixpmixOHifOHpOH TTCmTTCm

Here, the final temperature refers to as final temperature of the product and water

coming out from the equipment.

viii) Dryer

Dryer is use in order to remove water than dissolve in FAME when removal process

take place. It’s basically same like heating tank. ere when mixture of FA E and

water enter the system, the mixture will be heated up until 120 C. This is to make

sure all the water is evaporated.




Figure 22: Process Diagram for Dryer

Figure 23: Model Diagram for Dryer

Assumption that is use in this equipment modelling is:

- No heat loss occurs when drying process take place.

- Using a direct heating method.

- No other substance will be evaporating except for water.

- 100% water removal process.




Calculation of Total Heat Required for Equipment (Dryer) using Homogeneous

Catalyst.

The energy calculation in this process is divided into three types same like

calculation in heating tank for methanol removal process. The first Q1 is energy to

increase temperature of the mixture to boiling point of water. Second is Q2 and it is

vaporization enthalpy of water. The last one which is Q3 is energy to increase

temperature of mixture to operating temperature.

Figure 24: Profile Diagram for Heat Required

31 raisewateronvaporizatiraisetotalrequired QQQQ

)()(22222 ifpOHonvaporizatiOHifpOHtotalrequired TTCnHnTTCnQOHOH




vix) Heat Recovered System

Total Heat Recovered Calculation

Figure 25: Profile Diagram for Heat Recovered Stream

31 dropmethanoloncondensatidropreleasedmethanol QQQQ

)()( ifpMeOHonvaporizatiMeOHifpMeOHreleasedmethanol TTCnHnTTCnQMeOHMeOH

Since, we specify final temperature of methanol after recovered process, thus

we simplify how long for hot methanol must be in contact with water so that

our final temperature that we want can be achieve. Thus,

waterabsorbreleasemethanol QQ

timetotalTTAhQ MeOHwaterpipeMeOHOHreleasemethanol )(2




3.5 Project Result and Discussion

Both homogeneous heterogeneous catalysts have their own advantage and

disadvantage. From this project, although homogeneous shows positive result

compare to heterogeneous catalyst, it also has some limitations. Production using

homogeneous catalyst requires additional equipment such as washing and drying

process in order to produce high quality biodiesel. This somehow will reflect high

production cost due to additional equipment. Although both catalysts can achieve a

high conversion of vegetable oil to biodiesel, but when using homogeneous catalyst,

the catalyst cannot be recycle and thus the process will need to use a fresh catalyst

for every process. For heterogeneous catalyst, the efficiency of the catalyst can be

sustained because it can be recycle and reuse for next transesterification process.

This is one of the advantages using heterogeneous catalyst. Using heterogeneous

catalyst in biodiesel production also has some limitations. High amount of substance

are needed like catalyst itself and methanol due the ratio use. This somehow will

have a big impact on biodiesel production cost, because price of methanol and

catalyst is quite expensive. It also requires a filtration process so that the catalyst can

be reuse. Additional equipment also needed for decompose process if calcium

carbonate is use instead of calcium oxide. Although homogeneous catalyst have low

production cost compare to heterogeneous catalyst due to low ratio of methanol and

catalyst use, but there is some advantage using heterogeneous catalyst at certain

condition. The result obtain from this study shows that the biodiesel production cost

for heterogeneous catalyst is cheaper compare to homogeneous catalyst when the

process is running between 11 to 14 batches. This is because, heterogeneous catalyst

can be recycled and reuse for the next process. This somehow will reduce total

production cost. Different situation can be observed for homogeneous catalyst. The

production cost will keep on increasing due to cost of fresh catalyst need to be supply

to the process. This shows that heterogeneous catalyst also has its own advantage in

biodiesel production.




3.6 Project Recommendation

For recommendation of this project, additional factors must be study for both

catalysts such as labour cost, capital cost and much more. This is because these

additional factors will contribute and helps to determine which catalyst is better for

biodiesel production. Another important factor that must take into account is kinetic

factor. Kinetic study must be done in biodiesel production so that we can know

which catalyst reacts better with feedstock and optimal parameter needed for the

process. Kinetic study also helps to give better understanding especially in

mechanism of transesterification process. In term of calculation, a specific

calculation must be applied in order to obtain more accurate result. For example,

chemical thermodynamic calculation can be applied in liquid-liquid separation

process (water removal process).

4.0 LESSON LEARN AND EXPERIENCE GAIN

There are lots of valuable experiences that the author has learned during his eight

month internship periods at MTEC. These experiences really helps the author as a

student to understand more on working experience and can act as basic preparation

before going to real working life.

4.1 Leadership, Team Work and Individual Activities

Leadership is one important element that must have in every student. This is

because leadership will reflect how your personality and criteria as a person.

Basically the author didn’t learn much in leadership because being a trainee he was

at the bottom of the organizational ladder, had no subordinates and therefore, had

nobody to lead. Nevertheless, he did learn by observing how his managers handle

their subordinates in order to make sure that all work are completed on time and

reliable especially my supervisor.




Based on the observation during the internship, there are some abilities that must

be possessed by the project leaders such as:

Be Prepared and Motivation

The leader must have many knowledge especially in given projects. This is

because a leader must have the ability to explained to his or her subordinates

if they doing any mistake in the projects. The leader also must know how to

motivate his or her subordinates so that the projects can be complete

successfully.

Listening skill

Listening is the most important part when working with team. A good leader

must have good listening skills. This is because, through listening, a leader

can heard and understand his or her subordinates problems and ideas

regarding the project given.

Facing mistakes, complaint and criticism

The leader must be able to create an environment where people are open to

receive advice or constructive criticism. Leader also should accept their

mistakes and willing to face any criticism from subordinate.

In completing the tasks and project given, teamwork is key element to

complete the tasks and project successfully. In equipment analysis activity,

assistance from lab technician is needed so that the author can learn and understand

fully how to operate and conduct the equipment in the lab. In term of project,

teamwork plays important part because some of the author colleague also involve in

the project. This helps him to discuss with them the part that he don’t understand and

respect them as well.




4.2 Work Ethics, Management Skills and Valuable Experiences

A work ethic is defined as group of moral principles, standards of behavior,

or set of values regarding proper conduct in the workplace. During the author

internship period at MTEC, he learned that a good work ethics is important

especially when you working with people that come from different background.

Work ethics is not just toward responsible to our work, but also contains ethics

towards our manager, ethics towards our co-workers and other employees as well.

At MTEC, many of the workers are not fluent in speaking English but with a good

work ethics, it teach the author how to respect his colleague, how to mingle with the

workers that much older than him and communicate with them. He also gained many

valuable advices from them as well.

It is important to complete the task given in time. This is because it can show

how responsible you are when completing the task given. Thus, management skills

are very important especially when working in a project. Every task that been given

must be completed according to the time required. During the author internship

period, most part in the project must be complete as soon as possible. It is also

important to check all of the result that obtains from each part in the project so that it

won’t affect any future task.

Internship at MTEC has though the author to come close to learn Thailand

culture. He manages to explore wonderful places in Thailand such as the famous Phi

Phi and Phuket Island. He also learned how to speak Thai language and get to taste

variety of Thai food. Foremost, Thailand is really a great country and being here is a

privilege and wonderful experience.




4.3 Safety Training and Values of Practical Experiences

Safety is the most important element when conducting experiment in laboratory.

When doing experiment in Bioenergy Testing Laboratory at MTEC, the author must

obey the entire rule to avoid unwanted accident. This is because, all the experiment

that he done involve highly flammable and volatile materials. Before doing

experiment, a short briefing regarding safety and risk in conducting the equipment

were done by lab technician. This is to ensure that the student really understand how

to operate the equipments correctly. When doing experiment, it is important to wear

lab coat, safety shoes, rubber glove and mask. The author also manages to experience

fire training during my internship at MTEC. This training mainly to make sure that

we are aware if unwanted situation occur during working and what to do when such

things happen.

4.4 Problems and Challenged Faced

During internship period, there are several problems and challenges that the author

has to face. The problems faced have taught him to understand how hard life is and

train him to be more discipline in life. Below are several problems or challenges that

he has to face during the period of internship.

4.4.1 Language Barrier

any of Siamese didn’t know how to speak English and the author found that

it’s really hard for him to adapt especially when he started his internship here.

In order to solve the problems, the author took an initiative to learn how to

speak Thai language and it really helps him a lot especially when to buy some

things like grocery and food.




4.4.2 Adapting to a new environment

Coming to Thailand really makes the author learn how to adjust himself to

the new environment. The major problem that he has to face is regarding

food. As notices most of Thailand people are Buddhism and it’s really hard

to find halal food around. At first it’s really difficult time, but luckily there

are several Muslim students near the author workplace. They really friendly

and they help a lot during the author stay in Thailand.

4.4.3 Limited Skills, Experiences and Knowledge

As a trainee, it is normal to lack in skills, experience and knowledge. This is

the purpose of internship so that student will be able to learn and gain

experiences. This is one of the trainee’s problems when trainee was assigned

a task that requires a lot of skills and knowledge. Therefore, trainee needs to

do some additional work and research regarding the task that given. This can

helps the trainee to understand better and prepare them before doing the

actual tasks. Trainee also need to learn by asking and surveying how the other

trainee done their work. By doing this, they can discuss and can help each

other so that the task can be done efficiently.

4.4.4 Complete tasks within the timeline and meet the requirements

Time limitation is another major problem that the trainee has to face during

this internship programme. Every task in the projects required a lot of

calculation and simulation. This really a tedious process and it will cause

error in the whole calculation if one part of calculation is wrong. Thus careful

calculation must be done so that there is no mistake in the result and make

sure that the entire task is going according to schedule. If the project is behind

the schedule, the trainee should find the way to make sure the project is in

schedule for example do some overtime or complete the unfinished work at

home.




5.0 DISCUSSION AND RECOMMENDATION

5.1 Recommendation to Host Company

5.1.1 Attachment to different areas of expertise

Since the internship period is approximately 8 month, it is better if the host

company can relocate the trainee that doing their internship here with several

different departments. By doing this, trainee can learn and explore many

things and can gain many experience relate with their background. For

example, a chemical engineer trainee can enter department that related with

chemical such as polymer and environment research unit. This would give the

trainee more wider scope of knowledge during their training.

5.1.2 Hands on Task

Trainee should be given more hands on task rather than theoretical task. This

is because with hands on task, trainee should be able to apply all the

theoretical knowledge that they learn before this. Trainee also can learn more

by doing hands on task such as experiment, measurement, observation and

much more compare by doing theoretical tasks.

5.1.2 Proper Training Schedule

Trainee should be provided with proper training schedule when doing

internship. This is because, a proper training schedule can helps to organize

time and task given. Besides that, host company also should provide some

additional activities such as plant visit. This is because by just doing

calculation and simulation, trainee will not experience how biodiesel is

produce in real life. They just learn more on theoretically rather than

practically. This somehow will limit the knowledge and the experience that

the trainee will get during internship period.




5.2 Recommendation to UTP

5.2.1 Internship form and log book

It is suggested that UTP should reconsider the internship form and log book.

This is because the form is too many, tedious and sometimes it is time

wasting especially to supervisor who has many others commitment. The

format of log book also maybe needs to be reconsidered. The proper

computer format should be use so that the form can be neater and organized.

By doing this, student can avoid any loss form by saving them in external

devices.

5.2.2 Alert with Trainee Situation and Problems

UTP should be more concern and alert with current situation of trainee

especially the one who doing their internship at overseas. Recently, Thailand

had been hit by several anti-government groups called the “red shirt”. This

incident had cause fatalities and serious damaged. As a trainee who doing

internship at Thailand, we also had to take extra precautions by undergo

curfew and be more aware with current situation. Although our workplace is

not badly affected by this situation, but UTP should ask or noticed if

everything is safe before anything bad happen to us. This shows that UTP is

concern about their student’s welfare and safety during internship period.




6.0 CONCLUSION

Doing industrial training at National Metal and Materials Technology Center

(MTEC) gives opportunity for me on how to implement all the theory that I have

learn for the past 3 years with practice. The tasks and projects that been given by my

plant supervisors, really help and trained me to become more responsible students.

Besides that, I had experience the true working environment and being expose to

more valuable knowledge especially in renewable energy area.

In addition, internship programme not just tough me in term of technical or

academic, but it also tough me how developed my other skills as well. During my

internship programme, I manage to sharpen my communication skills, implement a

good work ethics at work place, become more responsible with the tasks and project

given, learn how to adapt to new environment and most importantly I learned the

value of time.

Basically, industrial training at National Metal and Materials Technology

Center (MTEC) is one of the most valuable experiences that I ever had since I

become a student of University Teknologi PETR NAS UTP . It’s a privilege to be

part of MTEC workers for past eight month. The working environment exposed,

lesson learned and experiences gained are very useful for future career of the student.

Therefore in the future, University Technology Petronas (UTP) and host company

National Metal and Materials Technology Center (MTEC) should continue their

efforts in giving the perfect learning experience for students.




7.0 REFERENCES

1. Sheehan John, Camobreco Vince, Duffield James, Graboski Michael,

Shapouri Housein. (May 1988). An Overview of Biodiesel and Petroleum

Diesel Life Cycle, NREL/TP-580-24772.

2. Steven A. Howell, B.S.. Research Director; J. Alan Weber, M.S., Program

Director. (1997). US Biodiesel Overview.

3. Bacovsky, Dina, Körbitz, Werner, Mittelbach, Martin, Wörgetter, Manfred.

(July 2007). Biodiesel Production : Technologies and European Provider.

4. Ahyan Demirbas, Department of Chemical Engineering Selcuk University,

Campus, Konya, Turkey. (2005). Biodiesel Production from Vegetable Oils

by Supercritical Methanol. Scientific & Industrial Research, (64), 858-865.

5. Maher K.D., Bressler D.C, Department of Agriculture, Food and Nutritional

Sciences, University of Alberta (2007). Bioresource Technology 98, 2351–

2368.

6. H. West Alex, Dusko Posarac, and Naoko Ellis. (2007). Simulation, Case

Studies and Optimization of a Biodiesel Process with a Solid Acid Catalyst.

International Journal of Chemical Reactor Engineering. 5(A37).

7. N. Saifuddin, Raziah A Z., and Nor Farah H. (2009). Production of Biodiesel

from High Acid Value Waste Cooking Oil Using an Optimized Lipase

Enzyme/Acid-Catalyzed Hybrid Process. E-Journal of Chemistry, 6(S1),

S485-S495.

8. Gerpen Van J., Shanks B., Prusko R., Clements D., Knothe G. (July 2004).

Biodiesel Production Technology. NREL/SR-510-36244

biodiesel prod cut ion

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