PRODUCTION OF BIOFUEL PRODUCTION OF BIOFUEL FROM USED COOKING OIL FROM USED COOKING OIL via CATALYTIC CRACKINGvia CATALYTIC CRACKING

Prepared by: Prepared by:

Khalisanni KhalidKhalisanni Khalid

INTRODUCTIONINTRODUCTION

• Biodiesel is an alternative fuel for diesel enginesBiodiesel is an alternative fuel for diesel engines• Biodiesel can be used easily because it can be Biodiesel can be used easily because it can be

mixed at any proportion with diesel oil, hence mixed at any proportion with diesel oil, hence enabling us to apply it immediately for diesel enabling us to apply it immediately for diesel engines without much modification; easy engines without much modification; easy biodegradability; 10 times less poisonous compared biodegradability; 10 times less poisonous compared to the ordinary diesel oil, the waste product is not to the ordinary diesel oil, the waste product is not black, less sulphur and other aromatic contents, black, less sulphur and other aromatic contents, hence the combustion emission produced is safe for hence the combustion emission produced is safe for environment and perform less accumulation of environment and perform less accumulation of carbon dioxide gas in atmosphere thus lessen carbon dioxide gas in atmosphere thus lessen further global heating effect (Chairil A. further global heating effect (Chairil A. et al.,et al., 2004). 2004).

• Biodiesel is very important alternatives Biodiesel is very important alternatives energy because the pollution of energy because the pollution of environment are increased, plus the environment are increased, plus the depletion of conservatives petro-diesel. depletion of conservatives petro-diesel. The biodiesel also contribute to greener The biodiesel also contribute to greener environment where the emitted gases environment where the emitted gases contained higher concentration of contained higher concentration of oxygen compared to petro-diesel.oxygen compared to petro-diesel.

• Used cooking oil has high potential for Used cooking oil has high potential for the production of biofuel. the production of biofuel. The local The local disposal of used frying oil becomes a disposal of used frying oil becomes a huge problem because of the large huge problem because of the large volumes involved. In the fast-food volumes involved. In the fast-food business alone, a single branch which business alone, a single branch which serves fried foods such as fried chicken, serves fried foods such as fried chicken, french fries and burgers can produce as french fries and burgers can produce as much as 15 liters of used frying oil per much as 15 liters of used frying oil per day. Considering that there are day. Considering that there are hundreds of these outlets in Malaysia, hundreds of these outlets in Malaysia, the total amount generated can reach the total amount generated can reach several thousand liters per day.several thousand liters per day.

• The way of disposal of waste cooking oil The way of disposal of waste cooking oil is an important things to be considered. is an important things to be considered. As ABPR (Animal By-Product As ABPR (Animal By-Product Regulation) has been regulated on May Regulation) has been regulated on May 2002, no more catering premises are 2002, no more catering premises are capable to sell their used cooking oil to capable to sell their used cooking oil to manufacturers for making animal feed. manufacturers for making animal feed. Thus, the caterers has the tendencies Thus, the caterers has the tendencies to dispose their used cooking oil into to dispose their used cooking oil into the drain, which contributes to flood, the drain, which contributes to flood, reducing the drainage system reducing the drainage system capabilities and aggregation of grease capabilities and aggregation of grease which cause smelly odor and diseases.which cause smelly odor and diseases.

• Alternative for the disposal of used Alternative for the disposal of used cooking oil should be sought.cooking oil should be sought.

LITERATURE REVIEWLITERATURE REVIEW

CATALYTIC CRACKINGCATALYTIC CRACKING

• breaks complex hydrocarbons into breaks complex hydrocarbons into simpler moleculessimpler molecules

• convert heavy hydrocarbon convert heavy hydrocarbon feedstock into lighter fractions feedstock into lighter fractions

CATALYSTCATALYST

• a material that assist a chemical reaction a material that assist a chemical reaction but does not take part in itbut does not take part in it

• increases the yield & improved quality of increases the yield & improved quality of products under much less severe operating products under much less severe operating conditions than in thermal cracking.conditions than in thermal cracking.

• The catalysts usually used in refinery The catalysts usually used in refinery cracking units are typically solid materials cracking units are typically solid materials (zeolites)(zeolites)

USED COOKING OILUSED COOKING OIL• Waste vegetable oil comes mainly from Waste vegetable oil comes mainly from

industrial deep fryers in potato processing industrial deep fryers in potato processing plants, snack food factories and fast food plants, snack food factories and fast food restaurantsrestaurants

• 10,593,458 tonnes of cooking oil per year 10,593,458 tonnes of cooking oil per year (MPOB, 2006) was produced from palm oil(MPOB, 2006) was produced from palm oil

• Carbon atoms in one molecule of used Carbon atoms in one molecule of used cooking oil mainly contains about 15-18 cooking oil mainly contains about 15-18 carbon.carbon.

Products from used cooking oilProducts from used cooking oil

• SoapSoap

• Animal feeder - except from catering Animal feeder - except from catering premises (ABPR-banned since May premises (ABPR-banned since May 2002 across EU)2002 across EU)

• Fatty acid product-basedFatty acid product-based

• Generation of electricity by Generation of electricity by incineratorincinerator

• AND NOW….BIODIESELAND NOW….BIODIESEL

PREVIOUS RESEARCHPREVIOUS RESEARCH

1.1. TransesterificationTransesterification– Transesterification reactions have been studied for many Transesterification reactions have been studied for many

vegetable oils such as palm oil, soybean, rapeseed, vegetable oils such as palm oil, soybean, rapeseed, sunflower, and safflower seed. Transesterification of sunflower, and safflower seed. Transesterification of vegetable oils and fats to methyl and ethyl esters using vegetable oils and fats to methyl and ethyl esters using different reactants, reaction conditions and catalysts. different reactants, reaction conditions and catalysts. Methyl esters derived from vegetable oil (biodiesel) have Methyl esters derived from vegetable oil (biodiesel) have good potential as an alternative diesel fuel. The cetane good potential as an alternative diesel fuel. The cetane number, energy content, viscosity, and phase changes of number, energy content, viscosity, and phase changes of biodiesel are similar to those of petroleum-based diesel biodiesel are similar to those of petroleum-based diesel fuel. Biodiesel is produced by transesterification of large, fuel. Biodiesel is produced by transesterification of large, branched triglycerides (TG) into smaller, straight-chain branched triglycerides (TG) into smaller, straight-chain molecules of methyl esters, using an alkali or acid as molecules of methyl esters, using an alkali or acid as catalyst (Cheng Sit Foon, Choo Yuen May, Ma Ah Ngan, catalyst (Cheng Sit Foon, Choo Yuen May, Ma Ah Ngan, Chuah Cheng Hock, 2004). Chuah Cheng Hock, 2004).

1.11.1 Alkali catalystAlkali catalyst

• For a basic catalyst, either sodium For a basic catalyst, either sodium hydroxide (NaOH) or potassium hydroxide (NaOH) or potassium

hydroxide hydroxide (KOH) should be used (KOH) should be used with methanol or with methanol or ethanol as well as ethanol as well as any kind of oils, refine, any kind of oils, refine, crude or crude or frying (J. M. Marchetti et. al., 2005) frying (J. M. Marchetti et. al., 2005)

1.21.2 Acid catalystAcid catalyst• This way of production is the second This way of production is the second

conventional conventional way of making the biodiesel. way of making the biodiesel. The idea is to use the The idea is to use the triglycerides with triglycerides with alcohol and instead of a base to alcohol and instead of a base to use an acid, use an acid, the most commonly used is sulfuric the most commonly used is sulfuric acid or acid or sulfonic acid. This type of catalyst gives sulfonic acid. This type of catalyst gives very very high yield in esters but the reaction is very high yield in esters but the reaction is very slow, requiring almost always more than one slow, requiring almost always more than one day day to finish (Freedman B, Butterfield R, Pryde to finish (Freedman B, Butterfield R, Pryde E, E, 1986) 1986)

2.2. Lipase as catalystLipase as catalyst• Lipases are enzymes used to Lipases are enzymes used to

catalyze some reaction such as catalyze some reaction such as hydrolysis of glycerol, alcoholysis hydrolysis of glycerol, alcoholysis and acidolysis, but it has been and acidolysis, but it has been discovered that they can be used as discovered that they can be used as catalyst for tranesterification and catalyst for tranesterification and esterification reactions too (Nelson esterification reactions too (Nelson LA, Folgia TA, Marmer W.N,1996) LA, Folgia TA, Marmer W.N,1996)

3.3. Supercritical alcoholSupercritical alcohol

It is easy to see from the works of Warabi It is easy to see from the works of Warabi and Kusdiana and their co-workers that and Kusdiana and their co-workers that alkyl esterification has a higher reaction alkyl esterification has a higher reaction rate compare to transesterification. This rate compare to transesterification. This shows that the free fatty acid that may shows that the free fatty acid that may be present in oils will get completely be present in oils will get completely transformed into the fuel under transformed into the fuel under transesterification. transesterification.

Lately, the used of microwave for production Lately, the used of microwave for production of biodiesel was discovered. The production of biodiesel was discovered. The production of biodiesel via microwave is a process for of biodiesel via microwave is a process for the production of the ethyl ester of used the production of the ethyl ester of used frying oil for use as a biodiesel. The essential frying oil for use as a biodiesel. The essential part of the process is the transesterification part of the process is the transesterification of the used frying oil with ethanol,in the of the used frying oil with ethanol,in the presence of a catalyst, to yield the ethyl presence of a catalyst, to yield the ethyl ester as a product and glycerine as a by-ester as a product and glycerine as a by-product (Saiffuddin et al.,2004).product (Saiffuddin et al.,2004).

• Recent study done by Xioping Tang et. al., Recent study done by Xioping Tang et. al., (2007 ECI Conference ; The 12th (2007 ECI Conference ; The 12th International Conference on Fluidization) International Conference on Fluidization) shows that dry gas, LPG, gasoline, diesel shows that dry gas, LPG, gasoline, diesel oil, slurry, coke and water was obtained oil, slurry, coke and water was obtained from the catalytic cracking process of from the catalytic cracking process of waste edible oil at 400-700waste edible oil at 400-700°C reaction °C reaction temperaturetemperature. The oil was chosen regarding . The oil was chosen regarding to the low raw material cost. to the low raw material cost.

• Yield based on ENGLER Yield based on ENGLER distillation:distillation:– Dry gasDry gas : 0.65: 0.65– LPGLPG : 10.26: 10.26– GasolineGasoline : 36.38: 36.38– Diesel oilDiesel oil : 26.96: 26.96– SlurrySlurry : 1.78: 1.78– CokeCoke : 10.8: 10.8– WaterWater : 13.17: 13.17– ConversionConversion %% : 100: 100– Desired product yield %Desired product yield % : 73.56: 73.56

• Limited research has been done Limited research has been done regarding on converting used regarding on converting used cooking oil to biofuel via catalytic cooking oil to biofuel via catalytic cracking. cracking.

• Intensive studies are recommended Intensive studies are recommended in this field.in this field.

PROBLEM STATEMENTPROBLEM STATEMENT

• Future shortage of petroleum supplyFuture shortage of petroleum supply– Energy crisisEnergy crisis– Fluctuation of petroleum price USD70/barrelFluctuation of petroleum price USD70/barrel

• Problem disposal of used cooking oilProblem disposal of used cooking oil– Animal feedAnimal feed– Fatty-acid product-basedFatty-acid product-based– SoapSoap

• Environmental awareness due to exhaust Environmental awareness due to exhaust emissionemission– Decrease of ozone layer from petroleum based Decrease of ozone layer from petroleum based

fuelfuel– Environmental pollutionEnvironmental pollution

GOAL OF THE RESEARCHGOAL OF THE RESEARCH

• The goal of the study is to produce The goal of the study is to produce value-added products as blending value-added products as blending component for the production of component for the production of biofuel.biofuel.

OBJECTIVESOBJECTIVES

• To characterize the used cooking oil To characterize the used cooking oil (palm oil and sunflower oil based)(palm oil and sunflower oil based)

• To investigate the production of To investigate the production of biofuel in a fluidised bed reactor.biofuel in a fluidised bed reactor.

• To carry out process optimisation.To carry out process optimisation.

• To isolate, purify and characterize the To isolate, purify and characterize the products (liquid, gas and residue) products (liquid, gas and residue) obtainedobtained

SCOPESCOPE

• The research will be conducted only on 2 The research will be conducted only on 2 types of used cooking oil (palm oil, and types of used cooking oil (palm oil, and sunflower oil).sunflower oil).

• Process optimization will also be carried out, Process optimization will also be carried out, based on the following parameters:based on the following parameters:

• Pressure Pressure

• TemperatureTemperature

• YieldYield

• Catalyst volume/ sizeCatalyst volume/ size

• Percentage yield of biofuel produced Percentage yield of biofuel produced will be used to select the optimal will be used to select the optimal condition in this study.condition in this study.

LIMITATIONLIMITATION OF STUDYOF STUDY

• The study will focus on process The study will focus on process optimisation and do not include optimisation and do not include reactor efficiency.reactor efficiency.

• Engine performance and exhaust gas Engine performance and exhaust gas emission will be determined under emission will be determined under different scope of research.different scope of research.

RESEARCH METHODOLOGYRESEARCH METHODOLOGY

Raw material acquisition•residential areas•stall

Impurities removalPhysical separation

of feedstock

Feed characterization•Metal content•Calorific value

•Chemical properties

Pre-treatment of feedstock

Setting up catalyst reactor

Catalytic cracking process

Products

Characterization of biodiesel properties

Liquid-GC-MS-FT-IR-NMR

GasGC

VOC

Char (solid) - AAS

Blending samples

BIOFUEL for possible commercialization

Comparison with standard

Condensers

Liquid collector 2

V7

V6

V5

H2O outH2O out

H2O in

Heater

H2O in

Recycled gas

Vx

Thermocouples

Mixture of steam and

catalystP1

‘’’’’’’’’’’’’’’’’’’’

P2

Feed

Scrubber

Gas collector

i.e: gas bag

Char

Heaters

Glass wool

V1

V2

Flow meter

Px

= Valve Figure 1: Schematic Diagram for Fluidised Catalytic Cracking

Liquid collector 1

V3

V4

Table 1.1: Blending sample of diesel and liquid sample (laboratory)

Diesel %Diesel %(PETRONAS)(PETRONAS)

Liquid sample %Liquid sample %(laboratory)(laboratory)

Methyl Ester %Methyl Ester %(MPOB)(MPOB)

Characterization for diesel Characterization for diesel propertiesproperties

100100 00 -- √√

9595 55 -- √√

9090 1010 -- √√

8585 1515 -- √√

8080 2020 -- √√

7575 2525 -- √√

7070 3030 -- √√

6565 3535 -- √√

6060 4040 -- √√

5555 4545 -- √√

5050 5050 -- √√

Table 1.2: Blending sample of diesel and methyl ester (MPOB)

Diesel %Diesel %(PETRONAS)(PETRONAS)

Liquid sample %Liquid sample %(laboratory)(laboratory)

Methyl Ester %Methyl Ester %(MPOB)(MPOB)

Characterization for diesel Characterization for diesel propertiesproperties

9595 -- 55 √√

9090 -- 1010 √√

8585 -- 1515 √√

8080 -- 2020 √√

7575 -- 2525 √√

7070 -- 3030 √√

6565 -- 3535 √√

6060 -- 4040 √√

5555 -- 4545 √√

5050 -- 5050 √√

SIGNIFICANCE OF STUDYSIGNIFICANCE OF STUDY

o Provide an alternative renewable energy Provide an alternative renewable energy source in the form of biofuel.source in the form of biofuel.

o Solve the problem of disposal of used Solve the problem of disposal of used cooking oil by converting it to value added cooking oil by converting it to value added products.products.

o Establish a database on the characterization Establish a database on the characterization of different types of used cooking oil for of different types of used cooking oil for reference in Malaysia.reference in Malaysia.

o Produce an environmental friendly energy, Produce an environmental friendly energy, biofuel which has potential to reduce risk of biofuel which has potential to reduce risk of green house effects and pollution.green house effects and pollution.

• Produce gases for petrochemical Produce gases for petrochemical industries/ household.industries/ household.

• Application of old technology for the Application of old technology for the noble route for biofuel production.noble route for biofuel production.

RESEARCH SCHEDULERESEARCH SCHEDULEYEAR 2007/2008

ACTIVITYACTIVITY

JulyJuly

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Aug

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JanJan

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Mar

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chch Apri

Apri

ll May

May

JuneJune

JulyJuly

Literature reviewLiterature review // // // // // // // // // // // // //

Raw materials acquisitionRaw materials acquisition // // //

Feed characterizationFeed characterization // // // // // // // //

Process development (fluidised bed catalytic Process development (fluidised bed catalytic cracking) cracking) Effect of temperatureEffect of temperatureEffect of pressureEffect of pressureEffect of catalystEffect of catalyst

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CHARACTERIZATION OF PRODUCTCHARACTERIZATION OF PRODUCT

Determination ofDetermination of flash point (liquid) flash point (liquid) // // // // // // // // // // //

Calorific valueCalorific value // // // // // // // // // // //

Chemical analysis (gas, liquid, residue)Chemical analysis (gas, liquid, residue) // // // // // // // // // // //

YEAR 2008/2009

ACTIVITYACTIVITY Aug

Aug

SeptSept

Oct

Oct

Nov

Nov

Dec

Dec

JanJan

FebFeb

Mar

Mar

chch

Apri

Aprill

May

May

JuneJune

JulyJuly

CHARACTERIZATION OF PRODUCTCHARACTERIZATION OF PRODUCT

DeterminationDetermination of cloud point (liquid) of cloud point (liquid) // // // // // // //

DeterminationDetermination of color (liquid) of color (liquid) // // // // // // //

Determination of acid value (liquid)Determination of acid value (liquid) // // // // // // //

Chemical analysis- NMR, FTIR, GC, UV-VIS- Chemical analysis- NMR, FTIR, GC, UV-VIS- (gas, liquid, residue)(gas, liquid, residue)

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Report writingReport writing // // //

Thesis writingThesis writing // // // // //

Submission/ datelineSubmission/ dateline //

Thank YouThank You