Biodiesel production by esterification of nonesterification of non

MERC

Biodiesel production by esterification of non-edible oilsesterification of non-edible oils

Control Number: 94

*Farah Halek Azarmidokht Hosseinnia Ali Kavousirahim*Farah Halek, Azarmidokht Hosseinnia, Ali Kavousirahim

Materials and Energy Research Centre (MERC),Tehran, Iran

Energy Usegy

h d f ?What do we use energy for?– Heating & Cooling– Lights, appliances, industries,cooking,

household uses– Manufacturing– Transportationp• Gasoline• Diesel (Biodiesel can be used to supplement

2

Diesel (Biodiesel can be used to supplement or replace diesel fuel)

Biodiesel as an alternative fuelBiodiesel as an alternative fuel

Fluctuation of increases in crude Fluctuation of increases in crude oil prices, limited recourses of oil prices, limited recourses of fossil oil, environmental worries, fossil oil, environmental worries, population increase and hence, population increase and hence, higher energy demand, biodiesel higher energy demand, biodiesel represents a promising represents a promising alternative fuel for use in alternative fuel for use in compression ignition (diesel) compression ignition (diesel) engines.engines.

What Is Biodiesel?What Is Biodiesel?

• Biodiesel is a diesel fuel made from vegetableoil, used cooking oils, alga and methanol and acatalyst.

• Biodiesel is the only alternative fuel that haspassed all of the EPA clean air fuelrequirements.

• Biodiesel is fully compatible with any dieselengine.

• Biodiesel is safe to handle and isbiodegradable, it is less toxic than table salt.

Continued …Continued …

• Chemically: Long chain fatty acid mono alkyl esters Exact chemical composition difference for different sources of oil.

• Its a good solventg

Continued …

• Raw material crops for Bio energy were mainly edible

Continued …

• Raw material crops for Bio energy were mainly ediblecrops oils such as Cloza, soybean, rapeseeds, palm,canola, mustard, corn and waste cooking oilscanola, mustard, corn and waste cooking oils→ Affects the international grain price→ Noted that it may agitate food shortage problems→ Noted that it may agitate food shortage problems

in underdeveloped and developing countries• Necessity of non-edible material crop developmentNecessity of non edible material crop development• Active support is required particularly for non-edible

oil crops that are lessp• affected by the international grain

Benefits of BiodieselBenefits of Biodiesel

E i t l (Ai W t W t )• Environmental (Air, Water, Waste)• Energy Independence (Domestic, Renewable)

E i /C t (W t t F l)• Economic/Cost (Waste to Fuel)• Quality/Standards• Energy Policy Compliance• Energy Policy Compliance• Biodiesel makes a great degreaser• The flash point of biodiesel is above 200 °C (of• The flash point of biodiesel is above 200 C (of

petrodiesel is 70° C) Therefore biodiesel and diesel-blends are safer to store, handle, and use than

7

conventional diesel fuel.

What are pollutant emissions?What are pollutant emissions?

R l t d ll t tRegulated pollutants:Carbon monoxide (CO) – a poisonHydrocarbons (HC) – causes formation of ozoney ( )Particulate matter (PM) – soot and aerosolsNitrogen oxides (NOx)–causes formation of ozone and fine particles

For diesel; PM , CO ,HC, CO2 , SO2 are really important

U l t d ll t tUnregulated pollutants:Aldehydes – highly reactive for ozone, have health effectsPolyaromatic hydrocarbons (PAH) – known carcinogensy y ( ) gNitro-PAH – known carcinogens

Biodiesel’s Effect on Emissions Old E i– Older Engines

EPA analysis:•data from many studies•engine models through 1997

•NOxxNo change for B5

2% up for B2010% up for B10010% up for B100

•PM5% down for B5

f12% down for B2048% down for B100

Analysis from EPA420-P-02-001, October 2002

Comparison of pollutant emissions f bi di l d di l f lfrom biodiesel and diesel fuels

PAHMutagenicity

CO2

Sulfates

PAHs

n-PAHsB100 **B20Diesel

Particulate Matter

**NOx

Sulfates

Total Unburned HCs

CO

0 20 40 60 80 100 120Percent

** B100 (100% biodiesel) with NOx adsorbing catalyst on vehicle

Biofuel: a Better Fuel vs. Diesel

Higher cetaneGreater lubricity More mileageGreater lubricitySuperior detergencyHigher flash point

More mileage Greater horsepowerLess smoke Smoother running enginesg gQuicker startsLonger engine lifeReduced maintenance

BenefitsFeatures

Why Use Biodiesel?Why Use Biodiesel?

• Amount of fossil energy used in biodieselproduction is similar to that used inpetroleum production

• A small fraction of fuel energy-trulyrenewable

Obstacles to Biodiesel AcceptanceObstacles to Biodiesel Acceptance

• Oil quality is more important• Limited supply• Limited supply

–Due to both demand and supply reasons

• Potential increase of NOx emissions• Lack of familiarity

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Biodiesel Production Process: Transesterfication

Oil & F tMethanol Oils & Fats(Feedstock) Catalyst

TransesterificationMethanol RecoveryRecovery

Purification

Water

MethylEsters

Glycerin

Glycerin &

Water

Esters(biodiesel)

yMethanol

Glycerin &Water

Glycerin, Water

& Methanol

Experimental: Experimental: TransesterificationTransesterification ReactionReaction

Catalyst

Solvent

Vegetable Oil Methanol Methyl Esters Glycerin

Experimental ConditionsExperimental Conditions

The common transesterification method was Adapted for

pp

The common transesterification method was Adapted forconversion of the colzy non-edible oil to the biodieselfuel.R1, R2, and R3 are fatty acids (could be different, or thesame), and depend on the type of oil. The fatty acids) p yp yinvolved determine the final properties of the biodiesel(Cetane number, cold flow properties, etc.)F d i th bi di l il 10 diff t tiFor producing the biodiesel oil, 10 different reactionswere carried on, using different ratios of colzy oil,methanol catalyst (sulfuric acid) The optimummethanol, catalyst (sulfuric acid). The optimumtemperature of the transesterification was 63 °C and thetime of the reaction was 1.5 hr.

Experimental Conditions Experimental Conditions pp(Continued)(Continued)

Using these optimum conditions, the yield ofconverting the base oil to the esterified oil wasconverting the base oil to the esterified oil wasreached to 93.5 %. The optimum ratio of theoil/alcohol was 0.1/1. Different catalysts (acidic,oil/alcohol was 0.1/1. Different catalysts (acidic,basic, nano and enzymes) could be used in thisreaction. In this experiment, sulfuric acid, which isp , ,cheap and produced in Iran, was chosen and used.The optimum amount of sulfuric acid was found tobe 1.8 % of the base oil.

Some of the characteristics of colzy oil feedstock

Test ValueBoiling Point (ºC) 280 300Boiling Point (ºC)Density (g/cm3)Water Content (%)

280 – 3000.9120 04Water Content (%)

Fatty Acid Contents (%) :Linoleic (C H O )

0.04

59 8Linoleic (C18H32O2)Oleic (C18H34O2)Palmitic (C H O )

59.824.965 87Palmitic (C16H32O2) 5.87

Transesterification reaction

Product of reaction

ASTM International SpecificationsASTM International Specifications

Specifications of the colzy oil based biodieselp y

Property Standard no(Value)

Biodiesel

Flash Point (ºC)Water Content and precipitates (% value)Kinetic Viscosit (mm2/s)

D93(180)D2709(0.05)D445(1 9 6)

2080.0422 83Kinetic Viscosity (mm2/s)

Copper CorrosionCetane No.

D445(1.9-6)D130(3)D613(47)

2.83249

Pour Point (ºC)ColorHeat value(mj/kg)

( )D97

D1500

-151.546 7Heat value(mj/kg) D1500 46.7

Effect of Biodiesel Blending on Di l P tiDiesel Properties

Cetane number increases – Better combustion, lower emissionLubricity improves – Protection to fuel injection equipmentLower Flash point More safetyLower Flash point – More safetyKinematic Viscosity – Higher but within range, better

protection to fuel injection equipmentprotection to fuel injection equipment

Low Sulphur content – Lower SO2 and Particulate emission2

Storage stability and material compatibility could be ofd f th i ti ticoncern – need further investigation.

Engine Tests

Effi i f h bi di l il l d

Engine Tests

Efficiency of the biodiesel oil was evaluated, using an agricultural engine. For loading the

i it t d t 400 k h iengine, it was connected to a 400 kw chassis dynamometer. In the experiment an emission

l (O t l d l AVL4000analyzer (Orast analyzer, model AVL4000, Belgium) was used in order to analyze the engine

h t ll ti t Thi t texhaust pollution parameters. This test component measures CO2 emission in volume

t CH CO d NO i t illipercentage, CH, CO and NOx in parts per million (ppm) and exhaust smoke in mg/m3.

Engine Tests

d f

(Continued)

Testing started after engine warmed up and reached the t d t t (20 30 i )steady state (20-30 min).

Engine cycle reached an average and then the maximumaverage and then the maximum values at speed 1400 to 2000 cycle/min respectively and thencycle/min respectively and then exhaust emission and engine torque were analyzed by smoketorque were analyzed by smoke analyzer and dynamometer.

Engine Specifications(M4 244)(M4-244)

Company Iranian Tractor Company

Engine volume (lit)Maximum power (hp)Maximum torque (nm)

3.9982

1300Maximum torque (nm)Turning directionElectric system (v)Cooling system

1300Clockwise

12Water and oilCooling system

Diameter x Piston course (mm)Combustion systemCombustion ratio

Water and oil127 x 100

Direct injection17 5 : 1Combustion ratio

Air inlet system17.5 : 1

Turbo charger

Engine (M4-244)g ( )

Test Working Placeg

Dynamometer (400 kw, magnetic)Dynamometer (400 kw, magnetic)

In this test 400KW Eddy current magneticIn this test 400KW Eddy current magnetic dynamometer made in Belgium were used

i h MT4 244 i 'to measuring the MT4-244 engine's power and torque. Dynamometer measuring process was done according to ISO-3046 standard and the torques was measured qautomatically by applying magnetic field and the result represented as data.and the result represented as data.

Emissions Analyzery

ResultsResults

f• CO is the result of incomplete ignition in air lack situation and the quantity of CO ll ti i tl d dCO pollution is greatly depends on mixing portion. High deference in various periods is because of Air/Fuelvarious periods is because of Air/Fuel portions.

Comparison of CO emissions from bi di l d di l f lbiodiesel and diesel fuels

2500

3000

1500

2000

ppm

) B20D80

B10D90

1000

1500

CO

(p

B5D95

D100

0

500

1400 2000R P M

Comparison of CO2 emissions from bi di l d di l f lbiodiesel and diesel fuels

12

14

8

10

(ppm

) B20D80

B10D90

4

6

CO

2 B5D95

D100

0

2

1400 20001400 2000R P M

Percentage of CO2 emission d ti i bi di l f lreduction using biodiesel fuel

-5

0

D100 B5D95 B10D90 B20D80

-10% 1400 rpm

-15CO

2

1400 rpm2000 rpm

-20

-25

Comparison of HC emissions from bi di l d di l f lbiodiesel and diesel fuels

9

789

456

C (p

pm) B20D80

B10D90

234

HC B5D95

D100

01

1400 2000R P M

• Production of incomplete or not ignited hydrocarbons, like CO is the result of y ,ignition air lacks. HC production source is the part of engine that the ignitionis the part of engine that the ignition flame doesn't exist. The gap between cylinder wall and the gaps were thecylinder wall and the gaps were the flame can't penetrate is effective in HC

ll tipollutions.

Comparison of NOx emissions from bi di l d di l f lbiodiesel and diesel fuels

1200

1400

1600

800

1000

1200

(ppm

) B20D80

B10D90

400

600NO

x B5D95

D100

0

200

1400 20001400 2000R P M

Comparison of Smoke emissions f bi di l d di l f l

350

from biodiesel and diesel fuels

250

300

350

B20D80

200

250

(mg/

m3 ) B10D90

B5D95

100

150

Smok

e (

D100

0

50

1400 20001400 2000R P M

Comparison of Torque using bi di l d di l f l

350

biodiesel and diesel fuels

330

340

350

m)

320

330

orqu

e (N

.m D100

B5D95

B10D90

300

310To

B10D90

B20D80

280

290

1400 20001400 2000R P M

Comparison of Power emissions using bi di l d di l f l

70

biodiesel and diesel fuels

50

60

70

)

D100

30

40

50

ower

(kw

)

B5D95

B10D90

10

20

30po

B20D80

0

10

1400 2000R P MR P M

Because of more thermal efficiency and fuel consistency, biodiesel fuel have

More torque and power efficiency thanMore torque and power efficiency than pure diesel fuels. It means that both the diesel and biodiesel compositionsthe diesel and biodiesel compositions inter more fuel to combustion area, but b f t t ibecause of more oxygen content in biodiesel fuel, this fuels have more complete ignition and as result the torque and power of engine increase.torque and power of engine increase.

High deference in various periods is because of Air/Fuel portions. This portionbecause of Air/Fuel portions. This portion in 2000 periods is AF=24.6 and in 1400 periods is AF=18 3 (Testing engine hasperiods is AF=18. 3 (Testing engine has turbo charging system).

SummaryBiodiesel is not toxicBiodiesel is not toxicBiodiesel degrades four times faster than diesel P bi di l d d 85 88 % i tPure biodiesel degrades 85 - 88 % in waterBlending of biodiesel with diesel fuel increase engine efficiency.The higher flash point makes the storage g p gsafer.Biodiesel is an oxygenated fuel, thusBiodiesel is an oxygenated fuel, thus implying that its oxygen content plays a role in making fatty compounds suitable as dieselin making fatty compounds suitable as diesel fuel by cleaner burning.

90% reduction in cancer risks, according to Ames mutagenicity testsAmes mutagenicity tests.

Provides a domestic renewable energy supplyProvides a domestic,renewable energy supply.Biodiesel does not produce greenhouse effects beca se the balance bet een theeffects, because the balance between the amount of CO2 emissions and the amount of CO absorbed by the plants producingCO2 absorbed by the plants producing vegetable oil is equal.Biodiesel can be used directly in compressionBiodiesel can be used directly in compression ignition engines with no substantial modifications of the enginemodifications of the engine.

Th i i f PAH d PAHThe emissions of PAHs and nPAHs compounds revealed very lower levels bi di l d t ti lbiodiesel are compared to conventional diesel fuel.Chemical characteristics revealed very

lower levels of some toxic and reactive hydrocarbon species when biodiesel fuels were used.

RecommendationA th t k f f il f l i tti d l t d h iAs the stock of fossil fuel is getting depleted emphasis should be given to renewable sources of fuel such as biofuel: Design, develop and popularize appliances and equipments specifically for rural application.Prime facie biodiesel seems to have significantPrime facie, biodiesel seems to have significant potential to contribute to Iran’s energy security, the need of the hour is to undertake R&D on sustainable l t ti t il t ti dplantation management, oil extraction and use

environmental and social impact assessment and build institutional models.Contact training programs to sanitize media personnel on latest technologies and developments related to rural development.rural development.Creating awareness regarding loan, insurance facilities subsidies, et.

Final statementWhy Bio diesel?

G f l f il f l ?Green fuel or fossil fuels?

O AOne Answer

Cheaper fuel for consumers

More energy security & diversified sources

Higher farm incomes & rural employment

Significant carbon emission reduction

Faster GDP growth Lower Imports & energy pricesFaster GDP growth, Lower Imports & energy prices

Thank you for pay attention

Thank you for attention