The Effect of an Oxygenated Additive on the Emulsification Characteristics of Diesel-Ethanol Blends The Petroleum and Petrochemical College, Chulalongkorn.

The Effect of an Oxygenated Additive on the The Effect of an Oxygenated Additive on the Emulsification Characteristics of Emulsification Characteristics of

Diesel-Ethanol BlendsDiesel-Ethanol Blends

The Petroleum and Petrochemical College, Chulalongkorn University, ThailandThe Petroleum and Petrochemical College, Chulalongkorn University, Thailand

The Royal Thai NavyThe Royal Thai Navy

Ms. Thanyatorn IsarachewaMs. Thanyatorn Isarachewa

Asst.Prof. Apanee LuengnaruemitchaiAsst.Prof. Apanee Luengnaruemitchai

Captain Dr. Samai Jai-InCaptain Dr. Samai Jai-In

IntroductionBackground & Literature ReviewObjectivesMethodologyResults and DiscussionConclusions

OUTLINEOUTLINE

2

INTRODUCTIONINTRODUCTION

Oil Cris

is

3

4

Motivation Motivation

1. Reduce Dependence on Imported Petroleum Fuels.1. Reduce Dependence on Imported Petroleum Fuels.

2. Increase Farm Income : Supply Management.2. Increase Farm Income : Supply Management.

3. The growing global concern with environmental pollution.

3. The growing global concern with environmental pollution.

Alternative Energy Alternative Energy which is currently promoted in Thailand

GasoholGasoholGasoholGasohol NGVNGVNGVNGV

BiodieselBiodieselBiodieselBiodiesel5PPC, Ms. Thanyatorn Isarachewa

Alternative Fuels Alternative Fuels for Diesel Enginefor Diesel Engine

DiesoholDiesohol BiodieselBiodiesel

6

Total Fuel Energy Demand in Thailand 2004 (thousand Barrels/day)

Diesel, 338.4

Fuel oil, 104.5

Jet oil, 73.1

Kerosene, 0.4

Gasoline, 132

LPG, 69.5

Total Fuel Energy Demand in Thailand 2004 (thousand Barrels/day)

Diesel, 338.4

Fuel oil, 104.5

Jet oil, 73.1

Kerosene, 0.4

Gasoline, 132

LPG, 69.5

Thailand diesel demand growing faster than gasoline!!Thailand diesel demand growing faster than gasoline!!

Reported by Ministry of Energy, ThailandPPC, Ms. Thanyatorn Isarachewa

Advantages of DiesoholAdvantages of Diesohol

Because alcohol is an oxygenate

Oxygen atoms inside ethanol join forces with oxygen molecules in the air to help ethanol burn more completely.

This extra amount of oxygen also helps diesel burn better when it is blended with ethanol.

Because alcohol is an oxygenate

Oxygen atoms inside ethanol join forces with oxygen molecules in the air to help ethanol burn more completely.

This extra amount of oxygen also helps diesel burn better when it is blended with ethanol.

Introduces greater oxygen to fuel mixture improve the efficiency of combustion

Introduces greater oxygen to fuel mixture improve the efficiency of combustion

An alternative fuel for diesel substitution.

An alternative fuel for diesel substitution.

Changes the combustion characteristics of the fuel.

Changes the combustion characteristics of the fuel.

Reduce air pollutant mission Reduce air pollutant mission

Impacts of Diesohol use. The alcohol component in the fuel:

Better combustion is an important

Better combustion is an important

factor leading to fewer

factor leading to fewer

harmful emissions

harmful emissions

www.eere.energy.gov/vehiclesandfuels 7PPC, Ms. Thanyatorn Isarachewa

Disadvantages of Diesohol

Low Cetane Number Low Cetane Number

Ethanol-diesel fuel blends-a review, Hansen(2005)

Impacts of Diesohol use. The alcohol component in the fuel:

Fuel instability due to phase separation Fuel instability due to phase separation

Low Flash Point Temperature Low Flash Point Temperature

8PPC, Ms. Thanyatorn Isarachewa

ADDITIVESADDITIVES

Improve solubilityImprove solubility Improve solubilityImprove solubility

Letcher, T.M., 1983. Diesel blends for diesel engines.

Improve fuel propertiesImprove fuel properties Improve fuel propertiesImprove fuel properties

Eg. DALCO, PEOPS , SB407 , GE BetZ

AAE 05, Octimax 4930, and Beraid ED10

The detail of additive components has not been revealed by any producer. 9

The price of commercial additives are still high and need to be imported.

Ethyl AcetateEthyl Acetate

Ethyl AcetateEthyl Acetate can be used an additive known as a co-solvent to prevent phase separation.

Ethyl AcetateEthyl Acetate can be used an additive known as a co-solvent to prevent phase separation.

CH3COOC2H5

It is soluble in most organic solvents, such as alcohol.

It can be produced easily from agricultural products in Thailand.

It is an oxygenate, contains 36.36wt% oxygen compound.

Ethyl Acetate contains 36.36wt% oxygen compoundEthanol contains 34.78wt% oxygen compound

Ethyl Acetate contains 36.36wt% oxygen compoundEthanol contains 34.78wt% oxygen compound


OBJECTIVES

To investigate the effect of an oxygenated additive on the emulsification characteristics of diesohol.

To investigate the effect of an oxygenated additive on the emulsification characteristics of diesohol.

To compare some basic fuel properties and emission of diesohol with diesel fuel.

To compare some basic fuel properties and emission of diesohol with diesel fuel.

15

To study the use of ethyl acetate as an additive in stabilizing ethanol in diesel blends.

To study the use of ethyl acetate as an additive in stabilizing ethanol in diesel blends.

PPC, Ms. Thanyatorn Isarachewa

MATERIALS

16

DieselDiesel : Rayong Purifier Public Co.Ltd.,

EthanolEthanol : The Royal Chitralada Projects, J.T. Baker Co.Ltd.,

Ethyl AcetateEthyl Acetate : White House Co.Ltd.,

DieselDiesel : Rayong Purifier Public Co.Ltd.,

EthanolEthanol : The Royal Chitralada Projects, J.T. Baker Co.Ltd.,

Ethyl AcetateEthyl Acetate : White House Co.Ltd.,

(95%,99.5%conc)(99.9%conc)


Methodology OutlineMethodology Outline

17

2. Stability Observation2. Stability Observation

3. Turbidity Measurement3. Turbidity Measurement

1. Splash-Blending1. Splash-Blending

2.1 Effect of temperature


4. Fuel Properties Testing4. Fuel Properties Testing

5. 5. EngineEngine TestTest

use Splash blending, which requires only miner stirring.

Experimental DesignExperimental Design

1. Splash Blending1. Splash Blending

18

10 ml.

• Diesel • Ethanol • Ethyl Acetate

1000 rpm, 5 min

Ratio variationDiesel : 0 – 100%Ethyl Acetate : 0 – 100%Ethanol : 0 – 100%

(10% increments)


““Effect of temperature”Effect of temperature”

2. Stability Observation2. Stability Observation

Keep Keep motionlessmotionlessFor 7 daysFor 7 days

66 samples for each Ethanol

Temperature variation

10, 20, 30, 40°C

Ternary Plot

% Diesel0 10 20 30 40 50 60 70 80 90 100

% Biodiesel

0

10

20

30

40

50

60

70

80

90

100

% EtOH

0

10

20

30

40

50

60

70

80

90

100

Ternary Plot

% Diesel0 10 20 30 40 50 60 70 80 90 100

% Biodiesel

0

10

20

30

40

50

60

70

80

90

100

% EtOH

0

10

20

30

40

50

60

70

80

90

100

%Ethyl Acetate%Ethyl Acetate

%EtOH%EtOH

%Diesel%Diesel

Ternary Plot at various

temperatures

19

After Splash-blending

After Splash-blending

reported

Observe the stabilities

Observe the stabilities

For long term stabilityFor long term stability, all the blends will be kept for 3 monthsfor 3 months.For long term stabilityFor long term stability, all the blends will be kept for 3 monthsfor 3 months.


RSCE 2005, Vietnam

Turbidity Meter Model Turb 350 IR “WTW”

Turbidity meterTurbidity meter is used to check relative sample clarity, to choose the clearest solution.

Turbidity meterTurbidity meter is used to check relative sample clarity, to choose the clearest solution.

20

3. Turbidity Measurement3. Turbidity Measurement

TurbidityTurbidity is the degree of opacity of a fluid.TurbidityTurbidity is the degree of opacity of a fluid.

Experimental Experimental DesignDesign

www.chevrontexacoursa.com

Low Turbidity High Turbidity

The ratios that have the percentage of diesel containing over 80% are measured for Turbidity.


Density at 15.6/15.6°C (g/cc) ASTM D1298Density at 15.6/15.6°C (g/cc) ASTM D1298

Distillation temp (°C) ASTM D86Distillation temp (°C) ASTM D86

Cetane Index ASTM D976Cetane Index ASTM D976

Pour Point ASTM D97Pour Point ASTM D97

4. Fuel Properties Testing4. Fuel Properties Testing

21


From the previous part, the ratios that have the percentage of diesel containing over 80% will be measured with some fuel properties.

Flash Point ASTM D56Flash Point ASTM D56

Heat of Combustion ASTM D240Heat of Combustion ASTM D240

Viscosity @40°C ASTM D445Viscosity @40°C ASTM D445


No. %Diesel %Ethyl acetate %Ethanol99.5%

1 100 0 0

2 90 0 10

3 90 5 5

4 90 10 0

5 85 0 15

6 85 5 10

7 85 10 5

8 85 15 0

9 80 5 15

10 80 10 10

11 80 15 5

12 0 100 0

13 100 0 0

Experimental Design

Ratio for testing fuel propertiesRatio for testing fuel properties


Model : DG3LE

Model : Eurogas 8020

5. Emission Testing5. Emission Testing


All of the blends after tested fuel properties

Vary %Load0, 30, 60, 100%

CO, NOx, HC

23

Observe fuel consumption

rate


Gas Analyser

Diesel Engine

Generator

( All the experiments were performed without any modifications of the engine )

Results and Discussion

24

Developed Ternary Developed Ternary DiagramDiagram



25

At Room TemperatureAt Room Temperature


95%purity of ethanol95%purity of ethanol 99.5%purity of ethanol99.5%purity of ethanol 99.9%purity of ethanol99.9%purity of ethanolTernary Plot at Room Temp.

Ethanol 95%0 10 20 30 40 50 60 70 80 90 100

Ethyl Acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100

(liquid) Clear solution, 1 phase


Ternary Plot at Room Temp.

Ethanol 99.5%0 10 20 30 40 50 60 70 80 90 100

Ethyl Acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100



Ternary Plot at Room Temp.

EtOH 99.9%0 10 20 30 40 50 60 70 80 90 100

Ethyl acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100



2 phase1 phase1 phase 1 phase

Solubility of diesel fuel in ethyl acetate and ethanol 99.5%, 99.9% is not limited. However solubility of diesel fuel in ethyl acetate and ethanol 95% is limited.

Solubility of diesel fuel in ethyl acetate and ethanol 99.5%, 99.9% is not limited. However solubility of diesel fuel in ethyl acetate and ethanol 95% is limited.

Using ethanol 99.5% have a tendency to give more one phase area than using ethanol 95% at room temp. And it’s less expensive than ethanol 99.9%.

Using ethanol 99.5% have a tendency to give more one phase area than using ethanol 95% at room temp. And it’s less expensive than ethanol 99.9%.


26


At Low temperaturesAt Low temperatures

The interest of the ethyl acetate is to prevent any risk of mixture separation

when the temperature drops, make it suitable for winter fuel formulation.

The interest of the ethyl acetate is to prevent any risk of mixture separation

when the temperature drops, make it suitable for winter fuel formulation.

Anhydrous ethanol (99.5%) is highly soluble in diesel fuel at contents of approximately

0–10% and 90–100% for 10°C, but at 0–20% and 80–100% for 20°C.

Anhydrous ethanol (99.5%) is highly soluble in diesel fuel at contents of approximately

0–10% and 90–100% for 10°C, but at 0–20% and 80–100% for 20°C.

1 phase 2 phase

Ethanol and Ethyl acetate present good fuel fluidity at low temperature.


Ternary Plot at 10*C

EtOH 99.5%0 10 20 30 40 50 60 70 80 90 100

Ethyl acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100

Liquid Crystalline, 1 phase

Liquid Crystalline, 2 phase


Temperature At 10Temperature At 10°C°CTernary Plot at 20*C

EtOH 99.5%0 10 20 30 40 50 60 70 80 90 100

Ethyl Acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100



Temperature At 20Temperature At 20°C°C

2 phase

1 phase

cloudiness in the mixture followed by separation.



EtOH 99.5%0 10 20 30 40 50 60 70 80 90 100

Ethyl Acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100



EtOH 99.5%0 10 20 30 40 50 60 70 80 90 100

Ethyl Acetate

0

10

20

30

40

50

60

70

80

90

100

Diesel

0

10

20

30

40

50

60

70

80

90

100


27


Temperature At 30Temperature At 30°C°C Temperature At 40Temperature At 40°C°C

At High temperaturesAt High temperatures

Ethyl acetate can produce the clear solution (one phase) area without any risk of diesel-ethanol mixture separation.

Ethyl acetate can produce the clear solution (one phase) area without any risk of diesel-ethanol mixture separation.

1 phase 1 phase




28

Turbidity MeasurementTurbidity Measurement


Ratio Turbidity Value

%Diesel%Ethyl acetate

%EtOHAverage (EtOH95%)

Average (EtOH99.5%)

Average (EtOH99.9%)

90 0 10 0.26 0.01 0.01

90 5 5 0.33 0.01 0.01

90 10 0 0.67 0.01 0.01

85 0 15 0.56 0.01 0.01

85 5 10 0.58 0.01 0.01

85 10 5 3.02 0.01 0.01

85 15 0 0.92 0.01 0.01

80 5 15 0.59 0.01 0.01

80 10 10 0.63 0.01 0.01

80 15 5 0.50 0.01 0.01

100 0 0 0.01 0.01 0.01

0 100 0 0.01 0.01 0.01

0 0 100 0.01 0.01 0.01

Turbidity MeasurementTurbidity Measurement

Turbidity value of the blends with ethanol 95%

it is not viable for using as fuel.

Turbidity value of the blends with ethanol 99.5%

it is possible to obtain the best clarity and stability of tri-component diesohol mixtures.

Turbidity value of the blends with ethanol 95%

it is not viable for using as fuel.

Turbidity value of the blends with ethanol 99.5%

it is possible to obtain the best clarity and stability of tri-component diesohol mixtures.


Results and DiscussionResults and Discussion

30

Test Fuel PropertiesTest Fuel Properties


No.%

Diesel%Ethyl acetate

%EtOH99.5

Density (g/cm3)

Cetane Index

Flash Point (°C)

Pour Point (°C)

Heat of Combustion

(MJ/kg)

Viscosity @40°C

(cSt)

1 90 0 10 0.8268 46.1 14.5 3 43,35 1.880

2 90 5 5 0.8339 44.7 12.5 3 43.45 1.825

3 90 10 0 0.8394 43.4 10.0 3 42.35 1.712

4 85 0 15 0.8247 45.8 13.0 3 42.48 1.812

5 85 5 10 0.8329 44.2 11.0 3 42.57 1.739

6 85 10 5 0.8378 43.2 9.0 3 41.63 1.591

7 85 15 0 0.8429 41.1 8.0 3 41.08 1.532

8 80 5 15 0.8309 43.5 9.5 3 41.71 1.639

9 80 10 10 0.8356 42.1 8.5 0 41.01 1.522

10 80 15 5 0.8406 39.9 7.5 3 40.38 1.413

11 0 100 0 0.9057 - -5 -84 23.11 -

12 100 0 0 0.8354 47.6 69 1 45.01 2.273

Fuel Properties Testing

37

Fuel Properties Fuel Properties TestingTesting


Results and DiscussionResults and Discussion

38

Engine TestEngine Test

CO Emission

ratio = %diesel : %ethyl acetate : %ethanol

100/0/090/0/10

90/5/590/10/0

85/0/1585/5/10

85/10/585/15/0

80/5/15

80/10/1080/15/5

CO

(%

vol)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

CO at load 100%CO at load 60%CO at load 30%CO at no load

Diesel fuel 100%

Ethyl acetate has less carbon than Diesel fuel and its oxygen content increases the oxygen to fuel ratio leading to more complete combustion.

100%Load

Engine testEngine test

39Results and Discussion

No and Light load : no significant different

Full load : CO ↓

NO (ppm vol)

100 200 300 400 500 600

%L

oa

d

0

20

40

60

80

100

120

100/0/080/5/1580/10/1080/15/5

Diesel 80%

NOx Emission

40

NO (ppm vol)

0 100 200 300 400 500 600

%L

oa

d

0

20

40

60

80

100

120

100/0/090/0/1090/5/590/10/0

Diesel 90%

NO (ppm vol)

100 200 300 400 500 600

%L

oa

d

0

20

40

60

80

100

120

100/0/085/0/1585/5/1085/10/585/15/0

Diesel 85%

No load : NOx ↓

Light and Full load : NOx ↑

More complete combustion

→ higher combustion temp→ high NOx formation

HC (ppm vol)

0 50 100 150 200 250

%L

oa

d

0

20

40

60

80

100

120

100/0/080/5/1580/10/1080/15/5

Diesel 80%

HC (ppm vol)

0 20 40 60 80 100 120 140 160

%L

Oa

d

0

20

40

60

80

100

120

100/0/085/0/1585/5/1085/10/585/15/0

Diesel 85%

HC Emission

41

No and Light load : HC ↑

Full load : HC ↓

Increase load

→ incomplete combustion→ produce HC emission

HC (ppm vol)

0 20 40 60 80 100 120 140 160

%L

oa

d

0

20

40

60

80

100

120

100/0/090/0/1090/5/590/10/0

Diesel 90%

%Load

0 20 40 60 80 100 120

Fu

el c

on

sum

ptio

n r

ate

(kg

/hr)

0.4

0.6

0.8

1.0

1.2

1.4

1.6

100/0/080/5/1580/10/1080/15/5

%Load

0 20 40 60 80 100 120

Fu

el c

on

sum

ptio

n r

ate

(kg/h

r)

0.4

0.6

0.8

1.0

1.2

1.4

100/0/085/0/1585/5/1085/10/585/15/0

%Load

0 20 40 60 80 100 120

Fu

el c

on

sum

ptio

n r

ate

(kg/

hr)

0.4

0.6

0.8

1.0

1.2

1.4

100/0/090/0/1090/5/590/10/0

Diesel 80%

Fuel Consumption Rate

Fuel consumption rate of those blend were higher than diesel fuel.

42

Diesel 90%

Diesel 85%

Engine Load ↑ Fuel Consumption Rate↑

Cetane No.↓ Ignition Delay Time ↑

Fuel Consumption Rate ↑

ConclusionsConclusions

43

1. Using anhydrous ethanol are thus more suitable than 95% ethanol for use as fuel.

2. In general, blends containing 90%diesel, 5%ethyl acetate and 5% ethanol has very close fuel properties compared to diesel fuel.

3. The presence of oxygenated compounds, ethanol and ethyl acetate, in diesel fuel significantly influences engine emissions and also the fuel consumption.

4. For further research, it’s necessary to evaluate the economic of ethyl acetate production for currently available in commercial use.


44

The Royal Chitralada ProjectsThe Royal Chitralada Projects

Rayong Purifier Public CompanyRayong Purifier Public Company

PTT Public CompanyPTT Public Company

The PPC consortiumThe PPC consortium

AcknowledgementsAcknowledgements

The Royal Thai NavyThe Royal Thai Navy


Energy Conservation Promotion Fund for Local Energy Conservation Promotion Fund for Local and Research supported by Energy Policy and and Research supported by Energy Policy and Planning Office, Ministry of EnergyPlanning Office, Ministry of Energy

My Friends and familyMy Friends and family

The Petroleum and Petrochemical College

THANK YOU


The Effect of an Oxygenated Additive on the Emulsification Characteristics of Diesel-Ethanol Blends The Petroleum and Petrochemical College, Chulalongkorn.

Documents

oxygen compound ethanol

thanyatorn isarachewa

diesel blends

fuel properties

fuel instability

fuel mixture

diesel substitution

oxygen molecules