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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
10PPC, Ms. Thanyatorn Isarachewa
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)
PPC, Ms. Thanyatorn Isarachewa
Methodology OutlineMethodology Outline
17
2. Stability Observation2. Stability Observation
3. Turbidity Measurement3. Turbidity Measurement
1. Splash-Blending1. Splash-Blending
2.1 Effect of temperature
PPC, Ms. Thanyatorn Isarachewa
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)
PPC, Ms. Thanyatorn Isarachewa
““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.
Experimental DesignExperimental Design
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.
PPC, Ms. Thanyatorn Isarachewa
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
Experimental DesignExperimental Design
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
PPC, Ms. Thanyatorn Isarachewa
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
22PPC, Ms. Thanyatorn Isarachewa
Model : DG3LE
Model : Eurogas 8020
5. Emission Testing5. Emission Testing
Experimental DesignExperimental Design
All of the blends after tested fuel properties
Vary %Load0, 30, 60, 100%
CO, NOx, HC
23
Observe fuel consumption
rate
PPC, Ms. Thanyatorn Isarachewa
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
PPC, Ms. Thanyatorn Isarachewa
Developed Ternary Developed Ternary DiagramDiagram
25
At Room TemperatureAt Room Temperature
Results and Discussion
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
(liquid) Clear solution, 2 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
(liquid) Clear solution, 1 phase
(liquid) Clear solution, 2 phase
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
(liquid) Clear solution, 1 phase
(liquid) Clear solution, 2 phase
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%.
PPC, Ms. Thanyatorn Isarachewa
26
Results and Discussion
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.
Developed Ternary Developed Ternary DiagramDiagram
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
(liquid) Clear solution, 1 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
(liquid) Clear solution, 1 phase
(liquid) Clear solution, 2 phase
Temperature At 20Temperature At 20°C°C
2 phase
1 phase
cloudiness in the mixture followed by separation.
PPC, Ms. Thanyatorn Isarachewa
Ternary Plot at 40*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) Clear solution, 1 phase
Ternary Plot at 30*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) Clear solution, 1 phase
27
Results and Discussion
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
Developed Ternary Developed Ternary DiagramDiagram
PPC, Ms. Thanyatorn Isarachewa
Results and Discussion
28
Turbidity MeasurementTurbidity Measurement
PPC, Ms. Thanyatorn Isarachewa
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.
29PPC, Ms. Thanyatorn Isarachewa
Results and DiscussionResults and Discussion
30
Test Fuel PropertiesTest Fuel Properties
PPC, Ms. Thanyatorn Isarachewa
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 Discussion
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.
PPC, Ms. Thanyatorn Isarachewa
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
PPC, Ms. Thanyatorn Isarachewa
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
PPC, Ms. Thanyatorn Isarachewa