BIODIESEL Benares 24092020 - Endri

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BIODIESEL

Biodiesel Characteristics & Specification


Endriastuti
Technical Manager (Lubricant & Fuel
Division)
Email : [email protected]
081325365522/ 085713591113
PALM OIL BIODIESEL (continued)

Elaeis guineensis

Mesocarp

Extracted

OIL (45-50%)
CPO

The rest of the fruit :


 Exocarp
 Endocarp/ shell
(eprints.polsri.ac,id)
 Kernel  Oil/ PKO
 Moisture
 Non fatty fiber

(Mamilla et al, 2012)


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CHAPTER 01 - 3
PALM OIL BIODIESEL (continued)

VARIATES OF PALM FRUIT

(eprints.polsri.ac,id)
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CHAPTER 01 - 4
HOW BIODIESEL IS MADE
BIODIESEL PROCESS

Trans
MONOGLYCERIDE
esterification
+ Methanol
+ GLYCERINE + DIGLYCERIDE
TRIGLYCERIDE
(CH3OH)
+ Base (NaOH)

REFINED OIL FAME


dr CPO

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CHAPTER 01 - 5
HOW BIODIESEL IS MADE (continued)
BIODIESEL PROCESS

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CHAPTER 01 - 6
PALM OIL BIODIESEL
TYPICAL FATTY ACID OF PALM OIL COMPARED TO OTHER OIL

(Douvartzides et al, 2019


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CHAPTER 01 - 7
HOW BIODIESEL IS MADE (continued)
TRANSESTERIFICATION

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CHAPTER 01 - 8
HOW BIODIESEL IS MADE (continued)
SIDE REACTION DURING PROCESS

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CHAPTER 01 - 9
HOW BIODIESEL IS MADE (continued)
SIDE REACTION DURING PROCESS

(Alenezi et al, 2010)


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CHAPTER 01 - 10
What Affects the Quality of
Biodiesel ?

FEEDSTOCK QUALITY

PRODUCTION PROCESS

STORAGE & DISTRIBUTION

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CHAPTER 01 - 11
What Affects the Quality of Biodiesel ? (continued)
FEEDSTOCK QUALITY
Indicator Parameters
Oxidation Stability (Rancimat Method EN 15751)

Cloud Point (ASTM D2500)


Pour Point (ASTM D97) -> Cold Flow Ability

Total Acid Number (ASTM D974 or ASTM D664) ->


Acidity
Phosphorus Content (ASTM D5185) (Dos Pasos, 2019)
Cetane Number (ASTM D 613) -> (affected by
degree of unsaturation)
Cetane Index (ASTM D 4737)

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CHAPTER 01 - 12
What Affects the Quality of Biodiesel ? (continued)
PRODUCTION PROCESS
Indicator Parameters
- FAME content

- Glycerine
- Impurities (Mono-, di-, tri-
glyceride)
- Methanol
- Phosphorus
- Ash content
- Water content
- Free fatty acid
- Copper Strip Corrosion
- Flash Point
- Kinematic viscosity

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CHAPTER 01 - 13
What Affects the Quality of Biodiesel ? (continued)
DISTRIBUTION & STORAGE
Indicator Parameters
Water ASTM D6304

Oxidation Stability (Rancimat Method EN 15751)


Acid Number
Total Contamination
Microbial Contamination

(EBTKE, 2018)

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CHAPTER 01 - 14
Biodiesel Vs Fossil Fuel
Characteristics
CHARACTERISTICS BIODIESEL FOSSIL DIESEL FUEL
Renewable Yes (vegetable oil) No
Degradable Yes, Biodegradable No/ difficult to degrade
Polarity More polar Non Polar
Hygroscopic Yes No
Composition Saturated and unsaturated fatty acid Hydrocarbon C14-C18
methyl ester
Density Higher density Lower density
Oxygen Contain Oxygen (O2) No O2
Calorific Value Lower (min. 35 MJ/kg) Higher (min. 45 MJ/kg)
Cetane Number Higher (min 51 - 60s) Lower (min. 48)
Sulfur Very low sulfur High sulfur
Oxidation Stability Moderate Good
Material Compatibility Limited (not compatible with natural Variuos material, Compatible
rubber) to rubber

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CHAPTER 01 - 15
Biodiesel Vs Fossil Fuel (continued)
Advantage Characteristics

Oxygen Content ↓ unburned HC , ↓ CO, ↓ PM

Renewable Natural vegetables


Degradable Biodegradable
Higher cetane number Shorter ignition delay. The injected fuel burns more
evenly and completely --> better quality exhaust air,
especially with regard to soot, particulate matter and
unburned hydrocarbons. Also affect the combustion
noise less noisy.
Higher lubricity Good for injector, piston

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CHAPTER 01 - 16
Biodiesel Vs Fossil Fuel (continued)
Challanging Characteristics

Unsaturated Fatty Acid Less stable to oxidation (palm oil -> moderate
oxidation stability)
Polar Hygroscopic --> lead to rust, corrosion
Solvency (Ester) Rinse the sludge/ deposit --> filter clogging
Swelling in elastomer/ natural rubber (crosslinking)
Organic compound as nutrient Microbial growth (initiated by high water content/
for microorganism free water)
Limited Material Compatibility
Impurities from process By product such as monoglycerides tend to
precipitate

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CHAPTER 01 - 17
Biodiesel Specification (continued)
Specs Comparison B100
Kep EBTKE 189-2019 ASTM D6751-12 EN14214
No. Parameters Unit
Method Min Max Min Max Min Max
3
1 Density at 40⁰C kg/m SNI 7182:2015 850 890 860 900
2
2 Kinematic Viscosity at 40⁰C mm /s (cSt) SNI 7182:2015 2,3 6,0 1,9 6,0 3,5 5,0
3 Cetane Number SNI 7182:2015 51 47 51,0
4 Flash Point PMCC ⁰C SNI 7182:2015 130 93
5 Copper Strip corrosion 3hrs/50⁰C No. SNI 7182:2015 1 3 1
6 Carbon Residue on 100% samples %mass SNI 7182:2015 0,05 0,05
Carbon Residue on 10% dist residue %mass SNI 7182:2015 0,3
7 Distillation Temperature 90 ⁰C SNI 7182:2015 360 360
8 Sulphated Ash %mass SNI 7182:2015 0,02 0,02 0,02
9 Sulfur mg/kg SNI 7182:2015 10 15
10 Phosphor mg/kg SNI 7182:2015 4 10 4
11 Acid Number mgKOH/g SNI 7182:2015 0,4 0,5
12 Free Gycerol %mass SNI 7182:2015 0,02 0,02 0,02
13 Total Glycerol %mass SNI 7182:2015 0,24 0,24 0,25
14 Methyl Ester content %mass SNI 7182:2015 96,5 96,5
15 Iodine Number %-mass(g-I 2 /100 g) SNI 7182:2015 115
16 Oxidation Stability (Rancimat) Mins SNI 7182:2015 600 180 480
Oxidation Stability (Petro oxy) Mins SNI 7182:2015 45
17 Monoglyceride %mass SNI 7182:2015 0,55 0,7
18 Color ASTM color ASTM D1500 3
19 Water content ppm ASTM D6304 350 500
20 CFPP ⁰C ASTM D6371 15
21 Metal Na+K mg/kg EN 14538(ASTM D5185) 5 5 5
22 Metal Ca+Mg mg/kg EN 14538(ASTM D5185) 5 5 5
23 Total contaminant mg/L ASTM D6217 20 24

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CHAPTER 01 - 18
Biodiesel Blend (B-XX)

Fossil Diesel Fuel Biodiesel


B0 B100
Spec Solar 48 : Spec Biodiesel :
Kep Dirjen Migas No. 28K/10/DJM.T/2016 Kep Dirjen EBTKE No. 189K/10/2019
Spec Solar 51 :
Kep Dirjen Migas No. 3675K/DJM/2006

Blend

BXX
Spec B30 (Biodiesel 30% + Solar 70%):
Kep Dirjen Migas No. 0234K/10/DJM/2019
Specs ASTM D7467 (for biodiesel B6 to 20)

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CHAPTER 01 - 19
Biodiesel Blend (continued)
How To Blend BXX

In Tank Blending In-line Blending


(EBTKE, 2018)

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CHAPTER 01 - 20
B30 Specification
Specs Comparison Fossil Fuel & B30
Solar 48 Solar 51 Biodiesel Blend 30% (B30)
Kep Dirjen Migas No Kep Dirjen Migas No
No Parameter Method Unit Kep Dirjen Migas No Kep Dirjen Migas No
234.K/10/DJM.S/2019 (CN 234.K/10/DJM.S/2019 (CN
28.K/10/DJM.T/2016 3675 K/24/DJM2006
48) 51)
Min Max Min Max Min Max Min Max
1 Cetane Number ASTM D 613 - 48 51 - 48 51 -
2 Cetane Index ASTM D 4737 - 45 48 - 45 48 -
3 Density at 15⁰C ASTM D 1298 kg/m3 815 870 820 860 815 880 815 860
mm2/s
4 Kinematic Viscosity at 40⁰C ASTM D 445 (cSt) 2,0 4,5 2,0 4,5 2 5 2,0 4,5
5 Sulfur ASTM D 5185 % mass 0,25 0,05 0,25 0,05
Distillation Temperature 90 - 370 - 340 - 370 -
6 Distillation Temperature 95 ASTM D 86 ⁰C - 360 - 370
End Boiling Point - 370 -
7 Flash Point PMCC ASTM D 93 ⁰C 52 - 55 - 52 - 55 -
8 Cloud Point ASTM D 2500 ⁰C - 18 - 18 - 18
9 Pour Point ASTM D 97 ⁰C - 18 - 18 - 18 - 18
10 Carbon Residue ASTM D189 %mass - 0,1 - 0,30 - 0,1 - 0,10
11 Water Content by KF ASTM D 6304 ppm - 500 - 500 0 425 - 300
12 Fame Content ASTM D 7371 %v - 20 - 10 30 30
Copper Strip Corrosion
13 3hrs/50⁰C ASTM D 130 No. - Kelas 1 - Kelas 1 - Kelas 1 - Kelas 1
14 Ash Content ASTM D 482 %mass - 0,01 - 0,01 - 0,01 - 0,01
15 Sediment Content ASTM D 473 % mass - 0,01 - 0,01 - 0,01 - 0,01
16 Strong Acid Number (SAN) ASTM D 974 mgKOH/g - 0 - 0 0 - 0
17 Total Acid Number (TAN) ASTM D 974 mgKOH/g - 0,6 - 0,3 - 0,6 - 0,6
18 Appearance - - Jernih dan terang Jernih dan terang Jernih dan terang Jernih dan terang
ASTM
19 ASTM Color ASTM D 1500 color - 3 - 1 - 3 - 2
Lubricity (HFRR wear scar dia.
20 @60 oC) ASTM D 6079 micron - 460 - 460 - 460 - 460
Oxidation Stability
21 (Rancimat) EN 15751 hour 35 - 35 - 35 -
EN 16091 min 45 - 45 -
22 Biological Growth - - nihil nihil
23 Metanol and Ethanol Content ASTM D 4815 %vol tak terdeteksi tak terdeteksi
24 Particulat Contaminant ASTM D 6217 mg/L - 10 - 10

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CHAPTER 01 - 21
Common problems in Biodiesel/
Biodiesel Blend

1. Carbon Residue in Injector Nozzle

Parameters Unit Significances


Carbon Residue (ASTM %mass an approximate measure of the carbon-depositing
D189) tendencies of a fuel
has implications for the fuel system and engine
components (deposit on injector, combustion chamber)
residues not only consist of carbon, but other impurities
are also associated as carbon

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CHAPTER 01 - 22
Common problems in Biodiesel/
Biodiesel Blend
2. Higher Water Content

Parameters Unit Significances


Water Content (ASTM ppm Sources of these contaminants include various aspects of
D6304) production, storage and distribution of the fuel
excess water can lead to corrosion (transform any sulfur
to sulfuric acid)
provides an environment for microorganisms which can cause
filter plugging

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CHAPTER 01 - 23
Common problems in Biodiesel/
Biodiesel Blend
3. Microbial Growth

Parameters Significances
Bacterial represent microbial growth (bacteria,
Growth fungi)
Grow in water/fuel interface

Potential problems : filter plugging,


injector damage, corrosion
ASTM D8070 Test kit (qualitative)
(on site testing)
ASTM D7463 unit : RLU (quantitative)
(lab)

Fuel Phase:
negligible – up to 150 μg/l;
moderate –150–750 μg/l;
heavy – greater than 750 μg/l;

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CHAPTER 01 - 24
Common problems in Biodiesel/
Biodiesel Blend
4. Clogging Problems in Fuel filter

Parameters Unit Significances


Monoglycerides (SNI %mass as impurities, saturated fatty acid, potential to presipitate
7182:2015)
monoglycerides can greatly increase the cloud point

can cause accumulation of deposits (fouling) on the injector


and play a role in the formation of deposits on the piston
and valve

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CHAPTER 01 - 25
4. Clogging Problems in Fuel Filter

Parameters Unit Significances


Glycerol Source :error in washing processes

glycerol can also be formed due to the hydrolysis process of


residual mono-, di- and triglycerides in the biodiesel storage
process
excessive free glycerin usually causes problems with glycerin
settling down in storage tanks
This creates a viscous mixture that can plug fuel filters and
create combustion problems in engines
free glycerol then settles and attracts other polar compounds
such as water, monoglycerides, and soap, further causing
damage to the injection system
Total glycerol (SNI %mass The total glycerin is related to the amount of nonconverted
7182:2015) glycerides present in the biodiesel
Free Glycerol (SNI %mass free glycerin is related to its purification steps
7182:2015)

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CHAPTER 01 - 26
4. Clogging Problems in Fuel Filter

Parameters Unit Significances


Cold Filter Plugging Point ⁰C Estimating the lowest temperature when the fuel begins to
(CFPP) ASTM D6371) clog filters and hinder the operation of the engine

Method ASTM D6371

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CHAPTER 01 - 27
5. Solid Particle Contamination

Parameters Unit Significances


Sulfated Ash (ASTM D874) %mass measure ash formed from inorganic metallic compounds.

biodiesel leaves some ash from unburned hydrocarbon and


from inorganic impurities
three forms: (1) abrasive solids, (2) unremoved catalysts, and
(3) soluble metallic soaps
Metal-containing fuel additives and unremoved catalysts are
the main contributors of sulfated ash
Abrasive solids contribute to injector, fuel pump, piston and
ring wear, and engine deposits
Soluble metallic soaps have little effect on wear but may
contribute to filter plugging and engine deposits

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CHAPTER 01 - 28
5. Solid Particle Contamination

Parameters Unit Significances


Metal Na+K (ASTM mg/kg usually come from the catalyst not being removed after the
D5185) reaction through water washing or other process
may be present in biodiesel as abrasive solids or soluble
metallic soaps
If water is present during biodiesel reaction, some soap is
formed and usually remains dissolved in biodiesel. That
also gives rise to a high level of sodium or potassium salt
Metal Ca+Mg (ASTM mg/kg can be introduced during the biodiesel production process
D5185) for example, through the use of calcium methoxide as a
solid base catalyst
may be present in biodiesel as abrasive solids or soluble
metallic soaps
can contribute to injector, fuel pump, piston and ring wear
as well as to engine deposits
Soluble metallic soaps have little effect on wear, but they
may contribute to filter plugging and engine deposits

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CHAPTER 01 - 29
Number of Particle per mL
5. Solid Particle Contamination Up to and
More Than Number (R)
including
80.000 160.000 24
Parameters Method
40.000 80.000 23
Cleanliness (ISO Code ISO 11500 20.000 40.000 22
Code 4406) 10.000 20.000 21
5.000 10.000 20
Significances
2.500 5.000 19
count the amounts of solid particles 1.300 2.500 18
640 1.300 17
WWFC 2013 recommendation for ISO Code 4406: Max
18/16/13 320 640 16
160 320 15
Solid particle can damage injector, piston & liner, fuel filter
80 160 14
40 80 13
Method 1999 : ISO R4/R6/R14 20 40 12
Shortening : ISO */R6/R14 10 20 11
5 10 10
R4 : jml Particle > 4 micron /mL 2,5 5 9
R6 : jml Particle > 6 micron /mL 1,3 2,5 8
R14 : jml Particle >14 micron/mL 0,64 1,3 7
0,32 0,64 6
0,16 0,32 5
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CHAPTER 01 - 30
Common problems in Biodiesel/
Biodiesel Blend
5. Oxidation

(EBTKE, 2018)

Parameters Unit Significances


Oxidation Stability (EN Minutes refers to the extent that a fuel can withstand the formation of
15751) oxidation byproducts
oxidation products including aldehydes, alcohol, carboxylic acids
The greater the level of unsaturation in a fatty oil or ester, the
more susceptible it is to oxidation

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CHAPTER 01 - 31
LUBRICANT AND FUEL LABORATORY

Refferences

https://www.e-education.psu.edu/ Alternative Fuel From Biomass Source : The Reaction of


Biodiesel: Transesterification, John A Dutton E education Institute
Alenezi et al, 2010, Continuous Flow Hydrolysis of Sunflower Oil for Biodiesel, Energy Sources, Part
A, 32:460–468, 2010 Copyright © Taylor & Francis Group, LLC ISSN: 1556-7036 print/1556-7230
online
Dev Shrestha, 2019, Biodiesel Fuel Quality, Farm Energy https://farm-
energy.extension.org/biodiesel-fuel-quality/
Dos Pasos et al, 2019, Degumming Alternatives for Edible Oils and Biodiesel Production, Food and
Public Health 2019, 9(5): 139-147 DOI: 10.5923/j.fph.20190905.01
Douvartzides et al, 2019, Green Diesel: Biomass Feedstocks, Production Technologies, Catalytic
Research, Fuel Properties and Performance in Compression Ignition Internal Combustion Engines,
Energies 2019, 12, 809; doi:10.3390/en12050809
EBTKE, 2018, Petunjuk Teknis Penanganan dan Penyimpanan Campuran Biodiesel 20% pada Aplikasi
Unit Alat Berat diPertambangan Mineral dan Batubara
Giakoumis et al, 2019, A Comparative Assessment of Biodiesel Cetane Number Predictive
Correlations Based on Fatty Acid Composition, Energies 2019, 12, 422; doi:10.3390/en12030422
Mamilla et al, 2012, BIODIESEL PRODUCTION FROM PALM OIL BY TRANSESTERIFICATION METHOD,
International Journal of Current Research Vol. 4, Issue 08, pp. 083-088. August, 2012
eprints.polsri.ac.id

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CHAPTER 01 - 32
LUBRICANT AND FUEL LABORATORY

THANK YOU

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CHAPTER 01 - 33

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