Programs at CCCC
Curriculum:AAS Sustainable Farming
Organic Crop Production
Livestock Management
AAS Biofuels TechnologyBiodiesel Production
AAS Sustainability
Renewable Energy
Green Building
Natural Chef Diploma
Biodiesel Production Lab Overview
Andrew McMahan
Central Carolina Community College
SEET Workshop 2010
VS
Biofuela solid, liquid, or gas fuel derived from, or consisting of biological material.
Ethanol Biodiesel
Primarily comes from corn
Created from sugars
Primarily comes from soy
Created from oils & fats
Distillation Process
Gasoline Engines
Transesterification Process
Diesel Engines
VS Biogas
Primarily comes animal waste
Created from organic materials
Anaerobic Digestion Process
Electrical Generation
Extreme Global Warminggave excessive Algal Growths
Organic debris
90 & 150 million years ago
Rifts formed as the Continents moved apart
Source: Campbell, May 2005
Chemical reactions converted organic debris into oil when buried & heated
Rifts filled by sediment washed in from borderlands
And then came the rains
Source: Campbell, May 2005
Gasoline30°C–180°CNaphtha110°C–195°C
Kerosene170°C–290°C
Heating oil260°C–350°C
Lubricating oil300°C–370°C
Residue
Gas
Heatedcrude oilat 370°C
Fractional Distillation
of Petroleum
Why it works…
Carbon chain length
Chemical properties
Energy content
A molecule of diesel fuel is typically a fully saturated hydrocarbon
FFA combines with alcohol molecule to make an alkyl ester (Biodiesel)
Fatty Acids
– Lipids are mostly made of fatty acids ~95% by weight– Both the physical and chemical properties of the fat or oil are greatly influenced by the kinds and proportions of fatty acids present
– Saturated Fatty Acids are those containing only single carbon‐to‐carbon bonds
– Unsaturated Fatty Acids are those containing one (or more) double carbon‐to‐carbon bonds
The differences between oil and fat feedstocks is determined by the types of fatty acids present
Feedstockpalmitic
(16:0)stearic (18:0)
oleic (18:1)
linoleic (18:2)
linolenic (18:3)
safflower trace 6 2 8 84soy 8 3 25 55 6
canola 4 1 60 20 15olive 8 2 80 10 trace
yellow grease 17 12 55 8 1lard 25 15 50 10 trace
butter 25 15 30 2.5 tracetallow 30 25 35 5 trace
Lower cetane More prone to oxidationBetter cold‐flow
Higher cetane Less prone to oxidationWorse cold flow
Transesterification
One triglyceride molecule is converted into three mono-alkyl-ester (biodiesel) molecules
Triglyceride
MethanolBiodiesel
Glycerol
Catalyst
Keys to a good transesterification reaction
TemperatureTurbulence
Time
Super CriticalCavitation
Mini Batch Lab
Making Methoxide
Methanol
Catalyst
Methoxide
•Highly caustic! USE PROPER SAFETY
•Must be made before combining with oil in reaction vessel
•Catalyst of choice is Potassium Hydroxide (KOH)
•Sodium Hydroxide (NaOH) can also be used
What’s in Crude FAME & Glycerin
FAME
Methyl Esters (biodiesel)
Methanol
Soap (FFA attached to KOH
Mono, Di, and Triglycerides
Glycerin
Water
Glycerin
Glycerin
Methanol
KOH
Soaps
Mono, Di, and
Triglycerides
Water
Basic Transesterification Lab
Virgin Oil Volumetric Mini‐batch 27/3 Test
•Allows for easy demonstration of biodiesel production and basic quality control•Requires one hours for mini‐batch, one hour for settling, 30 minutes for 27/3 test•Great for chemistry courses, environmental science courses, short workshops, public demonstrations
Materials Required:Store bought vegetable oil Water Bath (optional)Methanol (~99% purity) Wide mouth Mason jarPotassium Hydroxide (>90% purity) Graduated CylinderBalance (1g accuracy or better) 50ml centrifuge tubePlastic pipette (1ml accuracy) Personal Safety Equipment
Intermediate Transesterification Lab
Used Cooking Oil
Volumetric Titration
Volumetric Mini‐batch 27/3 Test
•Introduces students to free fatty acids (FFA) in oil•Requires an additional hour for titration lab•Further detail into variables of biodiesel production recipe•Great for RE survey course, extended workshops, or as first lab in a biofuels course
Materials Required:In addition to basic lab materials:
Used cooking oil *Isopropyl Alcohol *Balance (0.1g accuracy or better) *Phenolthalein (1% in EOH)*50ml burette *50ml beakers*Stir plate *Volumetric Flask
Advanced Transesterification Lab
Used Cooking
Oil
Titration by molar mass
Mini‐batch by mass
27/3 Test Soap Titration
Water Wash
Soap Titration
•Demonstrates biodiesel production process from beginning to end•Utilizes more accurate molar mass titrations •Additional titration allows students to measure soap content of fuel•Requires multiple days of settling time due to water wash•Great for students already familiar with biodiesel production process
Materials Required:In addition to intermediate lab materials:
Hydrochloric Acid (0.1N in water) Separatoy FunnelBromonphenol Blue (0.4% in EOH) Spray bottleAnalytical Balance (0.001 accuracy or better) 250ml beakers
Free Fatty Acid & Acid Value Titration Explanation: In this lab procedure, the goal is to determine the quality of a sample of a biodiesel feedstock. “Feedstock” is defined as any material suitable for producing biodiesel. This encompasses any type of triglyceride, including vegetable oil and animal fat. As fats or oils are exposed to heat, water, and the passage of time, the molecules begin to break down. Fatty acid chains break away from the triglyceride molecules, creating free fatty acids. A triglyceride undergoing this degradation process is illustrated below:
The level of acidity in a sample of fat or oil can be calculated by performing a titration. You will dilute a sample of biodiesel feedstock in isopropyl alcohol, add a pH indicator, and neutralize the sample by adding a solution of basic catalyst. The amount of catalyst required to neutralize the sample indicates the acidity of the oil. You will accurately determine and document their findings through repeated trials. sing a slightly different equation, this titration can also be used to measure the Acid Number of a uel sample. The same procedure is used for both titrations, the equation is the only difference. Uf Materials: Balance (0.01g accuracy or better) Ring Stand
Bar 10mL Buret
& Stireaker
Stir Plate50mL Bippette 2P
Reagents: Oil or Ester Sample Isopropyl Alcohol Phenolthalien (0.1%) Pottassium Hydroxide (0.1N or 0.01N Solution)
Bl k Titration Procedure:an
a1. Add 50ml isopropyl alcohol and 8 drops phenolthalien indicator to 2. Add 0.1N KOH solution in a drop wise manner until the solution ob3. Record the amount of KOH required to turn the solution magenta. If the solution remains
magenta after adding only one drop, record the amount as 0. This will be used as B in the following equations.
250ml beaker. tain a magenta color.
Ti ation Procedure:tr 1. Place a 250 mL beaker on the balance and tare weight to 0.0000g
Courtesy of CCCC Biofuels Program
Courtesy of CCCC Biofuels Program
“Homebrew” Oil Titration (by volume)
Materials:
• Volumetric Flask • curacy of 0.01g) Balance (ac
• • Stir Plate
• Ring stand Burette
• Burette holder • 3ml plastic Pipette
• 25mL Beakers • Graduated Cylinder • Distilled H2O
• • KOH (100% purity)
IsopropylPhenoltha
• Oil or Fat
Alcohol • lien (pH indicator)
Proced eur :
tion solution may be g volumetric flask
1. Mak .1 kept in airtight container for up to 1 month of use. e % KOH Titration solution ‐ Titra
a. Measure 500mL distilled H2O usinb. Using balance, weigh 0.5g KOH
is completely dissolved
c. Add KOH to flask containing H2O d. Place stir bar in flask and put on stir plate, cover, and stir until KOH
e. Transfer solution to properly labeled squeeze bottle for use
eaker 2. Fill burette with .1% KOH solution (record amount of solution in burette)
l alcohol, add to 25mL b
3. Using a graduated cylinder, measure 15mL isopropy
4. Using a small plastic pipette, measure 1mL oil and add to isopropyl alcohol
5. Add 5‐7 drops phenolthalein in alcohol/oil mixture 6. Stir while adding .1% KOH solution to alcohol/oil mixture until flashes of pink begin to appear
holds 7. Slowly add (short squirts or single drops) .1% KOH solution until the alcohol/oil mixture turns pink andcolor for 10‐15 seconds. Record remaining amount of .1% KOH remaining in burette
. Subtract remaining KOH solution from original amount and record. This is what we will refer to as the titration number.
8
Analysis:
1. Convert t of KOH – this is your titration numberhe number of milliliters used to titrate the oil into grams Example: Titration requiring of 5.7mL of titrate solution would be equivalent to 5.7g KOH ulate amount of KOH needed for reaction using the equation:
s KOH2. Calc
(9.0g KOH + Titration Number) X Liters to be reacted = Total gram for reaction Example: You have found that the oil you are to process has a titration number of 2.4 mL and you would like to use 1L of oil in reaction. The equation in this instance would be:
(9.0g KOH + 2.4g KOH) X 1L = 11.4g KOH/L
Courtesy of CCCC Biofuels Program
Volumetric MiniBatch (using “Homebrew” Equation) Materials:
• Warm Water Bath Wide mouth pint Mason Jar
• Balance (accuracy of 0.01g) •
• Graduated Cylinder • Quart Mason Jar • 500mL Separatory Funnel
Reagents:
• ide (100% purity) Potassium Hydrox55mL methanol
• 250mL Oil or Fat •
Procedure:
Measure 250m in warm water bath to 1 Calculate the
3. 2l oil in graduated cylinder, add oil to 1L mason jar, and heat4.
0OF titration number of the oil to be processed using the Homebrew Titration procedure. Measure 55mL of methanol and put into 1 quart Mason jar.
6. Under Hood ‐ Whave
5. Under Hoodeigh catalyst and carefully add to methanol. Shake until KOH is completely dissolved. You
now created potassium methoxide. Important: Work quickly but carefully to replace cap of catalyst container. KOH will absorb moisture fromair and become a solid block if allowed to sit in open container. Important: Potassium methoxide is extremely corrosive. Always use care when handling methoxide and should always be handled under the fume hood.
od next to 7. Once oil has reached 120OF, remove 1 Liter Mason jar from water bath and place it under the fume homethoxide. Add methoxide to oil and tightly replace lid of jar. Vigorously sh8. ake Mason jar for 60 seconds and then place back into warn water bath for 30 minutes.
9. Remove jar from water bath thirty minutes after original reaction and shake for additional 60 seconds. 10. Under Hood ‐Transfer contents of mason jar into 500mL separatory funnel, cap with stopper, and let sit
overnight.
2. Add approximately 20 g sample and record the weight to the nearest 0.0001g to 3. Add 125mL of titration solvent, 8 drops of phenolthalein indicator, and a magnetic stirrer
sample beaker
4. Fill the buret with 0.1N potassium hydroxide and place the buret in position for titration
n least 30 seconds.
5. Start the stirrer, vigorous but not splashing or stirring air into the solutio. Add KOH solution to beaker until a pink color appears and remains for at . Record the amount of potassium hydroxide needed for the color change 67 Analysis: Free Fatty Acid Content
the following equation: To cal
A‐B) x 0.1
culate the percent FFA in oil use
x 28.2 ( = %FFA in sample W
e in sample A= volume of titrant used to produce color chang
dure) B= volume of titrant used in blank
n this procef oleic acid
N= normality of titrant (0.1N i8.2 is the molecular weight o= weight of sample in gram
2W Total Acid Number
o calculate the T N of the sample use the equation: T A
x 56.1 (A‐B) x 0.1 = Total Acid Number of sample W
e in sample A= volume of titrant used to produce color chang
rocedure) B= volume of titrant used in blank
this p KOH
N= normality of titrant (0.1N in6.1 is the molecular weight of= weight of sample in grams
5W
Courtesy of CCCC Biofuels Program
Residual Catalyst & Soap Titration Explanation: Production of biodiesel using an alkali catalyst always produces some amount of soap. here will be more soap with recycled restaurant waste and animal fats and less with Trefined vegetable oils. After the transesterification reaction is complete, the leftover catalyst and soap tend to concentrate in the glycerol phase. However, some soap and a small amount of catalyst may be left in the biodiesel phase. During process development, it can be useful to know the mount of soap formed, where the catalyst resides, and how effective the washing process is n removing these two compounds. ai In the first titration, the HCl neutralizes the alkali catalyst, so when the phenolphthalein indicates that the solution has become neutral, then all of the catalyst has been counted. Then, if the titration is continued, the HCl, as a strong acid, begins to split the soap molecules to free fatty acids and salt. When the pH reaches about 4.6, where the bromophenol blue changes color, then this indicates that the HCl has split all of the soap. It is now lowering the pH, so it has protons to donate since the soap has all been split. Materials:
accuracy or better) Balance (0.01gRing Stand
Bar 10mL Burrette
& Stireaker
Stir Plate50mL Bippette 2P
Reagents:
e Ester Sample Isopropyl Alcohol or AcetonPhenolthalien (0.1%) romophenol Blue (0.04%) ydrochloric Acid (0.1N or 0.01N)
BH
Pr cedure:o
1. Measure 10g of unwashed esters to 250ml beaker. (Use 20g sample washed esters) 2. Add 10ml of 0.1N HCL to burrette. (May want to use 0.01N HCL for wasted esters)
3. Add 100ml of Isopropyl Alcohol to beaker containing ester sample. Place beaker on stirplate and begin stirring, being careful not to create splashing.
4. Add 5 drops of phenolthalien to alcohol/ester solution. If solution turns pink, add HCL until solution looses pink color. Record amount of HCL required to change solution color as “A”
This represents the amount of residual catalyst in your e
sters. If no pink color is seen, simply record the Excess Catalyst as 0 and move to the next step.
5. Add 20 drops of bromophenol blue to alcohol/ester solution. 6. Add HCL to solution until ester/alcohol mixture turns from blue to bright yellow and
holds color. Record amount of HCL required to change solution color as “B”.
Courtesy of CCCC Biofuels Program
Analysis: Residual Catalyst ow, the amount of HCl added during the first titration tells us how much free catalyst is in
oap. Nthe sample and the amount added during the second titration tells us the amount of s If you take the ml of HCl added for the first titration and do the following calculation: [“A” ml of 0.1 N HCl] x [1 liter/1000 ml] x [0.1 moles of HCl/liter] x [1 mole of OH/mole of HCl] x [56.1 g/mole KOH] / [grams of sample] = grams of KOH/gram of ample or Ks
.1A x 0.1 x 56 = grams of KOH catalyst / grams of sample 1000 x W This gives the amount of free catalyst in the sample, done here assuming the catalyst was OH. You can substitute the appropriate molecular weight for other catalysts (KOH =56.1, aOH = 40.0, NaOCH3 = 54.0).
KN Soap Content To ca e equation: lculate the amount of soap in ester sample use th
x 320.56(BA) x 0.1 = grams of soap / grams of catalyst 1000 x W
° B is the number of ml of HCl required to turn ester sample from blue to yellow. ° ding to the 0.1 represents the Normality of the titration solution (This will change accor
concentration of solution used for the titration.)
° 32
0.56 is used if ester sample was reacted using KOH as catalyst, if NaOH is used, 304.4 should be substituted in the equation.
W is the weight of the ester sample used in the titration. (weight is multiplied by 1000 to obtain milligrams.)
°
To convert your results to parts per million (ppm), multiply final result by 1,000,000.
Courtesy of CCCC Biofuels Program
27/3 Conversion Test Explanation: The 27/3 test can be used as a qualitative assessment of conversion. Due to the insolubility of triglycerides in methanol, any unconverted triglycerides will not be miscible in methanol and thus will precipitate to the bottom of the centrifuge tube. In general, if no precipitate is seen at the bottom of the tube the fuel being tested has been well converted. Materials: 0 ml Centrifuge tube 5 Reagents: ethanol ethyl Esters
MM Pr cedure:o
1. Measure 27ml of methanol and pour into centrifuge tube.
t shake. 2. Add 3ml of methyl esters to centrifuge tube.
vert 2‐3 times. Do no for falling droplets.
3. Securely place cap on centrifuge tube and inh
4. Hold centrifuge up to light source and watc
5. If possible, place centrifuge in refrigerator. . Allow mixture to settle for 10‐15 minutes. . Inspect tip of centrifuge tube for precipitate. 67 Analysis:
ted. If no precipitate is visible upon inspection, the fuel has been well conver
f precipitate is observed, conversion has not been taken to completion. I
Courtesy of CCCC Biofuels Program
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