The University of Arizona Biodiesel Pilot Plant Student Manual

Alexandra Downs
amdowns@email.arizona.edu December 11th, 2013

Table of Contents
Page Introduction Pilot Plant Overview. 2 What is Biodiesel? ... 2-4 The Chemistry of Biodiesel . 4-5 Fuel Quality Tests Soap Analysis Titration 6-7 Free Fatty Acid Titration . 8 Conversion Test .. 9-10 Acid Number Titration 11 Biodiesel Rancimat . 12-14 Karl Fischer Titration . 15-16 Chemical Safety Methanol 17-19 Sodium Methylate . 20 Sulfuric Acid . 21 References . 22

University of Arizona Biodiesel Pilot Plant Overview The University of Arizona Biodiesel Pilot Plant aims to convert waste cooking oil from the universitys student unions into biodiesel to fuel campus vehicles. With the help of the projects community industrial partner, Grecycle, students from a variety of majors have constructed a 100-gallon capacity production plant and quality-testing laboratory. The waste cooking oil is collected from student unions, filtered, and deposited at the plant. From there, students use chemical processes to convert the waste oil into biodiesel meeting the American Society for Testing and Materials quality standards. Upon satisfying industry standards, the fuel is sold to the university at $0.50 to $0.75 less per gallon than locally available commercial biodiesel. This project generates a wide range of benefits for students, the University of Arizona, and the Tucson community. Each month, up to 500 gallons of waste cooking oil can be collected from the student unions and converted into biodiesel. As a result, the university lessens its waste footprint, receives waste oil disposal services, and may purchase its own low-cost, locally produced fuel. The general community benefits from increased air quality as biodiesel releases less emissions, and from extension programs educating the public on biodiesel production. Furthermore, University of Arizona students gain valuable experience with chemical processing, fabrication, project management, and quality control testing. These skills apply to a wide range of jobs, and enhance students career opportunities.

What is Biodiesel? Biodiesel is a renewable fuel derived from vegetable oils or animal fats. These stock materials undergo chemical reactions to isolate mono-alkyl esters, the main component of biodiesel. Typically blended in various concentrations with regular diesel fuel, biodiesel may be used in diesel engines without modification. The main benefits of biodiesel use include the reduction of emissions harmful to human health, displacement of petroleum products, utilization of a plentiful waste supply, and growth of domestic energy production.

Figure 1: Conventional Diesel Exhaust Particle (Health Effects Institute 1995)

According to an extensive study conducted by the Environmental Protection Agency, pure biodiesel (B100) releases 67% less hydrocarbons, 48% less carbon monoxide, and 47% less particulate matter than conventional diesel. Thus, the use of biodiesel reduces the formation of smog and ozone. Furthermore, biodiesel produces essentially zero sulfur emissions (which trigger the formation of acid rain). Biodiesel emissions also demonstrate a 75-85% reduction in polycyclic aromatics hydrocarbons (PAH). EPA research on model organisms suggest that these PAHs lead to cancer formation (particularly of the lungs), organ damage, and reproductive harm. Figure 2: Average Emission Impacts of Biodiesel for Heavy-duty Highway Engines (EPA 2002)

In many respects, biodiesel poses significantly less risk of environmental damage than petroleum diesel. In the event of spillage, it biodegrades by 85-88% in only twenty-eight days. Because the lethal dose of biodiesel is ten times lower than household table salt, the substance poses minimal risks to living organisms. And with a flash point below 200F, both pure and blended biodiesel are much less flammable and safer to store than diesel. Conversion of waste oil into fuel reduces the need for imported petroleum products. In 2012 alone, the United States produced 1.1 billion gallons of commercial biodiesel. This

translates into both enhanced energy security, and the growth of domestic jobs. Today, about two hundred biodiesel plants in the U.S. employ an estimated 50,000 workers. Thus, the industry stimulates the growth of American jobs centered around an environmentally sustainable product. While the production and use of biodiesel have numerous benefits, like any energy source, it also holds drawbacks. Namely, the oxidative stability of biodiesel differs from traditional diesel. Because of this, its quality declines with factors such as time, exposure to moisture, and heat. Consequently, biodiesel should be used soon after production for optimal performance. In addition, the burning of pure biodiesel (B100) produces a 10% higher amount of nitrogen oxides, a component in the formation of smog (Figure 2). To counter this drawback, researchers at the National Renewable Energy Laboratory suggest the addition of cetane improvers, di-tertiary butyl peroxide and ethylhexylnitrate, to reduce NOx emissions without increasing particulate matter. For final consideration, B100 biodiesel has a slightly lower energy content than diesel. According to the U.S. Department of Energys Alternative Fuels Data Center, the energy content of B100 biodiesel is 118,296 Btu/gal. Compared to conventional diesel, whose energy content is 129,500 Btu/gal, this constitutes an 8.65% difference. B20 blend biodiesel, however, produces 127,259 Btu per gallon of energy. When blended, the energy difference between the two fuels averages at a mere 1.73%. Figure 3: Average Energy Content of Biodiesel and Diesel Fuel (US Dept. of Energy, 2004) Fuel Type Net Heating Value Avg., Btu/gal % Difference vs. No. 2 Diesel Avg. No. 2 Diesel 129,500 Biodiesel (B100) 118,296 8.65% B20 Blend 127,259 1.73% B2 Blend 129,276 0.17%

The Chemistry of Biodiesel Understanding the conversion of waste cooking oil into biodiesel requires a basic knowledge of acid-base chemistry and transesterification reactions. Before any chemical reactions can occur, the waste cooking oil is filtered to remove large particles of food or other contaminants. This material, sometimes referred to as yellow grease, consists mainly of chemical compounds called esters. As shown below, the ester corresponding to vegetable oil is a triglyceride composed of a glycerol backbone (in blue), and three long fatty acid chains (in black). Figure 4: Vegetable Oil Triglyceride

Through the process of transesterification, the triglyceride is split to form mono-alkyl esters (biodiesel) and glycerol (used to make soap and other products). Typically, an alcohol and a strong base catalyze this reaction. The Biodiesel Pilot Plant uses methanol and sodium methylate. During tranesterification, the base catalyst severs the bonds between the fatty acids and the glycerol backbone. Methanols CH3 group bonds with these detached fatty acid chains to form biodiesel. The hydrogen from the base catalyst then stabilizes the glycerol molecules. Figure 5: Transesterification Reaction

The speed of this reaction, which ranges from one to eight hours, increases with temperature. However, the reaction vessel temperature must remain below 148.5 F, the temperature at which methanol boils. As the reaction nears completion, the mixture forms a twophase column, with glycerol typically sinking to the bottom of the reaction vessel. This allows convenient removal of glycerine from the biodiesel. After the transesterification reaction takes place, several other steps are required to ensure the biodiesel meets quality standards for use as fuel. First, a conversion test is used to determine whether the transesterification reaction has reached completion. After that, a series of tests determine free fatty acid, moisture, glycerine, and alcohol levels. Dry washing the biodiesel by placing it into a dry column with ion exchange resin helps to remove leftover catalyst, water, and soaps. Addition of antioxidants or other additives may be necessary to obtain biodiesel meeting ASTM standards. The quality test section of this guide will provide further details on this process.

Fuel Quality Tests

Soap Analysis Titration This test is performed twice: after washing and drying the fuel, then prior to storage or use of fuel. After washing and drying the fuel, the fuel should contain less than 2000 ppm of soap. To avoid engine problems, soap concentration in finished biodiesel must contain less than 50 ppm. Materials: 5 g biodiesel Acetone, 99% Bromophenol blue indicator solution, .04% 0.1 M and 0.01 M HCl solution Titration burette Paper towels 125 mL erlenmeyer flask Analytical balance Glass container (at least 500 mL) Procedure: 1. To create soap test indicator solution, mix 400 mL acetone and 20 mL bromophenol blue solution in a closeable jar. The indicator solution should be yellow-colored. When not in use, keep jar closed to prevent evaporation. 2. In a clean 125 mL flask, weigh out 5 g of biodiesel. 3. Add 100 mL of the indicator solution to the biodiesel, and mix well. The solution should be blue-colored. 4. If testing after washing and drying, pour 0.1 M HCl into the titration burette. If testing prior to storage, pour 0.01 M HCl into the burette. To help view color change, place a white paper towel on surface beneath burette. 5. Take note of initial volume in titration burette. Slowly titrate .1 M HCl solution, swirling the flask to ensure even distribution. Stop titration when the solution turns from blue to yellow (see fig. 2). 6. Record the volume of HCl used to complete the titration, and insert it into the following formula to get the ppm of soap. Calculation: ppm soap = (( ____ mL HCl)( ___M HCl)(304,400)) / sample weight in grams

Figure 1: Soap Titration setup

Figure 2: Soap Titration Color Progression

Free Fatty Acid (FFA) Titration This test is performed after heating the oil in the reactor, before mixing methanol and sodium methylate. It determines how much lye catalyst must be added to neutralize free fatty acids that were produced when the oil was used for frying. Materials: (2) 125 mL erlenmeyer flask Isopropyl alcohol (91%+) 1 g oil Phenolphthalein indicator 50 mL Burette 0.1 M NaOH solution Analytical balance Transfer pipets Procedure: 1. Mix the oil sample with a transfer pipet to ensure homogeneity. 2. In a clean 125 mL flask, weigh out 1 g of oil. 3. In a separate 125 mL flask, pour 40 mL isopropyl alcohol. Using a clean transfer pipet, add 10 drops of phenolphthalein to the isopropyl alcohol. 4. To pre-neutralize this solution, add 0.1 M NaOH solution drop by drop until it turns a very light shade of pink. This should take only a few drops, so be careful not to add too much. A demonstration of proper pre-neutralization is shown in Figure 1. 5. Add the pre-neutralized isopropyl solution to the flask containing the oil. Swirl until mixed. The color should be a pale yellow. 6. Take note of initial volume in titration burette. Slowly titrate with 0.1 M NaOH solution, swirling the flask to ensure even distribution. Stop titration when the solution has turned from yellow to pink. 7. Measure the volume of NaOH used to complete the titration and insert it into the following formula to get the percent free fatty acid. 8. Repeat this titration 3 times and average values. Calculation: % Free Fatty Acid = (( _____mL 0.1 M NaOH)(0.1 M NaOH)(28.2))/ (1 gram sample) Figure 1: Proper (left) and improper (right) coloration for pre-neutralized isopropyl alcohol solution

Conversion Test This test is performed after methanol recovery. The test helps determine whether the conversion of oil to biodiesel has been completed. If complete conversion into biodiesel has not occurred, use of the fuel may cause engine problems. If the test fails, reprocessing of the biodiesel with a single stage reaction is necessary. Recover methanol and perform the conversion test again. Materials: 9 mL Methanol 1 mL biodiesel 15 mL centrifuge tube Transfer pipette Rubber stopper or cap Procedure: 1. Place 9 mL of methanol into 15 mL centrifuge tube. 2. Measure out a 1 mL sample of biodiesel and add it to the tube. 3. Place a cap on the centrifuge tube and shake vigorously for 30 seconds. 4. Allow the mixture to settle. If oil has been fully converted into biodiesel, the methanolbiodiesel mixture will appear completely clear. Depending on the type of oil being converted, the color ranges from clear to light yellow. If full conversion has not occurred, bubbles of oil will appear at the bottom of the tube/cylinder, or the mixture will look cloudy. These are indications of a failed test. Consult Figures 1 and 2 for visual representation.

Figure 1: Examples of passing oil samples

Both of these samples pass because the oil-methanol mixture is free of clouding, and there is no accumulation of oil at the bottom of the tube.

Figure 2: Example of failing oil sample

This sample fails because there is an accumulation of oil at the bottom of the tube.

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Acid Number Titration This test is performed after washing and drying fuel, before storing or using fuel. The test detects the acidity of biodiesel after processing. Materials: (2) 125 mL erlenmeyer flask Isopropyl alcohol (91%+) Phenolphthalein indicator 5 g biodiesel 50 mL Burette 0.1 M NaOH solution Analytical balance Transfer pipets Procedure: 1. Mix the oil sample with a transfer pipet to ensure homogeneity. 2. In a clean 125 mL flask, weigh out 5 g of biodiesel. 3. In a separate 125 mL flask, pour 40 mL isopropyl alcohol. Using a clean transfer pipet, add 10 drops of phenolphthalein to the isopropyl alcohol. 4. To pre-neutralize this solution, add 0.1 M NaOH solution drop by drop until it turns a very light shade of pink. This should take only a few drops, so be careful not to add too much. A demonstration of proper pre-neutralization is shown in Figure 1. 5. Add the pre-neutralized isopropyl solution to the flask containing the oil. Swirl until mixed. The color should be a pale yellow. 6. Take note of initial volume in titration burette. Slowly titrate with 0.1 M NaOH solution, swirling the flask to ensure even distribution. Stop titration when the solution has turned from yellow to pink. 7. Measure the volume of NaOH used to complete the titration and insert it into the following formula to get the percent free fatty acid. 8. Repeat this titration 3 times and average values. Calculation: Acid Number = 1.99*[( _____mL 0.1 M NaOH)(0.1 M NaOH)(28.2))/ (5 gram sample)] Figure 1: Proper (left) and improper (right) coloration for pre-neutralized isopropyl solution

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Biodiesel Rancimat Due to the effects of heat, light, moister, air exposure, and age, biodiesel oxidizes making the fuel less stable. If necessary, antioxidants can be added to the biodiesel to delay oxidation. The biodiesel rancimat measures the oxidative stability of biodiesel by quantifying a samples resistance to oxidation under steady heat and air flow. Materials: 873 Biodiesel Rancimat (located at Grecycle plant) Acetone DI water Lab soap 7.5 g biodiesel Analytical balance Transfer pipette Procedure: 1. On computer desktop, open program 873 Biodiesel Rancimat Control. 2. Click Heat to 110.9 for appropriate vessel block. The machine will take around twenty minutes to heat to 110.9. 3. While waiting for the rancimat to heat, cleanse the glass DI vessel, green DI vessel attachment, black connector tube, and white DI vessel air tube Wash each component thoroughly with lab soap, then soak in acetone (to remove water), and allow to air dry. It is critical that the rancimat components are completely clean and dust-free before use. 4. Place a sterile rancimat reaction vessel tube in a beaker or flask with a narrow opening. Place the tube and beaker on an analytical balance and tare. 5. Taking care not to allow oil to splash on the sides of the tubes (compromising a precise measurement), use a transfer pipette to measure 7.5 g of biodiesel into the reaction vessel. 6. As shown in Figures 4 and 5, insert glass tube with stability disk into reaction vessel. For an effective reading, the tube must extend into the biodiesel. Fix tube to reaction vessel cap with black O-ring and white screw. 7. Once the rancimat has finished heating up, place the reaction vessel in the appropriate heated slot. Attach the green and black tubing as shown in Figure 2 8. Place 60 mL of DI water into the DI vessel and place the green cover over the vessel. Place the vessel in the appropriate rancimat compartment and connect the green cover to the rancimat. 9. Attach black tube to the top of the DI vessel. 10. Click Start, and the rancimat will begin bubbling filtered air through the biodiesel sample, and measuring oxidation. The program will automatically stop running when testing has gone to completion. 11. Save test results for analysis.

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Figure 1: Overall rancimat setup

Figure 2: Tube connection

Figure 3: Reaction vessel setup

Figure 4: Submersion of glass tube into biodiesel

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Figure 5: Connection of cap, glass tube, and stability disk

Figure 6: Connection of reaction vessel and tubing

Figure 7: Test screen for finished samples

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Karl Fischer Titration Because biodiesel contains traces of emulsifying monoglycerides and diglycerides, it may hold small amounts of water. The water retaining capacity of biodiesel is higher than that of diesel. This water increases the amount of fuel gelling in cold climates, reduces heat of combustion, corrodes fuel system components, and triggers microbial growth. For optimal fuel stability and performance, the water content in biodiesel should fall below 500 ppm. A Karl Fischer Coulometric Titrator precisely determines the amount of water present in a biodiesel sample. Materials: Mettler Toledo C20 Coulometric KF Titrator 0.1 g biodiesel Gas syringe Analytical Balance Procedure: 1. To turn on the titrator, press the home button on the machine panel. 2. To begin the pretitration, press the Start button on the bottom right corner of the screen. Do not input a weight. 3. Once the pretitration has finished, the word Standby will appear on the screen. The titrator is now ready to accept a sample. 4. Using a gas syringe and analytical balance, weigh out a sample of biodiesel as close to 0.1 g as possible. Write down the sample weight accurate to three significant figures. 5. Carefully unscrew the white vessel cap and place all of the biodiesel sample in the vessel. The liquid inside the titrator is toxic, so avoid splashing when adding a sample. Avoid any form of direct contact with the titrator liquid. Screw the cap securely back onto the titrator vessel. 6. On the panel screen, press Start Sample. Input the exact weight of the sample. 7. The machine will automatically titrate the sample, and a results screen will display the water content in ppm. Once the results have been documented, press OK and the titrator will begin another pretitration. 8. If no further samples are to be tested, turn the titrator off by pressing the home button.

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Figure 1: Panel Start Screen

Figure 2: Pretitration Screen

Figure 3: Standby Screen

Figure 4: Results Screen

Figure 1: Karl Fischer Titrator Reaction Vessel

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Methanol
Basic Properties: Colorless liquid with faint alcohol odor. Extremely flammable, easily ignited in vapor and liquid form. Burns with a clear flame which is difficult to see (resembles shimmering air on pavement). Completely water soluble. Easily absorbs into the body, highly toxic to humans.

Forms of Exposure: Inhalation Most common form of exposure: vapors are easy to breathe in and can cause lung irritation. In case of inhalation, move to well ventilated area away from fumes. If irritation or difficulty breathing persists, seek medical attention. Keep methanol containers sealed at all times.

Eye Contact If eye contact occurs, rinse eyes (opening upper and lower lids) for at least fifteen minutes. Seek medical attention. Skin Contact Methanol tends to absorb into skin If methanol makes contact with skin, wash immediately with soap and copious amounts of water for 15 minutes. Immediately remove any contaminated clothing or shoes

Ingestion Methanol is highly toxic. Ingesting as little as cup can prove fatal. Causes weakness, dizziness, nausea, vomiting, blindness (symptoms may be delayed 18 to 24 hrs). Do not induce vomiting, seek medical attention immediately.

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Protective Personal Equipment: Closed toed shoes must be worn at all times, both in the reactor and lab area. When working with methanol in the reactor area, wear protective chemical goggles, a face shield, long pants, and thick protective gloves. An apron is also recommended. When working in the lab with small quantities of methanol, wear protective glasses, and gloves (nitrile, butyl, or latex). As methanol vapors are water soluble and may permeate contact lenses, consider removing lenses while working with large amounts of methanol.

Safety Protocol: All work done in reactor area must be done with two people present. When methanol is in use, curb fire risks by not using phones, operating power tools, or smoking near methanol. In case of methanol spill: -Eliminate potential sources of ignition -If small amount of methanol is spilled, contain the spill by pouring absorbant over it. Sweep absorbant into sealed container using a broom and pan -Do not walk through spilled methanol and remain upwind of it -Report any spills to Charlie and Mike -Report any methanol leaks immediately Static electricity can cause sparking. Special caution must be taken in dry, cold months when static electricity most readily generates. Sources of ignition are not allowed within 25 feet of area where methanol is stored. Do not park cars in front of reactor area. If a car is parked in front of the reactor area, please notify the vehicle owner of sparking risks and ask them to move their car outside of the 25 safety area.

For extended information on methanol properties and safety, please refer to the Methanol Institutes Methanol Safe Handling Manual.

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Methanol Transport Setup

Air Line

Meter

Reactor Tank Pump

Grounding Wire

Methanol Tank

A methanol tank will be installed inside of the reactor area. To reduce risks of sparking, this tank will be grounded to a bar located beside the reactor area. Using an air line attached to a compressor, a pump will transport methanol to the reactor tank. Grecycle will assist with replenishing the supply of methanol.

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Sodium Methylate
Basic Properties: Highly corrosive and flammable base Colorless solution Composed of 75% methanol, 25% sodium methanolate Used to catalyze biodiesel transesterification Forms of Exposure: For all forms of contact, seek medical attention after performing first aid measures.

Inhalation Toxic by inhalation. Repeated inhalation may cause blindness. If inhaled, keep calm, move to fresh air, and seek medical attention.

Eye Contact Causes eye burns. If eye contact occurs, rinse eyes (opening upper and lower lids) for at least fifteen minutes. Seek immediate medical attention. Skin Contact Causes skin burns. Immediately remove contaminated clothing and wash affected areas with water. Seek immediate medical attention. Ingestion Rinse mouth and drink plenty of water. Do not induce vomiting. Seek immediate medical attention.

Personal Protective Equipment: Protective equipment required is identical to that required for methanol handling. Please consult the PPE section of methanol for details. Safety Protocol: In case of fire, do not try to extinguish sodium methylate with water, or carbon dioxide. This could potentially trigger an exothermic reaction. To extinguish fire, use dry extinguishing media, sand, or alcohol resistant foam. Avoid sources of ignition, including sparks and heat.

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Sulfuric Acid
Basic Properties: Oily, colorless to slightly yellow solution Reacts violently with water Highly corrosive to metals Added to yellow grease prior to transesterification Modifies existing free fatty acids for conversion into biodiesel, instead of soap Forms of Exposure: For all forms of contact, seek medical attention after performing first aid measures. Inhalation Inhalation of fumes or acid mist can cause irritation or corrosive burns to the mouth, nose, throat, and lungs. If person who inhaled sulfuric acid is not breathing, administer artificial respiration. Eye Contact Depending on degree of exposure, eye contact could result in irritation, corneal burns, or blindness. If eye contact occurs, rinse eyes (opening upper and lower lids) for at least 15 minutes. Skin Contact Causes severe skin burns. Wash affected areas with water for at least 15 minutes. Remove all contaminated clothing while washing. Ingestion Causes burns of the mouth, throat, and stomach. If ingested, do not induce vomiting. Drink two glasses of water, and seek medical attention immediately. Personal Protective Equipment: Closed toed shoes, and chemical safety goggles must be worn at all times. When working in the reactor area, wear thick, black rubber gloves and an apron. Removal of contact lenses while working with sulfuric acid is recommended. Safety Protocol: When working with sulfuric acid in the laboratory, always remember to add acid to water, and not vice versa. In case of fire, do not attempt to extinguish with water. Adding water to concentrated sulfuric acid causes a strong exothermic reaction, which could result in boiling and splattering. In the event of a sulfuric acid spill: -Apply a neutralizer/absorbent to the area (such as sodium bicarbonate, soda ash, etc). The spill kit in the laboratory should contain an appropriate material. -When the absorbent has finished neutralizing the sulfuric acid, sweep it up and place it in a chemical safety bin.

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References McCormick, R.L.; Alvarez, J.R.; Graboski, M.S. NOx Solutions for Biodiesel. National Renewable Energy Laboratory. February 2003. http://www.nrel.gov/docs/fy03osti/31465.pdf A Comprehensive Analysis of Biodiesel Impacts on Exhaust Emissions. U.S. Environmental Protection Agency. October 2002. http://www.epa.gov/otaq/models/analysis/biodsl/p02001.pdf Biodiesel Handling and Use Guidelines. U.S. Department of Energy Efficiency and Renewable Energy. March 2006. http://www.biofuels.coop/archive/HandlingAndUse2006.pdf Environmental Benefits. National Biodiesel Board. http://biodiesel.org/docs/ffshealth_environment/environmental-benefits.pdf?sfvrsn=4 Environmental & Safety Information. National Biodiesel Board. http://www.biodiesel.org/docs/ffs-health_environment/environment-and-safetybenefits.pdf?sfvrsn=4 The Chemistry of Biodiesel: Differences Between Biodiesel, Diesel, and Vegetable Oil. Goshen College. http://www.goshen.edu/chemistry/biodiesel/chemistry-of/ Understanding the Chemistry of Biodiesel. Piedmont Biofuels. Pittsboro, NC. http://www.biofuels.coop/education/resources What is Biodiesel? University of Strathclyde Energy Systems Research Unit. http://www.esru.strath.ac.uk/EandE/Web_sites/02-03/biofuels/what_biodiesel.htm

I would like to specially thank Walter Diaz, Mike Kazz, and Dr. Stephen Poe for their extensive help forming and editing this guide.

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