Biodiesel Production: Lifecycle of Biodiesel Production

Barry Latham, M.A.Ed.Biodiesel Production & Curriculum

Chemistry & Physics InstructorChicago Heights, Illinois

Vegetable Oil Sources(Small Scale)In the U.S., most biodiesel is made from

soybean oil or recycled cooking oils◦Typically collected as waste oil from

restaurants◦Restaurants pay to have it removed, but you

remove it for free◦Times are changing, though, and waste oil is

getting expensive (regionally dependent)

Animals fats, other vegetable oils, and other recycled oils can also be used to produce biodiesel

Blends of all kinds of fats and oils may be used to produce biodiesel

Vegetable Oil Sources(Acreage Yields)

Crop US Gal/acre

oil palm 635

coconut 287

jatropha 202

olive 129

rapeseed 127

peanut 113

cocoa (cacao) 110

sunflower 102

safflower 83

sesame 74

linseed (flax) 51

hazelnut 51

soybean 48

hemp 39

corn (maize) 18

Soybean Oil Extraction Plant

What Type of Vehicles Can Use Biodiesel Blends?Blends such as B2 and B5 can be used

safely in any compression-ignition engine◦Light-duty and heavy-duty diesel cars◦Trucks, tractors, boats◦Electrical generators

Any diesel engine can use any percentage of biodiesel◦<1994 engines need updating (1st year of

use) Viton fuel lines, frequent fuel filter changes Biodiesel will corrode natural rubber

◦>1994 engines only need filter changes

Biodiesel UsesBeyond Diesel Vehicles

◦ a corrosion preventative◦ a parts cleaner and degreaser◦ a graffiti remover◦ a paint and resin cleanup◦ a hand cleaner◦ a crop adjuvant◦ a metal working lubricant◦ a screen printing ink remover◦ aircraft fuel◦ home heating oil◦ a lubricity additive for diesel

fuel◦ an adhesive remover◦ a mold release agent◦ an asphalt cleanup agent◦ an oil spill cleanup and

bioremediation agent◦ an auto wax remover

Environmental Benefits

Only alternative fuel in the country to have successfully completed the EPA-required Tier I and Tier II health effects testing under the Clean Air Act (2000)◦ Conclusively demonstrated biodiesel’s significant reduction of

virtually all regulated emissions◦ Showed biodiesel does not pose a threat to human health

Biodiesel contains no sulfur or aromatics Use of biodiesel in a conventional diesel engine results in

substantial reduction of unburned hydrocarbons, carbon monoxide and particulate matter

U.S. DoE showed that the production and use of biodiesel, compared to petroleum diesel, resulted in a 78.5% reduction in carbon dioxide emissions

Biodiesel has a positive energy balance◦ For every unit of energy needed to produce a gallon of biodiesel,

5.28 units of energy are gained

Closed-Carbon Cycle

Energy Security Benefits

Biodiesel can be manufactured using existing industrial production capacity

1996 estimates◦Annual military costs of securing foreign

oil was $57 billion◦Foreign tax credits accounted for another

estimated $4 billion annually◦Environmental costs were estimated at

$45 per barrel

Economic Benefits

2001 USDA study◦Annual increase of 200 million gallons of soy-

based biodiesel demand would boost total crop cash receipts by $5.2 billion cumulatively by 2010 Average net farm income increase of $300 million per

year The price for a bushel of soybeans would increase by an

average of 17 cents annually during the ten-year period

Positive performance attributes◦ Increased cetane, high fuel lubricity, high oxygen

content

Quality BenefitsBiodiesel is registered as a fuel and fuel additive with

the EPAMeets clean diesel standards established by the

California Air Resources Board (CARB)B100 has been designated as an alternative fuel by

the U.S. DoE and the U.S. DOTDecember 2001- the American Society of Testing and

Materials (ASTM) approved a specification (D6751) for biodiesel fuel

The National Biodiesel Board formed the National Biodiesel Accreditation Commission (NBAC) to audit fuel producers and marketers in order to enforce fuel quality standards in the US◦ NBAC issues a ‘Certified Biodiesel Marketer’ seal of

approval for biodiesel marketers that have met all requirements of fuel accreditation audits

Safety BenefitsBiodiesel is nontoxic◦Far less damage than petroleum diesel

if spilled or otherwise released to the environment

Biodiesel is less combustible◦Flashpoint for biodiesel is >150°C◦Petroleum diesel is ~52°C◦Preferred for marine applications

Biodiesel is safe to handle, store, and transport

EPAct BenefitsNovember 1998- Congress approved the use of

biodiesel as an Energy Policy Act (EPAct) compliance strategy◦ 450 gallons of pure biodiesel and burning it in new

or existing diesel vehicles in at least a 20% blend with diesel fuel

The Congressional Budget Office and the U.S. Dept. of Ag have confirmed that the biodiesel option is the least-cost alternative fuel option for meeting the Federal government’s EPAct compliance requirements

Biodiesel offers an immediate and seamless way to transition existing diesel vehicles into a cleaner burning fleet

Green House Gas BenefitsTotal life cycle GHG emissions from the

fossil fuel that is displaced◦82.32 g/MJ

Fossil fuel GHG emissions avoided by using biodiesel instead of fossil fuel◦39.76 g/MJ

Net GHG emissions saved by producing and using biodiesel◦33.32 g/MJ

Net fraction of GHG emissions saved by producing and using biodiesel◦40.5%

Glycerin TreatmentMeOH RemovalMeOH is still present and needs to be

removed before it can be used◦NOT a co-product, just used in excess◦Common misconception that MeOH is

produced

Distillation- separation of liquids based on boiling points◦MeOH has a lower boiling point than glycerin

Turns to vapor first Can be condensed, collected and reused

◦Glycerin turns thicker and darker◦Heating element, not flame, is used

Glycerin Distillation (Large Scale)~$1M to build Methanol

Recovery & Glycerin Purification Process

Crude (80% pure)◦By-product of biodiesel

Tech Grade (>97% pure)◦ Industrial applications only

Refined (>99.7% pure)◦USP & FCC Grade◦Cosmetics,

pharmaceuticals, food

Glycerin Price Trends

Glycerin Supply Trend

Glycerin Co-Product (Small Scale)Soap (1L batch) Remove the residual (toxic) methanol

first

KOH-based biodiesel makes liquid soap glycerin◦ NaOH-based production makes bar

soap

At 50°C, preheat any of the following ratios before mixing for 5 minutes◦ Glycerin 33mL 47mL 54mL◦ Water 7mL 5mL 5mL◦ KOH 1g 1g 1g

◦ Can not use KOH and NaOH inter-changeably

Fragrances and dyes can be added◦ D-limonene smells like oranges and is

cheaply made/purchased◦ Most dyes muddy the dark brown

color

Synthesis from GlycerolPropylene Glycol- similar applications as glycerol◦ “Low-pressure hydrogenolysis of glycerol to propylene

glycol.” Applied Catalyst A: General A 2005, 225-231.◦ “Reducing Byproduct Formation during Conversion of

Glycerol to Propylene Glycol.” Ind. Eng. Chem. Res. 2008, 47, 6878–6884.

Hydrogen- fuel applications◦ “A Comparative Thermodynamic and Experimental

Analysis on Hydrogen Production by Steam Reforming of Glycerin.” Energy & Fuels 2007, 21, 2306-2310.

Acrolein- polymers, acetonitrile, polyurethane◦ “Low-Pressure Packed-Bed Gas-Phase Dehydration of

Glycerol to Acrolein.” Ind. Eng. Chem. Res. 2009, 48, 3279–3283.

Glycerin Co-ProductOther UsesHealth supplement

◦ Increases blood volume◦ Enhances temperature regulation◦ Improves exercise performance in the heat◦ Helps "hyperhydrate" the body by increasing blood

volume levels and helping to delay dehydration◦ Tocopherol (vitamin E)

Other uses◦ Glycerine is also a source of lecithin

fat emulsifier and a vital component of all cell membranes in the body

◦ Skin moisturizer, lotion, deodorant, makeup, toothpaste, sweets and cakes, pharmaceuticals and patent medicines, paper manufacturing, printing ink, textiles, plastics, and electronic components

Glycerin Co-ProductOther Uses Paint brush cleaner

◦ Rinse brush as much as possible with water ◦ Work brush in a small container with about 20 mL of

glycerin◦ Rinse brush under water until all milky-ness is

removed◦ Repeat glycerin stage with fresh glycerin as needed◦ Check that brush doesn't smell of paint and store

brush as usual.

Safe sweetener:◦ Glycerin is an alcohol and is used as a preservative◦ It is very sweet, yet it contains no sugar◦ This makes it an ideal sweetener for patients who

cannot take sugar