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Biodiesel

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VEGETABLE OILS AS FUELS

• “THE USE OF VEGETABLE OILS FOR ENGINE FUELS MAY SEEM

INSIGNIFICANT TODAY. BUT SUCH OILS MAY BECOME IN

COURSE OF TIME AS IMPORTANT AS PETROLEUM AND COAL

TAR PRODUCTS OF THE PRESENT TIME”

- Rudolf Diesel at the Engg Society of St. Louis, 1912

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Transportation Energy Demand

• Total delivered energy consumption for transportation was 27.8 quadrillion Btu in 2004

• This accounted for over 25% of the entire U.S. energy consumption

• Projected to reach 39.7 quadrillion Btu in 2030 1

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The Alternative

• Biodiesel is a cleaner burning replacement fuel made from renewable sources like new and used vegetable oils and animal fats

• Low-level blends (≤20% biodiesel) can be used in almost any existing diesel engine

• High-level blends (>20% can be used in most new diesel engines

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Overview of Biofuel Production TechnologiesFirst Generation of Biofuels

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Overview of Biofuel Production TechnologiesSecond/Third Generation Biofuels

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Biomass to high added value chemicals

Biomass

Extraction of chemicals

Biodiesel production

Glycerol

Sugar fermentation

Thermochemicalconversion

• Ethanol• Lactic acid

Chemicals

• Proteins• Vitamins• Fragrances•

Pharmaceuticals

Bio-SNG

ChemicalsChemicals

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Biofuel/biofuel production technology selection criteria

• Technological criteria (energy content, non renewable• Financial criteria (static, dynamic, risk)

• Environmental criteria (CO2 , CO, NOx, SO2, etc.)

• Socio-economic criteria• Energy consumed, availability, carbon residue, sulfur

content, viscosity, density, efficiency, scale up, …)

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Comparison of technologies Economic versus environmental aspects

Source: IEE Leipzig, 2007

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Why make biodiesel?

Diesel fuel injectors are not designed for viscous fuels like vegetable oil

Glycerin (thick)

Biodiesel

11** B100 (100% biodiesel) with NOx adsorbing catalyst on vehicle

Relative emissions: Diesel and Biodiesel

0 20 40 60 80 100 120

Total Unburned HCs

CO

Particulate Matter

**NOx

Sulfates

PAHs

n-PAHs

Mutagenicity

CO2

Percent

B100 **B20Diesel

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The Chemistry of Biodiesel

• All fats and oils consist of triglycerides– Glycerol/glycerine = alcohol– 3 fatty acid chains (FA)

• Transesterification describes the reaction where glycerol is replaced with a lighter and less viscous alcohol– e.g. Methanol or ethanol

• A catalyst (KOH or NaOH) is needed to break the glycerol-FA bonds

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Biodiesel – General Definitions

Biodiesel is renewable fuel for diesel engines derived from fats and oils such as soybeans and animal fats.

Biodiesel can be used in any concentration with petroleum-based diesel fuel in existing diesel engines with little or no modification.

Biodiesel is not raw vegetable oil!

Biodiesel must be produced by a chemical process that removes glycerin from the oil.

0 50 100

B2

B5

B10

B20

B100

Biodiesel Petroleum diesel

Biodiesel blend, n. -- a blend of biodiesel fuel meeting ASTM D 6751 with petroleum-based diesel fuel designated BXX, where XX is the volume percent of biodiesel.

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Biodiesel Facts

• Lower energy content than Diesel– Biodiesel: 118,296 BTUs per gallon– No. 2 Diesel: 129,500 BTUs per gallon

• Source: National Biodiesel Board

• Energy Lifecycle– 3.2 units of energy are produced for each energy unit

used• Source: NREL

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Biodiesel Facts

• What type of oil is most biodiesel made from?– Soybean oil in the USA– Rapeseed oil in Europe– Jatropha oil in Indonesia ?

• Is biodiesel the same as vegetable oil?– No!

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Will biodiesel damage my engine?– No…if the biodiesel meets the standards of ASTM

6751– One exception:

• Biodiesel can damage certain natural rubber engine components over time

– Older engines may require the replacement of fuel lines and some gaskets

– These components are unlikely to fail immediately but may fail with increased biodiesel use

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Biodiesel Background

• Four main production methods– Direct use and blending– Micro emulsions– Thermal cracking– Transesterification

• Transesterification– Most common

production method– Uses vegetable oils and

animal fats as feed stocks

– The reaction of a fat or oil with an alcohol to form esters (biodiesel) and glycerol

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Base Catalysed Transestrification• Most popular of all method• >90% of all bio diesel by this method• Low temperature ( 150o F) and pressure (20 PSI)• High conversion (>98%)• Minimum side reactions• Direct conversion- No intermediate step• Ordinary material of construction

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Schematic of the Transesterification process

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BIODIESEL – Final Product

Biodiesel 100%

Glycerin

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Biodiesel Process Flow Diagram

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Energy CropR&D

Farming

Oilseed

Meal

Crushing Crop Oil

Biodiesel Production

Biodiesel

MarketGlycerin

From the Farmer to the Fuel Tank

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Vegetable Oil as Feedstocks

• Oil-seed crops are the focus for biodiesel production expansion

• Currently higher market values for competing uses constrain utilization of crops for biodiesel production

• Most oil-seed crops produce both a marketable oil and meal– Seeds must be crushed to extract

oil– The meal often has higher market

value than the oil

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Oilseeds and Oilseed Processing

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Types of Oilseeds

• Major Oilseed Crops– Soybean– Cottonseed– Sunflower

– Canola/Rapeseed– Flaxseed– Safflower

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• Other oil producing crops– Corn– Peanut– Camelina

– Palm– Olive– Coconut

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Oilseed Crops: 2007 Yields

Crop Ave. Yield Ave. Oil ContentSoybeans 41.7 bu/acre ≈ 22%Canola 1,250 lbs/acre ≈ 40%Flaxseed 16.9 bu/acre ≈ 38%Safflower 1,215 lbs/acre ≈ 35%Sunflower1,436 lbs/acre ≈ 42%Mustard 603 lbs/acre ≈ 36%

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Oilseed Processing

• The Oilseed Processing Industry:

– Separates the “whole seed” into 2 or more products

– The difference between the cost of the seed and the value of the products created is the “crushing margin”

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Oilseed Processing Technology

• Two General Methods– Solvent Extraction

• Standard technology for facilities with daily capacities of greater than 300 tons per day

• Commonly used in conjunction with some form of mechanical extraction

– Mechanical Extraction• Typically used for facilities with daily capacities of less

than 150 tons per day

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Solvent Extraction

• The basic process:

– Seed Preparation• Removal of foreign objects• Removal of seed hulls or shells for some seeds

– Pre-Pressing• Seed is crushed through a mechanical press

– Pre-Pressing removes some oil from high oil content seeds

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– Solvent Application• Solvent is applied to the pre-pressed material• The solvent bonds to the oil in the material

– Solvent & oil mixture is removed from the meal– The oil is then separated from the solvent which is

reused in the process

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• Solvent Extraction Benefits:– Solvent Extraction is capable of recovering of 99%

of the oil contained in the seed– Lowest cost per ton for commercial processing

• Challenges:– Large capital investment– Not feasible for small-scale processing– Environmental concerns

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Mechanical Extraction

• The basic process:

– Seed Preparation• Removal of foreign objects• Removal of seed hulls or shells for some seeds

– Extraction• Seed is processed by a mechanical press

– Removing 65-80% of oil contained in the seed

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• Required Equipment– Mechanical Press– Power source for the press– Seed Bins– Meal Bins– Oil Tanks– Pumps, Filters, Plumbing

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• On-Farm Example:

– If you plant 100 acres of canola,

– with an average yield of 1,100 lbs per acre,

– your production is approximately 55 tons

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• The 55 tons of seed will yield approximately:– 4,200 gallons of oil– 36 tons of meal

* Assuming: The seed has 38% oil content and press recovers 75% of the oil content in the seed.

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• On-Farm Example:– If you plant 100 acres of safflower,– with an average yield of 800 lbs per acre,– your production is approximately 40 tons

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• The 40 tons of seed will yield approximately:

– 2,800 gallons of oil– 27 tons of meal

* Assuming: The seed has 35% oil content and press recovers 75% of the oil content in the seed.

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Biodiesel Production Technology

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Biodiesel Process

• Basic Overview

– Inputs: Oil, Alcohol & Catalyst

– Outputs: Biodiesel & Crude Glycerin

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• Sample Recipe

– Oil 100 Parts– Alcohol 10 to 20 Parts– Catalyst 0.5 to 3 Parts

* Manufacturers often provide a “basic” recipe to use as a starting point.

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• Outputs

– Biodiesel 100 Parts

– Crude Glycerin 10-20 Parts

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• Pre-Reaction Equipment

– Oil Storage Tank– Alcohol Storage Tank– Catalyst Storage– Biodiesel “Reactor”– Pumps, Filters, Plumbing

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• Post-Reaction Equipment– Settling tanks and/or Separating Equipment– Washing Equipment– Drying Equipment– Biodiesel Storage Tank– Glycerin Storage Tank– Pumps, Filters, Plumbing

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• Biodiesel Equipment– Micro Scale Processors

• 100 gallons or less per batch• Numerous Manufacturers• Some sold as “kits”• Others sold as “ready to use”• Accessories included in the package varies

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• Micro Scale Biodiesel Processor

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• Biodiesel Equipment– Small-Scale Processors

• 75 to 300 gallons per batch• Fewer Manufacturers• Usually not sold as “kits”• Typically higher quality materials• Accessories included in the package varies

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• Small-Scale Biodiesel Processor

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• Processing 4,200 Gallons

– 40 gallon processor: 105 batches– 60 gallon processor: 70 batches– 100 gallon processor: 42 batches

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Final Products

• Biodiesel– On-Farm Use

• Blended Fuels

• Fuel Quality Important

• Vehicle Modifications– May need to replace natural rubber fuel lines and gaskets

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• Crude Glycerin– No Ready Market for Crude Glycerin– Quantity produced is 10% to 20% of biodiesel

production– Contains Methanol & Catalyst– Possible Uses:

• Compost• Fuel Oil• Refine to Pharmaceutical Grade Glycerin

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Government Involvement:Regulations, Incentives &

Policies

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• What agency is responsible for biofuel policy?– A) Energy– B) Agriculture– C) Commerce– D) Environmental Protection– E) Transportation

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Biofuels Policy

• Current govt. policy for biofuels:– Most of the biofuels policy is:

• Farm Energy• Energy Policy

– Other agency are involved:• Dept. of Transportation• Environmental Protection Agency• Internal Revenue Service• Department of Labor

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Government Policy

– Reduce nations dependency on foreign oil

– Requires certain policies

– Several grant programs

– Investment opportunities in certain refueling

infrastructure

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Other Regulations

• Fire Safety Issues– Methanol storage is subject to regulations of local

fire marshals. Contact your local fire marshal• Building Code Issues

– Production and storage of biodiesel, methanol and glycerin may violate building codes.

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Economics of Biodiesel Production

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Oilseed Processing

• Oilseed Processing Assumptions– Seed Cost $0.151 per pound– Oil Content 40%– Recovery Rate 72%

• Consistent with an average mechanical crush

– Labor Cost $10/hour– Meal Revenue $120 per ton

• Net of transportation costs

60-70% of the cost to process biodiesel is from feed stock costs

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• Assume 10 ton per day press– Installed Cost of $11,485– Financed for 10 years at 6%

Labor Cost $3,289 47%Other Costs $3,704 53%Total Cost $6,993Processing Cost per Ton $51

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Seed 274,110 lbs. @ $0.151 per lbs. Crushing 137 tons @ $51 per tonMeal 92.7 tons @ $120 per tonOil 10,000 gallons

Seed Cost $41,391Crushing Cost $ 6,993Total Cost $48,384Meal Revenue $11,124 Net Cost $37,260Net Cost Per Gallon of Vegetable Oil $3.73

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Technological Challenges

• Expensive feed stocks and inefficient production methods

• Strict standards for product quality

• NOx emissions • Transportation and

storage concerns

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Storage• Biodiesel should be stored 5-10 degrees F above cloud point.

• Above ground fuel systems should be protected with insulation, agitation, heating systems, or other measure.

Test Method

CloudPoint ASTM

D2500

Pour Point ASTM D97

Cold Filter Plug Point IP 309

B100 Fuel oF oC oF oC oF oC

Soy Methyl Ester 38 3 25 -4 28 -2

Canola Methyl Ester 26 -3 25 -4 24 -4

Lard Methyl Ester 56 13 55 13 52 11

Edible Tallow Methyl Ester 66 19 60 16 58 14

Inedible Tallow Methyl Ester 61 16 59 15 50 10

Yellow Grease 1 Methyl Ester -- -- 48 9 52 11

Yellow Grease 2 Methyl Ester 46 8 43 6 34 1

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ASTM D 6751 – Biodiesel Fuel Specification

Fuel quality is of the utmost concern and importance to the biodiesel industry.

ASTM D 6751 is the specification for biodiesel fuels irrespective of the feedstock source and/or processing method.

Standard ensures safe operation in a compression ignition engine.

ASTM International Specification D6751: Standard Specification for Biodiesel Fuel

In 2002, ASTM International issued a standard specification for biodiesel fuel called D6751. This specification states that the only form of biodiesel that can be legally resold for commercial operations must meet ASTM specifications. TABLE 1: Detailed Requirements for Biodiesel (B100) Property Test Method Limits Units

Flash point (closed cup) D 93 130.0 min °C Water and sediment D 2709 0.050 max % volume Kinematic viscosity, 40°C D 445 1.9–6.0 mm2/s Sulfated ash D 874 0.020 max % mass Sulfur D 5453 0.05 max % mass Copper strip corrosion D 130 No. 3 max N/A Cetane number D 613 47 min N/A *Cloud point D 2500 Report to customer* °C Carbon residue D 4530 0.050 max % mass Acid number D 664 0.80 max mg KOH/g Free glycerin D 6584 0.020 % mass Total glycerin D 6584 0.240 % mass Phosphorus content D 4951 0.001 max % mass Distillation temperature, atmospheric equiv. temp

D 1160 360 max °C

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Transportation

• Should not be contaminated

• Trucks or railcars should be washed from previous load to prevent mixing with leftover residuals or water.

• In cold weather can be shipped in several ways– Hot for immediate delivery (80-130 F)– Hot (120-130 F) in railcars for delivery within 7-8 days– Frozen in railcars equipped with steam coils– Blended with winter diesel, kerosene or other low cloud point fuel

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Emissions Reductions with Biodiesel Blends

Emission Type B100 B20 B2Total Unburned Hydrocarbons -67% -20% -

2.2%Carbon Monoxide -48% -12% -

1.3%Particulate Matter -47% -12% -

1.3%Oxides of Nitrogen (NOX) +10% + 2%***

+0.2%

“When considering the combined benefit of all these reductions, the small increase in nitrogen oxides (NOx) should not overshadow the net environmental gain with biodiesel use in North Carolina. Biodiesel is a viable part of the overall effort to improve our air quality.”B. Keith Overcash, PE, NC DE&NR, DAQ

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The Future of Biodiesel• Should be considered for use as an alternative and not a primary fuel

• Short and long term environmental benefits will be worthwhile

• Storage Issues with Stability and Transportation issues with high cost of delivered fuel compared to fossil fuels

• Fuel-supply reliability

• Lack of understanding of environmental impact - NOx emissions

• Complexity of biomass-power infrastructure compared to known well established coal and natural gas markets