Biodiesel

FEED STOCK REACTION PRODUDCTION

What is Biodiesel?

Alternative fuel for diesel engines

Made from vegetable oil or animal fat
Meets health effect testing (CAA)
Lower emissions, High flash point (>300F),
Safer
Biodegradable, Essentially non-toxic.
Chemically, biodiesel molecules
are monoFatty Acid
Alcohol
alkyl
from
FA esters produced usually
Glyceri
triglyceride esters
n
FA
FA
FA

Vegetable Oil

Biodiesel

Biodiesel can be used in

existing Diesel Engines

Pure Biodiesel (B100) or blended with

petroleum diesel (B20, BXX).

Rudolf Diesel: peanut oil.

Little or no engine modifications

Use existing fuel distribution network.

Available now

Environmental Issues

Burning fossil fuels increases atmospheric levels of carbon dioxide

Fossil fuels are a
finite resource
Biodiesels Closed
Carbon Cycle

30% Increase

Graph taken from USF Oceanography webpage

Relative Greenhouse Gas

Emissions
B100
B100 = 100% Biodiesel
B20 = 20% BD + 80% PD

Electric
Diesel Hybrid
B20
Ethanol 85%
Diesel
LPG
CNG
Gasoline
0

20

40

60

80

100

120

140

160

Data from A Fresh Look at CNG: A Comparison of Alternative

Fuels, Alternative Fuel Vehicle Program, 8/13/2001

Relative emissions: Diesel and Biodiesel

B100 **
B20
Diesel

CO2
Mutagenicity
n-PAHs
PAHs
Sulfates
**NOx

Particulate Matter
CO
Total Unburned HCs
0

20

40

60

80

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

100

120

Biodiesel Samples

Chemistry of Triglycerides

Biodiesel is made from the combination of a triglyceride

with a monohydroxy alcohol (i.e. methanol, ethanol).

What is a triglyceride? Made from a combination of

glycerol and three fatty acids:

Transesterification
While actually a multi-step process, the
overall reaction looks like this:
CH2OOR1
catalyst
CH2OH
|

|
CHOOR2 + 3CH3OH 3CH3OORx + CHOH
|
|
CH2OOR3
CH2OH
Triglyceride
3 Methanols
Biodiesel
Glycerin
R1, R2, and R3 are fatty acid alkyl groups (could be different, or
the same), and depend on the type of oil. The fatty acids
involved determine the final properties of the biodiesel (cetane
number, cold flow properties, etc.)

Individual step of
Transesterification
First step, triglyceride turned into diglyceride,
methoxide (minus Na) joins freed FA to make
biodiesel, Na joins OH from water (from
H O
Hformation) to make NaOH. Other H
methoxide
| |
|
joins
the diglyceride.
HCOR1
|
HCOOR2
|
HCOR3
|
|
H O

|
+ HCONa
|
H

+H2O

HCO
H O
|
| |
CHOOR2 + HCOR1 + NaOH
|
|
HCOR3
H

Triglyceride + Methoxide + H2O

H O
Diglyceride + Biodiesel + NaOH

Pictorial by Graydon Blair of the Utah Biodiesel Cooperative

http://www.utahbiodiesel.org/biodiesel_making.html

After Glycerin removal, biodiesel now just

needs to be cleaned/purified before use:

Biodiesel Production Process

Source: Brent Schulte, University of Arkansas. Biomass Magazine April 2008.

Biodiesel Production
Process

Oil Extraction

Degumming Process

Determine the Amount of Methanol and Catalyst

Transesterification Process

Neutralization

Methanol Recovery

Crude Glycerin and Biodiesel Separation

Crude Biodiesel Purification

Degumming Process

Figure: Degumming Process

Source: www.ndsu.edu. Small Scale Biodiesel Production

Figure: Clear Wash

Methanol Vs. Ethanol

Ethanol
Lower

is more expensive than methanol.

ethyl ester conversion.

Ethanol

is difficult to recycle.

Viscosity

of the ethyl ester is slightly higher

than that of methyl ester.

Cloud

and pour points are slightly lower than

that of methyl ester.

Source: Singh, 2008. Ph.D. Dissertation, MSU

Reaction Mechanism of Biodiesel

Production Process

Formation of Soap

Formation of soap inhibits the separation process and also

deactivate the catalyst.

Source: Gerpen et al., 2004. Biodiesel Production Technology

Hydrolysis of Triglycerides

At high temperature, water can hydrolyze triglycerides and form

free fatty acids (FFAs).

Source: Gerpen et al., 2004. Biodiesel Production Technology

Acid-catalyzed
Transesterification

Acid catalyzed transesterification is very slow compared to

base-catalyzed transesterification.

Suitable for oil that has higher FFAs.

This process uses strong acid to catalyze esterification of

the FFAs and transesterification of triglycerides.

The process does not produce soap with high FFAs because
no metal is present.

Esterification of FFAs is generally faster but produces water.

Source: Gerpen et al., 2004. Biodiesel Production Technology

Enzyme-Catalyzed
Transesterification

Use enzymes to produce esters from triglycerides.

Relatively longer period of reaction.

Expensive to produce because of the cost of enzymes.

No commercial plant using enzymes to produce biodiesel.

Catalyst separation issue can be solved easily.

Supercritical Transesterification

Liquid is defined as supercritical when its temperature and

pressure are above critical points.

Supercritical temperature and pressure for methanol are 240 oC

and 1140 psia, respectively.

No Catalyst is required but can be used.

Effect of Water Content and

FFA

Source: Ayhan Demirbas, 2008. Biodiesel: a realistic fuel alternative for diesel engines

High FFAs Feedstocks

Put excess catalyst to form soap and soaps are stripped

using centrifuges (caustic stripping).

Acid-catalysis followed by base-catalysis process.

Acid catalyzed transesterification.

Procedure for High FFA

Feedstocks

Measure FFA level.

Add 2.25 g methanol and 0.05 g sulfuric acid for each gram
of free fatty acid in the oil or fat.

Agitate for one hour at 60-65C.

Let the mixture settle. Methanol-water mixture will rise to

the top. Decant the methanol, water, and sulfuric acid layer.

Take bottom fraction and measure new FFA level.

Source: Gerpen et al., 2004. Biodiesel Production Technology

Fatty Acids and their Methyl

Esters (biodiesel molecules)

________________________Molecular___________________________Cetane__ Combustion_Heat
Name(s)_________Acronym__Weight___MeltC/F___BoilC/F_____Number__(kg-cal/mole)
Caprylic_acid______8:0___144.22___16.5/61.7___239.3/462.7_______-____________Capric_acid_______10:0___172.27___31.5/88.7___270.0/518.0_____47.6________1453.07
Lauric_acid_______12:0___200.32___44.0/111.2__131.0/267.8_______-_________1763.25
Myristic_acid_____14:0___228.38___58.0/136.4__250.5/482.9_______-_________2073.91
Palmitic_acid_____16:0___256.43___63.0/145.4__350.0/662.0_______-_________2384.76
Stearic_acid______18:0___284.48___71.0/159.8__360.0/680.0_______-_________2696.12
Oleic_acid________18:1___282.47___16.0/60.8___286.0/546.8_______-_________2657.40
Linoleic_acid_____18:2___280.45___-5.0/23.0___230.0/446.0_______-____________Linolenic_acid____18:3___278.44__-11.0/12.2___232.0/449.6_______-____________Erucic_acid_______22:1___338.58___33.0/91.4___265.0/509.0_______-____________Methyl_caprylate___8:0___158.24_______-_______193.0/379.4_____33.6________1313.00
Methyl_caprate____10:0___186.30_______-_______224.0/435.2_____47.7________1625.00
Methyl_laurate____12:0___214.35____5.0/41.0___266.0/510.8_____61.4________1940.00
Methyl_myristate__14:0___242.41___18.5/65.3___295.0/563.0_____66.2________2254.00
Methyl_palmitate__16:0___270.46___30.5/86.9___418.0/784.4_____74.5________2550.00
Methyl_stearate___18:0___298.51___39.1/102.4__443.0/829.4_____86.9________2859.00
Methyl_oleate_____18:1___296.49__-20.0/-4.0___218.5/425.3_____47.2________2828.00
Methyl_linoleate__18:2___294.48__-35.0/-31.0__215.0/419.0_____28.5________2794.00
Methyl_linolenate_18:3___292.46__-57.0/-70.6__109.0/228.2_____20.6________2750.00
Methyl_erucate____22:1___352.60_______-_______222.0/431.6_____76.0________3454.00

Biodiesel Challenges

Cold Weather Operation (Chemistry)

Producing enough feedstock oil to replace a large portion of

petroleum (biology, chemistry, physics, economics)

Engine and emissions optimization (chemistry, physics)

Biodiesel reactions

Biodiesel productionis the process of producing

thebiofuel,biodiesel, through thechemical reactions
trmansesterificationandesterification.

Biodiesel is composed of mono alkyl esters of long

chain fatty acids derived from renewable lipid sources,
such as vegetable oil or animal fats.

Esters are organic compounds composed of an alcohol and an

organic acid.

Alcohols are organic compounds that contain a functional group

OH (hydroxide).

Carboxylic acids are organic compounds that contain a functional

group COOH (carboxyl).

Long chain fatty acids are carboxylic acids that are composed of
single chains of 12 to 24 carbons with a carboxyl group.

The

process used to make biodiesel

is called transesterification because
it is a process of transforming one
type of ester into another.

Base-catalysed
transesterification mechanism
Any

strong base capable of

deprotonating the alcohol will do (e.g.
NaOH, KOH,sodium methoxide, etc.), but
the sodium and potassium hydroxides are
often chosen for their cost.

The

presence of water causes

undesirable basehydrolysis, so the reaction
must be kept dry

Reactions Contributing to Methyl

Ester Production
Transesterification

of Fats (Triglycerides) to
form Fatty Acid Methyl Esters and Glycerol

1 Triglyceride + 3 Methanol 3 Methyl

Ester + 1 Glycerol
The fatty acid R groups remain unchanged
This reaction is facilitated with a strong
base catalyst

Reaction

of Catalyst (NaOH) with

Methanol
CH3OH

+ NaOH CH3O-Na + H2O

CH3O-Na exists as the anion
CH3Oand the cation Na+

Feed stock

 Lipases

from bacteria and fungi are the most

commonly used for transesterification, and

optimal

parameters for the use of a specific

lipase depend on the origin as well as the
formulation of the lipase. In general, the
best enzymes are able to reach
conversions above 90%, while reaction
temperatures vary between 30 and 508C

Phenolphthalein has a broad pH range where it

changes color and as such is a great indicator for
titrating biodiesel.
It is colorless until 8.3, then it turns pink
(magenta), and red at its maximum of pH of10.4.
Phenol red, available at pool and spa supply
stores, also works.
It's range is not quite as good as phenolphthalein
but it does the job in a pinch. It is colorless until
6.8, then it turns yellow, and red at its maximum
pH of 8.2)

 High

quality oil (that means low FFA

concentration) phenol red is usually fine
but for higher FFA levels it is not as
accurate.

Supercritical process

An alternative, catalyst-free method for transesterification uses

supercriticalmethanol

at high temperatures and

pressures in a continuous process. In the supercritical state, the
oil and methanol are in a single phase, and reaction occurs
spontaneously and rapidly.

The process can tolerate water in the feedstock, free fatty acids
are converted to methyl esters instead of soap, so a wide
variety of feedstocks can be used. Also the catalyst removal step
is eliminated.

High temperatures and pressures are required, but energy

costs of production are similar or less than catalytic production
routes.

Lipase-catalyzed method

Large amounts of research have focused recently on the use of

enzymes as a catalyst for the transesterification. Researchers
have found that very good yields could be obtained from crude and
used oils usinglipases.

The use of lipases makes the reaction less sensitive to high free
fatty-acid content, which is a problem with the standard biodiesel
process.

One problem with the lipase reaction is that methanol cannot be

used because it inactivates the lipase catalyst after one batch.

However, if methyl acetate is used instead of methanol, the

lipase is not in-activated and can be used for several batches,
making the lipase system much more cost effective.

Comparison of Biodiesel and Hydrogen as Fuels of the Future

Biodiesel

Hydrogen

Technological Readiness

Can be used in existing diesel

engines, which have already been in
use for 100 years

Electrolyzing water (most likely using

fossil fuel energy) or reforming fossil
fuels. Most likely non-renewable
methods with large net CO2
emissions

Fuel Distribution System

Can be distributed with existing filling

stations with no changes.

No system currently exists, would

take decades to develop. Would cost
$176 billion to put one hydrogen
pump at each of the filling stations in
the US.

Fossil Energy Balance [higher is

better]

3.2 units (soy)

4.3 units (rapeseed)

0.66 units (steam reforming of natural

gas)

Large scale fuel development cost

analysis

For an estimated $1691 billion,

enough algae farms could be built to
completely replace petroleum
transportation fuels with biodiesel

To produce enough clean hydrogen

for our transportation needs would
cost $2.5 trillion (wind power) or $25
trillion (solar)

Safety

Flash point over 300 F (considered

not flammable)

Highly flammable, high pressure

storage tanks pose a large risk due to
store mechanical energy, as well as
flammability/explosiveness

Time scale for wide scale use

5-15 years

30-70 years optimistic assumption

Cost of engines

Comparable to existing vehicles

Currently 50-100 times as expensive

as existing engines.

Tank capacity required for 1,000 mile

range in conventional sedan

20 gallons

268 gallons

Transesterification

Transesterification is a chemical reaction where triglyceride

is reacted with alcohol in the presence of catalyst to
produce alkyl esters. Biodiesel is produced by the
transesterification process.

Every 100 gallons of oil produces about 100 gallons of

biodiesel and 10 gallons of glycerol.

What is Biodiesel?

Biodiesel is a petroleum diesel replacement fuel used in CI

engines.

It can be produced from any plant or animal based lipids.

Plant Based Oils:

Animal Fats:

Soybean oil; cotton seeds oil; sunflower oil.

Beef tallow; pork lard; poultry fat.

Recycled Cooking Grease:

Yellow grease.

Note: Raw or refined oil is not biodiesel.

Estimated Biodiesel Production

in US

Source: www.biodiesel.org

Benefits of Biodiesel

High energy return and displace petroleum based fuels.

Biodiesel reduces life-cycle greenhouse gas emissions.

Biodiesel reduces tailpipe emissions except NOx.

Biodiesel improves air quality and has positive impact in human

health.

Biodiesel improves engine operation and easy to blend.

Source: NREL , 2008. Biodiesel Handling and Use Guide

Emissions Impact of Biodiesel

Source: NREL , 2008. Biodiesel Handling and Use Guide

Other Biodiesel Attributes

Lower Energy Density: 8% less energy per gallon compare to

diesel.

Low Temperature Operability: biodiesel freezes at 20 to 30 oF

higher than that of petroleum diesel.

Storage Stability: additives should be used if stored more than a

few months. Acidity should be measured monthly.

Biodiesel is susceptible to microbial degradation. Minimize water

in contact and test for microbial contamination.

Biodiesel Production Process

Source: NREL , 2008. Biodiesel Handling and Use Guide

Commercial Processing Unit for

Home Made Biodiesel

Selected Properties of Biodiesel

and Diesel
1.9 6.0

Source: NREL , 2008. Biodiesel Handling and Use Guide

Source: NREL , 2008. Biodiesel Handling and Use Guide

ASTM Standards for Biodiesel

Important Properties to Look

Flash Point/Methanol Content

Water Content

Sulfated Ash Content

Free Glycerin

Total Glycerin

Na and K Content

Sulfur Content (if H2SO4 is used as catalyst)

B100

B100 refers 100% biodiesel and 0% diesel fuel.

Biodiesel is a very good solvent.

B100 freezes at much higher temperature than conventional

diesel.

Biodiesel is not compatible with certain hoses and gaskets.

Biodiesel is not compatible with certain metals and plastics.

Source: NREL , 2008. Biodiesel Handling and Use Guide

Source: NREL , 2008. Biodiesel Handling and Use Guide

Variation in Biodiesel
Properties
Feedstocks and Processes

Source: NREL , 2008. Biodiesel Handling and Use Guide

Fuel Properties as a Function of

Feedstocks

Heating Value of Fuel

Source: NREL , 2008. Biodiesel Handling and Use Guide

Cetane Number

Source: NREL , 2008. Biodiesel Handling and Use Guide

Oxidation Stability

Fuel aging and oxidation can lead to high acid number, high
viscosity and formation of sediments.

The higher the level of unsaturation, the more likely that

the biodiesel will oxidize.

Heat and sunlight will accelerate oxidation process.

Metals such as copper, brass, bronze, lead, tin, and zinc will
accelerate the degradation process.

Keeping oxygen from the biodiesel reduces or eliminates

fuel oxidation.

Source: NREL , 2008. Biodiesel Handling and Use Guide, pp.21

Long-Term Storage Stability

Source: NREL , 2008. Biodiesel Handling and Use Guide, pp.21

Example 1

Determine the amount of vegetable oil, catalyst and methanol

required to produce 35 x106 lb/yr (5 million gallons per year) of
biodiesel.

Molecular Weight of FAMEs = 292.2

Molecular Weight of Methanol = 32.1

Molecular weight of Glycerol = 92.1

Molecular weight of soybean oil = 885

35 x 106 lb of FAMEs x (1 lb mol/292.2 lb)

= 120 x 103 lb mol of FAMEs

Amount of VO = 40 x 103 lb mol = 35.06 x 106 lb
Assuming methanol/oil molar ratio = 6:1
Amount of Methanol = 6 x 40 x 103 lb mol
= 240 x 103 lb mol = 7.68 x 106 lb
Amount of Glycerol = 40 x 103 lb mol = 3.68 x 106 lb
Weight of Catalyst = 0.01 x 35.06 x 106 lb
= 350.6 x 103 lb

Chemical Properties of Biodiesel

Source: Singh, 2008. Ph.D. Dissertation, MSU

Transesterification Process

Base-catalyzed Transesterification

Acid-catalyzed Transesterification

Enzyme-catalyzed Transesterification

Supercritical Transesterification

Base-catalyzed
This is the
most widely used technique
Transesterification
biodiesel.

to produce

Possibility of formation soap if there is a high free fatty

acids (FFAs) content in triglycerides.
Excessive water can hydrolyze to form FFAs.

Recycling of catalyst is challenging and not cost effective.

Glycerol is in the crude form and has very little value.