Peak Oil and Biodiesel Fuel

Challenges and Opportunities

Kenneth A. Walz, Ph.D.

Madison Area Technical College
Chemistry and Engineering Instructor
Consortium for Education in
Renewable Energy Technology

July 8, 2008
ATEEC SEET Workshop
Golden, CO
Three Major Challenges
Concerning Our Use of
Transportation Fuel
 1) Peak Oil
(Era of cheap oil is over)

2) Regulated Emissions (SOx,

NOx, VOCs, CO, PM)

3) Unregulated CO2 Emissions

(greenhouse gas  global warming)
 We Are
Challenge #1: Here
The progress of oil
exploration is analogous to
that of geographic
exploration
 Continents Discovered First
(Australia, N. and S. America)
Shorelines Mapped in increasing Detail
Continental Interior Mapped
Large Islands Discovered
Small Islands Discovered
 Discovery of a natural
resources follows a bell-curve
pattern similar to geographic
exploration

Demand grows, “Low hanging fruit” has

exploration increases, been found, Size of each
technology improves discovery diminishes
(Continents Mapped) (large islands)

Initial discovery of Advanced

large deposits technology required
(Continents) Peak to find remaining
small reserves.
(uncharted islands)

Start End
 Production (extraction) of a
resource also typically follows a
bell shaped curve.

Time shift between

discovery and
production.
Discovery
V1 Production
V2 (extraction)

V1 = V2
You cannot extract more than has been discovered. This
places an finite limit on future extraction of the resource.
Titusville, PA Gulf of Mexico, Deepwater
Sour Lake, TX Offshore rig, AK
Drake Well, 1859-1875 Chevron Jack 2 Well, 2006
Oil found at 69 feet
1902-1912 1990s Oil found at 28,000 feet
 My father rode a camel;
I drive a car;
my son flies a jet;
his son will ride a camel.

--Saudi saying
 Gas

Fractional Gasoline
30°C–180°C
Distillation Naphtha
110°C–195°C
of Kerosene

Petroleum 170°C–290°C

Heating oil
260°C–350°C

Lubricating oil
300°C–370°C
Heated
crude oil
at 370°C
Residue
 H2 H2 H2 H2 H2 H2 H2
C C C C C C C CH3
H3C C C C C C C C
H2 H2 H2 H2 H2 H2 H2

CETANE (C16 H34 )

“Motor power can still be produced
from the heat of the sun, which is
always available from agricultural
purposes, even when our fossil
sources of solid and liquid fuels
have been exhausted.”

1875 -
Munich Polytechnic School
1878 -
Mechanic, Sulzer Machine Works
1880 -
Engineer, Linde Refrigeration
1892 -
Patent #608,845 for an
"internal combustion engine“
1898 – Diesel Engine featured at the
Paris Exposition
“The use of plant oil as fuel may seem insignificant
today. But such products can in time become just as
important as today’s kerosene and coal-tar-products”
- Rudolph Diesel
Diesel Engineering

Pressures of 2,000 to 30,000 psi Laser drilled spray holes < 0.1 mm in diameter
 What happens at the injector?

CONCEPTUAL MODEL OF IGNITION AND SOOT FORMATION PROCESSES IN A

DIESEL SPRAY FLAME

(Ref.: Kosaka, H., Aizawa, T. and Kamimoto, T., “Two-dimensional imaging of ignition and
soot formation processes in a diesel flame,” International Journal of Engine Research 6(1),
21-42, 2005)
 Carbon Residue on Injector Pintels

http://images.google.com/imgres?imgurl=http://www.floridafleetservices.com/images/mostwanted
Fats and oils are triglycerides
3 Fatty Acid Chains (R1, R2, R3)
3- ester bonds

Fatt
Glycerol
Backbone

If all Cs are single bonded  Chain is saturated with hydrogen

Aci
(contains the maximum amount of hydrogen)
H2 H2 H2 H2 H2 H2 H2 H2
ex: R = C C C C C C C C stearic
C C C C C C C CH3 acid
H2 H2 H2 H2 H2 H2 H2

If some Cs are double bonded  Chain is unsaturated with hydrogen

(contains less than the maximum amount of hydrogen)

ex: R =HC2 H2
C
H2
C
H2
C
H
C
H2
C
H
C
H2
C linoleic
C C C C C C C CH3 acid
H2 H2 H2 H2 H H H2
 Triglycerides are very
bulky molecules

« C h em 3 D E m bed »

R1=R2=R3 = stearic acid (18:0) Tristearin

This is a problem for modern diesel engines and fuel
injection systems!
 Making biodiesel – green refineries of the future?

Fat/oil + 3 methanol  biodiesel + glycerol

10.00 kg 1.10 kg 10.05 kg 1.05 kg
 History of biolipid
transesterification.

German scientists seeking a ready method to obtain

glycerin (in order to produce explosives for WWII)
began research on the trans-esterfication reaction.
One of the first uses of the resulting trans-esterified
vegetable oil (biodiesel) was powering heavy duty
vehicles in Africa before and during the war.
 Transesterfication products are
similar to conventional petrodiesel

Cetane
(C16 H34 )
« Chem3D Embed »
An unbranched alkane (paraffin)

PETERODIESEL COMPONENT
CETANE # = 100

Methyl Stearate
(C19 H38 O2)
« Chem3D Embed »
A fatty acid methyl ester (FAME)

BIODIESEL COMPONENT
CETANE # = 101
Knothe et al. Fuel 82:971-975 (2003)
 Chemical Processing
Issues
 Extent of reaction? (MG/DG vs MEs)
 Separation of Glycerol and Biodiesel
 Excess methanol must be removed from finished
fuel (& possibly from glycerol)
 KOH Catalyst is not consumed in reaction, and must
also be removed from fuel
 Other impurities? (sterol glucosides? others?)

- Gravimetric Separation R

- Water Washing
HO

HO

- Filtration O

- Adsorbent Treatment O
OH
- Flash Evaporation HO

- Fuel Quality ASTM Standard Tests

Biodiesel is not THE solution to
the Peak Oil Challenge… but it
may help!

Biodiesel also helps address

environmental challenges of a
chemical nature (i.e. regulated
and unregulated emissions)
Challenge #2: Regulated Emissions (exhaust)
Particulate Matter (PM) Air Pollution
BIodiesel greatly reduces
particulate emissions
 Biodiesel also reduces CO
and HC emissions

Note: Many recent studies have

questioned earlier NOx findings.
There is currently much disagreement
between laboratory dynamometer
tests, and on-road measurements.

Biodiesel does represent a

renewable
US EPA
resource that
uses agriculturally
2002

produced commodities as
the basic feedstock
A Promising
Potential
Application
Challenge #3: CO2 Emissions
and Global Warming
Greenhouse
Effect in a
Greenhouse

The air inside the

greenhouse is
warmer than the air
outside due to the
absorption
properties of the
glass.
Greenhouse Effect of the Atmosphere

• CO2 in the atmosphere allows light to penetrate, but

traps a significant amount of infrared that is radiated
outward.

‘Greenhouse gases’
in the atmosphere
act like glass in a
greenhouse
Who are the CO2 Polluters?
Note change in China’s emissions in
the past decade (almost doubled!)

China has ~20% of the world’s

population,
and emits about 1/4 of the
world’s CO2

The U.S. has ~6% of the world’s population,

and emits about 1/4 of the world’s CO2

Organization for Economic Co-operation and Development (OECD) Europe = EU15 plus the
Czech Republic, Hungary, Iceland, Norway, Poland, Slovak Republic, Switzerland, and
Biodiesel is a nearly “CO2 Neutral” fuel
How does this apply to me?

How can I get involved?

How can I learn more?

What can I do?

The Project: Design,
Construct, and Test a small
scale bio-diesel esterfication
reactor suitable for use in a
technical college setting for
training students.
Student generated CAD
drawings
MATC student Paul
Nielsen instructs UW
EPD-160 students,
Stacey Hoebel, Ashley
Paulick, and Mitch
Springer on welding the
biodiesel reactor
superstructure
 NEW COURSE!
Introduction to Biodiesel Fuel

Three day short-course (1 credit)

April, May, and August, 2007
June, 2008 – possibly Fall 2008?
www.matcmadison.edu
MATC Instructor Paul Morschauser Explains
the Operation of the Catalyst Tank
Measuring Flash Point
 Biodiesel pHLIP Tests

1 2 3 4 1 2 3 4
1) Bench Reaction – single KOH dose, unwashed
2) Bench Reaction – double KOH dose, unwashed
3) 50 gal Reaction – double KOH dose, washed
4) pHLIP Commerical biodiesel ASTM reference standard
(Supplied with kit)
WI Governor Jim Doyle visits with MATC Diesel Tech Instructors
 NEW COURSE!
Biofuels Train the Trainer

Four day intensive course (36 hrs, 2 cr)

May 2008 at Madison, WI campus
Possibly summer 2009?
www.matcmadison.edu
Renewable Energy for the
Developing World
Fall 2008, 3 credits
 Energy in Developing Countries

 Energy use directly correlates with health and

quality of life

Many rural areas lack access to public utilities (i.e.

off-grid)

Electricity primarily provided by diesel generators

Heat primarily provided by firewood or LP gas

Improved quality of life 

Increased Energy consumption 

 +
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 MATC International Education
US Department of Education Title VI
International Education Grant (2006-2008)
Geoff Bradshaw, Principal Investigator
- Create new courses with international focus
- Expand depth and breadth of global learning
in existing MATC courses

MATC Global Studies Certificate

15 Credits of International Focus Courses
+
Foreign Language
+
Study Abroad
 Renewable Energy for the
Developing World
 Students complete an 8 week hybrid/online course prior to
travel to Costa Rica.
 Ten days spent in country working on renewable energy
installations.
 Final debriefing session and student projects completed
upon return to the United States.
 Credits earned may be applied towards the MATC Global
Studies Certificate as well as the CERET Renewable
Energy Certificate
 Curriculum is currently under development. Course is
planned for initial offering in fall of 2008.
Mastatal (population ~ 120)
 Solar
Electric
Installation
and
Maintenanc
e
Construction
and Cooking
with Solar
Ovens
Anaerobic Digesters for Cooking
Gas
For More Information on
the Consortium for
Education in Renewable
Energy Technology
(CERET) or Renewable
Energy for the Developing
World:
www.ceret.us
Ken Walz, Co-Principal Investigator
kwalz@matcmadison.edu
608-246-6521
 The ATEEC Fellows
Institute
ATEEC selects outstanding math, science, and
environmental technology educators to participate
in the ATEEC Fellows Institute hosted each
summer by the University of Northern Iowa (UNI) in
Cedar Falls, Iowa. These secondary education and
two-year college teachers study cutting-edge
environmental technology issues and engage in
special projects designed to enhance the quality of
environmental technology education.

For more info contact Professor Maureen Clayton at maureen.clayton@uni.edu

ATEEC Fellows AK Virtual Field Trips
 “Just as certain as
death and taxes is
the knowledge that
we shall one day be
forced to learn to live
without oil.”
-BBC News
kwalz@matcmadison.edu
Acknowledgements:
MATC Diesel Equipment Program, Paul Morschauser, Paul Harrision, Paul
Nielsen, Jon Christian, Stacey Hoebel, Ramsey Kropp, Matt Johnston,
Stephanie Britton, Katie Cadwell