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Fuels From BiomassCHEN 313Group 04
Connor Armstrong
Katheryn Drake
Keith Sager
Breanna King
Natural Gases
Methane Ethane Propane Butane
http://baftechnologies.com/cng/natural-gas-from-well-to-consumer/
www.oilempire.us
geology.com
Natural gas tanker holding gas after it was taken from a deposit underwater
Natural Gas World Production Map in2006Flare of natural gas at a production
19th century-Natural gas was either released into the atmosphere or collected where demand was high
Bunson burner was invented in 1885
During the early 20th century natural gases were burned off as flares or harvested in areas of high demand
Now natural gas has a wide variety of uses, and flares are becoming less and less prevalent.
History
www.naturalgas.org
www.naturalgas.org
A Reconstruction of 'Colonel' Drake's First Natural Gas Well in Titusville, Pa
Bunsen Burner using Butane
Methane-
Ethane-
Propane-
Butane-
Chemistry of Natural Gas Components
BP: -162 °C
BP: -89 °C
BP: -42 °C
BP: 0 °C
1-4 carbon chains
19th century-Natural gases were used as light sources
Early 20th century-Natural gases were used for cooking and heating
Presently-Natural gases are used for◦ vehicles◦ electricity generation◦ heating and cooling
Uses
www.petrostrategies.org
lenpenzo.com
www.fossil.energy.gov
Natural gas Propane light
Natural Gas Methane Burner
Dry natural gas consists of almost all methane and natural gas liquids consist of ethane, propane, and butane
Impurities and other hydrocarbons must be removed
Usually accomplished through distillation or separation methods in plants
Synthesiswww.pentagonpost.com
Naturalgas.org
Naturalgas.org
Natural gas processing plants
Rig Natural Gas Flare
Uses depend on:◦ energy efficiency◦ cost◦ compression
Perform in appliances for heating, cooking, or drying.
Order of energy efficiency: Methane<ethane<propane<butane
Differences Between Natural Gases
griffisgas.com
Propane tank
www.bizjournals.com
Ethane production plant
o storageo boiling pointo risk factors
www.sciencedirect.com- Journal of Natural Gas Science and Engineering, Vol. 10, by Yangjun Zhang
Pressure VS Temperature Graph for Various Natural Gases
Notice the heavier natural gasses have a higher rate of pressure increase with temperature. This
determines what conditions they are used in.
Gasolinerandysidescartoons.wordpress.com
Gasoline is a natural by product in the distillation of kerosene.
19th century-First automotive combustion engines, Otto engines, were developed
The need for less volatile fuels that were economical to distill increased as combustion engines were being invented and the answer was gasoline
History
www.allposters.com
Spindletop field in the Southern
part of Beaumont, TX
http://en.wikisource.org/wiki/Page:Popular_Science_Monthly_Volume_18.djvu/500
Otto Engine
Hydrocarbon chains containing between five and ten carbons◦ Pentanes, hexanes, heptanes, octanes, nonanes, and decanes
Liquid at room temperatures
Easy to store, unlike natural gases
Chemistry
PentaneBP: 36.1 °C
DecaneBP: 175 °C
Higher the octane number, the more compression the fuel can withstand before detonating.
Octane rating is a measure of how likely a gasoline or liquid petroleum fuel is to self ignite.
Defined by comparison of iso-octane and heptane, which has the same anti-knocking capacity as the fuel under test
The percentage, by volume, of 2,2,4-trimethylpentane in that mixture is the octane number of the fuel.
What is octane rating?
www.pedrosgarage.com
http://forum.equis.com/forums/thread/36685.aspx
World Gasoline Consumption by region as of 2005. North America used nearly half of the gas consumed in the world.
Jet Fuels
www.scientificamerican.com
www.ehow.com
Fighter Jet
Shell gas tanker transporting Jet Fuel
All turbine and jet based aircraft use jet fuel
Hydrocarbon chains from 8 to 16 carbons
Kerosene based fuel
Lower flash point than other fuels, therefore safer to transport and burn
Chemistry
HexadecaneMP: 18 °CBP: 287 °C
OctaneMP:-57 °CBP:125 °C
Chemistry
Jet A-1
Jet A
Flash point (°C/°F) 42 / 108 51.1 / 124.0
Autoignition temperature
(°C/°F)210 / 410
Freezing point (°C/°F) −47 / −53 −40 / −40
Open air burning temperatures
(°C/°F)260–315 / 500–599
Density at 15 °C /59 °F
(kg/L).804 .820
Specific energy (MJ/kg) 43.15 43.02
Energy density (MJ/L) 34.7 35.3
"Handbook of Products". Air BP.
Separation processes: ◦ Separated based on boiling point◦ Does not change the feedstock◦ Example: distillation.
Upgrading processes: ◦ Improve material quality by removing impurities◦ Examples: sweetening, hydro-treating, and clay treatment
Conversion processes: ◦ Changes feedstock by “cracking” large molecules into small ones◦ Examples: catalytic cracking and hydro-cracking
Synthesis
http://gas2.org/2011/03/30/boeing-gets-busy-slick-new-planes-wild-new-patents/
747 commercial plane
World War II and the oil crises of the 1970’s saw brief interest in using vegetable oils to fuel diesel engines.
1937-Belgian inventor proposed transesterification to convert vegetable oils into fatty acid alkyl esters
Early 1990s-Europe and South Africa began developing biodiesel fuel industry
BioDiesel
The first car run on modern BioDiesel- the Citroen Rosalie
http://www.firstcarnow.com/first-biofuel-car.htm
BioDiesel chain- Blue ester functional group
BioDiesel is essentially diesel with an ester added to one end. ◦ Done by transesterification reaction
Small molecules that don’t gel like vegetable oil at low temperatures.
Only modification need for a diesel engine is replacing rubber tubing due to ester reactivity
Chemisty of BioDiesel
Because BioDiesel is so natural, it is fairly easy and inexpensive to manufacture.◦ Goshen College’s BioDiesel Lab
BioDiesel Manufacturing
Experimental BioDiesel plant schematic
First Tank-WVO (Waste Vegetable Oil) Dryer
Second Tank-Reactor Third Tank-Wash Tank
Methanol removed from reactor
Fourth Tank-Drying Tank
Final Product-BioDiesel
http://www.goshen.edu/chemistry/biodiesel/processor/All pictures courtesy of
Pure BioDiesel (B100) is produced from renewable feedstocks such as vegetable oils ◦ Does not diminish food supplies
Doesn’t require major modification to be used in a diesel engine
Reduced exhaust emissions and toxicity compaired to petroluem diesel.
BioDiesel as a Fuel
B100 produces no soot compared to diesel, undergoing more complete combustion.
http://www1.eere.energy.gov/vehiclesandfuels/facts/m/2006_fcvt_fotw449.html
Comparison of B100 and petroluem diesel (B20) emissions
http://agtheory.blogspot.com/2008/07/diesel-vs-biodiesel.html
1890s - First diesel engines created◦ Inventor envisioned vegetable oil as the fuel source
1900 World’s Fair - First demonstration of vegetable oil based diesel
◦ Diesel Engine used peanut oil
Coconut, peanut, WVO (waste vegetable oil) and pure plant vegetable oil have all been used
Vegetable Oil
http://www.jsme.or.jp/tsd/ICBTT/conference02/MasanoriOGATA.html
Engine displayed at the 1900 World’s Fair
Structure of typical vegetable oil
3 times the size of typical diesel fuel
Higher kinematic viscosity than regular diesel ◦ A heat exchanger is added to the engine to
prevent clogging◦ Larger proportion of esters increases
incomplete combustion if not heated properly before use
Chemisty Behind Vegetable Oil
http://www.vegoilmotoring.com/eng/why-veg-oil/vegoil-vs-biodiesel
This flow diagram shows that SVO (straight vegetable oil) has greater carbon neutrality than conventional
diesel
Use as a fuel in vehicles would drastically reduce CO2 and greenhouse gas emissions
Vegetable Oil as a Fuel‣ With slight modifications, can be used
as a substitute in residential furnaces and boilers‣ Using filtered WVO would have considerable
savings‣ According to Vegawatt®, WVO is 35% more
efficient than traditional oils.
Typical heating usage is 40%. That means using WVO could save you 14% on your electricity bill each month.
http://www.sa.gov.au/subject/Water,+energy+and+environment/Energy/Energy+efficiency/Home+energy+efficiency/How+energy+is+used+in+the+home
http://biodieselnc.org/page/2/
Fuel system set up for an engine that used SVO (Straight Vegetable Oil)
Methanol Ethanol BioButanol
Alcohol Based Fuels
www.motorauthority.com
http://www.resilience.org/stories/2013-04-11/perils-and-promise-of-turning-plants-into-gasoline
Corn Crop that will be turned into Ethanol
E85 Ethanol Gas Tank
Alcohol-based fuels consist entirely of alcohol or up to 15% mixtures for conventional vehicles.
Methanol:
Ethanol:
Chemistry
BP: 78.37 °C
BP: 64.7 °C
Methanol combustion: 2CH3OH + 3O2 → 2CO2 + 4H2O + heat
Ethanol combustion:C2H5OH + 3O2 → 2CO2 + 3H2O + heat
Cleaner burning compared to long hydrocarbons since less CO2 is produced by the smaller hydrocarbons
Chemistry cont.
Alcohol-based fuels (ethanol in particular) is produced from waste products, grain and corn
1. Enzymes convert corn meal to simple sugars2. Ammonia is added to control pH and as a nutrient for the yeast3. Yeast converts sugar into ethanol and carbon dioxide 4. Cooled in fermenters5. Distillation
Synthesis
www1.eere.energy.gov
Pros◦ Renewable◦ Environmentally friendly
Pros and Cons of biofuels Cons
◦ Higher Production costs◦ Increased cost of food
supplies such as corn◦ Controversial
http://en.wikipedia.org/wiki/Combine_harvester
Combine Corn Harvester for Ethanol production
http://www.southwestclimatechange.org/feature-articles/biofuels
Based on U.S. Department of Agriculture's long-term projections, biofuel production is expected to increase dramatically before leveling off at the end of the decade as motor vehicle blending requirements approach maximum limits.
History◦ Made from anaerobic bacteria
fermentation since 1851.
◦ 1912-Chad Weizmann isolates a bacteria species that produces more butanol per biomass.
◦ 1960s-butanol as a fuel source began using primarily Clostridium pasteurianum bacterium.
BioButanol
Flow diagram showing how BioButanol is produced from fermentation.
http://www.biobutanol.com/Biobutanol-feedstocks-include-sugars,-starches-and-even-wastes.html
N-butanol Sec-butanol Isobutanol Tert-butanol
Chemistry Behind BioButanol
‣ n-butanol and isobutanol are most common in BioButanol
‣ Covalent bonding
‣ Volatile and flammable because of weak intermolecular forces
‣ Miscible in water because of size, even though its nonpolar
Higher energy density and lower volatility than ethanol
Doesn’t affect food supply◦ Made from non-edible feedstocks such as algae and crop waste
Less corrosive than ethanol◦ Can be used in vehicles
without modifications
BioButanol as a Fuel
Feedstock Fermentation (years)
Sugarcane Juice, Corn Kernels (Sugar source)
0-2
Sugar beet, Sorgum (complex sugar) 0-2
Miscanthus, Switchgrass (cellulosic technology)
2-4
Wood waste, Crop waste, Poplar tree 2-4
Algae biomass 2-4
Food processing waste, household waste
4-6
This table shows BioButanol production from various feedstocks-years to commercialization
http://www.biobutanol.com/Biobutanol-feedstocks-include-sugars,-starches-and-even-wastes.html
Solid Fuels Flash PowderBlack Powder
Smokeless Gun PowderWood
1887-Germany used as flash lamps for cameras◦ Mixture of magnesium, potassium chlorate and antimony sulfide
Since 20th century chemical formula has been refined to make it simpler and safer to use
Historians date to Sui and Tang dynasties (~600-900 A.D.) in China, as precursor to gunpowder
Currently used to fuel fireworks around the world
Flash Powder
http://photo.tutsplus.com/articles/history/a-brief-history-of-photographic-flash/
Mixture of oxidizer and metallic fuel◦ Potassium Nitrate (oxidizer) - Saltpepter
2 KNO3 + Heat → 2 K2O + N2 + O2
Structure of a Firecracker◦ Layers of paper tubing.◦ Plugged at both ends with a dry clay-like substance◦ Flash powder in the middle.
Fuse ignites the flash powder, creating a large volume of gas in a short period of time.
◦ Pressure blasts the tube open
Chemistry of Flash Powder
Potassium Nitratehttp://scienceforyou.net/pyrotechnic-supplies/oxidizers/potassium-nitrate/
http://www.pyrouniverse.com/show/consumer/1.4Ginfo.htm
Layout of a typical fire cracker
1830s-Pyrotechnicians added a metallic salt to color fireworks ◦ Red Strontium◦ Green Barium◦ Blue Copper
Colors caused by atomic or molecular emission◦ Electrons take on energy and “jump” to a higher energy state◦ Electrons “relax” back down to ground state, passing extra energy in the form of light of a
specific wavelength◦ Colors depend on frequency distribution of transmitted and reemitted light beams
Materials absorb photons with energies greater than their band gap We see the colors that are not absorbed
Colors of Fireworks
http://munsell.com/color-blog/chemistry-fireworks-colors/
o White Magnesiumo Orange Calciumo Yellow Sodium
Graphic illustration of electrons jumping energy levels
Light Spectrum
Only explosive until mid 1800s Discovered in 7th century China
◦ Alchemists searching for elixir of immortality
Spread to Europe by the Mongols in 1241 Constant burn rate regardless of containment
Black Powder
http://www.militaryheritage.com/muskets.htm
Black Powder Muskets
Potassium Nitrate (Saltpetre)◦ Oxidizer
Charcoal◦ fuel
Sulfur◦ Fuel◦ Ignition temperature
Chemical Components
http://en.wikipedia.org/wiki/File:Black_Powder_Close_Up.jpg
Black Powder granules with quarter for size comparison
Simplified formula:10 KNO3 + 3 S + 8 C → 2 K2CO3 + 3 K2SO4 + 6CO2 + 5 N2.
Replacing C with Charcoal C7H4O:
4 KNO3 + C7H4O + 2 S —> 2 K2S + 4 CO2 + 3 CO + 2 H2O + 2 N2
Chemical Reaction
Sulfur –free◦ Removes smoke and soot
• Variable burn rate• Example: Cordite
Smokeless Gun Powder
http://www.cascity.com/forumhall/index.php?topic=35624.25
Cut away view of a colt 45 round
Nitroguanidine Nitroglycerin Nitrocellulose
◦ Guncotton
Cordite Components
Guncotton
Nitroglycerin
Nitroguanidine
http://en.wikipedia.org/wiki/Nitroglycerin
http://en.wikipedia.org/wiki/Nitroguanidine
http://en.wikipedia.org/wiki/Gun_cotton
6 KNO3 + C7H8O → 3 K2CO3 + 4 CO2 + 2 H2O+ 3 N2
Chemical Reaction
http://images.yourdictionary.com/gunpowder
Gunpowder from open bullet
Oldest fuels
Heating, cooking, steam engines, recreation
Categorized as Hard and Soft
Wood
http://www.britannica.com/EBchecked/media/109341/Log-burning-in-a-fire
Water Cellulose (40% - 50%)
◦ Crystal polymer◦ Strong in tension
Hemicellulose (15% - 25%)◦ Irregular five-carbon sugar
Lignin (15% - 30%)◦ Aromatic Rings give
hydrophobic properties◦ Resists compression
Interwoven Structure◦ Covalent links between lignin
and hemicellulose
Chemical StructureCellulose
Hemicellulose
Lignin
http://en.wikipedia.org/wiki/Lignin
http://en.wikipedia.org/wiki/Cellulose
http://en.wikipedia.org/wiki/Hemicellulose
Measured using Janka hardness test◦ Australian Buloke – 5060lbf◦ Balsa – 100lbf
Chemical derivation of lignin◦ Hard wood: sinaply alcohol and coniferyl alcohol◦ Soft wood: coniferyl alcoholof
Burning◦ Hardwood: radiant heat over long period of time◦ Softwood: Burns faster, produces less heat, more flames◦ Uses: Hardwood for cooking, Softwood for fire-starting
Hard vs Soft
Sinaply Alcohol
http://en.wikipedia.org/wiki/Sinapyl_alcohol
Coniferyl Alcohol
http://en.wikipedia.org/wiki/Coniferyl_alcohol
http://en.wikipedia.org/wiki/Janka_hardness_test
6 C10H15O7 + Heat —> C50H10O + 10 CH2O
(wood) + Heat —> (Char) + (volatile gas)
CH2O + O2 —> H2O + CO2 + C + N2
Chemical Reaction
http://www.mayang.com/textures/Wood/images/Other%20Wood/burnt_wood_with_sand_7090596.JPG
Charred Wood after partial burning
Lipinsky,E.P. Fuels from Biomass:Integration with Food and Materials Systems. 1978. Science Magazine Online Journal.
http://chemistry.about.com/od/howthingswork/a/fireworks.htm http://en.wikipedia.org/wiki/Rocket_candy http://en.wikipedia.org/wiki/Gunpowder http://science.howstuffworks.com/environmental/earth/geophysics/fire1.htm http://www.britannica.com/EBchecked/media/109341/Log-burning-in-a-fire http://en.wikipedia.org/wiki/Rocket_candy http://greenliving.nationalgeographic.com/hard-vs-soft-wood-fuel-efficiency-20321.html http://firewoodresource.com/faq/hardwood-vs-softwood/ http://baftechnologies.com/cng/natural-gas-from-well-to-consumer/ www.oilempire.us www.naturalgas.org theuticashale.com www.fossil.energy.gov www.petrostrategies.org www.pentagonpost.com www.bizjournals.com www.sciencedirect.com
Content Sources
Content Sources www.motorauthority.com www.scientificamerican.com http://www.biobutanol.com/Resources.html http://www.biodiesel.com/index.php/biodiesel/history_of_biodiesel_fuel http://www.goshen.edu/chemistry/biodiesel/chemistry-of/ http://www.vegawatt.com/2013bmc/2013bmc.php Http://en.wikipedia.org/wiki/Vegetable_oil_fuel http://www.britannica.com/EBchecked/topic/209575/flash-powder http://photo.tutsplus.com/articles/history/a-brief-history-of-photographic-flash/ http://www.pyrouniverse.com http://chemistry.about.com/od/howthingswork/a/fireworks.htm http://munsell.com/color-blog/chemistry-fireworks-colors/ http://www.fireflyfans.net/mthread.aspx?tid=54164
http://www.cascity.com/forumhall/index.php?topic=35624.25 http://en.wikipedia.org/wiki/Cordite#Uses_in_popular_culture
http://en.wikipedia.org/wiki/Wood_fuel http://en.wikipedia.org/wiki/Wood