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