Fossil-Fuel Based Carbon Dioxide Emissions METO658A: Carbon Cycle and Climate Jay Gregg 2/15/06.

Fossil-Fuel Based Carbon Dioxide Emissions

METO658A: Carbon Cycle and Climate

Jay Gregg2/15/06

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Background Fossil Fuels

http://www.pekerinsaat.com/pipe_line/pipe1.jpghttp://www.gulfstreamgas.com/images/flame.jpghttp://www.4to40.com/images/earth/science/petroleum/oil_extracting_machinery_derrick.jpg http://next.web-cars.com/monterey_img/74-8_s.jpg

http://tammi.tamu.edu/photos/Coal%20%20Stacks.JPGhttp://collections.ic.gc.ca/cnphoto/images/cn_today/45.jpg

http://www.sachsreport.com/electricity%20grid%20is%20one%20giant%20machine.jpg

Natural Gas

Petroleum(Oil)

Coal

Provide 85% of the energy used by humans on Earth

Produce CO2 when combusted

Background Global Carbon Cycle

http://earthobservatory.nasa.gov/Library/CarbonCycle/carbon_cycle4.html

2002 Anthropogenic Emissions= 6.995 GtC (CDIAC)

Background Atmospheric CO2 Reservoir

General increase likely due to anthropogenic sources

Atmospheric Carbon Dioxide

300

310

320

330

340

350

360

370

380

390

1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005

Year

Con

cen

trati

on

(p

pm

)

Antarctica

Mauna Loa

Seasonal pattern is due to Earth’s respiration

20% increase in CO2 in the last 50 years

BackgroundTemperature Record

Today's atmospheric CO2 concentrations are the highest in the last 420,000 years; maybe in the last 20 million years.

The rate of increase in atmospheric CO2 over last 100 years has not been seen in at least 20,000 years.

Global mean temperature has increased by 0.6 to 1o C in the last century

1990s the hottest decade on record, 1998 the hottest year

Sea rise of 10 to 20 cm last century; 40% decline in Arctic Sea ice

IPCC- Climate Change 2001: The Scientific Basis

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Coal

http://encyclopedia.farlex.com

vegetation accumulates, but is prevented from full decay, forming peat beds

peat is sandwiched between layers of sediment and is compressed to from lignite

bituminous coal forms after further compression and heat, removing water

anthracite coal forms after further heat and compression, removing methane

seam

Coal

Oil and Gas

http://encyclopedia.farlex.com

marine plants and animals die and are trapped beneath layers of sediment where they are broken down anaerobic bacteria

increasing heat and pressure transform the hydrocarbons into fatty acids, which are then changed into an asphaltic material, keragen

further increases in temperature and pressure cause oil to form

natural gas collects above the oil, and is also dissolved in the oil

gasoil

Oil

Source: EIA, Oil & Gas Journal, 12/23/02.   Copyright: Pennwell Publications, 2002.

Gas

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

CoalOpen Surface Mining

Mountain Top Removal Mining

Underground Mining

http://www.siahq.org/Images/lehighvalley/lmishkar/coalmine.gif

http://www.ohvec.org/galleries/mountaintop_removal/007/43.jpghttp://66.113.204.26/mining/coal/surf_min1.jpg

http://www.krunk.org/ns-nrv/vsalem/coal-train-at-salem-medium.jpg

Oil

http://www.novoenergytech.com/images/Tex-oil%20well%20005.jpghttp://shiftingbaselines.org/blog/images/offshore-oil-rig.jpg

http://www.maric.com.cn/images/ship/150000t-1.jpghttp://www.eas.purdue.edu/~braile/edumod/eqhazard/eqhazard2_files/image012.jpg

Gas

http://www.berkshiremoody.com/images/natural_gas_well.jpg

http://earthobservatory.nasa.gov/Newsroom/NewImages/images.php3?img_id=10313http://www.shell-usgp.com/images/6_lng-tanker-at-sea-_web.jpg

http://www.marxists.org/history/ussr/art/photography/workers/russia/siberia/taiga/natural-gas.jpg

Gas Flaring

http://www.eia.doe.gov/emeu/cabs/images/subafricagasflare.gif

http://arcticgems.org/ps/downloads/gas_flaring_low.jpg

Prudhoe Bay, AK Flares

“Every year, roughly 108 billion cubic meters of natural gas are flared around the world and global carbon dioxide (CO2) emissions from flaring amount to nearly 10 percent of the emissions that countries have committed to reduce under the Kyoto Protocol for the target period 2008–2012”(World Bank)

Region Flared gas

(bcm)

Share of world total (%)

Africa 37 34

Asia-Oceania 11 10

Europe 3 3

FSU 19 18

Central and South America 10 9

Middle East 16 15

North America 12 11

WORLD 108 100%

Venting of natural gas also leads to climate forcing, as CH4 is a more potent greenhouse gas than CO2. Moreover, 3% of U.S. commercial gas is lost in distribution (EIA; Gregg).

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Saturated Hydrocarbons (Alkanes)

H

H

HH C MethaneCH4

PropaneC3H8

H

H

H

H

H

CH C

H

C H

H

H

H

H

H

H

CC

H

C …AlkanesCnH2n+2

Saturated Hydrocarbons (Constitutional Isomers)

PentaneC5H12

IsopentaneC5H12

CH3

CH3

CH3CH3 C NeopentaneC5H12

H

H

H

H

H

CH C

H

C H

H

H

C

H

H

C

H

H

C

H

H

CH C

H

C H

H

H H

H

H

C

Alkanes

Name

Molecular Melting Boiling State

Formula Point (oC) Point (oC) at 25oC

methane CH4 -182.5 -164 gas

ethane C2H6 -183.3 -88.6 gas

propane C3H8 -189.7 -42.1 gas

butane C4H10 -138.4 -0.5 gas

pentane C5H12 -129.7 36.1 liquid

hexane C6H14 -95 68.9 liquid

heptane C7H16 -90.6 98.4 liquid

octane C8H18 -56.8 124.7 liquid

nonane C9H20 -51 150.8 liquid

decane C10H22 -29.7 174.1 liquid

undecane C11H24 -24.6 195.9 liquid

dodecane C12H26 -9.6 216.3 liquid

eicosane C20H42 36.8 343 solid

triacontane C30H62 65.8 449.7 solid

Unsaturated Hydrocarbons (Alkenes and Alkynes)

EthaneC2H6

H

H

H C

H

H

C H

EthyleneC2H4

H

HC

HC

H

(Lewis Structure)

H C C H

AcetyleneC2H2

H

HC

HC

H+

H

H

Ni

H

H

H C

H

H

C HHeat & Pressure

Natural Gas Refining

Liquefied and sold as LPG (Liquid Petroleum Gas or Propane)

Sold as commercial natural gas Methane CH4 70-90%

Ethane C2H6 5-10%

Propane C3H8 5-10%

Butane C4H10 0-5%

Pentane C5H12 0-5%

Carbon Dioxide CO2 0-8%

Oxygen O2 0-0.2%

Nitrogen N2 0-5%

Hydrogen sulphide H2S 0-5%

Rare gases A, He, Ne, Xe trace

http://chemed.chem.purdue.edu/genchem/topicreview/bp/1organic/coal.html

http://www.naturalgas.org/overview/background.asp

Petroleum Refining

http://www.eia.doe.gov

Petroleum Refining

Fraction

Boiling Range (oC) Number of Carbon Atoms

natural gas < 20 C1 to C4

petroleum ether 20 - 60 C5 to C6

gasoline 40 - 200 C5 to C12, but mostly C6 to C8

kerosene 150 - 260 mostly C12 to C13

fuel oils > 260 C14 and higher

lubricants > 400 C20 and above

asphalt or coke residue polycyclic

http://chemed.chem.purdue.edu/genchem/topicreview/bp/1organic/coal.html

Crude oil is a complex mixture that is between 50 and 95% hydrocarbon by weight

Over 500 different hydrocarbons in gasoline!

Gasoline Refining Principles:Branched alkanes and cycloalkanes burn more evenly than straight-chain alkanes. Short alkanes (C4H10) burn more evenly than long alkanes (C7H16). Alkenes burn more evenly than alkanes. Aromatic hydrocarbons burn more evenly than cycloalkanes.

Coal Types

e.g. C137H97O9NS

e.g. C240H90O4NS

Lignite (Brown Coal)

Bituminous (Soft Coal)

Anthracite (Hard Coal)

86% and 98% carbon by weight

69% and 86% carbon by weight

up to 70% water by weight

Peat

not valuable as a commercial fuel

Coal Gasification and Liquefaction

C(s) + H2O(g) CO(g) + H2(g) Ho = 131.3 kJ/molrxn

Coal Gas (Town Gas)

Synthetic Natural Gas (SNG)

CO(g) + 3H2(g) CH4(g) + H2O(g)

2CO(g) + 2H2(g) CH4(g) + CO2(g) Captured and Sequestered?

Methanol

CO(g) + 2H2(g) CH3OH (l)

http://chemed.chem.purdue.edu/genchem/topicreview/bp/1organic/coal.html

Combustion

CxHy + (x + y/4)O2 → xCO2 + (y/2)H2O + heat

CH4 + 2 O2 → CO2 + 2 H2O + heat

Methane Combustion:

General Combustion:

Incomplete Combustion:

Also forms CO, SO2, NOx, etc.

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Global Energy Production

Anthropogenic Emissions

0

1

2

3

4

5

6

7

81

75

0

17

60

17

70

17

80

17

90

18

00

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00

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Year

Pg

C o

r G

t C

Total

Gas

Liquids

Solids

Cement

Flaring

http://cdiac.esd.ornl.gov/ftp/ndp030/global00.ems

Increase in CO2 corresponds with a similar increase in FF Consumption

Carbon Emissions

UN, ORNL/ CDIAC, 2005

The Top 20

Rank Country2002 Emissions

Tg C% Global

Emissions Cumulative %

2002 Per Capita, Tonnes

C/person

1 United States 1592 22.8 22.8 5.52

2 China (Mainland) 957 13.7 36.5 0.74

3 Russian Federation 390 5.6 42.1 2.69

4 India 333 4.8 46.9 0.32

5 Japan 328 4.7 51.6 2.57

6 Germany 219 3.1 54.7 2.66

7 United Kingdom 145 2.1 56.8 2.50

8 Canada 141 2 58.8 4.49

9 Republic of Korea 122 1.7 60.5 2.55

10 Italy 118 1.7 62.2 2.05

11 Mexico 105 1.5 63.7 1.01

12 France 100 1.4 65.1 1.69

13 Iran 98 1.4 66.5 1.50

14 Australia 97 1.4 67.9 4.94

15 South Africa 94 1.3 69.2 2.07

16 Saudi Arabia 92 1.3 70.5 4.22

17 Brazil 85 1.2 71.7 0.49

18 Ukraine 84 1.2 72.9 1.73

19 Indonesia 84 1.2 74.1 0.39

20 Spain 83 1.2 75.3 2.03

UN, ORNL/ CDIAC, 2005

The Top 20

Rank Country2002 Emissions

Tg C% Global

Emissions Cumulative %

2002 Per Capita, Tonnes

C/person

1 United States 1592 22.8 22.8 5.52

2 China (Mainland) 957 13.7 36.5 0.74

3 Russian Federation 390 5.6 42.1 2.69

4 India 333 4.8 46.9 0.32

5 Japan 328 4.7 51.6 2.57

6 Germany 219 3.1 54.7 2.66

7 United Kingdom 145 2.1 56.8 2.50

8 Canada 141 2 58.8 4.49

9 Republic of Korea 122 1.7 60.5 2.55

10 Italy 118 1.7 62.2 2.05

11 Mexico 105 1.5 63.7 1.01

12 France 100 1.4 65.1 1.69

13 Iran 98 1.4 66.5 1.50

14 Australia 97 1.4 67.9 4.94

15 South Africa 94 1.3 69.2 2.07

16 Saudi Arabia 92 1.3 70.5 4.22

17 Brazil 85 1.2 71.7 0.49

18 Ukraine 84 1.2 72.9 1.73

19 Indonesia 84 1.2 74.1 0.39

20 Spain 83 1.2 75.3 2.03

UN, ORNL/ CDIAC, 2005

The Top 20Rank Country

2002 Emissions Tg

C% Global

Emissions Cumulative %2002 Per Capita, Tonnes C/person

At US Per Capita Emissions Tg C

1 United States 1592 22.8 22.8 5.52  

2 China (Mainland) 957 13.7 36.5 0.74 7139

3 Russian Federation 390 5.6 42.1 2.69  

4 India 333 4.8 46.9 0.32 5744

5 Japan 328 4.7 51.6 2.57  

6 Germany 219 3.1 54.7 2.66  

7 United Kingdom 145 2.1 56.8 2.50  

8 Canada 141 2 58.8 4.49  

9 Republic of Korea 122 1.7 60.5 2.55  

10 Italy 118 1.7 62.2 2.05  

11 Mexico 105 1.5 63.7 1.01  

12 France 100 1.4 65.1 1.69  

13 Iran 98 1.4 66.5 1.50  

14 Australia 97 1.4 67.9 4.94  

15 South Africa 94 1.3 69.2 2.07  

16 Saudi Arabia 92 1.3 70.5 4.22  

17 Brazil 85 1.2 71.7 0.49 958

18 Ukraine 84 1.2 72.9 1.73  

19 Indonesia 84 1.2 74.1 0.39 1189

20 Spain 83 1.2 75.3 2.03  

Global Distribution

NASA Visible Earth, Imhoff and Elvidge, 2000

Global Distribution

Saxon, Parris & Elvidge, 1997

Global Distribution

Carbon Em issions (Tg C )

0

100

G as Liquids Solids

50

Gregg, 2005

U.S. Distribution

0

5

10

15

20

25

30

35

40V

T HI

NY CT ID CA

MA

ME

NH

OR

MD FL

WA RI

VA NJ IL S

CN

CP

AA

ZM

IM

SS

DD

EW

IM

NG

AC

OT

NO

HM

ON

VA

LA

RN

EU

T IA OK

KY IN MT

NM TX

KS

LA

AK

WV

ND

WY

State

Ann

ual M

ean

Per

Cap

ita E

mis

sion

s (T

onne

s C

/Per

son)

GasLiquidsSolids

US Per Capita Emissions

US Per Capita Emissions, by State (1984-2002)

Gregg, (in prep)

U.S. Emissions by Sector

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Carbon Footprint

A personal measure of carbon emissions

E.g. Transportation

Each gallon of gas = 22 lbs CO2 = 2.7 kg C

Every mile flown = 0.9 lbs CO2 = .111 kg C

DC to Kyoto (Nagoya) = 7,057 mi x 2 x .111 kg C

= 1.5 tonnes C per person

How much CO2 is a Tonne of Carbon?1 mol C = 44/12 mol CO2 1 mol CO2 = 24.47 liters1 Tonne C = 3.667 Tonnes of CO2 3.667 Tonnes CO2 = 2,040 m3

http://www.icbe.com/carbondatabase/objectcalculator.asp

This is enough CO2 to fill two Boeing 747’s:

…or enough CO2 to fill the International Space Station:

http://members.nova.org/~sol/station/iss-sta2.jpg

http://superciliousness.com/hello/254/718/640/Australian%20767-300%20AirlinersNetPhotoID380141.jpg

Every year, the U.S. emits enough CO2 to cover its land area by 1-foot thick blanket of

CO2. (ICBE, 2000)

Outline

• Background: Fossil Energy and CO2

• Geological Formation

• Resource Extraction

• Fuel Chemistry, Refining and Combustion

• Current Emissions

• Your Carbon Footprint

• Future

Future Energy Demand

Demand increases exponentially, but how long can supplies keep up?

Peak Oil1950’s King Hubbert (a Shell Geologist) hypothesized that production would “peak” and production would decline.

Hubbert forecasted that US production would peak about 1970.

A few years after 1970, it was realized that Hubbert was correct. and the US began the era of foreign oil dependence.

Hubert predicted that global production would peak around 2000.

This could be delayed a few years by the oil embargo of the 1970s

Discoveries peaked in late 1960s

http://www.energybulletin.net/primer.php

Peak OilNew discoveries peaked in late 1960s

Production (demand) has continued to increase

Reserves are diminishing

http://www.peakoil.ie/downloads/newsletters/newsletter62_200602.pdf

(Graph: Dr. C.J. Campbell/Petroconsultants)

Energy Economics

IPCC Working Group III: Mitigation

Current Price: $65bbl

Controversy

• How much oil is there in the world (2 or 3 trillion bbls)?

• How will technology/economics change what we deem a reserve (e.g. tar sands and shale)?

• Have OPEC countries exaggerated their proven reserves to boost their quotas?

• How will OPEC manage prices after non-OPEC countries peak?

• Caspian Sea, South China Sea, Arctic, Africa- are these undiscovered elephant fields?

Implications for Carbon Cycle

1. Will climate concerns may take a “back seat” to energy security concerns? (Increase CO2)

2. Move to increased dependence on coal, syn gas, and methanol? (Increase CO2; Decrease if sequestered)

3. More attention to biofuel? (Decrease CO2? Increase CO2?)

4. More attention to renewable fuel sources? (Decrease CO2)

5. Will economic recession reduce consumption and emissions? (Decrease CO2)

6. Will an OPEC glut (for market power) make alternatives unfeasible economically? (Increase CO2)