PETROLEUM CHEMISTRY

Dr. Manoj Pandey

Pandit Deendayal Petroleum University
 1. Coal Chemistry:

Structure of coal, Effect of heat on coal,

Carbonization and pyrolysis, Recovery and
purification of by-products obtained from
coke ovens, Distillation of coal tar, Coal
chemicals
2. Crude oil and Natural Gas:

Introduction, origin of Petroleum, Modern

Concept of Formation of Petroleum,
Composition and Terminology of Petroleum,
Classification of Petroleum, Petroleum
Products from Crude Oil.
 3. Characterization and Analytical
Techniques for Crude Oil:

Physical properties, Thermal properties,

Electrical properties, Optical properties,
Chromatographic techniques, Spectroscopic
methods (Principles and Applications of UV
Visible, IR, and NMR Spectroscopy),
Characterization of formation water.
4. Processing and Refining of crude
oil:

Processing and Refining of crude oil: Distillation,

Sweetening and Cracking (basic concepts),
Reforming, Isomerization, Alkylation processes,
Polymerization processes, Solvent process,
Knocking, Octane number and Cetane number,
Additives to improve the quality of Diesel and
Petrol, Catalysis and Applications of Catalysts
(like Zeolite and other catalysts) in separation
processes and also in petroleum industries.
 4. Environmental issues of
refining:

Environmental regulations, Amendments and

Acts like clean air act amendments, clean
water act, safe drinking water act, resource
conservation and recovery act, oil pollution
act.
 Texts and References:

1. The Chemistry and Technology of Petroleum,

James G Speight, 5th Edition, CRC Press, New
York, 2010
2. Crude Oil Chemistry, Vasily Simanzhenkov,
Raphael Idem, Marcel Dekker, Inc.
 Method of Evaluation

• 50% End Semester Examination

• 40% Mid Semester Examination

• 10% Internal Evaluation

 Petroleum Chemistry Assignment

1. Define Gross calorific value and Net calorific value.

2. What is coke? How it differ from coal and Charcoal.
3. The net calorific value of a fuel is lower than its gross calorific
value why?
4. What are the advantages of solid fuels over liquid fuels?
5. What are proximate analyses of coal? How is it done? How
does it vary with the age of coal?
6. What is ultimate analysis of coal? Discuss its significance. How
does it vary with the type of coal?
7. What do you mean by term ‘Carbonization’ of coal?
FUEL
Heat produced by Coal-burning power plant.
burning pulverized coal
in a furnace boils water
to produce steam that
spins a turbine to
produce electricity.
The steam is cooled,
condensed, and
returned to the boiler
for reuse.
Waste heat can be
transferred to the
atmosphere or to a
nearby source
of water.
The largest coal-burning
power plant in the
United States, located in
Indiana, burns three
100-car trainloads of
coal per day
 Coal
Coal was discovered in eastern north America
in the 18th century. We needed to fuel steam
engines, and coal was a readily available fuel.
Fuel was burned to create steam to turn a
turbine. Today 50% of U.S. electricity comes
from coal. We have 300 years’ worth of coal!
CO2 emissions per unit of electrical
energy produced for various energy
resources, expressed as percentages
of emissions released
by burning coal directly. These
emissions can enhance the earth’s
natural greenhouse effect
Coal Chemistry
 What is Coal?
Coal:
– A sedimentary rock that burns
– Mineralized vetegatative material deposited over a
long period of time (although miniscule
geologically)
– altered chemical composition
– Formed by increased T and P
– Partial decay resulting from restricted access to
oxygen
 Coal

Fossil fuel formed millions of years ago by the
anaerobic decay of living plants.

Complex mixture of many compounds.

The chemical formula of coal has been

approximated as C135H96O9NS

This translates to a material with 85% C (which is

the energy producing component)

Most abundant of fossil fuels

World’s largest energy source

Type of rock composed of organic matter having

been trapped and compressed underground

Classified into four varieties

Constraints to future use more environmental

concerns than availability
 Coal Formation
Decaying plants + pressure of rocks  varying
degrees of removal of impurities, nitrogen, water +
Si, Na, Ca, Al, Ni, Cu, Zn, As, Pb, Hg leaving carbon
content.

Some examples of coal

– Peat and lignite – high moisture content; like plant
material, soft
– Bituminous or soft coal – most abundant
– Anthracite – very hard, very high C content
Coal Formed in Millions of Years
How is Coal Formed?
 Coal Varieties

• Lignite (brown coal)

Relative youngest, softest
Least valuable, lowest energy density
• Sub-bituminous
Higher energy density
Over 40 percent of US production
• Bituminous
Highest energy density
Half of US production
• Anthracite
Metamorphic, 86-97% carbon
Less abundant
 Coal Composition

Carbon > 50%

Impurities
– Volatile Matter
– Sulphur
– Chlorine
– Phosphorus
– Nitrogen
Trace amounts
– Dirt
– Other elements
 Coal Use and Availability

• World consumption roughly 5.5 billion short tons annually

• 67% shipped to electricity producers
• 30% shipped to industrial users
• Remaining 3% for commercial and residential heat
• Estimates of world’s recoverable reserves in 2004 were
998 billion short tons
– Enough for over 200 years at current rate of consumption
– Largest reserves by location:
• 27% -United States
• 17% -Russia
• 13% -China
• 9% -Australia
 Coal Use in United States
Coal is the dominant source for US electricity
generation
Of the 1,125 million short tons consumed
in 2005, about:
92% power generation
5% other industrial
2% coke
0.3% residential
Variety and Location of U.S. Coal
Reserves
U.S. Coal Production
 What is Peat?

Peat ≠ coal, but is the initial stage in coal

formation

A dark colored, brown to black, spongy

substance formed from partial decay of marsh
vegetation by moisture and bacteria
 Carbonization

The million years ago, the earth had dense forests in

low-lying wetland areas. Due to natural processes,
like flooding, these forests got buried under the soil.
As more and more soil deposited over them, they
were compressed. The temperature also rose as they
sank deeper and deeper. For the process to continue,
the plant matter was protected from biodegradation
and oxidization, usually by mud or acidic water. This
traps the carbon in immense peat bogs that are
eventually covered and deeply buried by sediments.
Under high pressure and high temperature dead
vegetation got slowly converted to coal. As coal
contains mainly carbon, the conversion of dead
vegetation into coal is called carbonization.
 Coal Mining
Surface Coal Mining

Surface mining occurs at exposed coal seams. It involves drilling above

ground and blasting to remove overburden. After the overburden is removed,
the mined coal is harvested.

Underground Mining

Room and Pillar Mining – rooms are cut into the coal bed leaving a series of
pillars or columns of coal to help support the mine roof and control the flow of
air. The miners advance while cutting out pillars. Once they reach the edge of
the mine, they work backwards in what’s called “retreat mining.”

Long Wall Mining – hydraulic roof supports are used while a cutting head goes
back and forth along the coal face. When the cutting head reaches one end of
the coal face, it dumps the coal onto a conveyor belt.
 Underground Mining

– Used when ore is far below surface

– Features:
• Vertical shaft or inclined passageway
• Drifts and crosscuts created to expose face

– Broken rock hauled from face and up to the

surface
Underground Mining: Drift
Underground Mining: Slope
Underground Mining: Shaft
Longwall Mining
Room & Pillar Mining
Coal is pretty cheap. In 2004, the average price for
a short ton of coal in the U.S. was $19.93 (although
this does represent an increase from the 2003 price
of $17.85).

It is estimated that there 265 billion short tons of

coal available in the United States to be mined.

Energy in coal:
Lignite – 13 million Btu per ton
Subbituminous – 18 million Btu per ton
Bituminous – 24 million Btu per ton
Anthricite – 23 million Btu per ton
There are several negative externalities attributed to the
combustion of coal, including:
- sulfer and acid rain,
- carbon Dioxide, and
- general destruction to the environment due to the actual coal
mining.

A 500 megawatt coal power plant will produce 10,000 tons of

Sulfur dioxide, 10,200 tons of nitrogen dioxide and 3.7 million
Tons of carbon dioxide per year.

OVERBURDEN
When mining, “overburden” is left over. Mining one ton of coal
leaves 25 tons of overburden. Pyrite is contained in
overburden; when pyrite is exposed to water and air, it forms
dangerous substances like sulfuric acid and iron hydroxide.
When this mixes with water, it forms acid lime drainage which is
highly destructive to the environment. So sad .
 C O A L G A S I F I C AT I O N

• Coal gasification can be used to produce syngas, a mixture of

carbon monoxide (CO) and hydrogen (H2) gas. This syngas can then
be converted into transportation fuels like gasoline and diesel
through the Fischer-Tropsch process.

• The hydrogen obtained from gasification can be used for various

purposes such as powering a hydrogen economy, making
ammonia, or upgrading fossil fuels.

• During gasification, the coal is mixed with oxygen and steam

(water vapor) while also being heated and pressurized. During the
reaction, oxygen and water molecules oxidize the coal into carbon
monoxide (CO) while also releasing hydrogen (H2) gas. This process
has been conducted in both underground coal mines and in coal
refineries.
 C O A L G A S I F I C AT I O N

• (Coal) + O2 + H2O → H2 + CO If the refiner wants to

produce gasoline, the syngas is collected at this
state and routed into a Fischer-Tropsc reaction. If
hydrogen is the desired end-product, however, the
syngas is fed into the water gas shift reaction where
more hydrogen is liberated.

• CO + H2O → CO2 + H2 High prices of oil and natural

gas are leading to increased interest in "BTU
Conversion" technologies such as gasification,
methanation and liquefaction.
The UK is developing underground coal gasification (UCG)!

This is a very clean method, as only gas is removed

from the ground, leaving all the overburden and ash
underground.
 Coal Gas
Coal + O2 + steam  CO + H2
Coal  CH4

These and other gases comprise coal gas or syn gas

For energy production. Products?

Late 18th c., for artificial lighting. Note Soho

House was lit up in 1802 with artificial lighting for
celebrate the Peace of Amiens.
 C O A L L I Q U E FA C T I O N

Coal can also be converted into liquid fuels such as gasoline or diesel
by several different processes. In the direct liquefaction processes,
the coal is either hydrogenated or carbonized. Hydrogenation
processes are the Bergius process.

In the process of low-temperature carbonization, coal is coked at

temperatures between 360 °C (680 °F) and 750 °C (1,380 °F). These
temperatures optimize the production of coal tars richer in lighter
hydrocarbons than normal coal tar. The coal tar is then further
processed into fuels. Alternatively, coal can be converted into a gas
first, and then into a liquid, by using the Fischer-Tropsch process. An
overview of coal liquefaction and its future potential is available.
 C O A L L I Q U E FA C T I O N

• Coal liquefaction methods involve carbon dioxide (CO2)

emissions in the conversion process. For most future
synthetic fuel projects, Carbon dioxide sequestration is
proposed to avoid releasing it into the atmosphere.
Sequestration will, however, add to the cost of production.
Currently all US and at least one Chinese synthetic fuel
projects, include sequestration in their process designs.
Here are two of several ways:

Direct liquefaction – involves the introduction of hydrogen gas

and catalysts into finely crushed coal to produce synthetic crude
oil. Need temperatures of 430-450*C and pressures of 50 to 25
MPA. Hydrogen is needed to remove the oxygen sulfur and
nitrogen. The product of direct liquefaction must still be refined
to gasoline or diesel.

Indirect liquefaction – first converted to gas through gasification.

Then methanol synthesis is used to convert the coal gas into
methanol, then the methanol can either be directly converted to
gasoline, or it can be used as fuel in and of itself.
 Fischer–Tropsch process
• The Fischer–Tropsch process (or Fischer–Tropsch
synthesis) is a set of chemical reactions that
convert a mixture of carbon monoxide and
hydrogen into liquid hydrocarbons. The process, a
key component of gas to liquids technology,
produces a petroleum substitute, typically from
coal, natural gas, or biomass for use as synthetic
lubrication oil and as synthetic fuel. The F–T
process used as a source of low-sulfur diesel fuel.
• The Fischer–Tropsch process involves a series of chemical reactions
that lead to a variety of hydrocarbons. Useful reactions give alkanes:

• (2n+1) H2 + n CO → CnH(2n+2) + n H2O where 'n' is a positive integer.

The formation of methane (n = 1) is generally unwanted. Most of the
alkanes produced tend to be straight-chain alkanes, although some
branched alkanes are also formed.

• In addition to alkane formation, competing reactions result in the

formation of alkenes, as well as alcohols and other oxygenated
hydrocarbons. Usually, only relatively small quantities of these non-
alkane products are formed, although catalysts favoring some of
these products have been developed.
 Fischer–Tropsch catalysts

• A variety of catalysts can be used for the

Fischer–Tropsch process, but the most
common are the transition metals cobalt, iron,
and ruthenium. Nickel can also be used, but
tends to favor methane formation
("methanation").
 Coke

Coal + oven temps of 200˚C without oxygen  high

carbon content coke, with water, coal gas,
ammonia, phenol, naphthalene, sulfur and other
volatile impurities driven off. (Today, the impurities
are collected and processed).

Used as fuel and reducing material for smelting.

 Why Coal?

• Coal associated with modern life?

• Energy source
• Industrial food
• Related to economic development
• Key to environment protection
 Coal utilization

• Fuel: power, heat, steam generation

• Coking for steel
• Gasification
• Liquefaction
• Cement and building materials
• Chemicals…?
 What is coal bed methane?

• Standard natural gas: CH4

• Methane forms along with coal
• It is held in the cleats with the coal
• Substantial water pressure needed to keep
methane in the coal: 400 to 1000 ft ?
 Process of Developing CBM

• Relieve pressure to release methane by

removing water
• Domestic wells completed in seams produce
methane due to drawdown caused by nearby
pumping
• 6-7 times more natural gas than in traditional
natural gas fields
 Coal Is a Plentiful But Dirty Fuel
• Used in electricity production
• World’s most abundant fossil fuel
• U.S. reserves should last about 250 years
• Sulfur and particulate pollutants
• Mercury and radioactive pollutants
• Heavy carbon dioxide emissions
• Pollution control and environmental costs
• China major builder of coal plants
 The Growing Problem of Coal Ash
• Highly toxic
• Often stored in ponds
– Ponds can rupture
• Groundwater contamination
• coal ash as hazardous waste
– Opposed by coal companies
http://www.coal-ash-spill.com/media/2008/12/coal-ash-spill-41.jpg

http://greenerloudoun.files.wordpress.com/2008/12/tennessee-spill.jpg
 Clean Coal Campaign
• Coal industry
– Rich and powerful
– Fought against labeling carbon dioxide a
greenhouse gas
• “Clean coal” touted by coal industry
– Mining harms the environment
– Burning creates carbon dioxide and toxic
chemicals
• Plan to capture and store carbon dioxide
1. Not all coal impurities can be removed. Clean coal is essentially an oxymoron! We
can’t remove all the impurities from coal. It still gives more emissions than wind or
solar power.
2. It is expensive. The manufacture and burning of clean coal costs quite a bit of
money, making renewable energy sources more cost-effective.
3. It may not even happen. There are too many faults with the technology right now,
and incorrect implementation will damage our environment because of the possible
leaks and emissions it can cause!

Clean coal is a bad choice due to better alternatives already available, like wind,
solar and hydroelectric.
 Extraction and Transportation

Two different mining techniques- surface or underground

– Surface mining is cheaper
• Coal seam must be no deeper than 200ft
• Accounts for 67% of US production while only 40% of world
production
• Coal typically must go to a preparation plant to first be
processed- increasing its heating value.
• Shipping costs frequently more expensive than mining it
Transportation represents up to 70% of delivered cost
Transportation 60% in US delivered by rail
 Effects on the
environment and Human health

CO2 ~ carbon dioxide pollution, making energy use the

single largest source of greenhouse gases in the U.S.
and the world

SO2
o Sulfur dioxide combined with nitrogen oxide react
with water and oxygen in the atmosphere to form
acidic compounds, which can mix with natural
precipitation and fall to the earth as acid rain.
Sulfur dioxide can also combine with nitrogen oxide and
other particles to form particulate matter.

 trigger heart attacks and strokes

 lead to cardiac arrhythmia (irregular
heartbeat)
 respiratory irritation, and worsen asthma.
 premature death (Both short-term and long
term exposure)

NOx
When nitrogen oxide (chemically) reacts with
volatile organic compounds (VOC’s) and sunlight
ground-level ozone or smog is formed.

• An estimated 140.5 million Americans live in areas with

unhealthy levels of smog according to the The American
Lung Association.

Mercury

One of the most dangerous pollutants
released into the air through the exhaust
system when coal is burned.
 Pollution/Environmental Impact
Concerns from both mining and burning
• Problematic emissions include:
– Sulfur
– Nitrous oxides
– Mercury
– Carbon dioxide
• Coal industry uses variety of techniques to comply with
Clean Air Act regulations
– Mine low-sulfur coal varieties
– Chemically cleaned in processing
– Emissions “scrubbers”
• Coal accounts for roughly 80% of carbon dioxide
emissions from US electricity generation
Future of Coal

Clean coal technology

A new generation of coal-burning power plants with energy
processes that reduce air emissions and other pollutants.
 Clean Air Acts
 Coal power plants technology must adapt to the changing
political climate towards environmental issues.
 What Are the Advantages and
Disadvantages of Fossil Fuels?
Oil, natural gas, and coal are currently abundant
and relatively inexpensive, but using them causes
air and water pollution, degrades large areas of
land, and releases greenhouse gases to the
atmosphere
Dependence on Oil
• Petroleum (crude oil)
– Also called light oil
– Trapped underground or under ocean with natural gas
– Fossil fuels
 Natural Gas Is a Useful and Clean-
burning Fossil Fuel
• Natural gas
• Conventional natural gas
• Unconventional natural gas
• Liquefied petroleum gas (LPG)
• Less carbon dioxide emitted per unit of energy
than with crude oil, tar sand, shale oil
 Natural Gas Is a Useful and Clean-
burning Fossil Fuel

Liquefied natural gas (LNG)

• World supply of conventional natural gas –
62-125 years
• Unconventional natural gas
– Coal-bed methane gas
– Methane hydrate