Lecture 1

Introduction

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 What is Petroleum?

C A complex mixture consisting mainly of hydrocarbon gases and

liquids.

C Formed from the residue of organic waste

- plankton floating in seas and land plants
- accumulated at bottom of oceans, lakes and coastal areas
- collected beneath layers of sediments
- pressure and underground heat converted organic matter
into hydrocarbon and natural gas

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 Chemistry of Petroleum

Element %wt

Carbon 84 - 87
Hydrogen 11 - 14
Sulphur 0 - 3
Oxygen 0 - 2
Nitrogen 0 - 0.6
Metals 0 - 1000ppm

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 Chemistry of Petroleum
C A major portion of compounds in petroleum are alkanes (or paraffins)

C The alkanes can be straight chain (or normal) compounds e.g.:

H H H H H H

H C H H C C H H C C C H

H H H H H H

Methane (CH4) Ethane (C2H6) Propane (C3H8)

H H H H H H H H H

H C C C C H H C C C C C H

H H H H H H H H H

Normal Butane (nC4H10) Normal Pentane (nC5H12)

... and so on to much larger molecules

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 Chemistry of Petroleum - continued
C Alkanes can also form branched (or iso) molecules.

H H H H H H H

H C C C H H C C C C H

H H H H H

H C H H C H

H H

Isobutane (iC4H10) Isopentane (iC5H12)

C Normal and iso compounds with the same formula have different boiling
points, densities and undergo different chemical reactions (important later -
see alkylation).

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 Chemistry of Petroleum - continued
C Cyclic alkanes (cycloalkanes or naphthenes) are found:
H H
H H H H
C
H H H H
C C C C C
H H
C C C C C C
H H H H H H
H H H H H H

Cyclopropane (C3H6) Cyclobutane (C 4H8) Cyclopentane (C 5H10)

H H H H

H C H H C H
C C C C
H H H H

H H H H Methyl Group
C C C C
H
H C H H C C
H
H H H H H
Cyclohexane (C 6H12) Methyl Cyclohexane (C 7H14)

... and so on to much larger molecules

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 Chemistry of Petroleum - continued

C Some hydrocarbons have double chemical bonds between carbon atoms -

alkenes (or olefins).

H H H H H

C C H C C C H H C C C C H

H H H H H H H H H

Ethylene C2H4 Propylene C3H6 Butylene C4H8

C Alkenes are highly chemically reactive.

C Alkenes are not found in crude oil but are formed by some refinery
processes.

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 Chemistry of Petroleum - continued
C Aromatic compounds (benzene and compounds that resemble benzene in
chemical behaviour) are found: H

H H C H

H H C H H C H
C C C C
H C H
C C C C
C C
C H C H
H H
C C
C H C H H C H
H H

H H H

Benzene (C6H6) Toluene (C7H8) para-Xylene (C8H10)

H H

H C HH H C H
H
H C C H C H
C C C C
H

C C C C H
C C
H H H C

H H H H

ortho-Xylene (C8H10) meta-Xylene (C8H10)

C Aromatic compounds derive their name from the pronounced odour
of many of the compounds
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 Chemistry of Petroleum - continued
C Polynuclear aromatics containing two or more aromatic rings are found :

Naphthalene Benzocyclohexane Anthracene

Phenanthrene Benzophenanthrene Pyrene

C Aromatics with only two rings are often called small ring aromatics
C The term polynuclear aromatics is usually reserved for aromatics with three
or more rings
C Molecular weights between 150 and 500 (hydrogen 9 to 12 wt %)
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 Chemistry of Petroleum - continued
C Not all compounds in petroleum are pure hydrocarbons
C Compounds involving sulphur, nitrogen and metals also occur
C Most common non-hydrocarbon compounds are the organic sulphur compounds e.g.

H H H H H
C C
H C S H H C C S H
C C
H H H H H
S
Methyl Mercaptan Ethyl Mercaptan Thiophene
H H H

H C H H C C H H
C C C C C C N

C C C C C C C
H N H H C N H H S H

H
Pyridine Quinoline Thiazole

.... and so on
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 Chemistry of Petroleum - continued
C Oxygen compunds may occur up to 2% by weight
e.g.
O
HO

OH O
Acetic acid Benzoic acid
(Methane carboxylic acid) (Benzene carboxylic acid)

C Oxygen compounds can promote corrosion

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 Chemistry of Petroleum - continued
C Resins contain one polynuclear aromatic surrounded by side chains of
paraffins and small ring aromatics with molecular weights between 500 and
1,500 (hydrogen 7 to 10 wt%) :

C Each polynuclear aromatic may have three to six rings containing sulphur,
nitrogen, oxygen, vanadium and nickel.
C The sidechains do not conatain appreciable heteroatoms
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 Chemistry of Petroleum - continued
C Asphaltenes are sheets of polynuclear aromatics with twenty or more rings
connected by paraffiric and naphthenic chains.

C Molecular weights 500 to 4,500 and up to 10,000 (hydrogen 5 to 8 wt%)

C Heteroatoms distributed throughout

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 Petroleum Refining

• The conversion of crude petroleum into useful products

• Carried out at over 750 sites worldwide, processing about 9

million tonnes of oil per day

• Each refinery uses different processes, depending on the

feed, products and history of the refinery

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 How did this
industry emerge?

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 Origins of the Petroleum Industry

C Bitumen seeping to the surface used as building material, lining water courses,
sealing joints in boats and lighting in middle East as far back as 3,000 BC.

C Petroleum encountered when digging salt wells in China 200 BC and used for
lighting and fuel.

C Petroleum industry developed in Eastern Europe in early 19th century - shafts

dug by hand.

C Primitive oil industry in Pennsylvania in mid 19th century gathering surface oil.

C Processes developed for the production of illuminant fluid termed “kerosene” in

1854.

C First scientific investigation into the properties of petroleum carried out by the
American chemist Benjamin Sillman Jr in 1855.

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 Origins of the Petroleum Industry - continued

C Around 1830 the Chinese method of salt boring or drilling imported into
Europe and United States.

C Salt-boring technique adapted to drill the first oil well by Edwin Drake in
Titusville, Pennsylvannia in 1859.

C Oil transported in barrels with volume standardised to 42 gallons in 1866

(after the size of barrels used for herrings in England) - still used as standard.

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 Origins of the Petroleum Industry - continued
In the earliest days of the oil industry they distilled oil
to get kerosene for lamps:

Crude Oil Pot Still 19th Century

Lamps
The lighter and heavier fractions were dumped in ditches
or the river or burned in pits!
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 Origins of the Petroleum Industry - continued
C Early batch distillation adapted from the design used for whale oil and coal tar
distillation :
Dephlegmator
Column Water
Condenser

Gas

Still
Separator
Flue

Product
Tar
Out Oil
feed

Fire Box

C Later crude oil vaporised inside pipes in the firebox (because

known as a pipestill)
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 Origins of the Petroleum Industry - continued

Later, when automobiles created a market for

gasoline, the lighter fraction became more valuable

lights waste

gasoline cars
Crude
Oil kerosene lamps

gas oils & ship fuel

fuel oil

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 Origins of the Petroleum Industry - continued
• Over the years 1920 ÷ 1960, processes were developed to
convert low value fractions into high value products

• Processes were also invented to improve the product

properties

• Petrochemicals (chemicals from petroleum) grew rapidly

from mid 20th century

• The refinery therefore evolved from a simple boiling

operation into the complex plant we see today

We’ll describe these processes in the lectures that follow.

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 Refinery Products

Fuel gas
Fuel or chemical feedstock
Liquified gases
Gasolines Motor transportation
Naphtha Chemical feedstock
Jet fuel Aviation fuel
Diesel fuels Motor, railroad and marine transportation
Fuel oils Industrial fuel
Lubricating oils Machine lubrication
White oils Electrical insulation, lubrication and pharmaceuticals
Waxes Coatings, polishes, candles and pharmaceuticals
Bitumen (asphalt) Roadmaking and waterproofing
Petroleum coke Fuel or electrodes for metal manufacture

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 Different types of refinery have evolved . . .

For different ranges of products:

Fuels Coke Lubricants Petrochemicals

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 And for different feeds

light
low sulphur
oil

heavy
high sulphur
oil

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 We will look at how the basic refinery processes are put
together to achieve these different objectives later.

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 Pipe lines

Y Y

Upstream Midstream Downstream

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 Here we shall concentrate on refining in
the downstream business - in particular
refining

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 Course Objectives

• To provide an understanding of the different technologies

used in petroleum refining

• To introduce methods for predicting refinery performance

• To describe the advances in technology and changes in

legislation that will shape the industry over the next few years

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 Correlations

• Correlations are used to describe the perfomance of typical

refinery processes

• To understand these, it is necessary to explain some of the

units and methods used

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 Refining Units

• Because the oil industry began in the United States, most of

the industry still uses archaic British measurements

Energy 1 MMBtu • 1GJ

1000 lb steam • 0.45 tonnes of steam

Gas flows 1 Mscf = 1000 scf = 28.3 Nm3

(at 0oC, 1 atm)

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 • Some units are only used in the oil industry:

Liquid flow 1 bbl (barrel) = 42 US gal

• 0.16 m3
1 bpd = 1 barrel per day
O
• API Gravity = 141.5 - 131.5
s

where s = specific gravity at 60OF (15.6oC)

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 Most of the correlations we develop will be per
bbl of feed:

e.g. process energy use

Steam X lb/bbl
Power Y kWh/bbl
Fuel Z MMBtu/bbl

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 Published data
• Hydrocarbon Processing “Handbook of Refinery Processes”
(Gulf)

• Gary and Handwerk “Petroleum Refining: Technology and

Economics” (Marcel Dekker)

• Maples “Petroleum Refinery Process Economics” (Pennwell)

• Meyer “Handbook of Petroleum Refinery Processes”

(McGraw Hill)

• Magee and Dolbear “Petroleum Catalysts in Nontechnical

Language” (PennWell)

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 These correlations

• Are indicative of the typical process performance at the time

the data were collected

• Can be used for a preliminary estimate of a process

performance

• Are no substitute for a detailed estimate provided by a

process licensor

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 Summary
C Petroleum is a rich source of fuels, lubricants and
petrochemical feedstock.

C Industry developed initially from a demand for illuminant

liquids but later transportation fuels.

C Crude oils and regional market demands vary significantly,

which leads to different refinery configurations.

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