Hydrocarbon Processing Manual

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SEGAS SERVICES CONSORTIUM
CHAPTER 1
INTRODUCTION TO ORGANIC CHEMISTRY
General Objectives
The student will be able to:
1. define “Organic Chemistry” and list the elements commonly found in organic
compounds
2. explain the reasons for the large number of organic compounds
3. describe the methods of analyzing organic compounds to determine the elements present
4. describe the types of bonds formed by carbon and draw structural formulas
5. define “saturated” and “unsaturated” and classify molecules as saturated or unsaturated
6. define “functional group” and identify those commonly found in organic compounds
7. describe the “intermolecular forces of attraction” that affect the physical properties of
organic compounds
1.1 Organic Chemistry

a) Definition
The terms “inorganic” and “organic” were originally based on the belief that
compounds found in living organisms contained a vital “life force” and were called
“organic”. All other compounds such as minerals and pure elements were
considered “inorganic”. Early in the nineteenth century urea was prepared from
ammonium cyanate which disproved the theory.
The modern definition of organic chemistry is “the study of carbon containing

compounds”. There are exceptions to this definition. Graphite, diamond, carbon
dioxide, sodium carbonate and other compounds do contain carbon but are not
considered organic. They are derived from minerals and have typical properties of
inorganic compounds. However, all compounds that are classified as organic do
contain at least one carbon atom. Some examples are listed below:
Inorganic Compounds Organic Compounds

Sodium Chloride (NaCl) Methane (CH4)
Ammonia (NH3) Ethanol (C2H5OH)
Sulphuric Acid (H2SO4) Acetic Acid (CH3CO2H)
Silver Chloride (AgCl) Chlorobenzene (C6H5Cl)
Potassium Phosphate (K3PO4) Butyl Lithium (C4H9Li)
Hydrogen Sulphide (H2S) Methyl Mercaptan (CH3SH)
b) Common Elements
The most common elements found in organic compounds are Carbon, Hydrogen,
Oxygen, Nitrogen and Sulphur. Other elements include Phosphorus, halogens
(Fluorine, Chlorine, Bromine, Iodine) and metals (Lithium, Magnesium, Lead,
Copper, etc.)
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Exercise:
List five compounds that are inorganic and list five compounds that are organic. Find their
molecular formulas to see if they contain carbon.
1.2 Number of Organic Compounds

There are over four million known organic compounds and millions more possible
compounds that have not been made or identified. This can be explained by four
factors.
a) Bonding of Carbon to Carbon

Carbon has the ability to form long chains of atoms bonded to each other. Some
“polymers” (poly means many and mer means units) like polyethylene contain
chains over 100,000 carbons long.
Example: Pentadecane (C15H32) Structural Formula
H H H H H H H H H H H H H H H
H C C C C C C C C C C C C C C C H
H H H H H H H H H H H H H H H
b) Bonding of Carbon to Other Elements

Carbon can bond to many other elements including halogens and metals. Each
carbon can have up to four different elements attached to it.
Example: Bromochlorofluoromethanol (CHBrClFO)
Cl
F C O
Br H
c) Multiple Bonds
Carbon can form multiple bonds to itself and other atoms including Oxygen,
Nitrogen and Sulphur:
Examples: Ethene (C2 H4) Ethyne (C2 H2)Propanone (C3 H6O)

Common Names (Ethylene) (Acetylene) (Acetone)
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O
H H
H H
C C H C C H C
C C
H H H H
H H
d) Isomers
The order that atoms are attached to each other (connectivity) and the orientation of
the atoms in space determine the physical and chemical properties of the compound.
i) “Structural isomers” have the same molecular formula but different
connectivity.
Example: Ethanol (C2 H6O) Dimethylether (C2 H6O)

H O H H H
H C C H H C O C H
H H H H
ii) “Stereoisomers” have the same molecular formula and connectivity but the
atoms are orientated differently in space. (This only occurs in certain
molecules.)
Example: trans-2-butene (C4 H8) cis-2-butene (C4 H8)

H H H H H H
H H
C C C C
C C H C C H
H H
H H H H
1.3 Elemental Analysis of Organic Compounds

The exact composition of a compound can be determined by analyzing a sample in one
of two ways. The results will provide either an empirical formula or a molecular
formula but will not provide the structural formula.
a) Elemental Analysis
Organic compounds can be oxidized using pure oxygen at high temperatures to form
carbon dioxide, water, nitrogen oxides and sulphur oxides. Using a very sensitive
instrument, a known amount of compound is analyzed and the amount of each
product is measured. The results provide a percentage of carbon, hydrogen, nitrogen
and sulphur. Oxygen is measured by pyrolysis in helium and conversion to carbon
dioxide. From the percentage by mass in the original sample an empirical formula
can be determined.
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Example: The compound C2H5NOS would be analyzed to contain:
Carbon 26.359% Hydrogen 5.530%

Nitrogen 15.370% Oxygen 17.555%
Sulphur 35.186%
b) Mass Spectrometry
Organic compounds can be broken down into ions by bombarding them with
electrons under vacuum. The ions are then passed through a magnetic field that
separates them by their mass to charge ratio. The instrument is so sensitive that the
mass of the ions can be measured to four decimal places. The largest ion will be the
molecule with one electron missing.
The exact composition of this molecular ion can be calculated to determine the
number of carbon, hydrogen, oxygen, nitrogen atoms present in the molecule. This
method can also be used to measure other elements including sulphur, phosphorus,
halogens and metals. The results provide the actual molecular formula rather than
just an empirical formula.
Example: The compound C4H6NO would produce a molecular ion at 84.0449. Other
similar compounds are:
CN4O 84.0073 C2N2O283.9960

C2H2N3O 84.0198 C2H4N484.0437
C3O3 84.9847 C3H2NO2 84.0085
1.4 Carbon Bonding

Carbon has an electronegativity of approximately 2.5 which is near the middle of the
scale of electronegativities for the elements. As a result, the difference in
electronegativity between carbon and other atoms is less than 1.5 so when carbon bonds
to itself or other atoms the bonds are “covalent” (sharing electrons) rather than “ionic”
(transfer of electrons to form ions).
a) Number of Bonds to Carbon

Carbon has four “valence electrons” (electrons in the outermost energy level) that it
uses to form four covalent bonds. Each covalent bond contains one shared pair of
electrons and is represented by one line. The four valence electrons of carbon may
be found in single bonds or multiple bonds. There are four possible situations:
i) Carbon forms four single bonds to four different atoms by sharing one of its
electrons with each atom.
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Examples: Methane (CH4) Methanol (CH3OH)

2 electrons are shared
H (1 from each atom) H H
H C H H C O
H H
ii) Carbon forms one double bond by sharing two of its electrons with one atom and
two single bonds by sharing one of its electrons with each other atom.
Examples: Methanal (CH2O) Methanoic Acid (CH2O2)
Common Names (Formaldehyde) (Formic Acid)

O (2 from each atom) O
C C H
H H H O
iii) Carbon forms one triple bond by sharing three of its electrons with one atom and
one single bond by sharing one of its electrons with another atom.
Examples: Ethyne (C2H2) Ethanenitrile (C2H3N)

Common Names (Acetylene) (Acetonitrile)
(3 from each atom) H
H C C H N C C H
iv) Carbon bonds to two different atoms by sharing two of its electrons with each of
the other atoms. (These compounds are very unstable.)
Examples: Allene (C3H4) Methylisocyanate (C2H3NO)

H H (2 from each atom) H
C C C O C N C H
H H H
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b) Types of Bonds to Carbon

The first bond that carbon forms with another atom is called a sigma bond. It is a
very strong bond that is hard to break. All single bonds are sigma bonds. When a
double or triple bond is formed weaker bonds called pi bonds are formed. A double
bond contains one sigma and one pi bond. A triple bond contains one sigma and two
pi bonds. The types of bonds found in a compound accounts for its chemical
reactivity.
Example: A “double bond” between two carbon atoms.

strong sigma bond
nucleus C C weak pi bond
c) Structural Formulas of Organic Compounds

“Decane” has the molecular formula C10H22. There are actually 75 compounds that
have that same molecular formula. “Icosane” has the molecular formula C20H42.
There are 366,319 structural isomers with that same molecular formula. By
changing the connectivity (order that atoms are attached to each other) different
structural isomers (also known as constitutional isomers) are produced. As a result,
the large numbers of organic compounds that have the same molecular formulas
make it necessary to identify each isomer by drawing a unique structural formula
and assigning an appropriate name.
To draw structural formulas for organic compounds follow these steps:
i) Draw a chain of carbon atoms with lines representing bonds between atoms.
ii) Attach atoms that form more than one bond to the carbon chain.
iii) Insert atoms that form more than one bond between carbon atoms in the
chain.
iv) Attach atoms that only form one bond. (Halogens rarely bond to O, N, or S.)
vi) If there are not enough atoms, make multiple bonds or rings.
Example: C2H5ClO
Step i) There is only one possible way of joining the 2 carbon atoms.
C C
Step ii) There is only one structure with the oxygen attached to a carbon.
O
C C C C O C C
or or
O
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The oxygen can be attached at any position since the molecules are 3
dimensional.
Step iii) There is only one structure with the oxygen atom between the carbons.
C O C
Step iv) There are three possible structures that can be drawn.
H O H H H H H
H
H C C H + H C C O + H C O C Cl
H Cl Cl H H H
1-chloroethanol 2-chloroethanol chloromethoxymethane
If chlorine is attached to the same carbon as the oxygen it is a different isomer

than if it is attached to the other carbon. (The position of chlorine on each carbon
does not matter.)
Step v) Molecular formula C2H4. Molecular formula C2H4O.
H H H O O
C C H C C + H C C H
H H H H H H
Exercise:
Draw structural formulas for organic compounds with the following molecular formulas.
1. C5H12 (3) 2. C4H8 (5) 3. C3H6BrCl (5) 4. C3H9N (4) 5. C3H6O (9)
1.5 Saturated and Unsaturated Compounds

Compounds that contain only single bonds between the atoms are called “saturated”
while compounds that contain double or triple bonds are called “unsaturated”.
These terms are used when describing petroleum constituents. Most compounds found
in oil and gas contain only hydrogen and carbon atoms bonded together with single
bonds. These are called “Saturated Hydrocarbons”. Some of the compounds contain
hydrogen and carbon with double or triple bonds between the carbons. These are called
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“Unsaturated Hydrocarbons”. The terms are based on the fact that hydrogen (H2) can
be chemically reacted with the unsaturated compounds until they are saturated.
Example: Ethene (C2H4) reacts with Hydrogen (H2) to form Ethane (C2H6)
H H H H
C C + H2 H C C H
H H H H
Unsaturated Hydrocarbon Saturated Hydrocarbon
Exercise:
Identify each of the following compounds as “saturated” or “unsaturated”.
H H H
H H H H
H Cl N
O C C C H
H C C C H H C C
H
C C C H
H H H H H C
H
H H H H
1.6 Functional Groups in Organic Compounds
A “functional group” is an atom or group of atoms in a molecule that determines the

physical and chemical properties of the molecule. Molecules that contain only carbon
and hydrogen and have only single bonds between the carbon atoms are not considered
to have any functional groups. These are the “alkanes” which make up the bulk of
compounds found in gas and oil. The following table summarizes the most common
functional groups found in organic compounds.
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Functional Structure Description Example

Group
Only carbon and Ethane (Component in gas.)
hydrogen atoms. H H
Alkane All atoms are joined
C C by only single bonds. H C C H
H H
Only carbon and Ethene (Common Name:
hydrogen atoms. At least Ethylene)
Alkene two carbon atoms are H H
C C joined by a double bond.
C C
H H
Only carbon and Ethyne (Common Name:
hydrogen atoms. At least Acetylene)
Alkyne C C two carbon atoms are
joined by a triple bond. H C C H
Rings of carbon atoms Benzene (Product of petroleum
containing alternating refining)
C single and double bonds. H
C C
Aromatic H C H
C C C C
C
C C
H C H
H
One or more halogens Dichloromethane (Solvent
(Fluorine, Chlorine, made from gas.)
Bromine or Iodine) H
Organohalide C X attached to a carbon.
Cl C Cl
H
An oxygen attached to a Methanol (Common Name:
carbon with a hydrogen Methyl Alcohol) Solvent
attached to the oxygen. H
Alcohol C O
H C O
H
H H
An oxygen atom Dimethyl ether.
attached to two carbons. H H
Ether C O C H C O C H
H H
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Functional Structure Description Example

Group
An sulphur attached to a Methyl mercaptan (Compound
carbon with a hydrogen added to gas to give it odor.)
Thiol C S attached to the sulphur. H
H H C S
H H
An sulphur atom Dimethylsulphide.
attached to two carbons. H H
Sulfide
C S C H C S C H
H H
H A nitrogen attached to Methylamine
one, two or three carbons H H
Amine C N
H C N
H
H H
An oxygen atom with Methanal (Common name:

H a double bond to a carbon Formaldehyde)
atom. At least one H
Aldehyde C O hydrogen atom is also
bonded to the carbon. C O
H
An oxygen atom with Propanone (Common name:
O a double bond to a carbon Acetone)
atom. Two other carbon H O H
Ketone C C C atoms are also bonded to
the carbon. H C C C H
H H
Two oxygen atoms Methanoic acid (Common
bonded to a carbon. One name: Formic Acid)
Carboxylic O of the oxygen atoms by a O
Acid double bond and one by a
C O H single bond. The oxygen H C O H
with a single bond is also
bonded to a hydrogen
atom.
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Two oxygen atoms Methyl Methanoate (Common

O bonded to a carbon. One name: Methyl Formate)
of the oxygen atoms by a O H
Ester C O C double bond and one by a
single bond. The oxygen H C O C H
with a single bond is also
bonded to a carbon atom.
H
One oxygen atom and one Methanamide (Common name:
nitrogen atom bonded to a Formamide)
O carbon. The oxygen atom O H
Amide by a double bond and the
C N nitrogen atom by a single H C N H
bond. The nitrogen is also
bonded to a hydrogen or
carbon atoms.
One nitrogen atom Ethanenitrile (Common name:
bonded to a carbon atom Acetonitrile)
by a triple bond. H
Nitrile C N
H C C N
Example: Monoethanolamine (C2H7NO) contains two functional groups.
H H H H
Alcohol O C C N Amine
H H H
Example: 4-aminobenzoic acid (C7H7NO2) contains three functional groups.
H H
H C C O
Amine N C C C OH Carboxylic Acid
H C C
H H
Aromatic
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Exercise:
Identify the functional groups in each of the following molecules.
H H
H H
C C O
H C C H
H C C C O
H C C C O
C C H C C C C
H O H
C H H H H
C
H
O
H H H Cl
H O H C C H O
C C
H O C C N C C H Cl C C O C C
C C C C H OH
H
H H H H
1.7 Forces Affecting Physical Properties of Organic Compounds
A “physical property” is any characteristic of a compound that can be measured

without a change in chemical composition. The most important physical properties of
organic compounds related to the petroleum industry include: melting point, boiling
point, solubility, density and viscosity. These physical properties depend on the
attractive forces between the molecules. The term “intermolecular force of attraction”
means the attractive forces between molecules. The stronger the attractive forces
between molecules, the higher the melting point and the higher the boiling point.
Solubility also depends on the strength of attractive forces between molecules. The term
“like dissolves like” refers to the fact that solute molecules with weak attractive forces
will dissolve in solvent molecules that also have weak attractive forces.
a) London Dispersion Forces

The weakest intermolecular force of attraction between organic molecules is called
“London Dispersion Forces”. At any point in time the electrons are not located
equally around the nucleus of atoms. As a result there is a “temporary dipole” or
unequal balance between positive and negative around atoms. An example is the
Helium atoms shown below.
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e- + +
e-
e- pp e- p+p+
- + - +
temporary dipole temporary dipole
Attractive Force
b) Dipole-Dipole Attraction
A stronger intermolecular force of attraction between organic molecules is called
“Dipole-Dipole Attraction”. In molecules containing polar covalent bonds (bonds
between atoms that have a difference in electronegativity of greater than 0.5) there is
a “permanent dipole” or unequal balance between positive and negative around the
atom. An example is the formaldehyde molecules shown below.
H H
- - - -
ee ee
C -O
ee
- C -O
ee
-
H -
H -
+ +
permanent dipole permanent dipole
Attractive Force
c) Hydrogen Bonding
The strongest intermolecular force of attraction between organic molecules is called
“Hydrogen Bonding”. In organic molecules with a hydrogen atom bonded to an
oxygen or nitrogen there is a very strong “permanent dipole”. An example is the
water molecules shown below.
H -
ee
- H -
ee
-
O
- - O
- -
ee ee
H H
+ - + -
permanent dipole permanent dipole
Attractive Force
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Chapter Exercises:
1. Which of the following is not an organic compound ?

a. C6H5Cl
b. C3H6O2
c. C20H42
d. FeCl3
e. BrCH2F
2. Which of the following is a factor in explaining the large number of organic compounds ?
a. Carbon can only bond to metals.
b. Carbon can form multiple bonds to itself and other atoms.
c. Carbon can only form bond to four other carbon atoms.
d. Only one compound can have the molecular formula C10H22.
e. Organic compounds must not contain any carbon atoms.
3. What is the percentage of carbon by mass in the compound C10H20?

a. 10.000 %
b. 14.383 %
c. 33.333 %
d. 50.000 %
e. 85.617 %.
4. When a carbon atom is bonded to three other atoms which of the following is true?
a. It forms four single bonds.
b. It forms three single bonds and one triple bond.
c. It forms two single bonds and one double bond.
d. It forms one single bond and one triple bond.
e. It forms two double bonds and one single bond.
5. Compounds that have the same molecular formulas but different connectivity are known
as “structural isomers”.
a. True
b. False
6. Draw four possible structural isomers for the compound C4H9Cl.
7. Which of the following compounds is “unsaturated”?

H H O
H H
C C H H Cl H H
H H H H C
C C C C F C O
C C
H H S
C C H H Br H H H
H H H H
H H
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8. What is the functional group that contains one oxygen atom attached to two carbons?
a. Alcohol
b. Sulfide
c. Ester
d. Organohalide
e. Ether
9. Circle and identify the three functional groups found in each of the following molecules:
O H
H
O C N H H
H
C C C C C C H
C H
H H H H H
H
H O
H H C C H
H O C C C H C C
S H
H
O H H H H
10. What is the intermolecular force of attraction between the molecules of methanol shown
below?
H
H H
H C O
H O C H
H
H
11. Which of the following physical properties in not affected by the intermolecular forces
of attraction?
a. melting point
b. boiling point
c. color
d. solubility
e. viscosity
Chapter 2
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Structure, Nomenclature and Classification of Hydrocarbons
General Objectives
The student will be able to:

1. define, write molecular formulas and describe the shapes of “alkanes” and
“cycloalkanes”
2. draw expanded, condensed and bond line structural formulas of alkanes and
cycloalkanes
3. name alkanes and cycloalkanes using the IUPAC system and common names
4. define, write molecular formulas and describe the shapes of “alkenes” and
“cycloalkenes”
5. define “stereoisomer” and “geometric isomer” and identify “cis” and “trans” isomers.
6. draw and name alkenes and cycloalkenes including “cis/trans” and common names
7. define, write molecular formulas and describe the geometry of “alkynes”
8. draw and name alkyne compounds using the IUPAC system and common names
9. define “aromatic”, describe the geometry and identify aromatic systems
10. draw and name aromatics as well as substituted aromatics and heterocyclics
2.1 Alkanes and Cycloalkanes

a) Definition
The terms “alkane” and “paraffin” both refer to compounds which:
i) contain only hydrogen and carbon atoms (hydrocarbon)
ii) have only single bonds between carbon atoms (saturated)
iii) have open chains of carbon atoms (not cyclic)
The alkanes may have a single continuous chain of carbon atoms (unbranched) or
there may be side chains bonded to the main chain of carbons (branched).
The terms “cycloalkane”, “naphthene” and “cycloparaffin” all refer to compounds

which:
ii) have only single bonds between carbon atoms (saturated)
iii) have one ring of carbon atoms (cyclic)
The cycloalkanes may have a single ring of carbon atoms (unsubstituted) or there
may be side chains bonded to the main ring of carbons (substituted)
b) Molecular Fomulas
Regardless of the amount of branching all “alkanes” or “paraffins” have the general
molecular formula CnH2n+2 where “n” is a whole number (1,2,3,…)
Example: C4H10 is the molecular formula for both butane and isobutane
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H H H H H H
H H
C
H
H C C C C H H C C
H
H C
H H H H H
H
butane (unbranched) isobutane (branched)
Regardless of the amount of branching all “cycloalkanes” or “naphthenes” have the

general molecular formula CnH2n where “n” is a whole number (1,2,3,…)
Example: C6H12 is the molecular formula for cyclohexane and methylcyclopentane
H H
H HH H
H H
C H C
C
H C C H H
H C C H
H C C H
C C C
H H H H
H H H H
cyclohexane (unsubstituted) methylcyclopentane (substituted)
c) Geometry of Alkanes and Cycloalkanes
The three dimensional structure of organic compounds is related to the number of

other atoms that are bonded to them. The “Valence-Shell Electron-Pair Repulsion”
theory (VSEPR) can be used to determine the geometry of each atom. The theory is
based on the pairs of electrons (each bond is a pair of negative electrons) repelling
each other. All alkane carbons have four other atoms (carbon or hydrogen) attached
to them. The furthest apart that four pairs of electrons can get from each other is
109.5o. The result is a tetrahedron (a pyramid with 3 sides and a base that match).
Example: Methane (CH4) has 4 hydrogen atoms attached to the carbon.
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H
109.5o
109.5o
C
H
H 109.5o
109.5o
H
When carbon chains are drawn the atoms are drawn to indicate the bond angles that
more closely match the 109.5o.
Example: Pentane (C5H12) has 5 carbons with each one bonded to 4 other atoms.
(Lines show bonds in the plane, wedges show bonds coming out of the
plane and dashes show bonds going behind the plane.)
H H H H H H
H H
H C C H H C C H
C C C C C C
H H H H H H
H H H H H H
In cycloalkanes the bond angles are affected by the number of carbon atoms in the
ring. The cycloalkane with bond angles that more closely match the 109.5o is
cyclohexane.
Example: Cyclohexane (C6H12) has 6 carbons that form a “chair” shaped structure.
H H
C H C
H H C H
H C
H
C H C
H
H H
2.2 Drawing Structural Formulas for Alkanes and Cycloalkanes

There are three basic formats used to draw the structures of organic compounds. Each
format has advantages and disadvantages.
a) Expanded Structural Formulas
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In the “expanded” format all atoms and all bonds are shown with minimal attention
paid to bond angles and bond lengths. Often the unshared pairs of electrons on
oxygen, nitrogen, sulphur and halogens are also shown. This format is used to make
sure that each atom has the correct number of electrons.
Examples: Pentane (C5H12) Monoethanolamine (C2H7NO)
H H H H H H H H H
H C C C C C H :O C C N:
:
H H H H H H H H
b) Condensed Structural Formulas

In the “condensed” format the hydrogen atoms are written next to the carbon,
nitrogen, oxygen or sulphur atom without showing the bonds to them (The actual
position of the hydrogen atoms may be before or after the atom that they are bonded
to.) The unshared pairs of electrons on oxygen, nitrogen, sulphur and halogens may
be shown. This format is faster to use while still showing all of the atoms in the
molecule. The bond angles and lengths are more accurate in representing the three
dimensional structure.
Examples: heptanol (C7H16O) cyclohexene (C6H10)
CH2
CH2 CH2 CH2 OH H2C CH
CH3 CH2 CH2 CH2
H2C CH
CH2
c) Bond Line Formulas
In the “bond line” format carbon atoms (and the hydrogen atoms attached to them)
are not shown. Only the bonds between the carbon atoms are shown as lines. The
unshared pairs of electrons on oxygen, nitrogen, sulphur and halogens are not
shown. This format is much faster to use but requires practice to keep track of the
atoms. The bond angles and lengths are more accurate in representing the three
dimensional structure of the carbons in the molecule.
Examples: Butane(C4H10) Propanone(C3H6O) Monoethanolamine(C2H7NO)
O
HO
NH2
At the end of each line there is a carbon with the correct number of hydrogen atoms.
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d) Combinations of Formats for Drawing Structural Formulas

Often the “bond line” format is used for cycloalkanes while carbon branches are
shown using a condensed format. Sometimes this is also done for open chains.
Examples: Methylcyclopentane(C6 H12) 2,4-Dimethyloctane (C10 H22)
CH3 CH3
CH3
Another format used in “writing” condensed structures of alkanes is to combine a

number of similar groups and show them as a single unit (in brackets). Branches
may also be shown as units (in brackets) following the carbon atom that is bonded to
them.
Examples: Hexane (C6H14) 2,3-Dimethylbutane (C6 H14)
CH3(CH2)4CH3 CH3CH(CH3)CH(CH3)CH3
CH3
CH2 CH2 CH3 H3C CH
H3C CH2 CH2 CH CH3
CH3
2.3 Nomenclature of Alkanes and Cycloalkanes
Just like the different ways of drawing structures of organic compounds, there are a
variety of ways to name organic compounds. The most widely used system of
nomenclature was developed by the International Union of Pure and Applied Chemistry
(IUPAC). Another common system is derived from the primary functional group in the
molecule. Other systems are derived from a unique structure, a particular use or a
special property.
Example: One of the isomers of C3H6O has three different names: “Propanone”
(IUPAC), “Dimethylketone” (Functional Group) and “Acetone” (Common)
"an" (single O "one" or ketone

bonds between
carbons) C
H3C CH3 Methyl (1 carbon
attached to a
chain or group)
"Prop" (3 carbons)
a) International Union of Pure and Applied Chemistry (IUPAC) System
Phase 1
UNION FENOSA gas
The IUPAC system has three parts to each name. The “parent” or “root” of the name
describes the number of carbon atoms in the main or “parent” chain. The “suffix” or
ending describes the types or bonds between carbon atoms in the chain as well as the
most important functional group attached to the main carbon chain. The “prefix” or
beginning describes any atoms or groups of atoms that have substituted for hydrogen
atoms on the main chain.
Example: 4-chlorobutanol can be divided into the three parts:
"4-chloro" "ol" (alcohol) is the most

(chlorine replaces CH2 CH2 OH
Cl CH2 CH2 important functional group
hydrogen on the
fourth carbon)
"butan" (4 carbons joined by single bonds)
i) Parent Codes
The codes that represent the number of carbons in a chain are shown below:
Number Number Number Number

Code of Code of Code of Code of
Carbons Carbons Carbons Carbons
meth 1 hex 6 undec 11 hexadec 16
eth 2 hept 7 dodec 12 heptadec 17
prop 3 oct 8 tridec 13 octadec 18
but 4 non 9 tetradec 14 nonadec 19
pent 5 dec 10 pentadec 15 icos 20
ii) Suffix
The codes that represent the most important functional group are shown below:
Functional Functional Functional

Code Group Code Group Code Group
*ane alkane thiol thiol nitrile nitrile
*ene alkene ol alcohol amide amide
*yne alkyne one ketone oate ester
amine amine al aldehyde oic carboxylic
acid acid
*these codes are always used either by themselves or with other codes when
there is more than 1 functional group.
Examples: Propane Propene Propanol Propenol
Phase 1
UNION FENOSA gas
CH2 CH CH2 OH CH OH
H3C CH3 H2C CH3 H3C CH2 H2C CH2
ii) Prefix
The codes that represent the most important prefixes are shown below:
*Code Atom or Group Structure
cyclo “Parent” or “main” chain of carbons CH2
is in a ring
H2C CH2
cyclopropane
methyl 1 carbon branch CH3
ethyl 2 carbon branch CH2 CH3
propyl 3 carbon branch (attached by an end CH2 CH2 CH3
carbon)
isopropyl 3 carbon branch (attached by the CH3
middle carbon) CH
CH3
butyl 4 carbon branch (attached by an end CH2 CH2 CH2 CH3
carbon)
sec-butyl 4 carbon branch (attached by a carbon CH3
second from the end)
CH CH2 CH3
isobutyl 3 carbon branch with a 1 carbon CH3
branch attached to the second carbon (attached CH2 CH
by an end carbon) CH3
t-butyl 3 carbon branch with a 1 carbon CH3
branch attached to the second carbon (attached
by the central carbon) C CH3
CH3
vinyl 2 carbon branch that has a double
bond between the carbons CH CH2
phenyl 6 carbon aromatic ring (attached by CH CH
any of the carbon atoms)
C CH
CH CH
fluoro a fluorine atom F
chloro a chlorine atom Cl
bromo a bromine atom Br
iodo an iodine atom I
methoxy 1 oxygen with 1 carbon (attached by
the oxygen) O CH3
Phase 1
UNION FENOSA gas
* The underlined letters are used in determining alphabetical order in a name.

Except for the “cyclo” prefix, all atoms or groups of atoms must be preceded by
the number of the carbon atom that they are attached to in the parent chain. If
there is more than one identical group, the terms “di”(2), “tri”(3), “tetra”(4) and
“penta”(5) are used to indicate the number of identical groups. The prefixes
(with their numbers) are listed in alphabetical order in front of the parent name.
Examples: 3-ethyl-4-isopropyloctane 2,2,3-trimethylbutane

CH3 ethyl octane butane
H2C CH3 methyl
H3C 2 CH 4 CH2 6 CH2 8 H3C 2 CH 4
1 CH2 3 CH 5 CH2 7 CH3 1 C 3 CH3
CH methyl H3C CH3 methyl

H3C CH3 isopropyl
To name organic compounds using the IUPAC system the following steps should be
used to develop a correct name:
i) Find the longest continuous chain of carbon atoms. (This is not necessarily a
straight chain.) If there is more than one possibility, choose the one with the most
branches (substituents).
ii) Write the parent name. If it is a cyclic put the prefix “cyclo” directly in front of
the parent name.
iii) Number the carbon in the chain from the end closest to the first branch
(substituent). If there is more than one branch, number the chain so that each
subsequent branch has the lowest number.
iv) Write the names of the branches (substituents) in alphabetical order in front of
the parent name. Be sure to include the number of the carbon atom that each
branch (substituent) is attached to as well as the proper term for more than one
identical branch (substituent). Use commas to separate any numbers and dashes
to separate any numbers from letters.
Example:
H3C CH3 CH3
9
CH CH CH2 CH2
3 4 7 8
H2C 2 CH2 CH
1 5 6
CH3 CH2 CH3
i) The longest continuous chain of carbon atoms is nine.
Phase 1
UNION FENOSA gas
ii) “Nonane” is the parent chain.

iii) Numbering from the left reaches a methyl branch at the third carbon.
(Numbering from the right would reach an ethyl branch at the fourth carbon.)
iv) The name is: 6-ethyl-3,4-dimethylnonane
Example:
H3C
H3C
C CH2 CH2 CH3
HC 1 2 3CH CH2
H3C
4
H2C 6 5 CH2
CH2
i) The longest continuous chain of carbon atoms is six. (The chain can not contain
carbons of a ring and carbons of an open chain.)
ii) “Cyclohexane” is the parent chain.
iii) Numbering from the left has a t-butyl branch at the first carbon. (Numbering
from the right would have a propyl branch at the first carbon. Since “t”, “sec”
“di”, “tri”, “tetra” and “penta” are not part of the substituent, the b of “butyl”
comes alphabetically before the p of “propyl”. Cyclo and “iso” are used in
determining alphabetical order.)
iv) The name is: 1-t-butyl-3-propylcyclohexane
Exercise:
Draw structural formulas for each of the following organic compounds.

1. 2,2,4-trimethylpentane 2. 1-ethyl-2-isopropylcyclobutane
3. 5-sec-butyldecane 4. 4-t-butyl-3-ethylnonane
5. 4-propylheptane 6. 1-cyclopropyl-3-isobutylcyclohexane
Name each of the following compounds using the IUPAC system.
CH2 CH2
H3C CH2 CH3 H3C
CH CH CH2 H3C
CH2 CH2
CH CH2 H3C CH CH CH3
H3C CH2 CH2 CH2
CH2 CH2
Phase 1
UNION FENOSA gas
H3C H3C
H3C CH CH3 H3C CH2
CH
C CH CH3
H3C CH HC H3C CH2
CH2 CH2 CH3 H2C CH2
CH2
CH3 H3C
CH3 CH2
H3C CH2
CH
CH CH
CH2 HC H3C CH2 CH CH3
H3C CH2 CH
CH3 CH2 CH2
H3C
CH3
b) Functional Group System

The Functional Group system has only two parts to each name. The “parent”
describes the most important functional group in the compound. The “prefix” or
beginning describes the atoms or groups of atoms that are bonded to the parent
functional group. This system is limited to simple compounds that do not have
many branches (substituents). It is not often used on hydrocarbons.
Example: Dimethylketone can be divided into the two parts:

O "ketone" (functional group)
C
H3C CH3
"Di"(2 units) "methyl"(1 carbon chains attached to the functional group)
Example: methyl-t-butylether (MTBE) has two branches attached to an oxygen:

"ether" (functional group) O CH3
"methyl"(1 carbon chain) H3C C
CH3
"t-butyl"(3 carbons attached by the CH3
center carbon and a 1 carbon branch)
c) Common Names
Some organic compounds that have complex IUPAC names are often referred to by a
more simple name. There is no real system involved in determining the names.
Many of the compounds encountered in the oil and gas industry are referred to by
their common names. One of the structural isomers of C8H18 that is used in rating
Phase 1
UNION FENOSA gas
gasolines is commonly referred to as “isooctane”. The IUPAC name is 2,2,4-

trimethylpentane.
The unbranched isomer of C16H34 (hexadecane) is called “cetane” which is used in
rating diesel fuel.
H3C
CH2 CH3
C CH CH3(CH2)14CH3
H3C
CH3 CH
3
“isooctane” “cetane”
2.4 Alkenes and Cycloalkenes
a) Definitions
The terms “alkene” and “olefin” both refer to compounds which:
ii) have at least one double bond between two of the carbon atoms (unsaturated)
iii) have open chains of carbon atoms (not cyclic)
The alkenes may have a single continuous chain of carbon atoms (unbranched) or
The terms “cycloalkene” and “cycloolefin” both refer to compounds which:

i) contain only hydrogen and carbon (hydrocarbon)
ii) have at least one double bond between two of the carbon atoms (unsaturated)
iii) have one ring of carbon atoms (cyclic)
The cycloalkenes may have a single ring of carbon atoms (unsubstituted) or there
may be side chains bonded to the main ring of carbons (substituted)
b) Molecular Formulas
Regardless of the amount of branching all “alkenes” or “olefins” have the general
molecular formula CnH2n where “n” is a whole number (1,2,3,…)
Example: C4H8 is the molecular formula for both butene and isobutene
H H H H
H H
C
H
C C C C H C C
H
H H C
H H H H
H
butene (unbranched) isobutene (branched)
Phase 1
UNION FENOSA gas
Regardless of the amount of branching all “cycloalkenes” or “cycloolefins” have the

general molecular formula CnH2n-2 where “n” is a whole number (1,2,3,…)
Example: C6H10 is the molecular formula for cyclohexene and 1-

methylcyclopentene
H H H
H
H
C H H H
C C
H C C
H C C
H C C H
C H C C
H H H
H H H H
cyclohexene (unsubstituted) 1-methylcyclopentene (substituted)
c) Geometry of Alkenes and Cycloalkenes

All alkene carbons have three other atoms (carbon or hydrogen) attached to them.
The double bond electrons act similar to a single bond. The furthest apart that the
double and single bonds can get from each other is 120o. The resulting geometry is
called trigonal planar. (a planar or flat triangle).
Example: Ethene (C2H4) has a double bond between the carbon atoms.
120o 120o
H H
120o C C 120o
H H
120o 120o
When carbon chains are drawn the atoms are placed to indicate the bond angles that
more closely match the 120o.
Example: Propene (C3H6) has a double bond between the first two carbons.
(Lines show bonds in the plane, wedges show bonds coming out of the
plane and dashes show bonds going behind the plane.)
H H H H
C C H C C H
C C
H H H H
H H
In cycloalkenes the bond angles are affected by the number of carbon atoms in the
ring and are not exactly 120o. The smaller the ring, the further from 120o which
makes the compounds less stable. Cyclopropene is very unstable.
Phase 1
UNION FENOSA gas
Example: Cyclohexene (C6H10) has 6 carbons that form a “twisted chair” shape.
H H
CH2 C H C
H2C CH2 H
C H
H C H
H2C CH C C
CH H
H H
2.5 Stereoisomers in Alkenes, Cycloalkenes and Cycloalkanes

When comparing the structure of organic compounds it is sometimes necessary to
consider the three dimensional structures. Compounds that seem to be the same in two
dimensions may actually be different. These differences can affect the chemical and
physical properties of the molecules. The existence of stereoisomers can be
demonstrated using a person’s hands. Both hands have four fingers and a thumb
connected to them but there is a difference between a “right hand” and a “left hand”.
The orientation of the fingers, thumb, wrist and palm are actually mirror images of each
other. Some but not all molecules may have mirror image isomers (called
“enantiomers”).
a) Definitions
Stereoisomers are compounds which have the same molecular formula and the same
“connectivity” but the “orientation of atoms in space” are not the same. There are
several types of stereoisomers but only one type is relevant to the hydrocarbon
industry. This type of isomer is referred to as a “geometric isomer”.
“Geometric isomers” are compounds with the same molecular formula and same
connectivity but the orientation or the atoms in space are different because of
restricted rotation of the bonds in the molecules. In an open chain alkane there is
free rotation of all the bonds in the molecule. (Even at room temperature the atoms
are moving all the time and the shape of the molecule is changing.) Because the
carbon atoms form a ring in a cyclic alkane, they can no longer rotate 360o. In both
open chain and cyclic alkenes the rotation is restricted by the ring and double bond.
Example: The single bond between the carbons in ethane has free rotation.
H H
C C H
H
H H
Phase 1
UNION FENOSA gas
Example: The single bonds between the carbons in cyclohexane do not have free
rotation.
H H
H C H
C C
H H
H C C
C H
H H
H H
Example: The double bond between the carbons in ethene does not have free
rotation.
H H
C C
H H
b) Stereoisomers in Cycloalkanes
Since the atoms can not rotate freely, any atoms or branches of atoms attached to the
carbons of the cycloalkanes will be restricted to one side of the ring. When two
atoms or branches of atoms are attached to different carbons on the ring they will
either be on the same side “cis” or on opposite sides “trans”. The terms cis and trans
are used to designate the relative orientation of the atoms or branches of atoms in
space.
Example: The stereoisomer cis-1,2- dimethylcyclohexane.
CH2 CH3 CH2 H

H2C C H2C C
H or CH3
H CH3
H2C C H2C C
CH2 CH3 CH2 H
Example: The stereoisomer trans-1,2- dimethylcyclohexane.
CH2 CH3 CH2 H

H2C C H2C C
H or CH3
CH3 H
H2C C H2C C
CH2 H CH2 CH3
Phase 1
UNION FENOSA gas
c) Stereoisomers in Alkenes and Cycloalkenes

Since the carbon atoms of a double bond can not rotate freely, any atoms or branches
of atoms attached to the carbons of the double bond will also be restricted to one
side of the plane of the double bond. When atoms or branches of atoms are attached
to each carbon of the double bond they will either be on the same side “cis” or on
opposite sides “trans”. (The double bonds in the ring of cycloalkenes with less than
nine carbon atoms are always “cis” so they are not included in the names.)
Example: cis-2-butene vs trans-2-butene
H3C CH3 H3C H
C C C C
H H H CH3
Because all 4 carbons are in the plane, wedges and dashes are not used.
Exercise:
Identify each of the following isomers shown below as “cis” or “trans”.
H
CH2 CH3
CH3 H2C C
C CH3
H H
CH2 C
C CH2
H H3C
CH2
H3C CH2 CH2 CH3 H2C C
H H CH3
C C C CH2
H H H3C
2.6 Drawing and Naming Alkenes and Cycloalkenes

In the IUPAC system, any compound with a double bond in the parent chain has the
suffix code “ene”. To indicate where the double bond is in the chain, the number of
the first carbon involved in the double bond is placed either directly in front of the
“ene” suffix code or directly in front of the parent code. If the double bond is
between the first and second carbon it is not necessary to include the number “1” but
Phase 1
UNION FENOSA gas
it can be included. If a particular stereoisomer is not shown, it is not necessary to

include the “cis” or “trans” prefix at the front of the name.
Examples: Pent-2-ene (2-Pentene) Hexene (1-Hexene)
H2C CH2 CH2

H3C CH CH CH2 CH3
CH CH2 CH3
The position of the double bond is more important than the positions of any branches
or substituents. As a result, an open chain alkene must be numbered from the end
closest to the double bond. If the first carbon of the double bond is the same number
of carbons from either end of the open chain, then the chain is numbered like a
branched alkane so that the first branch is on the lowest number carbon. Even if
there is a longer chain of carbon atoms without the double bond, the parent chain
must contain the double bond.
Examples: 4-methyl-2-pentene 2-methyl-3-hexene
H3C CH CH3 H3C CH CH2

CH CH CH3
CH HC
CH3 CH3
On a cycloalkene the ring carbons are numbered so that the carbons of the double
bond are numbers “1” and “2”. If there are no branches, it is not necessary to include
the number “1” but it can be included. If there are branches on the ring, then the
ring is numbered in the direction so that the first branch is on the lowest number
carbon.
Examples: Cyclohexene (1-Cyclohexene) 3-Methylcyclopentene
CH2 CH
H2C CH CH3
HC CH
H2C CH
CH2 CH2
CH2
If there are two double bonds in the compound, then the suffix “adiene” must be
used along with the numbers for the first carbon of each double bond.
Phase 1
UNION FENOSA gas
Examples: 1,4-pentadiene 2-methyl-1,3-butadiene
H2C CH
CH CH C CH2
H2C CH2 CH2
CH3
If a specific stereoisomer is indicated, then the prefix “cis” or “trans” must be used
to indicate which stereoisomer is present. Because the terms “cis” and “trans” refer
to the orientation of the atoms in space, there must be two different atoms or groups
of atoms bonded to each of the carbons of the double bond. If there is an atom (or
group of atoms) that is exactly the same bonded to each of the carbons, their
orientation in space is used to determine the stereochemistry. Alternately, the
orientation of the parent chain is used to determine the stereochemistry.
Examples: cis-2-pentene trans-3-ethyl-2-heptene
H H H CH2 CH2
CH2 CH3
C C C C
H3C CH2 CH3 H3C CH2 CH3
b) Common Names for Alkenes

The simplest alkene has only two carbon atoms double bonded to each other. This
compound (“ethene” in the IUPAC system) is also known as “ethylene”. Many
petrochemicals that are made from ethylene have names based on this common
name. Some examples are “ethylene oxide”, “ethylene glycol” and “polyethylene”.
(These compounds do not have the double bond.)
Examples: Ethylene Ethylene oxide Ethylene glycol

O
H2C CH2 CH2 OH
H2C CH2 HO CH2
As a branch or substituent the “ethenyl” group is called “vinyl”. Some examples of

petrochemicals containing this group are “vinyl benzene”, “vinyl acetate” and “vinyl
chloride”. Polymers made from these three compounds are known as
polyvinylbenzene (also known as polystyrene), polyvinyl acetate and polyvinyl
chloride.
Phase 1
UNION FENOSA gas
Example: Vinyl chloride Polyvinyl chloride
Cl Cl
H2C CH CH2 CH
100,000
Exercise:
1. 4-methyl-2-pentene 2. 1-ethyl-3-isopropylcyclohexene
3. 5-t-butyl-1,3-decadiene 4. trans-4-nonene
5. 2,5,5-trimethyl-2-heptene 6. cis-1-isobutyl –4-propylcyclohexane
2.7 Alkynes
a) Definitions
The terms “alkyne” and “acetylene” both refer to compounds which:
ii) have at least one triple bond between two of the carbon atoms (unsaturated)
iii) have open chains of carbon atoms
The alkynes may have a single continuous chain of carbon atoms (unbranched) or
Cycloalkynes do not easily form in carbon chains less than eight carbons long and
are very unstable.
b) Molecular Formulas
Regardless of the amount of branching all “alkynes” or “acetylenes” have the
general molecular formula CnH2n-2 where “n” is a whole number (1,2,3,…)
Example: C4H6 is the molecular formula for 1-butyne and 2-butyne
H H H H
H C C C C H H C C C C H
H H H H
1-butyne 2-butyne
c) Geometry of Alkynes and Cycloalkynes

All alkyne carbons have two other atoms (carbon or hydrogen) attached to them. The
triple bond electrons act similar to a single bond. The furthest apart that the triple
Phase 1
UNION FENOSA gas
and single bonds can get from each other is 180o. The resulting geometry is called
linear.
Example: Ethyne (C2H2) has a triple bond between the carbon atoms.
180o 180o
H C C H
180o 180o
When carbon chains are drawn the atoms are drawn to indicate the bond angles that
more closely match the 180o.
Example: 1-Octyne (C8H14) has a triple bond between the first two carbons.
CH
H3C CH2 CH2 C
CH2 CH2 CH2
8. Drawing and Naming Alkynes

In the IUPAC system, any compound with a triple bond in the parent chain has the
suffix code “yne”. To indicate where the triple bond is in the chain, the number of
the first carbon involved in the triple bond is placed either directly in front of the
“yne” suffix code or directly in front of the parent code. If the triple bond is between
the first and second carbon it is not necessary to include the number “1” but it can be
included. There are no stereoisomers involving the triple bond of alkynes
.
Examples: Pent-2-yne (2-Pentyne) Hexyne (1-Hexyne)
H3C C C CH2 CH2 CH2

C CH2 CH3
CH3 HC
The position of the triple bond is more important than the positions of any branches
or substituents. As a result, an open chain alkyne must be numbered from the end
closest to the triple bond. If the first carbon of the triple bond is the same number of
carbons from either end of the open chain, then the chain is numbered like a
branched alkane so that the first branch is on the lowest number carbon. Even if
there is a longer chain of carbon atoms without the double bond, the parent chain
must contain the triple bond.
Phase 1
UNION FENOSA gas
Examples: 4-methyl-2-pentyne 2-methyl-3-hexyne
CH3 H3C
H3C C C HC CH C C CH2
CH3 H3C CH3
If there are two triple bonds in the compound, then the suffix “adiyne” must be used
along with the numbers for the first carbon of each double bond.
Example: 1,4-pentadiyne
CH2
C C
HC CH
If a compound contains a double and a triple bond the suffix used is “enyne”. The
number of the first carbon of the double and triple bond are usually placed in the
suffix to indicate the positions. If the number of carbons from the end of the chain to
the double and triple bonds are the same, then the chain is numbered from the end
closest to the double bond.
Examples: hex-4-en-1-yne hex-2-en-4-yne
CH2 C CH CH3
C
CH CH
CH C
H3C H3C CH
b) Common Names for Alkynes

The simplest alkyne has only two carbon atoms triple bonded to each other. This
compound (“ethyne” in the IUPAC system) is also known as “acetylene”. In the
functional group system for common names, the two carbon atoms are treated as the
parent and named “acetylene”. Any carbon chains attached to the carbons are named
as branches or substituents.
Examples: Acetylene Dimethylacetylene (2-butyne)
HC CH H3C C C CH3
Phase 1
UNION FENOSA gas
Exercise:
1. 4-ethyl-2-heptyne 2. 5-isopropyl-3-octyne
3. 6-sec-butyl-4-decyne 4. 2,4-nonadiyne
5. 2,6-dimethylhept-3-yne 6. ethylpropylacetylene
9. Aromatic Hydrocarbons
a) Definitions
The term “aromatic hydrocarbon” refers to compounds which:
ii) have electrons evenly shared over all carbon atoms
iii) have flat rings of carbon atoms
Although the original term “aromatic” was used to describe the pleasant smell of
certain compounds, the term is currently used to describe unusually stable cyclic
compounds. The simplest aromatic hydrocarbon that has been studied extensively is
“benzene”. This compound has a ring of six carbon atoms. Each carbon atom has
one hydrogen atom and two other carbon atoms attached.
Chemists who first studied benzene suggested that there were three single and three
double bonds alternating in the ring producing the structure 1,3,5-cyclohexatriene. It
was later discovered that all of the bonds between carbon atoms in the ring were
identical. This unusual characteristic is referred to as the delocalization of electrons
and is responsible for the stability of the compound.
Examples: 1,3,5-cyclohexatriene benzene

(theoretical structure) (actual structure)
H H
H C H H C H
C C C C
C C C C
H C H H C H
H H
Phase 1
UNION FENOSA gas
b) Geometry
Because all of the carbons are similar to those in alkenes, the benzene ring is a flat
molecule with the hydrogen atoms and carbon atoms all in the same plane. This is
quite different from cyclohexane that has a “chair” shape with all the carbon atoms
having only single bonds.
Example: Benzene ring tipped up at the back to show planar structure.
c) Identifying Aromatic Hydrocarbons

Most aromatic hydrocarbons contain one or more rings of six carbons. They may be
shown with single and double bonds or with a single circle in the middle of the
atoms. There are often branches attached to the rings in place of hydrogen atoms.
Examples: Benzene Naphthalene Biphenyl
CH CH CH CH CH CH CH
HC CH HC C CH
HC C C CH
HC CH HC C CH
CH CH CH CH CH CH CH
2.10 Drawing and Naming Aromatic Compounds

The IUPAC system has accepted the names “benzene”, “naphthalene” (not to be
confused with “naphthenes” which is a general term for cycloalkanes), and
“anthracene” for aromatic fused ring systems containing 1,2 and 3 rings. The
carbons in the ring are named as the parent chain and any branches or substituents
attached are named the same way as branches on cycloalkanes. Since the rings are
all planar, there are no stereoisomers involving the aromatic rings.
Phase 1
UNION FENOSA gas
Examples: ethylbenzene 1,4-dimethylbenzene 1-t-butyl-2-isopropylbenzene
CH3
CH CH2 CH CH3 CH CH
HC C CH3 HC C HC C CH3
CH3
HC CH C CH HC C
CH H3C CH CH C
CH3
H3C
b) Common Names for Aromatic Compounds

Many of the aromatic compounds with branches of carbon atoms have common
names. A unique system applied only to disubstituted benzenes (two branches on
benzene) uses the terms “ortho” or “o” for branches on carbons 1 and 2 “meta” or
“m” for branches on carbons 1 and 3 and “para” or “p” for branches on carbons 1
and 4 rather than numbers to show the position of the substituents.
Examples: o-dimethylbenzene p-ethylisopropylbenzene
CH CH3 H3C CH CH CH3

HC C
CH2 C C HC
HC C
CH CH3 CH CH CH3
The aromatic hydrocarbons shown below are used in the petroleum and
petrochemical industry. The IUPAC names are in brackets below the common
names.
Toluene Cumene Styrene or Vinylbenzene

(methylbenzene) (isopropylbenzene) (ethenylbenzene)
CH CH CH CH CH3 CH CH
HC C CH3 HC C HC HC C CH
CH CH CH CH CH3 CH CH CH2
When naming compounds using common names, the benzene ring is numbered
starting at the carbon where the main substituent or branch is attached.
Phase 1
UNION FENOSA gas
Examples: 4-ethyltoluene 3-chlorostyrene
CH CH CH CH
CH2 C C CH3 HC C CH
H3C CH CH C CH CH2
Cl
o-Xylene m-Xylene p-Xylene

(1,2-dimethylbenzene) (1,3-dimethylbenzene) (1,4-dimethylbenzene)
CH3 CH3
CH C CH C CH CH
HC C CH3 HC CH H3C C C CH3
CH CH CH C CH CH
CH3
c) Heterocyclic Aromatic Compounds

There are a number of aromatic compounds that also contain atoms of chlorine,
nitrogen, oxygen and sulphur. The examples below are also found in the petroleum
and petrochemical industry.
Aniline Phenol or Carbolic Acid Phenyl

chloride
(Benzenamine) (Benzenol) (Chlorobenzene)
CH CH CH CH CH CH
HC C NH2 HC C OH HC C Cl
CH CH CH CH CH CH
Phenylmercaptan or Thiophenol p-Cresol o-Nitrotoluene

(Benzenethiol) (4-methylbenzenol) (1-methyl-2-nitrobenzene)
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CH CH CH CH CH CH3
HC C
HC C SH H3C C C OH
HC C
CH CH CH CH NO2
CH
Exercise:
1. 1,2,4-triethylbenzene 2. 4-isobutyltoluene
3. p-dichlorobenzene 4. m-propylphenol
5. 2-t-butylaniline 6.2,4,6-trinitrotoluene(TNT)
Chapter 2 Exercises:
1. Which of the following is the molecular formula for an “alkane” or “paraffin”?

a. C6H6
b. C3H6
c. C10H22
d. C2H3Cl
e. C4H10O
2. Which of the following terms best describes the geometry of an “alkane” carbon ?
a. tetrahedron
b. trigonal planar
c. linear
f. planar
g. octahedron
3. What format used to draw structural formulas shows all atoms, all bonds and unshared
electrons ?
a. bond line
b. condensed
c. expanded
d. semicondensed
e. isotopic notation
4. Which of the following represents the compound with the molecular formula C4H10 ?
H3C CH3
CH CH3 H2C CH2 H3C C
a. H C b. CH c. d.
2 CH2 C CH3
H2C CH2
CH3
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5. Which of the following represents a compound with the molecular formula C5H10?
a. b. c. d.
6. What is the “parent” or “root” of the name for the following compound?
CH3 CH3 CH3
H3C CH CH CH2
CH CH2 CH2
H3C
CH2
a. hex b. hept c. oct d. non e. dec
7. Which of the following “branches” or “substituents” represents a “t-butyl”group?

H3C
CH CH3 CH3 H2C CH CH2 CH
a. CH CH2 b. C c. d.
H2C CH2 H3C CH3
CH3
8. What is the IUPAC name for the following compound?
CH3 CH2 CH2 CH3
H3C
CH CH CH3
H3C CH CH2 CH2
a. 2,3-dimethyl-4-propylheptane d. 5-ethyl-2,3-dimethyloctane
b. 3-ethyl-2-isopropylhexane e. 2-isopropyl-4-propylhexane
c. 4-ethyl-6,7-dimethyloctane

H
CH2 CH2 C H
H3C CH2 CH C
H3C CH2 CH2 CH3
a. cis-5-butyl-3-heptene d. cis-1,3-diethyl-1-heptene
b. trans-5-ethyl-3-nonene e. cis-5-ethyl-3-nonene
c. trans-4-ethyl-1-methyl-2-octene
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CH3
H3C C CH2
CH3 CH2 C C CH3
a. 2,2-dimethyl-5-heptyne d. 6,6-dimethyl-2-heptene
b. 5-t-butyl-2-pentyne e. t-butylmethylacetylene
c. 6,6-dimethyl-2-heptyne

H3C CH2 CH CH2 CH3
CH2 C C CH
HC CH CH3
CH
a. o-dipropylbenzene d. m-isobutylpropylbenzene
b. p-butylisopropylbenzene e. 1-isopropyl-3-isobutylbenzene
c. 1-butyl-3-isobutylbenzene
Chapter 3
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Composition of Natural Gas and Oil
3.1. Natural Gas – Well Head Gas
In the reservoir, crude oil almost always contains dissolved methane and other light
hydrocarbons that are released when the pressure on the oil is reduced (i.e. bringing the oil from
the high pressure reservoir to the surface separator). As the gas evolves, the remaining crude oil
liquid volume decreases; this is known as shrinkage. The gas produced is called associated gas,
separator gas or solution gas, etc.
Natural gas produced from a gas reservoir may contain small amounts of heavier hydrocarbons
that are separated as a liquid called condensate. Natural gas containing condensate is said to be
wet gas. Conversely, if no condensate forms when the gas is produced to surface, the gas is
called dry gas.
The main constituent of natural gas is methane, which is used as fuel for residential and
industrial applications (furnaces, heaters, steam generation, etc.). When natural gas comes from
the reservoir, it may have any of the following constituents:
Class Component Formula Shorthand

Hydrocarbons Methane CH4 C1
Ethane C2H6 C2
Propane C3H8 C3
i-Butane iC4H10 iC4
n-Butane nC4H10 nC4
i-Pentane iC5H12 iC5
n-Pentane nC5H12 nC5
Cyclopentane C5H10
Hexanes and C6+
heavier
Inert Gases Nitrogen N2 N2
Helium He
Argon A
Hydrogen H2 H2
Oxygen O2 O2
Acid Gases Hydrogen H2S H2S
Sulfide
Carbon CO2 CO2
Dioxide
Sulphur Mercaptans R-SH
compounds
Sulfides R-S-R’
Disulfides R-S-S-R’
Water Vapor H2O
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Liquid Slugs Free water or

brine
Corrosion
inhibitors
Methonal CH3OH
Solids Millscale and
rust
Iron sulfide FeS
Reservoir fines
(sand)
Remember that it is the methane (and ethane) that are desirable as heating fuel or commercial
“natural gas”. The heavier components have an undesirable effect of raising its hydrocarbon
dew point to an unacceptable temperature.
Conversely, natural gas usually has some nitrogen included, which has no heating value. The
heavier ends may be required to compensate for the diminished heat value of the gas. When the
nitrogen content is too high, cryogenic processing (extreme cold) may be required to remove it.
This is very expensive and could render a gas field uneconomic to produce.
Depending on the composition of the gas, a gas plant may be built in the field to remove the
heavier ends. If enough producers are leaving small quantities of propane and butane etc. in the
pipeline gas, a “straddle plant” may be built downstream to remove these components. Straddle
plants must process huge volumes of gas to recover enough heavy ends to make them
economical. LNG plants are a type of “straddle plant” designed to take preprocessed gas
in a pipeline and liquefy it for transportation or petrochemical feedstock.
Acid gases; Hydrogen sulfide (H2S) and carbon dioxide (CO2) must be removed to specified
minimum levels before the gas is pipelined or fed into an LNG plant. This process is termed
sweetening and there are various methods employed in gas plants to do this.
Produced gas is regarded as saturated with water even if no liquid water is produced. This water
must be removed or “dehydrated”. LNG plants have strict hydrocarbon, water, and CO2
specifications to prevent the formation of solids in the cryogenic (very cold) conditions of
an LNG plant.
3.2. Field Processing of Natural Gas
Field processing is the treatment of gas soon after it has reached the surface and left the well
head. It generally consists of two distinct categories of operations:
1. Separation of the gas/liquid/water well effluent into its individual phases.
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2. Removal of impurities from the separated phases to meet sales /transportation

/reinjection specifications and/or environmental regulations.
The individual unit operations that may be required include:

 Basic field-processing
 Prevention of hydrate formation
 Separation of free liquids and solids from the gas
 Sweetening (removing H2S, CO2)
 Dehydration using TEG, solid desiccants, LTX and CaCl2
 Condensate recovery and HC dew-point control
 Compression
 Flow measurement
 Pipeline transport of natural gas
3.3. Natural Gas Specifications
3.3.1. Product Specifications – Gas Feedstock to an LNG Plant
As a producer, the gas from the reservoir must be processed in the field to meet specifications
set out by the pipeline or LNG plant. These specifications ensure that the gas sold to market has
predictable qualities such as heating value, corrosion tendency and water dew point. These
specifications are usually the feedstock to the LNG plant.
There are many types of gas plants producing a variety of products and to different
specifications Three types of plants are:
 Liquefied Natural Gas (LNG) Plants typically liquefy the C1 and C2 components of
natural gas.
 Liquefied Petroleum Gases (LPG’s) are the C3 and C4 components.
 Natural Gas Liquids (NGL’s) are the C3, C4, and C5+ components.
Natural gas has to be highly process before it enters an LNG plant – the impurities of CO2, H2S
and water must be removed almost completely before liquefaction takes place because these
components are solids at the temperatures and pressures found in an LNG plant. Similarly the
NGL fractions of Natural Gas should also be removed before the C1 and C2 components are
liquefied.
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3.3.2. Quality requirements for gas received by gas plants are as follows:
1. Free of sand, dust, gums, crude oil, contaminants, impurities and other objectionable
substances;
2. Hydrocarbon dew point less than minus ten (-10) degrees Celcius at operating pressures;
3. Not more than twenty three (23) milligrams of Hydrogen Sulphide per one (1) cubic metre;
4. Not more than one hundred fifteen (115) milligrams of total sulphur per one (1) cubic metre;
5. Not more than two (2) percent by volume of carbon dioxide;
6. Not more than sixty five (65) milligrams of water vapour per one (1) cubic metre;
7. Water dew point less than minus ten (-10) degrees Celcius at operating pressures greater
than 8275 kPa;
8. Not to exceed forty nine (49) degrees Celsius in temperature;
9. As free of oxygen as possible (in no cases to exceed 0.4% by volume);
10. Minimum Gross Heating Value of thirty six (36) megajoules per cubic metre.
Summary:
Component Specification
o
HC dew point < -10 C @ operating pressure
Water dew point < -10oC @ pressure exceeding 8275
kPa
H2S 23 mg/m3 (max)
Total Sulphur 115 mg/m3 (max)
CO2 2% vol (max)
Water vapour 65 mg/m3 (max)
O2 0.4% vol (max)
Temp 49oC (max)
Gross Heating 36 MJ/m3
Value
Notes:
Water content:
Water vapour must be removed in a dehydration process. The most typical is glycol
dehydration, but many plants use a dry desiccant technology such as mole sieves to remove
water. If free water forms, it may form hydrates and is also very corrosive in the presence of
carbon dioxide.
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H2S content:
H2S is corrosive and very toxic. The gas is typically sweetened using an amine process. The
concentrated acid gas is either converted to elemental sulphur or re-injected into another
formation (fairly recent technology).
Hydrocarbon dew point:

Too much propane or butane (+ other heavy ends) would tend to condense in the pipeline and
cause problems such as slug flow. Pipeline companies have a spec that requires a producer to
remove the heavy ends so that no liquid is formed in the line.
Gross heating value:

The gross heating value of a gas depends on its composition. A pure, 100% methane gas would
have a heating value of approx 38 MJ/m3. This would meet pipeline spec, but if any inerts
(methane, argon, helium) are present, they have the effect of lowering the heating value.
Therefore, other molecules such as ethane (66 MJ/m3), propane (  94 MJ/m3) or n-butane ( 
122 MJ/m3) are required to bring the heating value back up to pipeline spec. This must be
accomplished without exceeding the Hydrocarbon dew point spec.
3.3.3. EXERCISES
Determine the Gross Heating Value of the following gas compositions:
Example:
Component Mol % Fraction of a m3 Gross Heat Total Gross

Value kJ/m3 Heating value
(kJ/m3)
C1 92 0.92 37,708 34,691
C2 6 0.06 66,065 3,964
C3 2 0.02 93,936 1,879
Total 100 1.00 40,534
Calculate:
Component Mol % Fraction of a m3 Gross Heat Total Gross

Value kJ/m3 Heating value
(kJ/m3)
C1 90 37,708
C2 6 66,065
C3 2 93,936
n-C4 2 121,794
Total 100 1.00
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Calculate:
Component Mol % Fraction of a Gross Heat Total Gross

m3 Value kJ/m3 Heating value
(kJ/m3)
C1 85 37,708
C2 4 66,065
C3 1 93,936
n-C4 1 121,794
N2 5 0
CO2 4 0
Total 100 1.00
Is this gas suitable for pipeline?
Depending on the pressure, temperature and composition of the gas, surface facilities are
designed to process the specific gas from the field. Rarely are any two fields processed exactly
the same.
Within each process (separation, dehydration, etc.) there are many variables and many options
on the technology and hardware that can be used.
3.4. Sampling and Analysis
Gas is often sampled at various locations in the process. Initially, the most important sample
provided is the wellhead or “raw gas” sample. This will provide the necessary information for
the entire design of the gas processing facilities.
Since almost all natural gas is considered to be water saturated in the reservoir, dehydration is
essential. If gas is not dehydrated, liquid water will drop out as soon as the gas is cooled.
Compression is also normally required to get the gas from the field to the plant or to get the gas
from the plant into the pipeline.
Other facilities such as methanol injection, sweetening, and refrigeration will depend on the
composition of the gas.
 The probability of hydrate formation depends on H2S levels, C2+ content, pressure and
temperature.
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 The hydrocarbon dew point temperature depends on the composition of the gas. If too
many C3+ fractions are present in the gas, they will liquefy at an undesirable
temperature.
 If H2S is present in a level above 16ppm, it must be removed. CO2 must also be removed
if it is above 2%.
 High levels of inerts such as helium (rare) or nitrogen (common) will lower the heating
value of the gas. Nitrogen may have to be removed through cryogenics if the economics
are profitable.
Samples are taken from the process in many locations to determine the efficiency of the process
or to troubleshoot a piece of hardware.
3.5. DISCUSSION
1. What processes will be required to prepare a gas for pipeline if the composition is 98%

methane, 1% ethane and 1% Hydrogen Sulphide?
methane, 5% ethane, 5% propane, 3% isobutane, 3% n-butane and 4% C5+?
methane, 8% ethane, 15% condensate liquids, 5% Hydrogen Sulphide, and 7% Carbon
Dioxide. Free water is produced in some of the wells.
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Chapter4
Plant Processing of Natural Gas
The raw product often referred to as Natural Gas comes from two main sources – gas fields where
the hydrocarbon leaving the well head is predominantly gas with some associated liquids or from oil
field where the gas (often called solution gas) escapes from the crude oil when the pressure is
reduced.
Natural gas must be preconditioned very close to the wellhead before it can be taken to a gas plant
for further processing. The gas product from a standard gas plant is the feedstock to an LNG plant.
4.1 Field Processing of Natural Gas
Two essential processes occur very quickly after the gas, gas/oil mixture reach the surface from the
reservoir – gas liquid separation and dehydration.
4.1.1. Gas-Liquid Separation
Separation of liquids. This is usually carried out in horizontal or vertical separators that often
contain baffles to promote the coalescence of the liquid droplets that are carried in the gas
stream. These liquids are referred to as condensate and are usually stored at the well site for
later removal by truck.
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4.1.2. Separation Principles
 Separation of well stream liquids is by far the most common of all field processing operations
and at the same time, one of the most critical.
 Well effluent is a complex mixture of liquid and gaseous hydrocarbons, with water and other
impurities often present.
 It is necessary to separate hydrocarbon liquids and water from the hydrocarbon gas.
 The separation of natural gas, liquid hydrocarbons, and impurities is accomplished by various
field processing methods which include:
i) gravity
ii) heat
iii) mechanical
iv) electrical
v) chemical
4.1.3. Separation Processes
A combination of these methods is used to separate hydrocarbon gas, liquid and water phases.
1) Gravity
- simplest and most common method in use today.
- dependant upon the principle that the liquid components have a greater density than the gas
components.
- water present is usually heavier than the hydrocarbon liquid and therefore settles due to
gravity.
2) Impingement
- relies upon the difference in momentum between a gas particle and a liquid droplet.
- takes place when liquid-laden gas approaches an obstacle and liquid droplets impinge upon
the barrier and increase in size.
- the effects of gravity become significant and the drop falls to the liquid section of the
vessel.
3) Centrifugal
- occurs when the stream to be separated rotates at high velocities inside a vessel.
- centrifugal force moves the liquid to the wall of the vessel where it coalesces and drains to
the liquid section by gravity.
- Allows a smaller vessel to be used than other types.
There are two main classes of separation: Two Phase and Three Phase
Two Phase Separation

- one combined raw product separated into two distinct products; hydrocarbon gas and
hydrocarbon liquids.
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- has an application mainly in fields with little or no produced water.
Three Phase Separation

- Splits the raw well effluent into three distinct phases or products; hydrocarbon gas,
hydrocarbon liquid and water
- Used where free water is produced with the oil or gas stream.
- Inlet separators at the gas plant are usually three phase type.
- Water may be withdrawn by manual dump or by automatic level control.
4.1.4. Staged Separation of Oil and Gas
- Pressure is reduced a little at a time, resulting in a more stable stock tank liquid.
- A large pressure drop can cause a reduction in stock tank liquids.
- The objective is not to lose valuable LPG’s. C3, C4 and C5 to the hydrocarbon gas phase.
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Discussion
1. Give an example of 3-phase separation.
2. Where might a 2-phase separator be used?
3. Theoretically, what would be the best way to separate hydrocarbon liquid from hydrocarbon
gas?
4.2. Separators
Separation is defined as the division of the phases present in a hydrocarbon stream to:
a) obtain more pure liquid and gas products
b) allow testing or metering of the individual phases
c) ensure that downstream equipment or processes are protected from exposure to
components of the hydrocarbon stream. For example, condensed hydrocarbon liquids
should be removed from compressor suction lines
d) isolate the downstream equipment and processes from the field
A properly designed separator will provide a clean separation of free gas from the free hydrocarbon
liquids. A separator must perform the following.
a. Cause a primary phase separation of the mostly liquid hydrocarbons from those that are
mostly gas.
b. Refine the separation process by removing most of the entrained liquids from the gas.
c. Further refine the separation by removing the dissolved gases from the liquids.
d. Discharge gas and liquids into clean production streams.
4.2.1 Types of Separators
The terms “flash drum”, “Free water knockout (FWKO)”, “accumulator”, “scrubber”, “traps”,
“slug catcher” and “inlet separator” are all terms for separators used for specific applications.
The selection of the type of separator is dependent on several factors including:
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- Gas to oil ratio

- Emulsion tendency of the HC gas, HC liquid and water
- Possibility of large liquid “slugs”
- Available room, both equipment footprint and height restrictions.
4.2.2. Vertical Separators
- common type of separator in the oil industry.

- used when there is either a very high GOR (scrubbers) or a very low GOR.
- the inlet stream enters near the midpoint of the vessel.
- can provide either two phase separation or three phase separation.
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4.2.3. Horizontal Separators

- most common application is in streams with relatively high gas/oil ratios.
- gas/liquid interface area is large which results in a quicker gas breakout
- the double barrel type consists of an upper separation section and a lower liquid
retention and level control chamber.
- Tend to require a large “footprint” so space can be a limitation (offshore for example.)
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4.2.4. Spherical Separators

- Commonly used for separation of small amounts of liquid from large volumes of gas.
- The advantage of a spherical separator is that it is more compact for a given gas flow than
other separators.
- Almost never specified any longer because of difficulties ($$$) in fabrication with no
significant advantage other than size efficiency and pressure containment.
4.2.5. Slug Catchers (or Inlet Separators)

- horizontal separators located at the inlet of a gas processing facility.
- removes entrained liquid either not removed at the well site or formed by dropping
temperature in the gathering system.
- protects the operation of downstream equipment from liquid slugs originating in the
pipeline system resulting from changes in pipeline flow rate.
- isolates the plant from transient conditions in the field.
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4.2.6. Sections of a Separator
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4.3. Gas Dehydration
4.3.1. Hydrates and Hydrate Composition
A hydrate is a physical combination of liquid water and other smaller molecules to

produce a solid which has an ice-like or dirty wet-snow appearance but possesses a
different structure than ice.
They are 90% (by weight) water; the other 10% is composed of one or more of the
following compounds: methane, ethane, propane, iso-butane, n-butane, nitrogen, carbon
dioxide and hydrogen sulphide.
The simplified structure of the hydrate crystal is water molecules with the smaller
hydrocarbon molecules occupying spaces between the water. In a sense, the water
molecules trap the hydrocarbons in a crystal lattice.
Hydrates have specific gravities ranging from 0.96 to 0.98 and therefore float on water
and sink in liquid hydrocarbons.
Hydrates are found in most areas of a gas producing operation:

- Downhole,
- Gathering systems
- Processing systems
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Hydrates are a constant challenge in producing natural gas and must be considered in all
designs and production practices.
4.3.2. Hydrate Formation
Dangers and problems created by Hydrates
An obstruction caused by a hydrate formation can:

a) reduce or block flow
b) increase back pressure
c) increase differential pressure through a process
The pressure differential across a hydrate “plug” can cause it to break loose and
travel down the pipe at very high velocities. People have been killed by hydrate plugs
dislocating and smashing through process equipment.
Hydrates can form single or multiple plugs in lines.
The formation of hydrate plugs can cause pressure to be trapped between two plugs.
Once formed, hydrates cause a threat to personnel and equipment if not handled properly during
removal. Pressure on both sides of a plug must be reduced to keep it from dislocating and moving
to the low pressure side.
The conditions that affect hydrate formation are:

 Pressure
 Temperature
 Composition
 Gas must be at or below its water dew point or saturation condition
Note that when the natural gas is in the reservoir, it is assumed to be in contact with water at
equilibrium. The gas is saturated with water. Therefore, even if free water is not present,
changing the conditions (pressure or temperature) can cause free water to form. An example of
changing the conditions would be passing the gas through a choke.
Pressure and Temperature
Hydrates tend to form when the pressure is high and the temperature is low.
All compositions have different points at which hydrates will form. The most important point to
remember is that it does not have to be colder than 0oC in order to have the conditions
necessary for hydrate formation.
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When the formation of a hydrate causes a restriction in a flow line, the restriction causes a pressure
drop. The resulting expansion of gas causes a cooling of the gas (Joule-Thomson effect).
This scenario is referred to as auto-refrigeration and can cause the further growth of hydrates until
the flow is blocked completely.
Hydrates often form at chokes, orifices, thermowells, bends in pipe etc.
4.3.3. Composition
The composition of the gas has a large effect on the formation of hydrates.
e.g. A small amount of propane or iso-butane in methane will cause hydrates to form at warmer
temperatures than in pure methane alone.
The presence of H2S will also affect the formation of hydrates. When H2S is present in a gas
composition, it will result in the formation of hydrates at warmer temperatures at a given
pressure.
The presence of CO2 has a much smaller impact and often reduces the hydrate formation
temperature at fixed pressure for a hydrocarbon gas mixture.
4.3.4. Hydrate Inhibition
It is convenient to divide hydrate formation into two categories:

1) Hydrate formation due to a decrease in temperature with no sudden pressure drop, such as in
the flow string or surface line, and
2) Hydrate formation where a sudden expansion occurs, such as in flow provers, orifices, back-
pressure regulators or chokes.
A review of the conditions that tend to promote the formation of natural gas hydrates are:
1) Natural gas at or below its water dew point with liquid water present.
2) Temperatures below the “hydrate formation” temperature for the pressure and gas composition
considered.
3) High operating pressures that increase the “hydrate formation” temperature.
4) High velocity or agitation through piping or equipment.
5) Presence of a small “seed” crystal of hydrate.
6) Presence of H2S or CO2 is conducive to hydrate formation since these acid gases are more
soluble in water than hydrocarbons.
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Now, if you consider the first 2 points and the second 6, some of the techniques which could be used
to inhibit the formation of hydrates are:
 Raise the temperature so it doesn’t hit its hydrate formation temperature

 Lower the pressure so it doesn’t hit its hydrate formation temperature.
 Remove the water so it doesn’t hit its water dew point conditions.
These techniques are all used to some degree. Line heaters are used to keep the gas temperature
high. Keeping the pressure low is often not an option but restrictions which cause a sudden pressure
drop and subsequent drop in temperature are avoided. Dehydration units are used at the wellsite and
at plants to remove the water. Another technique used to lower the hydrate formation temperature is:
 Chemical injection to depress hydrate formation temperature.
Many chemicals depress the temperature at which hydrates and/or ice form. Ammonia and brine
were used in the past, but the current choice is either a glycol or methanol. Methanol is the common
field choice for our situations and glycol would tend to be used in a plant refrigeration system.
4.4. Dehydration - Overview
 removal of water associated with the production of natural gas.

 prevents hydrates and reduces corrosion.
 Prepares gas for further processing (e.g. cryogenic)
 Removal of free water to prevent accumulations and promote single-phase pipeline flow.
 Three major methods of gas dehydration are commonly used:
a) Absorption (wet)
i) triethylene glycol (TEG)
ii) diethylene glycol (DEG)
b) Adsorption (dry)
i) molecular sieves (commonly called zeolites)
ii) silica gel (essentially SiO2 in bead or powder form)
iii) activated alumina (in extrudate or pellet form)

TEG is by far the most common glycol used in dehy’s (probably 90 to 95%). DEG may be used in fields where
minimal gas is available for heating the glycol; DEG does not have to be heated to as high a temperature to
release the water.
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c) Low Temp Processes
i) Processes that intentionally form and melt hydrates (LTX)

ii) Processes that use hydrate inhibitors
iii) Processes that use mechanical refrigeration
4.4.1. Absorption
 dehydration by glycol absorption is one of the most common methods of dehydration used to
bring the water content of a gas stream to pipeline spec.
 a common dehy unit consists of a absorption tower (contactor) in which wet gas is contacted
with lean glycol and a stripper in which heat is used to remove water from the rich glycol.
 glycols are used for dehydration as water and glycol are mutually soluble in the liquid phase.
Water boils at a lower temp than glycol, so “rich” glycol is heated to a temperature above the
boiling point of water but below the boiling point of the glycol. This creates “lean” glycol.
 Commonly used in the field at a wellsite for hydrate and free water protection, or in a plant
handling greater volumes of gas for final pipeline spec drying.
 The advantages of a glycol unit over a solid desiccant unit are:
a. Lower installed costs
b. Lower pressure drop in the contacting tower
c. Continuous process rather than batch
d. Glycol make-up is simple vs. recharging dry beds
e. Glycol units require less make-up heat to regenerate
f. Glycol systems operate in the presence of contaminants that would foul a solid desiccant.
g. Glycol systems are adequate at water removal for most spec’s (except cryogenic
processing).
 The disadvantages of a glycol unit are:
a. Very low water dew-points cannot be achieved
b. Glycol is susceptible to contamination
c. Glycol is corrosive when contaminated or decomposed.
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4.4.2. Process Description
Gas Stream:
a. Gas enters inlet separator and liquids are removed.
b. Gas enters contacting tower and starts upward through a chimney tray.
c. The gas passes through the trays or packing, contacting glycol as it travels. The water in
the gas has an affinity for the glycol and attaches to it.
d. The gas exits the tower through a mist eliminator to the next process or to the flowline.
Glycol Stream:
a. Lean glycol in the accumulator is pumped to the top of the contactor tower.
b. The glycol picks up water from the gas as it travels down from tray to tray (or through the
packing).
c. The glycol exits as rich glycol, is warmed through the accumulator and is dumped into the
stripping column of the reboiler.
d. The rich glycol is heated in the reboiler by a natural gas flame in a burner tube. The
temperature causes the water to vaporize and exit the stripping tower (where it contacts
more incoming rich glycol).
e. The lean glycol spills over into the accumulator ready for its next pass through the
contacting tower.
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4.4.3. Dehydrator Components
Inlet Scrubber
- simple two phase separator used to remove water and liquid hydrocarbons from the wet gas
stream.
Glycol - Gas Contactor

- vessel in which wet gas is contacted with lean glycol.
- utilizes counter-current flow: gas upward and lean glycol downward.
- trays exist in the contactor (valve or bubble cap) to increase the contact time between the wet
gas and lean glycol.
- mist extractor is located at the top of the vessel to remove any glycol entrained in the gas.
- lean glycol is pre-cooled by a double pipe heat exchanger prior to entering the vessel (glycol can
absorb more water at cooler temps).
- Glycol should enter the dehy at about 10o hotter than the gas temperature. If it is too hot, it can
lead to foaming and inefficient dehydration, and if it is too cold, hydrocarbons can condense in
the glycol.
Filter and Pump

- rich glycol exits the bottom of the contactor and is filtered prior to entering a pump.
- filter removes solid components from glycol in order to protect the pump and decrease
operational problems with fouling of the dehy. unit.
- the hydraulic pump utilizes rich glycol from the contactor as the power fluid to pump lean
glycol from the surge tank to the contactor.
Stripping Still
- the warm rich glycol enters the stripping still after being preheated in a heating coil (tube
side) in the surge tank.
- The stripping still is usually filled with ceramic packing or structured packing to improve
the surface area contact of the water vapour with the rich glycol.
- allows any glycol vapors to be condensed to eliminate losses.
- water vapor exits the top of the stripping still.
- Fins on the stripping still condenser section cool the vapor to help drop out any glycol which
may be entrained or vaporized in the water vapor. A temperature just above the boiling point of
water is optimal for the condensing section.
Reboiler
- vessel in which rich glycol is heated to 175 – 200oC to vaporize water.
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- heat source is a natural gas flame in a fire tube.

- glycol is regenerated to 99% glycol.
- Glycol regeneration efficiency can be improved with a “Stahl column”
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- Dry stripping gas (usually fuel gas) is injected into a column between the reboiler and
accumulator
- The dry gas mixes with the lean glycol (99%) and strips out more water. Glycol concentrations
of 99.9% can be achieved.
- The gas enters the reboiler and exits with the water vapour.
- The cost to operate a Stahl column must be weighed against the benefits. The costs are fuel gas
(and hydrocarbon to the environment).
Heat Exchange/Surge Tank

- regenerated glycol leaves the reboiler through an overflow pipe and enters the shell side of
the Surge Tank.
- the lean glycol is cooled by the rich glycol on the tube side of the exchanger.
- the surge tank is a liquid accumulator for the glycol pump to ensure the pump receives a
uninterrupted supply of glycol.
- A sweet gas blanket is often maintained in the vapour space above the glycol in the accumulator.
A slight pressure is held which prevents oxygen from the atmosphere and water vapour from the
reboiler from entering.
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4.4.4. Exercise
Label the following components on this field dehy unit:
- Lean glycol tower

Contacting pump -- Lean glycol
Wet gas inletheat -- Leangas
Dry glycol
outletinlet to
exchanger contactor
- Rich glycol outlet - Glycol filter - Condensate separator
- Reboiler still - Reboiler - Fire tube
- Lean glycol accumulator - Stripping still - Fire tube stack (chimney)
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4.5. Adsorption
 Adsorption is the process of using solid desiccant to dry natural gas.

 Adsorber systems use at least two towers – one onstream and the other in regeneration.
 When an adsorber has accepted all the water that it can on its cycle, it is taken offstream and
hot gas is passed through it to remove the water.
4.5.1. Types of Solid Desiccants
Silica Gel
i) Essentially pure silicon dioxide SiO2
ii) Purchased in bead or powder form
iii) Outlet dewpoints of –60oC can be achieved
Alumina
i) Hydrated form of alumina oxide (AlO3)
ii) Purchased in extrudate or pellet form
iv) Less heat is required to regenerate alumina than for molecular sieve.
Molecular Sieves
i) Often termed “Mole Sieve” or “zeolites”
ii) Can be used to simultaneously sweeten and dry gas
iv) Often used upstream of ethane extraction plants because of the need for extreme cold
(cryogenic) conditions to remove the ethane.
v) Most expensive option for dehydration
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4.5.2. Desiccant Cycle
As the wet gas passes the desiccant, the water is picked up in the pore spaces of the solid.
During the adsorption cycle, the bed is operating in three zones:
The Saturation or Equilibrium Zone:

- the upper portion of the bed is saturated and in equilibrium with the wet gas. It is no longer
active.
The Middle or Mass Transfer Zone (MTZ)

- This portion of the bed is picking up water as the gas passes by.
- If the bed is operated too long, the MTZ moves to the bottom of the vessel and
“breakthrough” occurs.
The Bottom or Active Zone:

- This is the portion of the bed which is waiting to be used.
- The gas which is passing by this portion of the bed has already been dried in the upper
portion.
 regeneration will start just before the water content of the the outlet gas from a tower on
adsorption reaches an unacceptable level.
 under operating conditions the gas velocity through the adsorbing tower should be 0.1 - 0.25
m/s.
 in order to maximise the adsorbing ability of the desiccant, the gas temperature should be
kept within the 25oC - 40oC range.
4.5.3. Desiccant Bed Life

 Desiccant is expected to last 3-5 years, depending on the conditions of operation.
 New desiccant is more efficient at accepting water than older desiccant.
 This means it picks up more water and the reaction is faster with new desiccant.
 When designing systems, desiccant capacity should be calculated using 3-5 year old
product.
 For example, new mole sieve could accept 20 kg of water for every 100 kg of desiccant.
Design estimates should use a lower figure of 13 kg of water for every 100 kg of
desiccant.
 Gas that is not saturated (already dried in an absorber for instance) will prolong the life
of the desiccant bed. In plant applications where very low dewpoints are required, it is
common to dry the gas in a glycol tower before passing it through the adsorber.
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4.5.4. Regeneration
 Regens are done with dried, heated gas from the outlet stream of the adsorbing tower.
 Regen gas is heated to a specific temperature dependant on the type of desiccant used.
Temperatures of 150 to 325oC may be used for different types of desiccant.
 The vapours leaving the regeneration tower are cooled, condensed and then passed through a
separator.
 The gas from the separator is then recombined with the main gas stream and then passed
through a drying tower.
 Towers are cooled prior to being used in the drying stage.
 A rough guide to regen cycles is: Heating (55% of the cycle), Cooling (35% of the cycle),
and standby (10% of the cycle).
4.5.5. Adsorption Systems

 adsorption systems can consist of two or three tower systems.
 a three tower system would be used if additional regeneration and cooling time is required.
 in a two tower system a typical operational cycle is : ..
Adsorber Cycle – 8 hrs Regeneration Cycle – 8 hrs

- Heat with gas – 4 ½ hrs
- Cool to operation Temp – 3 hrs
- Switching & Standby – ½ hr
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 the entire cycle is controlled by automatic valves.
4.5.6. Potential Concerns

 desiccants can be poisoned by H2S which will reduce the affinity for H2O.
 gas streams with significant amounts of C5+ can cause problems in the regeneration stage as
some of the aromatic hydrocarbons decompose leaving carbon and tar on the desiccant.
4.5.7. Advantages
 changes in the inlet temperatures and pressures can better be accommodated with a solid
desiccant system than with a glycol unit.
 the capital cost of a solid desiccant system can be 3 times that of a comparable glycol unit,
and the operational costs are also usually higher.
 glycol units can not compete with the dewpoint and flexibility of a solid desiccant system.
BUT, solid desiccant systems are expensive $$$.
Adsorber Process Diagram
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4.5.8. Adsorber Components
Inlet Separator
- absolutely necessary to protect the desiccant from impurities such as water, liquids, compressor
oils, solids, etc.
- If liquids are entering the desiccant towers, desiccant can be broken or powdered, causing
plugging and pressure drop problems.
Adsorber Towers:
- Typically, the gas moves down through the bed during adsorption to permit higher gas velocities
without lifting the bed.
- the regen gas moves upward through the bed.
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Regeneration Gas Heater:

- providing hot gas for the regeneration of the desiccant.
- Hot gas vapourizes the water and hydrocarbons trapped and removes them to a separator.
Regen Condenser (or cooler):

- lowering the temperature of the regen gas leaving the regeneration tower. Water in the vapour
phase will start to drop out as liquid.
Regen Separator:
- separates the condensed liquids (water and liquid hydrocarbons) from the regen gas stream.
- The gas outlet from the separator is now wet and is returned to the main gas flow.
4.6. Low Temperature Processes
 uses cooling to reduce the saturation level of the gas for water below the allowed water content
for the requirements of the sales or process gas.
 when wellhead pressure is high enough (exceeding pipeline pressure), low temperature
separation is very efficient.
 Gas is passed through a choke or constant enthalpy Joule-Thomson expansion to provide
cooling.
The low temp separator can be horizontal or vertical.
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- Especially in vertical units, the temperature difference between the hot section and the cold
section can be very significant. The top portion can be frosted up and the bottom quite warm.
This leads to the term HBU or Hot Bottom Unit.
4.6.1. Low Temp Separator without Hydrate Formation

Hydrate inhibitors such as glycol or methanol are injected into the gas stream previous to
cooling through expansion.
Alternatively, the temperature drop is controlled to remain above the hydration temperature.
4.6.2. Refrigeration-aided Low Temp Separation

A refrigerant (almost always propane) is used to cool the gas to remove the liquids in a
downstream separator.
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 Follow the 4 streams through the process:

i) Gas stream
ii) Glycol stream
iii) Condensed hydrocarbon stream
iv) Propane refrigerant stream
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Chapter 5
Gas Plant Processes

After a natural gas has been conditioned in the field by removal of the majority of the heavy liquids
(separation) and water (dehydration), it if further processed at a natural gas plant. Most gas plants
have processes as described in the following block diagram:
Typical Gas Plant
5.1 Inlet Separation
The separation at the inlet of the plant is very similar to field separation. Usually a large
horizontal separator can be found at the plant inlet to catch liquid slugs that could disrupt the
rest of the plant. See section 4.3.5 for a description of the typical inlet separation facilities.
5.2 Stabilization
The stabilization of the liquids from the inlet separation plant are intended to remove the low
boiling point, volatile components from the hydrocarbon liquid so that it can be stored at
atmospheric pressure. The “condensate” if mainly pentanes and heavier hydrocarbons and is
often called C5+. Some C3 and C4 remain in the condensate but the distillation process
removes most of the C4 and lighter hydrocarbons to the gas side of the plant. A condensated
stabilization tower is shown on the next page. More information on the distillation process
will occur later in the training program.
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Condensate Stabilizer Distillation Tower
5.3 Gas Sweetening
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Sour Gas contains either components H2S or CO2. H2S is by far the most dangerous but CO2 can
cause problems with solids formation in compression and cooling. Both these components are acid
gases and are removed by similar “sweetening” processes.
5.3.1 Introduction
Quality requirements for gas entering LNG plants include:
i) Shall not contain more than 23 mg of H2S per m3. (16 ppmv)
ii) Shall not contain more than 115 mg of total Sulphur per m3
iii) Shall not contain more than 2% by volume of CO2.
- sweetening processes remove sour and undesirable gases from the gas stream:
H2S - Hydrogen Sulphide

CO2 - Carbon Dioxide
COS - Carbonyl Sulphide
CS2 - Carbon Disulphide
5.3.2 Reasons for Sweetening

 Safety and Environmental Protection
 Product Specification (see above)
 Corrosion Prevention
 Improved Heating Values
 CO2 Solid formation (cryogenic operations)
 Economics (sometimes)
- sour gas is supplied to the sweetening system from the inlet separator and the condensate
stabilizer.
- sour products recovered in this process are further processed in a sulphur recovery unit (SRU)
- if the volume is low enough (less than 1 tonne of sulphur per day in the inlet gas), the gases are
incinerated and released to atmosphere as CO2 and SO2.
- various types of sweetening processes are employed in industry today. All processes utilize a
solid or liquid desiccant to recover the sour component. After the desiccant has recovered the
sour component it must be regenerated to release the sour components so it can be reused.
- The most common liquid desiccants in use are “amines”.
5.3.3 Process Flow

Amine systems tend to be located in a central plant to service the entire sour gas production for
a field.
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A typical amine sweetening process is shown in the following diagram.
Inlet Separator
 Removal of liquids and/or solids
 Separator should be sized to handle surge capacity. Poor separator design can cause problems
in the treating facilities.
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Contactor
 Sour gas enters the bottom of the tower and moves upward through the trays
 H2S and CO2 in the gas react with the liquid amine solution and are removed from the gas
stream.
 The reaction is often assisted by placing fresh lean amine on various trays down the tower.
This ensures that the gas will contact lean amine a few times as it moves up the tower.(This
is not shown on the diagram).
 As the sweet gas leaves the tower, it is often contacted with water to remove any amine that
has vapourized and is travelling with the gas. The top 2 or 3 trays may be used for this
function. This is considered a “water wash” section of the tower.
 The water wash is often used if the contactor temperature is especially high or if MEA is
used as the amine.
Outlet Separator
 The sweetened gas is passed through a separator to remove any amine solution (or liquid
water) that may be travelling with the gas flow
 The gas is now saturated with water and must proceed through dehydration facilities to lower
the water dew point before sale.
Rich Amine
The amine picks up H2S and CO2 in the contactor tower.
Flash Drum
 From the contactor, the amine may enter a flash drum to allow any hydrocarbon an
opportunity to leave the amine solution.
Heat Exchanger (HTEX)

 The rich amine passes through a heat exchanger where it picks up heat from the hotter lean
amine on its way to the contactor.
 Since this service is clean, plate and frame exchangers can be used, but often a more
common shell and tube exchanger is put in service.
Stripper
 The rich amine enters the stripper, where hot acid gas and steam heat the rich amine,
removing the H2S and CO2 that is bound into the product.
Reboiler
 The amine at the bottom of the stripper tower is heated to 105oC – 140oC (depending on the
type of amine being used).
 This causes the acid gas/amine reaction to reverse and the acid gas vapourizes with steam
from the amine solution.
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 The acid gas/steam vapour re-enters the stripper and contacts new rich amine on its way out
the top. Amine carried with the acid gas/steam vapour tends to reunite with the rich liquid
amine thereby removing it from the vapour flow.
Condenser
 After leaving the top of the stripper tower, the acid gas/steam vapour is cooled to remove
heat and condense out the water from the flow.
 The water is separated in a reflux drum and returned to the stripper tower as a liquid.
 The acid gas vapour is sent downstream to a Sulphur Recovery Unit (SRU).
 If the plant has a gas sulphur inlet rate of less than 1 tonne/day (this is a very small amount),
the acid gas may be incinerated. Burning the H2S creates SO2 which is a monitored pollutant.
Reclaimer
 a reclaimer may be used in MEA or DGA service.
 A reclaimer heats a slipstream of the amine from the reboiler to higher temperatures. In MEA
service, a caustic solution is added to increase the pH of the mixture.
 This higher temperature (and higher pH) cleans out some products of “side reactions” and an
amine sludge is created. This must be disposed of properly.
Lean Amine
 A lean amine stream from the bottom of the reboiler (or bottom of the tower) is pumped back
to the contactor.
 The lean amine is often passed through a charcoal filtration system to remove entrained
solids
 If anti-foam additives are added to the system, the charcoal filters will remove them, so they
should be taken off-line during addition.
 The lean amine must be cooled to approximately 6oC warmer than the inlet gas temperature
before it enters the contactor.
5.4 Sulphur Recovery
5.4.1 Acid Gas Options
 The acid gas stream from the sweetening unit contains mainly H2S and CO2. The proportion
of each will depend on the inlet gas composition and the type of amine that you are using.
 The H2S in the acid gas is very toxic (and smelly) so it could not possibly be released to the
atmosphere without some further processing.
The options facing an operator are:

1. Re-inject the acid gas into a formation.
2. Burn the acid gas, converting the H2S into SO2. Release the SO2 to the atmosphere.
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3. Convert the H2S into elemental sulphur (S). Sell the sulphur into the world market.
The most common method of converting H2S into S is the Claus process.
5.4.2 Modified Claus Process
 If H2S is reacted with oxygen (burned), it will form SO2 and water. This is a very
exothermic reaction – it creates a lot of heat. Even though SO2 is not as deadly as H2S, it
is still a pollutant that can have adverse health effects in high concentrations. Therefore
creating SO2 is undesirable.
 The “Modified Clause Process” was developed in 1937 and involves a Combustion
Reaction & Catalytic Reaction (in stages)
 The combustion reaction occurs in a reaction furnace where acid gas from the sweetening
system is reacted with oxygen to form H2O and SO2,
But….
 Only 1/3 of the H2S is converted. This means that only enough oxygen (air) is fed into
the reaction to convert 1/3 of the H2S stream to SO2.
 This gas is then cooled and any pure sulphur that has formed is condensed out.
 The gas mixture is then reheated and fed into a vessel with a catalyst bed of activated
alumina. The remaining H2S and SO2 react with each other to form elemental sulphur (S)
and H2O.
 2H2S + SO2  2H2O + 3S
 This creates more heat as the reaction occurs. Therefore, as the gas mixture leaves the
first catalytic reactor, it is cooled and sulphur condenses out and drains to a holding tank
(usually heated with steam coils and located underground).
 The remaining gas is again reheated and enters a second reactor where the same reaction
takes place.
 Depending on the amount of conversion required, 3 or 4 reactor vessels may be
employed. (Four reactors is uncommon)
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 Acid gas is made up of H2S + CO2 and often contains small amounts of hydrocarbons
also. The efficiency of the Modified Claus Process depends on the concentration of the
H2S in the acid gas (because of partial pressures).
 If the concentration of acid gas is high – say > 80% by weight, then you could expect the
following conversion efficiencies as the acid gas works its way through the process:
Initial reaction furnace  62% of the H2S converted to S

1st catalytic bed  86% of the H2S converted to S
2nd catalytic bed  93% of the H2S converted to S
3rd catalytic bed  97% of the H2S converted to S
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4th catalytic bed  98% of the H2S converted to S
 Lower conversion percentages can be expected with lower concentrations of H2S because
of lower partial pressures – reactions are slower.
 You can see that sulphur is created in the reaction furnace. This is because the H2S and
SO2 start to react on their own without help from any catalyst.
The H2S product is then processed in a Claus Plant.
reaction (1) 2 H2S + 3 O2  2SO2 + 2 H2O
reaction (2) SO2 + 2 H2S Alumina > 3S (stockpile) + 2 H2O

catalyst
• Tail gas is gas that exits the Claus plant with residual SO2. It may be cleaned up according
to environmental restrictions.
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EXERCISE:
1. What does acid gas consist of?
2. Why would a low concentration of H2S in the acid gas cause the plant to have lower
efficiencies per reactor?
3. How many Claus reactors would be required for a plant with a 25 tonne per day of
sulphur inlet rate?
4. How many for a 50 tonne per day inlet rate?
5. How do you know when a reactor needs regeneration? What happens to the catalyst to
cause it to become less active?
5.5 LPG Recovery
In a gas plant, the liquefied petroleum gas components C3 and C4 are usually removed before
the dry “sales gas” leaves the plant. This “sales gas” is typically the feed to an LNG plant and
is mainly C1 and C2 that is to be liquefied. There are two main methods of removing the LPG
fraction from a gas stream – 1. refrigeration process and 2. lean oil adsorption. Only the
refrigeration process will be discussed.
5.5.1 Refrigeration Process
Refrigerant (usually propane) is placed into a heat exchanger, a “chiller” in this case, where it is
allowed to boil. The heat required to boil (latent heat of vaporization) the propane is extracted
from the natural gas which is flowing through pipes that are in contact with the propane. This
drops the temperature of the natural gas causing liquid hydrocarbons and liquid water to form
and drop out.
Propane is chosen as the refrigerant as it:

- Is relatively inexpensive
- Is readily available
- Has good thermodynamic properties
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A typical refrigeration with EG injection process flow looks like this:
5.5.2 The Propane Refrigeration Cycle
If we now look specifically at the propane cycle, knowing how much duty is expected of it from
the previous calculations:
hot vapour
Condenser
Col d Vapour Compressor

cool l iq
col d, Chiller
boil ing l iq
Accumulator
col d l iq +vap
Expansion Valve
cool l iquid
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The refrigeration cycle can be broken down into four distinct steps:
1. Expansion
2. Evaporation
3. Compression
4. Condensation
Remember that in the refrigeration cycle, we are focusing on the propane or refrigerant in the
system.
We use “Pressure – Enthalpy” (P-H) diagrams to calculate the changes. (Fig 24-27 in the EDB
for Propane.) This is discussed in detail in the thermodynamics course
5.5.3 Refrigeration Circuit Equipment

5.5.3.1 Compressor and Driver
- reciprocating compressors are used for systems requiring less than 500 - 800
KW.
- the screw compressor is suitable in the 200 KW to 1500 KW range. Typically,
most systems of any substantial size will use a modern screw type compressor.
5.5.3.2 Condenser
- both water-cooled and air-coooled condensers can be used.
- water cooling is favored (if feasible) as a substantially lower propane condensing
temperature can be obtained, reducing power costs.
- Condensers should be designed so that pressure drop is not more than about 35 kPa.
- Propane is put on the shell side in the water cooled exchangers.
5.5.3.3 Surge Drum/Accumulator
- The surge drum is typically designed to hold 10 minutes of propane circulation
when operating half full.
5.5.3.4 Expansion Valve
- A standard control valve is used, normally operating on chiller shell level control.
5.5.3.5 Chiller
- is similar to kettle reboiler with the boiling propane on the shell side.
- disengaging space is provided (with mist extractors) above the tube bundle to
prevent liquid entrainment.
5.5.3.6 Suction Scrubber
- This vessel usually contains an entrainment separator and has a level control to
dump any liquid.
5.5.3.7 Reclaimer (De-oiler or Heavy ends Blow case)
- an optional vessel which should be considered when screw compressors are used
(i.e. oily service).
- placed alongside the chiller and connected to the chiller shellside at both top and
bottom with an isolation valve in the liquid (bottom) connection.
- a heating coil is included in the Reclaimer vessel.
- when de-oiling is required the liquid isolation valve is closed and the refrigerant and
oil mix is boiled down using the coil until a vessel sample shows that only oil is left.
- the low point of the reclaimer should be lower than the bottom of the chiller vessel.
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-
5.5.3.8 Insulation
- All lines and vessels between the throttling valve and the compressor suction should
be insulated.
5.5.3.9 Materials of Construction
- As soon as temperatures are expected to reach minus 29oC and lower, a different
ANSI code is used for the pipe specs. This special code ensures that the piping and
equipment is able to withstand the temperatures and pressures expected.
5.6 Ethane Stripping and LNG Processing
Ethane stripping is often carried out cryogenically in "straddle plants" that sit on gas trunk
lines. C2H6 is then sent to ethane crackers to provide ethylene for the petrochemical
industry.
LNG processing liquefies both the C1 and C2 components of natural gas using several types
of processes, the most common being turbo-expansion as shown below.
A typical ethane extraction plant is shown below – this process will be covered in a
subsequent course in the training program.
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Chapter 6
Composition of Crude Oil
Crude oil consists primarily of a large variety of hydrocarbons and of some heterocompounds,
i.e. compounds containing sulfur, nitrogen and oxygen. Compounds containing metals,
primarily nickel (Ni) and vanadium (V) may also be present.
In addition, the produced crude oil may contain water, dissolved gases, salt and sand. These
have to be removed before the actual petroleum is subjected to refinery processes.
Because of the geological age of petroleum, the most reactive compounds that might have been
present at some time, have already reacted away. In the hydrocarbon series, the more stable
compounds are alkanes (paraffins) including cycloalkanes, and the aromatics. Therefore, the
major building blocks of molecules found in petroleum are based on alkane, cycloalkane and
aromatic (especially polyaromatic) structures. Typically, a given molecule might contain
structural elements from each of these compound types. As mentioned above, sulfur, nitrogen
and oxygen may also be present in these compounds.
The more reactive hydrocarbons, i.e. alkenes (carbon-carbon double bonds) and alkynes
(carbon-carbon triple bonds) are not present in crude oil compounds. However, they might be
formed as the crude is being subjected to chemical reactions during refinery processes.
6.1 Elemental Composition:
Carbon and hydrogen content:

Crude oil being composed mostly of hydrocarbons, the carbon content and the hydrogen
content of crude oil are of interest. Typical values are
Wt%
Carbon 83.5 – 86
Hydrogen 11 – 14
Often, the atomic H/C ratio is used describe a stream. This approach is being used for crude
oil streams and for product streams.
For example:
Formula Name Atomic H/C ratio

C10H22 decane 22 / 10 = 2.2
C10H8 naphthalene 8 / 10 = 0.8
CH4 methane 4/1= 4
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The following figure illustrates the range of atomic H/C ratios for feed stocks (streams entering
a refinery) and products (streams leaving a refinery).
Premium
Products
Coke Heavy Distillates
Crude
oil
0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
Example:
The atomic H/C ratio can also be calculated from the elemental analysis. A sample
contains 84.3 wt% carbon and 12.3 wt% hydrogen. Note that the sum of the two
elements does not equal 100 wt%. This is often the case because of the presence of
other elements, i.e. sulfur, nitrogen and oxygen.
To calculate the atomic H/C ratio, we divide the wt% value for carbon and hydrogen by
their respective molar masses, and then calculate the ratio.
For carbon: 84.3 / 12.01 = 7.02

For hydrogen: 12.3 / 1.01 = 12.2
The atomic H/C ratio is 12.2 / 7.02 = 1.74

This means that, on average, there are 1.74 hydrogen atoms per carbon atom.
Exercise:
The elemental analysis of petroleum stream is:
Wt%
Carbon
82.7
Hydrogen 13.5
Calculate the atomic H/C ratio for this stream and identify the stream type, based on above H/C
ratio data.
Sulfur content:
The sulfur content of crude oil can range from less than 0.5 wt% to more than 5 wt%. Sulfur
compounds often contain a thiophene, thioether and mercaptan structural element.
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Sulfur is removed to product specification levels during the refining process.
Exercise:
Write the chemical structure for a thiophene, thioether and a mercaptan (thiol). (Consult the
section on organic chemistry. Thioethers are the sulfur analogues of ethers).
Nitrogen content:
The nitrogen content of crude is typically low falls in the range of 0.1 – 1 wt%. In general, the
heavier the oil, the higher its nitrogen content.
Nitrogen is mostly present in ring structures, i.e. pyridine, quinoline and pyrrole structures.
Nitrogen is removed to product specification levels during the refining process.
Oxygen content:
The oxygen content of crude oil is generally low. Considerable discrepancy exists in the
reported numbers due to the difficulty in determining the oxygen content. Usually, the
reported oxygen values represent the difference to mass balance closure after C, H, N,
and S have been measured. In this approach, the value reported for oxygen contains the
combined errors for these measurements.
A direct oxygen determination is also possible, but is a complex procedure.
Oxygen is mostly present as part of a phenol structure.
Oxygen is removed to product specification levels during the refining process.
Metal content (mostly Ni and V)

Metal content is typically in the ppm (parts per million) range, as opposed to the percent range
used for C, H, N, and S.
Typical ranges are:
ppm
Ni 2.5 - 140
V 3 - 1500
These metals are removed during the refining process.
Salt content
Salt (mostly NaCl) is often associated with crude oil. Although salt is not soluble in
hydrocarbons, it can be present as very small solid particles, or it can be dissolved in the
water that is often present in the oil.
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Salt will cause corrosion (particularly chloride ion stress corrosion) in process equipment,
and has to be removed prior to the actual refining operations.
A typical cut-off value is 10 lb salt per 1000 barrels oil. Crude oils with a higher salt content
are subjected to a desalting process. A lower salt content than 10 lb salt per 1000 barrels oil is
desirable.
Exercise:
Express the typical cut-off value for salt content in metric units (i.e. kg / m3). The following
conversion factors are available: (assume a density of 1000 kg/m3).
Conversion factors
1 barrel (bbl) 42.2 US
gallons
158.8 liters
1 m3 1000 liters
1 pound (lb) 0.454 kg
6.2 Crude oil classification
Crude oils can be classified according to a variety of criteria. These might include chemical or
physical properties of the crude.
It is important to note that more than one criterion can be applied to the same oil. The particular
criterion being used depends on the specific processing properties that is being considered. For
example: crude oils with a high sulfur content are described as “sour crude oil”. The sulfur
content of the crude oil is important when the sulfur removal, i.e. the plant capacity for sulfur
removal, is being considered.
Another type of crude oil classification is according to the hydrocarbon type. Mixing of various
types crude oils of a different type can lead to incompatibility issues. For example,
precipitation of solid compounds can occur in such a situation. Obviously, this is a
consideration when crude oils of different types arrive at the same refinery, such as for example
by tanker.
Alternatively, crude oils might be simply described according to their country or reservoir (oil
field) of origin.
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6.2.1 Chemical properties used for classifying crude:
The hydrocarbon type is often used to describe a crude oil. A common thought is that the
hydrocarbon type used in the name of the oil is the main component of an oil of this type. It is
important to realize that, in each type, hydrocarbons other types are also present. Also, there
will be compounds containing sulfur, nitrogen, metals, etc.
i) Hydrocarbon type:
According to the hydrocarbon type, one can distinguish between:
 Paraffinic crudes
o Typically more than 5 % of the residuum consists of paraffins
 Naphthenic crudes
o Less than 2 % paraffins in residue
 Mixed crudes
o Paraffin content in residue: 2 – 5 %
ii) Sulfur content:
Sulfur is present in a chemically bonded form, i.e. not as elemental sulfur. Sulfur can also
be present as part of H2S dissolved in the crude oil. The classification is made on the basis
of sulfur that is incorporated in the sulfur containing organic compounds (mercaptans,
thiophenes, etc.) that are in the crude oil.
 Sour crude
o Sulfur content > 0.5 wt%
 Sweet crude
o Sulfur content < 0.5 wt%
6.2.2 Physical properties used for classifying crude
i) Density
Density has long been used to describe crude oil. Different scales can be used to describe
the density, namely the metric scale (in g/cm3 or in kg/m3) or the API (American
Petroleum Institute) scale. The density is a function of temperature: the standard
temperature is 15.6 oC or 60 oF).
o
API = (141.5 / sp. gr. 60/60) – 131.5
The specific gravity (sp. gr.) represents the value of the density of the oil in question
divided by the density of water. This value being a ratio, is dimensionless.
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Specific gravity (sp. gr.) = density of sample / density of water
In the API formula, sp. gr. 60/60 represents the specific gravity of the oil in question,
measured at 60 oF, relative to the density of water also measured at 60 oF.
Typical ranges are:
 Light crude oil

o > 20 oAPI ( < 934 kg /m3)
 Heavy crude oil

o 10 – 20 oAPI (934 – 1000 kg /m3)
 Extra-heavy crude oil (often residuum, i.e. fraction from which the lighter
components were removed)
o < 10 oAPI (> 1000 kg /m3)
Reference:
Crude oils with a specific gravity higher than water have an API gravity < 10 oAPI.
Crude oils with a specific gravity less than water have an API gravity > 10 oAPI.
Exercise:
A crude oil sample has an API of 34.0 oAPI (60/60). Calculate the specific gravity of
this sample. Is this a light crude or a heavy crude?
Phase 1

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INTRODUCTION TO ORGANIC CHEMISTRY

1.1 Organic Chemistry

The modern definition of organic chemistry is “the study of carbon containing

Inorganic Compounds Organic Compounds

1.2 Number of Organic Compounds

a) Bonding of Carbon to Carbon

Example: Pentadecane (C15H32) Structural Formula

b) Bonding of Carbon to Other Elements

Example: Bromochlorofluoromethanol (CHBrClFO)

Examples: Ethene (C2 H4) Ethyne (C2 H2)Propanone (C3 H6O)

Example: Ethanol (C2 H6O) Dimethylether (C2 H6O)

Example: trans-2-butene (C4 H8) cis-2-butene (C4 H8)

1.3 Elemental Analysis of Organic Compounds

Example: The compound C2H5NOS would be analyzed to contain:

Carbon 26.359% Hydrogen 5.530%

CN4O 84.0073 C2N2O283.9960

1.4 Carbon Bonding

a) Number of Bonds to Carbon

Examples: Methane (CH4) Methanol (CH3OH)

Examples: Methanal (CH2O) Methanoic Acid (CH2O2)

Common Names (Formaldehyde) (Formic Acid)

Examples: Ethyne (C2H2) Ethanenitrile (C2H3N)

Examples: Allene (C3H4) Methylisocyanate (C2H3NO)

b) Types of Bonds to Carbon

Example: A “double bond” between two carbon atoms.

c) Structural Formulas of Organic Compounds

If chlorine is attached to the same carbon as the oxygen it is a different isomer

Step v) Molecular formula C2H4. Molecular formula C2H4O.

1.5 Saturated and Unsaturated Compounds

1.6 Functional Groups in Organic Compounds

A “functional group” is an atom or group of atoms in a molecule that determines the

Functional Structure Description Example

Functional Structure Description Example

An oxygen atom with Methanal (Common name:

Two oxygen atoms Methyl Methanoate (Common

Example: Monoethanolamine (C2H7NO) contains two functional groups.

Example: 4-aminobenzoic acid (C7H7NO2) contains three functional groups.

1.7 Forces Affecting Physical Properties of Organic Compounds

A “physical property” is any characteristic of a compound that can be measured

a) London Dispersion Forces

1. Which of the following is not an organic compound ?

3. What is the percentage of carbon by mass in the compound C10H20?

6. Draw four possible structural isomers for the compound C4H9Cl.

7. Which of the following compounds is “unsaturated”?

Structure, Nomenclature and Classification of Hydrocarbons

The student will be able to:

2.1 Alkanes and Cycloalkanes

The terms “cycloalkane”, “naphthene” and “cycloparaffin” all refer to compounds

Regardless of the amount of branching all “cycloalkanes” or “naphthenes” have the

Example: C6H12 is the molecular formula for cyclohexane and methylcyclopentane

c) Geometry of Alkanes and Cycloalkanes

The three dimensional structure of organic compounds is related to the number of

Example: Methane (CH4) has 4 hydrogen atoms attached to the carbon.

2.2 Drawing Structural Formulas for Alkanes and Cycloalkanes

a) Expanded Structural Formulas

Examples: Pentane (C5H12) Monoethanolamine (C2H7NO)

b) Condensed Structural Formulas

Examples: heptanol (C7H16O) cyclohexene (C6H10)

Examples: Butane(C4H10) Propanone(C3H6O) Monoethanolamine(C2H7NO)

d) Combinations of Formats for Drawing Structural Formulas

Examples: Methylcyclopentane(C6 H12) 2,4-Dimethyloctane (C10 H22)