International Oil & Gas Exploration Contracts

Chapter 1 Basics of Process Engineering

Chapter 1
Basics of Process
engineering

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Chapter 1 Contents
1.1 Basic Terminology
1.1.1 Elements and Atoms
1.1.2 Chemical Compounds and Molecules
1.1.3 Physical Compounds
1.1.4 Relative Atomic Mass (Weight)
1.1.5 Relative Molecular Mass (Weight)
1.1.6 The Mole
1.1.7 Valence
1.1.8 Mixture

1.2 Basic Hydrocarbon Nomenclature

1.2.1 Paraffin Series
1.2.2 Olefin or Ethylene Series
1.2.3 Acetylene or Alkyne Series
1.2.4 Diolefins Series
1.2.5 Aromatic (Benzene) Series
1.2.6 Naphthene Series

1.3 Paraffin Hydrocarbon Compounds

1.3.1 Radicals
1.3.2 Alcohols
1.3.3 Mercaptans
1.3.4 Other Carbon-Sulfur Compounds
1.3.5 Organic Nitrogen Compounds Amines
1.3.6 Glycols

1.4 Acids, Bases and Salts

1.5 Analysis of Mixtures

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Chapter 1 Basics of Process Engineering

Chapter 1

Basic of Process Engineering

1.1 BASIC TERMINOLOGY
Throughout this course we will be using some basic chemistry and physics
terminology. This is reviewed briefly.

1.1.1 Elements and Atoms

All matter in the universe is composed of elements which cannot be broken down or
subdivided into smaller entities by ordinary means. Over 100 materials have been
found (or created) which are classed as elements. These include carbon, hydrogen,
sulfur, oxygen, nitrogen and helium - all materials occurring in petroleum systems.
The atom is the basic unit of each element that can combine with it or the atoms of
other elements to form a compound.

1.1.2 Chemical Compounds and Molecules

A true compound is a substance composed of more than one atom that satisfies both
of the following conditions.
1. The atoms have combined chemically.
2. The compound formed possesses properties different from the atoms of
which it is composed.
Chemical compounds are formed by the union of atoms in the simplest possible
numerical proportions. The molecule is the unit of a compound. A molecule of water
is H2O, two atoms of hydrogen combined with one atom of oxygen.
A diatomic molecule is formed by the combination of two atoms of the same
element. Nitrogen (N2) and oxygen (O2) are the most common examples.

1.1.3 Physical Compounds

A type of physical compound, called a clathrate, may be formed. A gas hydrate is
one example of a clathrate. These compounds are relatively unstable.

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1.1.4 Relative Atomic Mass (Weight)

In forming a compound, elements always combine according to fixed mass ratios. It
is convenient to use relative atomic weight, the relative mass of the atoms of
different elements, to express these ratios. The word "relative" means that the
number used is a relative one. Currently, Carbon-12 is used as the standard, being
assigned the relative atomic weight of 12. On this basis, the relative atomic weights
of common oil and gas components are shown below (to the nearest whole number).
Atom
Hydrogen
Carbon
Nitrogen
Oxygen
Sulfur

Symbol
H
C
N
O
S

Relative Atomic
Weight
1
12
14
16
32

A relative atomic weight of one element contains about the same number of atoms as
a relative atomic weight of any other element. One gram of hydrogen and 12 grams
of carbon each contain about 6 x 1023 atoms. Since relative weights represent a fixed
number of atoms, they may be substituted for atoms in calculations.

1.1.5 Relative Molecular Mass (Weight)

The relative molecular weight of a molecule is the sum of the relative atomic weights
of the atoms combining to produce the molecule. Water has a relative molecular
weight of 18 (H2O =2+16=18). A diatomic molecule like oxygen (O2) has a
molecular weight of 32.

1.1.6 The Mol

The term "mol" is the historical abbreviation of the words "gram molecule." The
current definition of the mol is: "The mol is the amount of substance of a system
which contains as many elementary entities as there are atoms in 0.012 kilogram
of Carbon-12.". These elementary entities must be specified but include atoms,
molecules, ions, electrons, etc.
The quantity 0.012 kg is 12 g, the relative atomic weight of carbon. Thus, the mol
can be defined for engineering usage as that mass in grams equal numerically to the
sum of the relative atomic weights of the atoms in the molecule of that substance.

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By virtue of the definition, whenever the mol is used as a mass quantity without a
prefix, a mass in grams is implied. If a relative molecular or atomic weight is
expressed in pounds mass or kilogram, we will use the terms lb-mol and kmol,
respectively, to denote this is not a standard mol. A kilomol (kmol) is simply 1000
mol.
1 kmol = 1000 mol = 2.205 lb-mol
1 lb-mol = 454 mol
Throughout this course the mol will be used in many cases as a mass term in those
processes where no chemical changes occur. It is particularly useful for gas
calculations. At a given pressure and temperature equal volumes of different gas
contain the same number of molecules. At 0C [32F] and 101.325 kPa [14.7 psia] a
mol of any gas contains about 6x10 molecules and occupies a volume of 22.4 liters.
The mol is thus a useful conversion factor from volume to mass, for the number of
mols per unit volume is independent of gas composition.

1.1.7 Valence
Valence is a measure of the ability of atoms to form molecules by filling the electron
shells of the atoms involved. The valence number is plus or minus, denoting the
number of excess or shortage of electrons needed to fill its outer shell.
The question of atomic bonding is a complex subject involving many factors, as
discussed in standard chemistry references. The concept is mentioned only to point
out that the number of bonds or linkages used in the structural formulas that follow
in the next section reflect the valence of the atoms in these compounds.

1.1.8 Mixture
A mixture is a combination of elements and compounds which may be separated by
physical means. The properties of the mixture are a reflection of the properties of the
constituents.
Natural gas and crude oil are mixtures. They are analyzed by separating the mixture
into its component parts and identifying each by its properties.

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1.2 BASIC HYDROCARBON NOMENCLATURE

By definition, a hydrocarbon is any compound composed solely of carbon and
hydrogen atoms. These atoms can combine in a number of ways to satisfy valence
requirements. For convenience, these are separated into "families" or homologous
series, each of which is given a name.
The carbon atoms can link together to form "chains" or "rings." Crude oil and natural
gas mixtures consist primarily of "straight chain" hydrocarbon molecules, the bulk of
which are paraffins.

1.2.1 Paraffin Series Formula: CnH2n + 2

Hydrocarbons in this series are saturated compounds - all four carbon bonds are
connected either to another carbon atom or a hydrogen atom, with one such atom for
each bond.

Notice that, all names end in -ane, the ending used for the paraffin series. In
each case, the number of hydrogen atoms is two times the number of carbon atoms
plus two more for the ends of the chain.
The paraffin hydrocarbons are the most stable of the lot because all valence bonds
are fully satisfied as indicated by the single line linkage. Most reactions involve the
replacement of hydrogen atoms with other atoms; the carbon linkage remains stable.
Each successive molecule in the paraffin series is created by adding a carbon and two
hydrogens to the previous molecule. The incremental change in relative molecular
weight is thus fourteen. Long chains containing scores of carbon atoms in series may
be formed. However, the only ones normally identified by name contain ten or less
carbons.

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Name
Methane
Ethane
Propane
Butane
Pentane

Form
ula
CH

Mol.
Wt.
16

C2H6
C3H8
C4H10
C5H12

30
44
58
72

Chapter 1 Basics of Process Engineering

Name

Formula

Mol. Wt.

Hexane
Heptane
Octane
Nonane
Decane

C6H14
C7H16
C8H18
C9H20
C10H22

86
100
114
128
142

In referring to a given paraffin hydrocarbon, the abbreviation C3 for propane, C4 for

butane, etc. may be used. Statements like "propanes plus fraction (C3+)" refer to a
mixture composed of propane and larger atoms.
Paraffin isomers: When the paraffin series molecule contains four or more carbon
atoms there are different ways these can be connected without affecting the formula.
Compounds which have the same chemical formula but a different atomic structure
are called isomers. They possess different physical and chemical properties.
There are only two isomers of butane. In the structural diagram shown for i-butane
we could draw the carbon atom below instead of above the carbon chain. But, this
would be just a "mirror image" of the molecule as drawn. It is the same molecule
with the same properties. The adjective "normal" is used to designate a molecule
wherein all of the carbon atoms are in a straight line. An "isomer" has the same
formula but a different arrangement of the carbon atoms. In an analysis, these are
often abbreviated as "n" and "i" respectively.

Normal butane
(n-butane)

Isobutane
(I-butane)

1.2.2 Olefin or Ethylene Series (Alkenes) Formula: CnH2n

The olefin group of compounds is a simple straight chain series in which all the
names end in -ene. Ethylene (ethene) C2H4 is the simplest molecule in the series.
Hydrocarbons in this series combine easily with other atoms like chlorine and
bromine, without the replacement of a hydrogen atom. Since they are so reactive,
they are called unsaturated hydrocarbons.
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Unlike the paraffins, the maximum bonding capacity of the carbon atom is not fully
satisfied by hydrogen or carbon atoms. Two adjacent carbon atoms form a
"temporary" bond (in the absence of other available atoms) to meet bonding
requirements fixed by valence. It is a necessary but unstable alliance. The structural
formula for the olefins uses a double line to indicate the double carbon-carbon
linkage, the most reactive point in the molecule.

Ethylene (Ethene)

Propylene (Propene)

With four or more carbon atoms, isomers also may result from the position of the
double bond as well as the arrangement of the carbon atoms.

1-Butene

2-Butene

These molecules possess many different properties. They may furthermore react at
the double bond or be split into two molecules at the double bond to form
compounds with different characteristics.
The amount of olefins in natural gas usually is fairly small. Certain crude oils contain
them in measurable amounts.

1.2.3 Acetylene or Alkyne Series Formula: CnH2n-2

This series is of basic importance only in certain refining and petrochemical
applications. Acetylene is the most important member of this series. It has the
formula C2H2. The structural formula for acetylene is
H - C C - H
There is a triple bond between the carbon atoms. This satisfies the valence
requirements but the carbon linkage is very weak.
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Acetylene is even more reactive than the olefins. Carbon likes the sharing of three
valence linkages even less than sharing two. Acetylene not only is unsaturated, it is
almost unstable chemically. In the liquid state it is explosive if subjected to a sudden
shock.

1.2.4 Diolefins Formula: CnH2n-2

The diolefins have the same formula as acetylene. The members of this series
contain two double linkages. They normally are named by replacing the -ane for
paraffins by -diene.
Diolefins are primarily of concern in petrochemical plants. Butadiene is possibly the
most interesting and useful since it is a primary ingredient in synthetic rubber
compounds. It has the formula:
CH2 = CH CH = CH2
All of these unsaturated compounds are reactive. They may be hydrogenated.
Liquid cooking oils (unsaturated) may be hydrogenated to form solid fats.
These compounds also polymerize - the process wherein a very large molecule is
built up from the self-addition reaction of small identical molecules (monomers).
Ethylene and propylene polymerize to form polyethylene and polypropylene, the
basic ingredients in plastic materials. Acetylene polymerizes to form benzene, a
cyclic hydrocarbon.

1.2.5 Aromatic (Benzene) Series Formula: CnH2n-6

Aromatic is the word used to describe an unsaturated
hydrocarbon molecule where the carbon atoms form a ring, a
cyclic compound. Benzene, the parent compound of this
series, has the structural formula of C6H6.
Since the aromatics are unsaturated, they react readily. They
may be oxidized to form organic acids. They also promote
foaming and other operational problems in the production
and handling of crude oil and natural gas.
Most petroleum contains only a trace of aromatics. Some
contain significant amounts. Any analysis of crude oil and
natural gas should include aromatics. Even small amounts
can influence physical behavior and affect design.

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1.2.6 Naphthene Series Formula: CnH2n

The naphthene series has a ring structure but is
saturated. Naphthenes may be found in most crude oils
but are seldom shown in routine analyses. Being
saturated molecules, they are not very reactive.
Cyclohexane is a common member of this series. Its
structural formula is C6H12.
Cyclohexane is similar to benzene except that it is
saturated. On chromatographic analysis it occurs
between n-hexane and n-heptane.
Cyclopentane
(C5H10) also occurs. On chromatographic analysis it
occurs between n-pentane and n-hexane.

Cyclohexane

1.3 PARAFFIN HYDROCARBON COMPOUNDS

In the production, gathering, conditioning, and processing of natural gas and its
associated liquids, the primary concern is the behavior of the paraffin series
hydrocarbons with 10 or less carbon atoms (C1 C10). This concern includes nitrogen
and water and contaminants in the gas, such as sulfur compounds.
Paraffin hydrocarbons are less reactive with other materials than many hydrocarbons,
but it must be remembered that they have been in contact with the chemicals present
in the reservoir rock for many millions of years. They are also conditioned by use of
alcohols, glycols, and amines in which they are soluble and with which they react to
some degree.

1.3.1 Radicals
A radical represents a group of atoms that act as a single unit in the formation of
many common compounds.
Alkyl Radical: At least the simpler paraffins often react by replacing one hydrogen
with some other radical or element. This alkyl radical has the formula:

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CnH2n+1 : (CH3),
Methyl

Chapter 1 Basics of Process Engineering

(C2H5),
ethyl

(C3H7)
propyl

The parenthesis indicates the radical group. The alkyl radical normally has a valence
of +1.
In many cases the alkyl radical is indicated by the symbol "R." The formula for
methanol is CH3 OH; for ethanol it is C2H5OH. Both may be written as ROH. When
"R" is used, one cannot identify the specific alkyl radical. It is used only to show
general reaction characteristics.
Hydroxyl Radical, (OH). This combination occurs in many common compounds. It
combines with hydrogen to form water - H (OH) or H2O; with metallic salts like
sodium, calcium and magnesium to form hydroxides (bases, caustics); and with alkyl
radicals to form alcohols, such as methanol, ethanol, etc.
(SO4), (CO3). If radicals like these combine with hydrogen, an acid is formed. When
combined with metallic salts like sodium, calcium, and magnesium, a salt is formed
(which occurs commonly in water systems). The scale formed in water systems is
caused by precipitation of salts like these. The common names for some common
radicals of this type are:
SO4 - sulfate
SO3 - sulfite

CO3 - carbonate
HCO3 - bicarbonate

Each of the radicals has a valence found from the valence of its elements. The
hydroxyl radical (OH) has a valence of minus one and is sometimes written as (OH)-1.
It therefore combines in proportions fixed by this valence: H(OH), NaOH, Mg(OH)2
- so that the sum of plus and minus valences equals zero.

1.3.2 Alcohols
The common alcohols are formed from the addition of a single hydroxyl radical to an
alkyl radical. The name of the alcohol ends in "ol," or the name of the alkyl radical is
followed by the word "alcohol."

Methanol or methyl alcohol

Ethanol or ethyl alcohol

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Both C2H5OH and CH3OH could be written as ROH in denoting the general reaction
of an alcohol.

1.3.3 Mercaptans
Compounds with the general formula RSH are known as mercaptans. They may be
regarded as sulfur alcohols since the formula is the same if you replace the oxygen
atom in the (OH) radical by a sulfur atom.
Formulas for typical mercaptans are:
CH3SH - methyl mercaptan

C2H5SH - ethyl mercaptan

1.3.4 Other Carbon-Sulfur Compounds

There are several other carbon-sulfur compounds present in sour petroleum fluids.
Some are:
Carbonyl sulfide - COS

Carbon disulfide CS2

Thiophene - an unsaturated compound having the formula:

HC = CH S HC = CH
Sulfur is a very reactive element that combines chemically with many other elements
and compounds. Its compounds react with carbon steel to form sulfides and oxides of
iron. Many compounds polymerize and form the "sludge" so common in sour
petroleum systems. This sludge is often very corrosive and should be removed by
filtration.

1.3.5 Organic Nitrogen Compounds - Amines

There are a number of common organic compounds formed by the reaction of
organic materials with ammonia (NH3). In this basic reaction one or more hydrogen
atoms are replaced by an organic radical. The word "amine" is used commonly to
denote this type of compound. There are a large number of amines used in the
chemical industry.
The alkanolamines are commonly used for treating sour gases and liquids,
particularly monoethanolamine and diethanolamine. As the names indicate, the
alkanolamines may be considered a combination of an alcohol and ammonia.

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Monoethanolamine

Chapter 1 Basics of Process Engineering

Diethanolamine (DEA)

Notice that the only difference in the above compounds is how many hydrogen atoms
of ammonia are replaced by the radical (C2H4OH), ethanol minus one hydrogen
atom.

1.3.6 Glycols
The glycols are a family of chemicals, sometimes called diols. They may be
regarded as complex alcohols since they contain alkyl and hydroxyl radicals. The
glycols used for dehydration are based on the ethyl radical.
As with most compounds containing hydroxyl groups, the glycols react readily with
other compounds and elements. In DEG and TEG the oxygen atom also is very
reactive.

Ethylene Glycol (EG)

Diethylene Glycol (DEG) Triethylene Glycol (TEG)

1.4 ACIDS, BASES AND SALTS

We are always talking about acids and bases in the handling of petroleum-water
mixtures, processing, and other such functions of the petroleum industry.
Except for water and hydroxides (compounds containing the OH radical), all
inorganic compounds of hydrogen are acids. They consist of hydrogen combined
with an acid radical (anion).

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Acid Radical (anion)

Chloride
Carbonate
Sulfate
Nitrate
Phosphate

Symbol
Cl-1
CO3-2
SO4-2
NO3-1
PO4-3

Chapter 1 Basics of Process Engineering

Acid
Hydrochloric
Carbonic
Sulfuric
Nitric
Phosphoric

Formula
HCl
H2CO3
H2SO4
HNO3
H3PO4

Notice that hydrogen (valence of +1) combines with the acid radical in a proportion
such that the net valence of the compound formed is zero. This is the rule to be
followed in all compound formation. Since the valence of the sulfate radical is -2, it
takes two hydrogens.
The combination of a metal cation such as sodium with the hydroxyl anion (OH)
produces a base. Sodium hydroxide (NaOH) is commonly called caustic.
pH. The acidity or alkalinity of a material is measured on a scale similar to that of a
thermometer. This pH scale is the logarithm of the reciprocal of the hydrogen ion
concentration. It runs between 0 and 14. A pH of 7 is neutral. Acids have a pH less
than 7; bases (alkaline solutions) have a pH greater than 7.
Since pH is a logarithmic function, a solution possessing a pH of 5.0 is 100 times
more acidic than one with a pH of 7.0.

1.5 ANALYSIS OF MIXTURES

A routine analysis of a hydrocarbon mixture is shown in Table 1.1. Notice that only
paraffin hydrocarbons are shown. This is not entirely correct, although the paraffins
may be the predominant series present. Notice also that all molecules heptane and
larger are lumped together as a heptanes plus fraction.
The hydrocarbon portion of an analysis like this usually is obtained from a
chromatograph. The printed output from this technique is a series of "peaks" rising
from a base line. The area under the peak for any component is proportional to the
amount present. The instrument is calibrated using standard samples of known
analysis so that peak area can be converted to the amount present.
Figure 1.1 is an example of a chromatogram (chart) from a chromatographic analysis.
When the ordinary peak height is so low it is difficult to measure, it is attenuated
(multiplied). The attenuation factor is used to convert the peak height shown to
analysis.

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Table 1.1 Fluid Analysis

The chromatograph used to obtain Figure 1.1 was capable of showing hydrocarbons
other than paraffins. Notice that all of these occur in the hexane-heptane range of
molecules. Many chromatographs, particularly those used for routine gas analyses,
are unable to detect all of these components. The nonparaffins combine with a single
peak which is reported (erroneously) as being a paraffin material.
Many system operating problems are the direct or indirect result of inadequate
analysis. This may result from failure to:
1. Analyze for CO2 and sulfur compounds
2. Identify the presence of aromatics and other nonparaffin hydrocarbons
3. Adequately characterize the heaviest fraction

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Figure 1.1 Chromatogram of Condensed Liquid

There are, however, some general guidelines.
1. Always analyze for CO2 and H2S. Sulfur contents as low as 3-10 parts
per million may prove troublesome. If the sulfur content (reported as
H2S) is higher than this, a special analysis for carbonyl sulfide (COS),
carbon disulfide (CS2) and mercaptans is intelligent.
2. Some crude oil may contain up to 10-12% aromatics. Failure to be aware
of this affects mechanical design problems and reduces validity of
equilibrium calculations.
3. If the gas is from a separator, characterizing the heaviest fraction
through C7+ may be adequate; if it is wellbore gas it may not be
adequate. Crude oil may need to be characterized through C20+ to
achieve reliable equilibrium predictions.
The prompt and proper analysis of representative samples is a critical factor. Any
calculation is an exercise in futility unless the analyses used are reliable. Inadequate
sampling and analysis is a major cause of problem systems.
A sampling program should be planned carefully.

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Appendices
Nomenclature of Hydrocarbons

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A-1 Some Paraffinic Hydrocarbons

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A-2 Some Naphthenic Hydrocarbons

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A-3 Some Olefinic Hydrocarbons

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A-4 Some Diolefinic Hydrocarbons

Petroleum Processing
A-5 Some Acetylenic Hydrocarbons

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A-6 Some Aromatic Hydrocarbons

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A-6 Some Aromatic Hydrocarbons (Continued)

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