Chapter 1

[This chapter includes data about petroleum

and corrosion in general]
Chapter 1 200
9

Petroleum, first used in the treatise De Natural Fossilium published in

1546 by the German mineralogist Georg Bauer, or crude oil is a naturally
occurring, flammable liquid found in rock formations in the Earth
consisting of a complex mixture of hydrocarbons of various molecular
weights, plus other organic compounds.

Composition:-

Crude oil is a mixture of hydrocarbon molecules, which are organic

compounds of carbon and hydrogen atoms that may include from one to 60
carbon atoms. The properties of hydrocarbons depend on the number and
arrangement of the carbon and hydrogen atoms in the molecules. The
simplest hydrocarbon molecule is one carbon atom linked with four
hydrogen atoms: methane. All other variations of petroleum hydrocarbons
evolve from this molecule. Hydrocarbons containing up to four carbon
atoms are usually gases; those with five to 19 carbon atoms are usually
liquids; and those with 20 or more are solids. The refining process uses
chemicals, catalysts, heat, and pressure to separate and combine the basic
types of hydrocarbon molecules naturally found in crude oil into groups of
similar molecules. The refining process also rearranges their structures and
bonding patterns into different hydrocarbon molecules and compounds.
Therefore it is the type of hydrocarbon, (paraffinic, naphthenic, or aromatic)
rather than its specific chemical compounds that is significant in the refining
process.

The principal groups or series of hydrocarbon

compounds that occur naturally in crude oil are as the
following:-

1-Paraffins:-

The paraffinic series of hydrocarbon compounds found in crude oil have the
general formula CnH2n+2 and can be either straight chains (normal) or
branched chains (isomers) of carbon atoms. The lighter, straight-chain
paraffin molecules are found in gases and paraffin waxes. Examples of
straight-chain molecules are methane, ethane, propane, and butane (gases

2
Chapter 1 200
9

containing from one to four carbon atoms), and pentane and hexane (liquids
with five to six carbon atoms). The branched-chain (isomer) paraffins are
usually found in heavier fractions of crude oil and have higher octane
numbers than normal paraffins. These compounds are saturated
hydrocarbons, with all carbon bonds satisfied, that is, the hydrocarbon chain
carries the full complement of hydrogen atoms.

2-Aromatics:-

Aromatics are unsaturated ring-type (cyclic) compounds which react readily

because they have carbon atoms that are deficient in hydrogen. All aromatics
have at least one benzene ring (a single-ring compound characterized by
three double bonds alternating with three single bonds between six carbon
atoms) as part of their molecular structure. Naphthalenes are fused double-
ring aromatic compounds. The most complex aromatics, polynuclears (three
or more fused aromatic rings), are found in heavier fractions of crude oil.

3-Naphthenes

Naphthenes are saturated hydrocarbon groupings with the general formula

CnH2n , arranged in the form of closed rings (cyclic) and found in all fractions
of crude oil except the very lightest. Single-ring naphthenes with five and six
carbon atoms predominate, with two-ring naphthenes (dicycloparaffins)
found in the heavier ends of naphtha.

Other Hydrocarbons

1-Alkenes

Alkenes are mono-olefins with the general formula C(n)H(2n) and contain
only one carbon-carbon double bond in the chain. The simplest alkene is
ethylene, with two carbon atoms joined by a double bond and four hydrogen
atoms. Olefins are usually formed by thermal and catalytic cracking and
rarely occur naturally in unprocessed crude oil.

3
Chapter 1 200
9

2-Dienes And Alkynes

Dienes, also known as diolefins, have two carbon-carbon double bonds. The
alkynes, another class of unsaturated hydrocarbons, have a carbon-carbon
triple bond within the molecule. Both these series of hydrocarbons have the
general formula CnH2n-2. Diolefins such as 1,2-butadiene and 1,3-butadiene,
and alkynes such as acetylene occur in C 5 and lighter fractions from
cracking. The olefins, diolefins, and alkynes are said to be unsaturated
because they contain less than the amount of hydrogen necessary to saturate
all the valences of the carbon atoms. These compounds are more reactive
than paraffins or naphthenes and readily combine with other elements such
as hydrogen, chlorine, and bromine.

Nonhydrocarbons

1-Sulfur Compounds

Sulfur may be present in crude oil as hydrogen sulfide (H(2)S), as

compounds (e.g., mercaptans, sulfides, disulfides, thiophenes, etc.), or as
elemental sulfur. Each crude oil has different amounts and types of sulfur
compounds, but as a rule the proportion, stability, and complexity of the
compounds are greater in heavier crude-oil fractions. Hydrogen sulfide is a
primary contributor to corrosion in refinery processing units. Other corrosive
substances are elemental sulfur and mercaptans. Moreover, the corrosive
sulfur compounds have an obnoxious odor.

Pyrophoric iron sulfide results from the corrosive action of sulfur

compounds on the iron and steel used in refinery process equipment, piping,
and tanks. The combustion of petroleum products containing sulfur
compounds produces undesirables such as sulfuric acid and sulfur dioxide.
Catalytic hydrotreating processes such as hydrodesulfurization remove
sulfur compounds from refinery product streams. Sweetening processes
either remove the obnoxious sulfur compounds or convert them to odorless
disulfides, as in the case of mercaptans.

4
Chapter 1 200
9

2-Oxygen Compounds

Oxygen compounds such as phenols, ketones, and carboxylic acids occur in

crude oils in varying amounts.

3-Nitrogen Compounds

Nitrogen is found in lighter fractions of crude oil as basic compounds, and

more often in heavier fractions of crude oil as nonbasic compounds that may
also include trace metals such as copper, vanadium, and/or nickel. Nitrogen
oxides can form in process furnaces. The decomposition of nitrogen
compounds in catalytic cracking and hydrocracking processes forms
ammonia and cyanides that can cause corrosion.

4-Trace Metals

Metals including nickel, iron, and vanadium are often found in crude oils in
small quantities and are removed during the refining process. Burning heavy
fuel oils in refinery furnaces and boilers can leave deposits of vanadium
oxide and nickel oxide in furnace boxes, ducts, and tubes. It is also desirable
to remove trace amounts of arsenic, vanadium, and nickel prior to processing
as they can poison certain catalysts.

5-Salts

Crude oils often contain inorganic salts such as sodium chloride, magnesium
chloride, and calcium chloride in suspension or dissolved in entrained water
(brine). These salts must be removed or neutralized before processing to
prevent catalyst poisoning, equipment corrosion, and fouling. Salt corrosion
is caused by the hydrolysis of some metal chlorides to hydrogen chloride
(HCl) and the subsequent formation of hydrochloric acid when crude is
heated. Hydrogen chloride may also combine with ammonia to form
ammonium chloride (NH4Cl), which causes fouling and corrosion.

6-Carbon Dioxide

5
Chapter 1 200
9

Carbon dioxide may result from the decomposition of bicarbonates present

in or added to crude, or from steam used in the distillation process.

7-Naphthenic Acids

Some crude oils contain naphthenic (organic) acids, which may become
corrosive at temperatures above 450 degrees F when the acid value of the
crude is above a certain level.

Composition by weight
Element Percent range
Carbon 83 to 87%
Hydrogen 10 to 14%
Nitrogen 0.1 to 2%
Oxygen 0.1 to 1.5%
Sulfur 0.5 to 6%
Metals less than 1000 ppm

Four different types of hydrocarbon molecules appear in crude oil. The

relative percentage of each varies from oil to oil, determining the properties
of each oil.

Composition by weight
Hydrocarbon Average Range
Paraffins 30% 15 to 60%
Naphthenes 49% 30 to 60%
Aromatics 15% 3 to 30%
Asphaltics 6% Remainder

Overview Of The Petroleum Refining Industry And Its

History:-

6
Chapter 1 200
9

Petroleum refining has evolved

continuously in response to
changing consumer demand for
better and different products.
The original requirement was to
produce kerosene as a cheaper
and better source of light than
whale oil. The development of
the internal combustion engine
led to the production of
gasoline and diesel fuels. The
evolution of the airplane
created a need first for high-
octane aviation gasoline and then for jet fuel, a sophisticated form of the
original product, kerosene. Present-day refineries produce a variety of
products including many required as feedstocks for the petrochemical
industry.

Distillation Processes

The first refinery, opened in

1861, produced kerosene by
simple atmospheric distillation.
Its by-products included tar and
naphtha. It was soon discovered
that high-quality lubricating oils
could be produced by distilling
petroleum under vacuum.
However, for the next 30 years
kerosene was the product
consumers wanted.

Two significant events

changed this situation:

(1) Invention of the electric light decreased the demand for kerosene

7
Chapter 1 200
9

(2) Invention of the internal combustion engine created a demand for diesel
fuel and gasoline (naphtha).

Thermal Cracking Processes

With the advent of mass production and World War I, the number of
gasoline-powered vehicles increased dramatically and the demand for
gasoline grew accordingly. However, distillation processes produced only a
certain amount of gasoline from crude oil. In 1913, the thermal cracking
process was developed, which subjected heavy fuels to both pressure and
intense heat, physically breaking the large molecules into smaller ones to
produce additional gasoline and distillate fuels. Visbreaking, another form of
thermal cracking, was developed in the late 1930s to produce more desirable
and valuable products.

Catalytic Processes

Higher-compression gasoline engines required higher-octane gasoline with

better antiknock characteristics. The introduction of catalytic cracking and

8
Chapter 1 200
9

polymerization processes in the mid- to late 1930s met the demand by

providing improved gasoline yields and higher octane numbers.

Alkylation, another catalytic process developed in the early 1940s, produced

more high-octane aviation gasoline and petrochemical feedstocks for
explosives and synthetic rubber. Subsequently, catalytic isomerization was
developed to convert hydrocarbons to produce increased quantities of
alkylation feedstocks. Improved catalysts and process methods such as
hydrocracking and reforming were developed throughout the 1960s to
increase gasoline yields and improve antiknock characteristics. These
catalytic processes also produced hydrocarbon molecules with a double bond
(alkenes) and formed the basis of the modern petrochemical industry.

Treatment Processes

Throughout the history of refining, various treatment methods have been

used to remove nonhydrocarbons, impurities, and other constituents that
adversely affect the properties of finished products or reduce the efficiency
of the conversion processes. Treating can involve chemical reaction and/or
physical separation. Typical examples of treating are chemical sweetening,
acid treating, clay contacting, caustic washing, hydrotreating, drying, solvent
extraction, and solvent dewaxing. Sweetening compounds and acids
desulfurize crude oil before processing and treat products during and after
processing.

Following the Second World War, various reforming processes improved

gasoline quality and yield and produced higher-quality products. Some of
these involved the use of catalysts and/or hydrogen to change molecules and
remove sulfur. A number of the more commonly used treating and reforming
processes are described in this chapter of the manual.

Major Refinery Products

Gasoline

9
Chapter 1 200
9

The most important refinery product is motor gasoline, a blend of

hydrocarbons with boiling ranges from ambient temperatures to about 400
degrees F. The important qualities for gasoline are octane number
(antiknock), volatility (starting and vapor lock), and vapor pressure
(environmental control). Additives are often used to enhance performance
and provide protection against oxidation and rust formation.

Kerosene

Kerosene is a refined middle-distillate petroleum product that finds

considerable use as a jet fuel and around the world in cooking and space
heating. When used as a jet fuel, some of the critical qualities are freeze
point, flash point, and smoke point. Commercial jet fuel has a boiling range
of about 375-525 degrees F, and military jet fuel 130-550 degrees F.
Kerosene, with less-critical specifications, is used for lighting, heating,
solvents, and blending into diesel fuel.

Liquefied Petroleum Gas (Lpg)

LPG, which consists principally of propane and butane, is produced for use
as fuel and is an intermediate material in the manufacture of petrochemicals.
The important specifications for proper performance include vapor pressure
and control of contaminants.

Distillate Fuels

Diesel fuels and domestic heating oils have boiling ranges of about 400-700
degrees F. The desirable qualities required for distillate fuels include
controlled flash and pour points, clean burning, no deposit formation in
storage tanks, and a proper diesel fuel cetane rating for good starting and
combustion.

Residual Fuels

Many marine vessels, power plants, commercial buildings and industrial

facilities use residual fuels or combinations of residual and distillate fuels

10
Chapter 1 200
9

for heating and processing. The two most critical specifications of residual
fuels are viscosity and low sulfur content for environmental control.

Coke And Asphalt

Coke is almost pure carbon with a variety of uses from electrodes to

charcoal briquets. Asphalt, used for roads and roofing materials, must be
inert to most chemicals and weather conditions.

Solvents

A variety of products, whose boiling points and hydrocarbon composition

are closely controlled, are produced for use as solvents. These include
benzene, toluene, and xylene.

Petrochemicals

Many products derived from crude oil refining such as ethylene, propylene,
butylene, and isobutylene are primarily intended for use as petrochemical
feedstocks in the production of plastics, synthetic fibers, synthetic rubbers,
and other products.

Lubricants

Special refining processes produce lubricating oil base stocks. Additives

such as demulsifiers, antioxidants, and viscosity improvers are blended into
the base stocks to provide the characteristics required for motor oils,
industrial greases, lubricants, and cutting oils. The most critical quality for
lubricating-oil base stock is a high viscosity index, which provides for
greater consistency under varying temperatures.

Common refinery chemicals

Leaded gasoline additives

11
Chapter 1 200
9

Tetraethyl lead (TEL) and tetramethyl lead (TML) are additives formerly
used to improve gasoline octane ratings but are no longer in common use
except in aviation gasoline.

Oxygenates

Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE),
tertiary amyl methyl ether (TAME), and other oxygenates improve gasoline
octane ratings and reduce carbon monoxide emissions.

Caustics

Caustics are added to desalting water to neutralize acids and reduce

corrosion. They are also added to desalted crude in order to reduce the
amount of corrosive chlorides in the tower overheads. They are used in some
refinery treating processes to remove contaminants from hydrocarbon
streams.

Sulfuric Acid And Hydrofluoric Acid

Sulfuric acid and hydrofluoric acid are used primarily as catalysts in

alkylation processes. Sulfuric acid is also used in some treatment processes.

Petroleum Refining Operations

Introduction

12
Chapter 1 200
9

Petroleum refining begins with the distillation, or fractionation, of crude oils

into separate hydrocarbon groups. The resultant products are directly related
to the characteristics of the crude processed. Most distillation products are
further converted into more usable products by changing the size and
structure of the hydrocarbon molecules through cracking, reforming, and
other conversion processes as discussed in this chapter. These converted
products are then subjected to various treatment and separation processes
such as extraction, hydrotreating, and sweetening to remove undesirable
constituents and improve product quality. Integrated refineries incorporate
fractionation, conversion, treatment, and blending operations and may also
include petrochemical processing.

Refining Operations

Petroleum refining processes and operations can be separated into five basic
areas:

Fractionation

Fractionation (distillation) is the separation of crude oil in atmospheric and

vacuum distillation towers into groups of hydrocarbon compounds of
differing boiling-point ranges called fractions or cuts.

Conversion

Conversion processes change the size and/or structure of hydrocarbon

molecules. These processes include:

• decomposition (dividing) by thermal and catalytic cracking

• unification (combining) through alkylation and polymerization, and

• alteration (rearranging) with isomerization and catalytic reforming

13
Chapter 1 200
9

Treatment

14
Chapter 1 200
9

Treatment processes are intended to prepare hydrocarbon streams for

additional processing and to prepare finished products. Treatment may
include the removal or separation of aromatics and naphthenes as well as
impurities and undesirable contaminants. Treatment may involve chemical
or physical separation such as dissolving, absorption, or precipitation using a
variety and combination of processes including desalting, drying,
hydrodesulfurizing, solvent refining, sweetening, solvent extraction, and
solvent dewaxing.

Formulating And Blending

Formulating and blending is the process of mixing and combining

hydrocarbon fractions, additives, and other components to produce finished
products with specific performance properties.

Other Refining Operations

Other refinery operations include light-ends recovery, sour-water stripping,

solid waste and wastewater treatment, process-water treatment and cooling,
storage, and handling, product movement, hydrogen production, acid and
tail-gas treatment, and sulfur recovery.

Auxiliary operations and facilities include steam and power generation;

process and fire water systems; flares and relief systems; furnaces and
heaters; pumps and valves; supply of steam, air, nitrogen, and other plant
gases; alarms and sensors; noise and pollution controls; sampling, testing,
and inspecting; and laboratory, control room, maintenance, and
administrative facilities.

Corrosion
Corrosion is a natural process and is a result of the inherent tendency of
metals to revert to their more stable compounds, usually oxides. Most
metals are found in nature in the form of various chemical compounds

15
Chapter 1 200
9

called ores. In the refining process, energy is added to the ore, to produce
the metal. It is this same energy that provides the driving force causing the
metal to revert back to the more stable compound.
Four Conditions must exist before corrosion can
occur:-
1. The presence of a metal that will corrode (anode)
2. The presence of dissimilar conductive materials (cathode)
which has less tendency to corrode
3. Presence of a conductive liquid (electrolyte)
4. Electrical contact between the anode and cathode
Rust or corrosion that occurs with most metals is a result of the tendency
for metals to return to their natural state.
Nobel metals like gold and platinum do not corrode since they are
chemically uncombined in their natural state.

Forms of corrosion
A-General/Uniform Corrosion:
Corrosive attack dominated by uniform thinning due to even regular loss of
metal from the corrosion surface
Atmospheric

16
Chapter 1 200
9

Corrosion or degradation of material exposed to the air and its pollutants

rather than immersed in a liquid.

Galvanic
Corrosion that occurs when a metal or alloy is electrically coupled to
another metal or conducting nonmetal in the same electrolyte

17
Chapter 1 200
9

Stray-current
Caused by an externally induced electrical current

General biological
Corrosion of metals generally over the entire exposed surface in aqueous
Environments

18
Chapter 1 200
9

Molten salt
Corrosion of metals due to molten or fused salts
Liquid metals
Types of corrosion found in liquid metal / containment / component
combinations
High-temperature
Corrosion by direct reaction of exposed metals to oxidizing agents at
elevated temperatures Oxidation carburization sulfidation

B - Localized Corrosion:
All or most of the metal loss occurs at discrete areas
Filform Occurs on metallic surfaces coated with thin organic film, typically
0.1 mm thick, characterized by the appearance of fine filaments in semi-
random directions from one or more sources

19
Chapter 1 200
9

Crevice
Corrosion in narrow openings or spaces in metal to metal or non-metal to
metal component sites

Pitting
Extremely localized corrosion marked by the development of pits localized
microbiological cases where biological organisms are the sole cause or an
accelerating factor in the localized corrosion

C-Metallurgically Influenced Corrosion:

Forms of attack where metallury plays a significant role.
1-Intergranular
Occurs when the corrosion rate of the grain boundary areas of an alloy
exceeds that of the grain interiors

20
Chapter 1 200
9

2- Dealloying
A form of corrosion characterized by the preferential removal of one
constituent of an alloy leaving behind an altered residual structure.

D-Mechanically Assisted Degradation:

Form of attack where velocity, abrasion, hydrodynamics etc. Play a major
role
Erosion
Removal of surface material by the action of numerous individual impacts
of solid or liquid particles

21
Chapter 1 200
9

Fretting
Combined wear and corrosion between contacting surfaces when motion
between the surfaces is restricted to very small amplitude oscillations

Cavitation & Water Drop Impingement

Occurs on a metal surface in contact with a liquid, pressure differentials
generate gas or vapor bubbles which upon encountering high-pressure
zones, collapse and cause explosive shocks to the surface occurs in metals
as a result of the combined action of a cyclic stress and a corrosive
environment.

22
Chapter 1 200
9

E-Environmentally Induced Cracking:

Forms of cracking that are produced in the presence of stress Stress
Corrosion Cracking
Service failures in engineering materials that occur by slow environmentally
induced crack propagation
Hydrogen damage

23
Chapter 1 200
9

Results from the combined action of hydrogen and residual or tensile stress

Liquid metal embrittlement

Brittle failure of a normally ductile metal when coated with a thin film of a
liquid metal and subsequently stressed in tension

Solid metal embrittlement

Occurs below the melting point of the solid in certain liquid metal
embrittlement couples

24
Chapter 1 200
9

www.hghouston.com
www.wikipaedia.com

25