PETROLEUM REFINERY ENGINEERING

Petroleum is a combustible oily liquid of reddish brown to almost black colour, produced from oil
wells. It is a complex mixture of hydrocarbons and their derivatives containing oxygen, sulphur,
nitrogen and minor quantities of some other materials. The importance of petroleum crude oil and natural
gas has been realized with the development of its numerous applications as fuel and feedstock. The
invention of the internal combustion engines in the last quarter of the nineteenth century gave an
impetus to the development of petroleum processing. The most basic refining process is aimed at
separating the crude oil into its various components. Crude oil is heated and put into a still -- a distillation
column -- and different hydrocarbon components boil off and can be recovered as they condense at
different temperatures. Additional processing follows crude distillation, changing the molecular structure
of the input with chemical reactions, some through variations in heat and pressure, and some in the
presence of a catalyst.

The main constituents of petroleum _hydrocarbons _ may differ in the number of carbon and
hydrogen atoms in the molecular structure. The hydrocarbons are present in the following groups or
homologous series: paraffins (saturated st. chain hydrocarbons, alkanes), naphthenes (cycloalkanes),
and benzene hydrocarbons (aromatics). In most grades of petroleum, paraffins and naphthenes prevail
mostly.

Based on the chemical composition of the crude

(1) Paraffin-Base Crude Oils These contain higher molecular weight paraffins which are solid at
room temperature, but little or no asphaltic (bituminous) matter. They can produce high-grade lubricating
oils.

(2) Asphaltic-Base Crude Oils Contain large proportions of asphaltic matter, and little or no
paraffin. Some are predominantly naphthenes so yield lubricating oil that is more sensitive to temperature
changes than the paraffin-base crudes.

(3) Mixed-Base Crude Oils The "gray area" between the two types above. Both paraffins and
naphthenes are present, as well as aromatic hydrocarbons. Most crude fit this category.

CRUDE OIL PHYSICAL PROPERTIES

The physical properties of crude are as follows

Specific Gravity: 0.669 to 0.99

API Gravity: 10 – 50

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Viscosity: 1 – 4 centipoises

The American Petroleum Institute (API) has developed the term Degrees

API Gravity (°API) which is widely used as another general characterization of

the density of crude oils. The relationship is as follows:

°API = (141.5/Specific Gravity at 60 degrees Fahrenheit) - 131.5

“ Specific Gravity at 60 degrees Fahrenheit” is the density of the crude oil

measured at 60°F divided by the density of water at 60°F.

Therefore, when comparing two crude oils, the higher density crude (i.e., the one

with the highest specific gravity) will have a correspondingly lower °API. For

example, the 34.5°API West African crude oil Bonny Light is heavier than the

40.4°API North Sea crude oil Forties.

Chemical composition

On an average crude oil is [ultimate analysis] made up of the following components:

· Carbon - 84%

· Hydrogen - 14%

· Sulphur - 1 to 3% (hydrogen sulfide, sulfides, disulfides, elemental sulfur)

· Nitrogen - less than 1% (basic compounds with amine groups)

· Oxygen - less than 1% (found in organic compounds such as carbon dioxide, phenols, ketones,

carboxylic acids)

· Metals - less than 1% (nickel, iron, vanadium, copper, arsenic)

· Salts - less than 1% (sodium chloride, magnesium chloride, calcium chloride)

Crude oils are complex mixtures containing many different Hydrocarbons compounds that vary in

appearance and composition from one oil field to another. Crude oils are generally classified as

paraffinic, napthenic or aromatic based on the predominant proportion of similar Hydrocarbons.

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Hydrocarbons found in crude may be of the following types

1. Paraffins (Alkanes)

· General formula: CnH2n+2 (n is a whole number, usually from 1 to 20)

· These compounds are saturated hydrocarbons with all carbon bonds satisfied, that is, the

hydrocarbon chain carries the full complement of hydrogen atoms.

· Consist of straight chain (normal)- or branched-chain ( isomers) atoms

· The lighter straight chain molecules are found in gases and heavier in paraffin waxes.

The branched chain (isomer) parrafins are usually found in heavier fractions of crude oil and

have higher octane numbers than normal parrafins.

· examples: methane, ethane, propane, butane, isobutane, pentane, hexane

2. Aromatics

· General formula: C6H5 - Y (Y is a longer, straight molecule that connects to the benzene ring)

· They are unsaturated ring type (cyclic) compounds which react because they have carbon

atoms that are deficient in hydrogen.

· ringed structures with one or more rings. They have at least one benzene ring.

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 rings contain six carbon atoms, with alternating double and single bonds between the carbons

· typically liquids and are found in heavier fractions of crude oil.

· examples: benzene, naphthalene

3. Napthenes or Cycloalkanes

· General formula: CnH2n (n is a whole number usually from 1 to 20)

· ringed structures with closed rings (cyclic)

Found in all fractions of crude except the very lightest.

· rings contain only single bonds between the carbon atoms

· typically liquids at room temperature

· examples: cyclohexane, methyl cyclopentane

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 Nonhydrocarbons.

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

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 non basic 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.

Fractionation Processes:

Process name Action Method Purpose feedstocks products

Atmospheric separation thermal Separate Desalted Gas, Gas oil,
distillation fractions Crude oil distillate,
residue
Vacuum separation thermal Separate w/o Atm. tower Gas oil, lube
distillation cracking residue stock, residue

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 An oil refinery is an industrial process plant where crude oil is processed and
refined into more useful products. Oil refineries are quite large industrial complexes with
extensive pipelines carrying streams of fluids between large chemical (thermal and
catalytic) processes.

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  Temperature
 (Petroleum Gas)  increases
 down the column

 Petrol

 Naphtha

 Kerosene

 Diesel

 Lubricants

 Bitumen

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Catalytic Reforming
Although motor gasolines have numerous specifications that must be
satisfied to provide the performance demanded by our high-performance motor
vehicles, the most widely recognized gasoline specification is the octane number.
Gasolines are typically retailed in grades of regular, mid-grade and premium,
which are differentiated by the posted octane number.
The Octane Number of a test fuel refers to the percentage by volume of

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isooctane in a mixture of isooctane and heptane in a reference fuel that when
tested in a laboratory engine, matches the antiknock quality, as measured by a
knockmeter, of the fuel being tested under the same conditions. The octane
number posted at the gasoline pump is actually the average of the Research
Octane Number (RON) and Motor Octane Number (MON), commonly referred to
as (R+M)/2. RON and MON are two different test methods that quantify the
antiknock qualities of a fuel. Since the MON is a test under more severe
conditions than the RON test, for any given fuel, the RON is always higher than
the MON.
Unfortunately, the desulfurized light and heavy naphtha fractions of crude
oils have very low octane numbers. The heavy naphtha fraction is roughly 50
(R+M)/2. Catalytic Reforming is the refinery process that reforms the molecular
structure of the heavy naphtha to increase the percentage of high-octane
components while reducing the percentage of low-octane components.
The hydrocarbon compounds that constitute heavy naphtha are classified
into four different categories: paraffins, olefins (a very low percentage of olefins
occur in the heavy naphthas from crude), naphthenes and aromatics. In lieu of a
complete course in organic chemistry, simplistically the paraffins and olefins are
compounds with straight or branched carbon chains, whereas the naphthenes
and aromatics are carbon rings. The paraffins and naphthenes are saturated
hydrocarbons. Saturated means that they have the maximum number of
hydrogen atoms attached to the carbon atoms. The olefins and aromatics,
however, are unsaturated hydrocarbons because the compounds contain carbon
atoms that are double bonded to other carbon atoms. The straight chain,

saturated compounds exhibit very low octane numbers, the branched, saturated
compounds exhibit progressively higher octane numbers, while the unsaturated
compounds exhibit very high octane numbers.
Catalytic Reforming uses a precious metal catalyst (platinum supported by
an alumina base) in conjunction with very high temperatures to reform the
paraffins and napthenes into high-octane components. Sulfur is a poison to the
Catalytic Reforming catalyst, which requires that virtually all the sulfur must be
removed from the heavy naphtha through Hydrotreating prior to Catalytic
Reforming. Several different types of chemical reactions occur in the Catalytic
Reforming reactors.olefins are converted to paraffins, paraffins are isomerized
to branched chains and to a lesser extent to naphthenes, and naphthenes are
converted to aromatics. Aromatic compounds are essentially unchanged. The
resulting reformate product stream from Catalytic Reforming has a RON from 96-
102 depending on the reactor severity and feedstock quality. The
dehydrogenation reactions which convert the saturated naphthenes into
unsaturated aromatics produce hydrogen. This hydrogen is available for

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distribution to other refinery processes which consume hydrogen.
The Catalytic Reforming process consists of a series of several spherical
reactors which operate at temperatures of approximately 900°F. The reforming
reactions are .endothermic. meaning that the reactions cool the hydrocarbons.
The hydrocarbons are re-heated by direct-fired furnaces in between the
subsequent reforming reactors. As a result of the very high temperatures, the
catalyst becomes deactivated by the formation of .coke. (i.e., essentially pure
carbon) on the catalyst which reduces the surface area available to contact with
the hydrocarbons. A simplified process flow for the Catalytic Reforming process
is presented above.

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Fluidized Catalytic Cracking

The Fluidized Catalytic Cracking (FCC) process unit is considered by many refiners to be the heart of the
petroleum refinery. This derives from the fact that the FCC is a key tool to correct the imbalance reflected
by the markets demand for predominantly lighter, lower boiling petroleum products, whereas fractionated
crude oils typically provide an excess of heavy, high boiling range oils. The FCC process converts heavy
gas oils into lighter products which are then used as blend stocks for gasoline and diesel fuels. The
olefinic FCC catalytic naphtha product exhibits a very high-octane value for gasoline blending. The FCC
process cracks the heavy gas oils by breaking carbon-to-carbon bonds in the large molecules comprising
the gas oils and splitting them into multiple smaller molecules which boil at a much lower temperatures.
The FCC may achieve conversions of 70-80% of the feed hydrocarbons boiling above the gasoline range
(i.e., 430°F) to products boiling below 430°F. The lower density of the FCC products relative to the gas oil
feedstocks has the added benefit of producing a volume gain in which the combined volume of the liquid
product streams is greater than the volume of the unit feed stream. Since most petroleum products are
bought and sold on a volume basis, the volume gain aspect of the FCC process is a key aspect in how it
enhances refinery profitability. The resulting FCC product hydrocarbons are highly olefinic (i.e.,
unsaturated). Virgin is a term used to distinguish straight-run (i.e., crude distillation and possibly
hydrotreated only) hydrocarbons stocks from those that are products of conversion units such as the
FCC.

The FCC cracking reactions are catalytically promoted at very high temperatures of 950-1,020°F. At these
temperatures, coke (i.e., essentially pure carbon) formation deactivates the catalyst by blocking catalyst
surface area which prevents intimate contact between the catalyst and the hydrocarbons. To retain
catalyst activity, the FCC utilizes a very fine powdery, zeolite catalyst that behaves like a fluid (i.e., is able
to flow). The fluidized catalyst is continuously circulated in the FCC from the reactor to a regenerator
vessel and then returned to the reactor. Coke is removed from the catalyst in the regenerator vessel
through the controlled incomplete combustion of the carbon with oxygen to form carbon monoxide and
carbon dioxide.

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 PETROLEUM REFINERY ENGINEERING

Books for Reference:

1. Petroleum Refinery Engineering, 4th Ed., 1958, W.L. Nelson, McGraw-Hill Book

Company

2. Handbook of Petroleum Processes, 3rd Edition, R. A. Meyers McGraw-Hill

3. Fundamentals of Petroleum and Petrochemical Engineering. Uttam Ray

Chaudhuri, CRC Press, 2010

4. Mcketta S. (Ed), “Petroleum Processing Hbk”, Marcell Dekker Inc. 1992.

5. Gary J., Handework G., “Petroleum Refining Technology and Economics”,

Marcell Dekker Inc. 1984.

6. B. K. Bhaskara Rao, "Modern Petroleum Refining Processes",2nd Edn., Oxford and

IBH Publishing Company, New Delhi, 1990.

7. G. D. Hobson and W. Pohl., “Modern Petroleum Technology", Gulf Publishers, 2nd

Ed., 1990

8. An Introduction to Industrial Organic Chemistry, 2nd ed., P. Wiseman, (1979), Applied

Science Publishers, London.

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 About „Fundamentals of Petroleum and Petrochemical Engineering‟.

BY Uttam Ray Chaudhuri, CRC Press, 2010:

The supply of petroleum continues to dwindle at an alarming rate, yet it is the source of a range of
products - from gasoline and diesel to plastic, rubber, and synthetic fiber. Critical to the future of this
commodity is that we learn to use it more judiciously and efficiently.

Fundamentals of Petroleum and Petrochemical Engineering provides a holistic understanding of

petroleum and petrochemical products manufacturing, presented in a step-by-step sequence of the entire
supply chain. Filled with crucial information relevant to a range of applications, the book covers topics
such as:

 The essential preliminaries for the exploration and production of crude petroleum oil and gas
 Analysis of crude oil and its petroleum products
 The processing of petroleum in refineries
 The fundamentals of lubricating oil and grease Petrochemicals - their raw materials and end
products, and
 manufacturing principles of industrially important products
 Theories and problems of unit operations and the processes involved in refineries and
petrochemical plants
 Automatic operations in plants Start up, shutdown, maintenance, fire, and safety operations

Commercial and managerial activities are necessary for the ultimate success of a refining or
manufacturing business. Due to the advancement of technology, new petrochemicals are being invented
and will continue to be relevant to the petroleum industry in the near future.

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