Introduction :Composition of petroleum,laboratory tests,refinery

feedstocks and products

Fig:1.1[15]

Fig.1.2 Distribution of world energy resources.

(From World Energy Outlook 2005, International Energy Agency.)[16,17]

Introduction to petroleum refinery

Petroleum refineries have goal to convert as much of the barrel of crude oil into transportation fuels
which is economically practical. Refineries produce many profitable products however, the high-volume
profitable products are the transportation fuel gasoline, diesel and turbine (jet) fuels, and the light
heating oils. These transportation fuels have boiling points between 25 and 350oC. Although products
such as lubricating oils, refrigeration and transformer oils, and petrochemical feedstocks are
profitable.They amount to less than 5 percent of the total crude oil charged to refineries. The
processing equipment indicated is for processing crude oils of average gravities and sulfur contents.
Crude oils with low API gravities (high specific gravities) and high sulfur contents require additional
hydrotreating equipment. The quality of crude oils processed by worldwide refineries is expected to
worsen slowly in the future with the sulfur contents and densities to increase. Therefore refineries will
require processing the entire barrel of crude rather than just the material boiling below (550 oC).Sulfur
restrictions on fuels, coke and heavy fuel oils affects the bottom-of-the-barrel processing as well.
These factors requires extensive refinery additions modernization the shift in market requirements
among gasolines and reformulated fuels for transportation challenges.[16]

Refinery Overview[15-20]

The crude oil is heated in a furnace and charged to an atmospheric distillation tower, where it is
separated into light gas (C1-C4), light naphtha, heavy naphtha, kerosine, atmospheric gas oil, and
reduced (topped) crude . The reduced crude is sent to the vacuum distillation tower and separated into
vacuum gas oil stream and vacuum reduced crude bottoms (residua, resid). The reduced crude
bottoms from the vacuum distillation tower is thermally cracked in a delayed coker to produce gas,
coker gasoline, coker gas oil, and coke. The atmospheric and vacuum crude unit gas oils and coker gas
oil are used as feedstocks for the catalytic cracking or hydrocracking units where heavy molecules get
converted into lower molecular weight compounds boiling in the gasoline and distillate fuel ranges. The
hydrocracked products are saturated whereas catalytic cracker products are unsaturated and further
need improvement in quality by either hydrotreating or by reforming. The light naphtha streams from
the crude tower, coker and cracking units are sent to an isomerization unit to convert straight-chain
paraffins into isomers which have higher octane numbers. The heavy naphtha streams from the crude
tower, coker, and cracking units are fed to the catalytic reformer to improve octane numbers. The
products from the catalytic reformer can be blended into regular and premium gasolines for marketing.
The wet gas streams from the crude unit, coker, and cracking units are separated in the vapor recovery
section (gas plant) into fuel gas, liquefied petroleum gas (LPG), unsaturated hydrocarbons (propylene,
butylenes, and pentenes), normal butane, and isobutane. The fuel gas is burned as a fuel in refinery
furnaces and the normal butane is blended into gasoline or LPG. The unsaturated hydrocarbons and
isobutane are sent to the alkylation unit to react olefins with isobutane to yield isoparaffins. The
alkylation is done at high pressure and low temperature in the presence of sulfuric or hydrofluoric acid
as catalyst. The product is called alkylated gasoline, which is a high-octane product blended into
premium motor gasoline and aviation gasoline. The middle distillates from the crude unit, coker, and
cracking units are blended into diesel and jet fuels and furnace oils. In some refineries, the heavy
vacuum gas oil and reduced crude from paraffinic or naphthenic base crude oils are processed into
lubricating oils. The asphaltenes are removed in a propane deasphalting unit, and the reduced crude
from bottoms are processed with the vacuum gas oils to produce lubeoil base stocks (LOBS). The
vacuum gas oils and deasphalted stocks are solvent-extracted to remove the aromatic compounds
followed by dewaxing to improve the pour point. These LOBS are further treated with acid clays to
improve their color and stability before being blended into lubricating oils. Each refinery has its own
unique processing scheme which is determined by the process equipment available, crude oil
characteristics, operating costs, and product demand.

Refinery Feed Stocks[19-20]

The basic raw material for refineries is petroleum or crude oil. The chemical compositions of crude oils
obtained from various sources are almost uniform although their physical characteristics vary widely.
The elementary composition of crude oil usually falls within the following ranges: C 84-88; H 11-15; S
up to 5%, N up to 0.5 %. Crude oils are classified as paraffin base, naphthene base, asphalt base, or
mixed base depending upon the composition of the residue left after distillation. Crude oils which have
up to 80% aromatic content are known as aromatic-base oils. The U.S. Bureau of Mines has developed
a system which classifies the crude according to two key fractions obtained in distillation: No. 1 from
250 to 275 oC at atmospheric pressure and No. 2 from 275 to 300 oC at 40 mmHg pressure. The API
gravity of these fractions varies depending upon paraffinic and naphthenic grade of the crude(Paraffin :
API 40 for No. 1 and 30 for No. 2, Naphthene : API < 30 for No. 1 oil and <=20 for No. 2 oil). The
paraffinic and asphailtic classifications in common use are based on the properties of the residuum left
from nondestructive distillation and are more descriptive to the refiner because they convey the nature
of the products to be expected and the processing necessary.

Composition Of Petroleum[19-20]

Crude oils are composed of many members of homologous series of hydrocarbons. Petroleum is
essentially a mixture of hydrocarbons, and even the non-hydrocarbon elements are generally present
as components of complex molecules predominantly hydrocarbon in character, but containing small
quantities of oxygen, sulfur, nitrogen, vanadium nickel, and chromium. The composition of the total
mixture, in terms of elementary composition, does not vary a great deal, but small differences in
composition can greatly affect the physical properties and the processing required to production
marketable products. The hydrocarbons present in crude petroleum are classified into three general
types: paraffins, naphthenes, and aromatics. Olefins are generally not present in crude oil, however
these are formed during processing by the dehydrogenation of paraffins and naphthenes. The paraffin
series of hydrocarbons is characterized by the rule that the carbon atoms are connected by a single
bond and the other bonds are saturated with hydrogen atoms.The general formula for paraffins is
CnH2n+2. Crude oil contains molecules with up to 70 carbon atoms, and the number of possible
paraffinic hydrocarbons is very high .Olefins do not naturally occur in crude oils but are formed during
the processing. They are very similar in structure to paraffins but at least two of the carbon atoms are
joined by double bonds. The general formula is CnH2n. Olefins are generally undesirable in finished
products because the double bonds are reactive and the compounds are more easily oxidized and
polymerized to form gums and varnishes. Olefins containing five carbon atoms have high reaction rates
with compounds in the atmosphere that form pollutants and, even though they have high research
octane numbers, are considered generally undesirable. Some diolefins (containing two double bonds)
are also formed during processing, but they react very rapidly with olefins to form high-molecular-
weight polymers consisting of many simple unsaturated molecules joined together. Diolefins are very
undesirable in products because they are so reactive they polymerize and form filter and equipment
plugging compounds. Cycloparaffin hydrocarbons in which all of the available bonds of the carbon
atoms are saturated with hydrogen are called naphthenes. There are many types of naphthenes
present in crude oil, but except for the lower-molecular-weight such as cyclopentane and cyclohexane,
are generally not handled as individual compounds. They are classified according to boiling range and
their properties determined with the help of correlation factors such as the characterization (Kw) factor
or correlation index ( CI) . The aromatic series of hydrocarbons is chemically and physically very
different from the paraffins and cycloparaffins (naphthenes). The cyclic hydrocarbons, both naphthenic
and aromatic, can add paraffin side chains in place of some of the hydrogen attached to the ring
carbons and form a mixed structure.

Petroleum /crude oil[19]

Petroleum (also called crude oil) is a mixture of gaseous, liquid , and solid hydrocarbon
compounds.
 Petroleum occurs in sedimentary rock deposits throughout the world and also contains small
quantities of nitrogen oxygen and sulfur-containing compounds as well as trace amounts of
metallic constituents.

Petroleum[19]

The fuels derived from Petroleum contribute approximately one-third to one-half of the total world
energy supply and are used for transportation fuels (gasoline,diesel fuel,and aviation fuel,among
others) and heating buildings.
Petroleum products have a wide variety of uses that vary from gaseous and liquid fuels to near-
solid machinery lubricants. Residue of many refinery processes asphalt—is now a premium value
product for highway surfaces, roofing materials, and miscellaneous waterproofing uses.
Crude petroleum is a mixture of compounds boiling at different temperatures that can be
separated into a variety of different generic fractions by distillation and the terminology of these
fractions has been bound by utility and often bears little relationship to composition.

Major Processes:[19-20]

Desalting
Sweetening
Hydrogen Generation Unit
DHDS/DHDT
Reformer
Isomerisation
Amine Treating
Sulphur Recovery Unit
Bitumen Blowing Unit
Lube and wax
Solvent Extraction
Solvent dewaxing
Solvent Deoiling
Solvent deasphalting
Lube isomerisation
Hydrodesulfurisation

Fig:1.3[15]A typical REFINERY PROCESS CHART

Typical Refinery Products

LPG 2.1%
NAPHTHA 5.0%
MS 11.2%
OTHERS 18.3%
LIGHT DISTILLATE 36.6%
ATF 9.0

Chemistry in Fuel refining

Key properties of Fuels

MS: Octane number, Sulphur, distillation, Oxidation stability, Bz/ Aromatics/ Olefin content.
HSD: Cetane number,Sulphur,distillation,lubricity.
Kerosene: Smoke Point.
ATF: Freezing point.
Furnace oil: Stability.
Bitumen: Penetration, viscosity, Softening point.
LOBS: Viscosity, Viscosity Index.

Definations and Terminology[19,20]

Petroleum is a mixture of gaseous, liquid, and solid hydrocarbon compounds that occur in sedimentary
rock deposits throughout the world and also contains small quantities of nitrogen, oxygen, and sulfur-
containing compounds as well as trace amounts of metallic constituents.Petroleum is a naturally
occurring mixture of hydrocarbons, generally in a liquid state, which may also include compounds of
sulfur, nitrogen, oxygen, metals, other elements .Any naturally occurring hydrocarbon, whether in a
liquid, gaseous, or solid state may found explorations.

Complexity of a refinery[19,20]

The combination of refining processes and operations employed (complexity) varies from one refinery
to another.Modern refinery is highly complex, energy and capital intensive. Role of catalytic processes,
secondary processing and hydroprocessing is increasing .Factors deciding the complexity of a refinery.

Nature/source of crude oils- flexibility to process variety of crudes.

Demand pattern in the markets.
Product quality - current/ future.
Production of feedstocks for downstream units.
Inter-fuel substitution.

Separation : Heavy on the bottom, light on the top

The separation of crude oil by atmospheric and vacuum distillation into groups of hydrocarbon
compounds of different boiling point ranges called “fractions” or “cuts”.
The first step in crude oil processing, where the first separation takes place is called Crude
Distillation Unit (CDU) Atmospheric & Vacuum Unit (AVU).
This step is performed in all refineries :These units are called “Mother Units”
Typical products from CDU are : Gas, LPG, naphtha, SKO/ATF, HSD and RCO.
Vacuum Distillation of RCO produces VGO (or LOBS cuts) and VR
All products need further treatment/processing.