Introduction: Composition of petroleum, laboratory tests, refinery

feedstocks and products

Fig:1.1

Fig.1.2 Distribution of world energy resources.

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.

Refinery Overview

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

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

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

 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

 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

 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:1.3A 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

Definations and Terminology

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

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.

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.