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Petroleum Refining
Engineering
Introduction
Petroleum Pathway
Petroleum Products
Overview
Petroleum or crude oil is a complex hydrocarbon mixture (mostly
gasoline) that is refined to get its constituents or feedstock for chemical
transformations.
The typical fuels refinery has as a goal the conversion of as much of the
barrel of crude oil into transportation fuels as is economically practical.
Although refineries produce many profitable products, the high-volume
profitable products are the transportation fuels gasoline, diesel and
turbine (jet) fuels, and the light heating oils, and etc.
Overview (continue)
Modern refinery operations are very complex processes.
Crude oils with low API gravities (high specific gravities) and high
sulfur contents require additional hydrotreating equipment.
The quality of the product in refinery can be easily alter (to worsen
quality) if sulfur contents and densities increase.
The greater densities will mean more of the crude oil will boil above
566C (1050F).
High-boiling material or residue has been used as heavy fuel oil but
the demand for these heavy fuel oils has been decreasing because of
stricter environmental requirements.
This will require refineries to process the entire barrel of crude
rather than just the material boiling below 1050F (566C).
Processing Challenges
Sulfur restrictions on fuels (coke and heavy fuel oils)
will require extensive refinery additions and modernization and the
shift in market requirements among gasoline and reformulated fuels
for transportation will challenge catalyst suppliers and refinery
engineers to develop innovative solutions to these problems.
Implementation of Technologies
Oil Refining
This is what happens in an oil refinery - in one part of the process, crude oil
is heated and the different chains are pulled out by their vaporization
temperatures.
Each different chain length has a different property that makes it useful in a
different way.
To understand the diversity contained in crude oil, and to understand why
refining crude oil is so important in our society, look through the following
list of products that come from crude oil:
Heavy gas or Fuel oil - used for industrial fuel; starting material for
making other products liquid
Classification of Petroleum
The first crude oil classification is by the types of hydrocarbons
(paraffinic, naphthenic, and aromatics). This rating is important to the
refinery since the value
of the crude oil decreases
from classification 1 to 6.
Refinery Products
Some of the common aromatics found in petroleum and crude oils are benzene
and its derivatives with attached methyl, ethyl, propyl, or higher alkyl groups.
Aromatics:
Examples: benzene, methylbenzene
Cycloalkanes(Naphthenes):
CnH2n , ringed structures with one or more
rings contain only single bonds between the
carbon atoms. Examples: cyclohexane, methyl
cyclopentane.
Low-boiling products
The compounds which are in the gas phase at ambient temperatures and
pressures.
C1 is usually used as a refinery fuel, but can be used as a feedstock for hydrogen
production by pyrolytic cracking and reaction with steam.
On a volume basis, gasoline has a higher sales value than that of LPG, thus, it is
desirable from an economic viewpoint to blend as much normal butane as
possible into gasoline.
Gasoline
Most refiners produce gasoline in two or three grades, unleaded regular,
premium, and super-premium, and in addition supply a regular gasoline to
meet the needs of farm equipment and pre-1972.
The principal difference between the regular and premium fuels is the
antiknock performance.
Gasolines are complex mixtures of hydrocarbons having typical boiling
ranges from 100 to 400F (38 to 205C) as determined by the ASTM method
Components are blended to promote high antiknock quality, ease of starting,
quick warm-up, low tendency to vapor lock, and low engine deposits.
Refinery Feedstocks
The basic raw material for refineries is petroleum or crude oil,
even though in some areas synthetic crude oils from other sources
(Gilsonite, tar sands, etc.) and natural gas liquids are included in
the refinery feedstocks. The elementary composition of crude oil
usually falls within the following ranges.
Petroleum Standards
There are a number of international standard organizations that
recommend specific characteristics or standard measuring techniques for
various petroleum products. Some of these organizations are as follows:
1. ASTM (American Society for Testing and Materials) in the United
States
2. ISO (International Organization for Standardization), which is at the
international level
3. IP (Institute of Petroleum) in the United Kingdom
API Gravity
Specific gravity and API gravity refer to the weight per unit volume (density) of
crude oil at 60F and 1 atm as compared to water at 60F and 1 atm. In general,
API is a measure of how heavy or light a petroleum liquid is compared to water.
Crude oil gravity may range from less than 10API to over 50API but most
crudes fall in the 20 to 45API range.
Generally, a crude with the API gravity of less than 20-22 is called heavy crude
and with API gravity of greater than 33-40 is called light crude. Similarly, if the
sulfur content of a crude is less than 0.5 wt% it is called a sweet oil.
The equation to calculate API gravity from Specific Gravity (SG) is given by:
141.5
=
131.5
Example:
Calculate API of a heavy oil with a specific gravity of 1.0 (i.e., with the same density as pure
water at 60 F and 1 atm, pure water density is 999.017 kg/m3)
141.5
131.5 = 10
1
The specific gravity is defined by the following equation:
( )
() =
2 ( )
API =
Calculating the approximate number of barrels per metric ton for a given crude oil based on its
API gravity is given by:
Barrels of crude oil per metric ton=
+.
..
For example, a metric ton of West Texas Intermediate (39.6 API) has a volume of about 7.6
barrels.
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The pour point of the crude oil, in F or C, is a rough indicator of the relative
paraffinicity and aromaticity of the crude.
The lower the pour point, the lower the paraffin content and the greater the content of
aromatics.
Pour point represents the lowest temperature at which an oil can be stored and still
capable of flowing under gravity. When temperature is less than pour point of a
petroleum product it cannot be stored or transferred through a pipeline.
Carbon Residue, wt%
Carbon residue is determined by distillation to a coke residue in the absence of air.
Related to the asphalt content of the crude and to the quantity of the lubricating oil
fraction that can be recovered. In most cases the lower the carbon residue, the more
valuable the crude.
If the salt is not removed, severe corrosion problems may be encountered. If residue
are processed catalytically, desalting is desirable at even lower salt contents of the
crude.
Metals Content, ppm
The metals content of crude oils can vary from a few parts per million to more than
1000 ppm and, in spite of their relatively low concentrations, are of considerable
importance.
Cloud point is the lowest temperature at which wax crystals begin to form by a
gradual cooling under standard conditions. At this temperature the oil becomes
cloudy and the first particles of wax crystals are observed.
Low cloud point products are desirable under low-temperature conditions. Wax
crystals can plug the fuel system lines and filters, which could lead to stalling
aircraft and diesel engines under cold conditions.
Cloud points are measured for oils that contain paraffins in the form of wax and
therefore for light fractions (naphtha or gasoline) no cloud point data are
reported
Characterization Factors
Distillation Range
Distillation Data
Distillation curve
A-True Boiling Point (TBP)
A plot of the boiling point of crude oil
B- ASTM: standard test
1) D-86 for light fractions atmospheric pressure
2) D-1160 for heavier fractions (> 500oF) carried out in vacuum
C-Equilibrium Flash Vaporization (EFV)
Temperature versus the volume percent boiled off . The temperature at which a product
(or cut or fraction) begins to boil is called the initial boiling point (IBP). The
temperature at which it is 100% vaporized is the end point (EP). So every cut has two
cut points the IBP and EP.
Generally there are three kinds of gasolines: regular, intermediate, and premium
with PON of 87, 88-90, and 91-94, respectively. Improving the octane number
of fuel would result in reducing power loss of the engine, improving fuel
economy, and a reduction in environmental pollutants and engine damage.
There are a number of additives that can improve octane number of gasoline or
jet fuels. These additives are tetra-ethyl lead (TEL), alcohols, and ethers.
For diesel engines, the fuel must have a characteristic that favors auto-ignition. The
ignition delay period can be evaluated by the fuel characterization factor called cetane
number (CN). The shorter the ignition delay period the higher CN value.
Quality Measures
Gravity, API
Characterization factor
Sulfur content, wt%
Pour point, F (C)
Carbon residue, wt%
Salt content, lb/1000 bbl
Nitrogen content, wt%
Metal content, ppm
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