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By Marisa Werner

Refinery

History
Process Units
Refinery Products
Refinery Laboratory
Applications and
Instrumentation
Refinery Laboratory
Challenges
Websites

Mid-1800s First practical combustion engines


1861-1876 Dr. Otto compression engine with
controlled ignition with a four stroke
cycle. Limited gas supply.
1885
Damler & Benz built first single-cylinder motor car.
1914-1918 World War I changed demand and quality requirements.
Quality was improved by using crudes rich in aromatics
versus paraffins.
By the end of the war, it was clear that any improvements in
mechanical
engine efficiency by increasing compression ratio required
improved fuel
quality.
Research in the United States and Great Britain established that
HCs rich
in aromatics resisted knock,and normal paraffins were least
resistant.Also,the benefits of benzene, toluene, xylene and alcohol were
discovered.
1921
Midgely developed a test engine that was adopted as the
international
standard for measuring antiknock quality ( CFR)
engine).using this
engine, TEL was selected as the best
additive for improved quality.

1920s
1929
1930s

Government investigated toxicity of lead.


Octane scale established using N-heptane and iso-octane.
Refining process improvements.
Cracking to increase yield +olefins.
Polymerization- cracked gases to polymers
Alkylation-cracked to alkylates
Mid 1930s
Producing octane values around 70 for compression ratios around 5.5:1
World War II Enormous demand for gasoline and 100 octane fuel for aircraft required
rapid progress in refining technology.
* Continuous catalytic cracking
* Reforming
* Catalytic desulfurization
1950s-1960s Octanes up about 95 RON, enabled engine design to advance
1970s
crude price rise drives search for fuel economy, shake out of refining
industry.
1980s
Environmental concerns drive out TEL, increase demand for oxygenates.
Environmental regulations driving change to the existing processing
technologies as well as improved gasoline blending components.
Birth of unleaded gasoline, Reformulated Gasoline, etc.
Refineries forced to upgrade technology as well as blending capabilities.

Diesel engine
1890s
Dr. Rudolf Diesel conceived the idea of compression
engine to improve thermal efficiency.
1897
Diesel engine is successful.
1890-1930
Robert Bosch advanced fuel injection equipment.
1930For the last 40 years ,Europe and Japan have seen significant
growth
un number of passenger car fitted with diesel engines,
since 2006 USA
diesel market are increasing and the diesel
automobiles are mainly
imported.

Diesel Fuel
From the 1860s, kerosene lamp oil was the most valuable petroleum
fraction. Gasoline was burned, heavy residue was dumped in pits ,and middle
distillate was used to enrich towns gas.
The diesel engine created specific role for middle distillate.
Fuel quality improvements began with focus on:
Viscosity
Elimination of hard combustion residues
As higher speed engines were developed, so did the need to improve
ignition
quality,originally expressed as: DI= API Gravity x Aniline Point/100
A highly paraffinic fuel with high API and high aniline point had great
startability, but poorest cold properties, so the CFR cetane engine test( ASTM
D603) was adopted.

Poor precision led to the cetane index(ASTM D 976)


Later, expanded to include T-10% and T90%ASTMD4737

Over the last 40 years


*Additives for improving cetane number
*Limits in viscosity and sulfur
*Dominant fuel characteristics because of its low
temperature performance
*Cloud point-waxes start to separate
* Pour point-lowest temperature to pour

Today, we must consider the following:


*Legal definitions
*Levels of water, sediment, and acidity.
*Ash and carbon residue
*Safety standards
*Seasonal and environmental constraints.
*Blends od residues and distillates
*Initial stages of petroleum production of fuel oil were considered
product with no value.
*Early applications included industrial use only: then residual fuel
marine transportation increased demand.
*World reconstruction after World War II created a need for
fuels resulting in increased use of residual fuel oil.
*Viscosity found to be critical for handling.
*Fuel oil characteristics are dependent on crude quality.
*Environmental regulations have reduced its demand.

a byoil use for


additional

The Refining Process


A barrel of crude oil has a mixture of all sorts of
hydrocarbons in it. Oil refining separates everything
into useful substances. Chemists use the following
steps:
The oldest and most common way to separate things
into various components (called fractions), is to do it
using the differences in boiling temperature. This
process is called fractional distillation. You basically
heat crude oil up, let it vaporize and then condense
the vapor.
Newer techniques use Chemical processing on some
of the fractions to make others, in a process called
conversion. Chemical processing, for example, can
break longer chains into shorter ones. This allows a
refinery to turn diesel fuel into gasoline depending
on the demand for gasoline.
Refineries must treat the fractions to remove
impurities.
Refineries combine the various fractions (processed,
unprocessed) into mixtures to make desired
products. For example, different mixtures of chains
can create gasolines with different octane ratings.
The products are stored on-site until they can be
delivered to various markets such as gas stations,
airports and chemical plants. In addition to making
the oil-based products, refineries must also treat the
wastes involved in the processes to minimize air and
water pollution.

The Refining Process

Generally, crude petroleum is heated and changed into a gas. The hot gases are passed into the
bottom of a distillation column and become cooler as they move up the height of the column. As the
gases cool below their boiling point, they condense into a liquid. The liquids are then drawn off the
distilling column at specific heights, ranging from heavy residues at the bottom, raw diesel fuels in the
mid-sections, and raw gasoline at the top. These raw fractions are then processed further to make
several different finished products.

Although all fractions of petroleum find uses, the greatest demand is for gasoline. One barrel of crude
petroleum contains only 30-40% gasoline. Transportation demands require that over 50% of the crude
oil be "converted" into gasoline. To meet this demand some petroleum fractions must be converted to
gasoline. This may be done by cracking breaking down large molecules of heavy heating oil and
residues; reforming changing molecular structures of low quality gasoline molecules; and
isomerization rearranging the atoms in a molecule so that the product has the same chemical
formula but has a different structure, such as converting normal butane to isobutene.

Generally, the simplest refineries consist of crude,


crude, vacuum, reforming and some hydrotreating
capacity.
capacity. The next level of complexity adds cat cracking and some additional hydrotreating.
The most complex refineries add coking, more hydrotreating and hydrocracking.

Refining separates crude oil into components used for a variety of purposes, from high-performance
fuels to plastics.

The Facts About Crude Oil

The refining process begins with crude oil. Crude oil is unrefined liquid petroleum, which
ranges in color from yellow to black, and may have a paraffin, asphalt or mixed base.
Crude oil is composed of thousands of different chemical compounds called
hydrocarbons, all with different boiling points. For example, a typical crude oil may
begin to boil at 104 F to produce petroleum gas used for heating and making plastics,
and finish boiling at greater than 1112 F to produce residuals such as petroleum coke,
asphalt and tar.

Crude oil is generally described as sweet or sour according to its sulfur content, and
heavy or light according to its API Gravity. The API Gravity index is a relative measure of
weight-the lower the number, the heavier the material; the higher the number, the
lighter the material. While there are no exacting definitions for these types of crudes, a
general rule of thumb is:

A heavy crude is less than 30API, while a light crude is greater than 30API.

If crude contains a sizable amount of sulfur or sulfur compounds, it is called sour


crude; if it has little to no sulfur, it is sweet crude. Sour crude may contain 1%5%
sulfur content, while sweet crudes will have less than 1% sulfur content.

Refining Process Definitions


Coker Unit: processes vacuum resid, which is heated to over 900 F and put into the coke drums, where it
undergoes thermal cracking as the oil decomposes under the extreme heat. Products include butane and
lighter material, naphtha for Reforming, turbine and diesel fuel, gas oil for Cat Cracking, and fuel grade
petroleum coke.

Reformer Unit: using heat, catalyst and moderate pressure, the reformer changes the molecular structure
of crude and coker naphthas to produce a high octane primary gasoline blend stock called reformate.

Alkylation Unit: uses acid catalyst to combine small molecules into larger ones collectively called alkylate,
which has a high octane and is the cleanest burning of the gasoline blendstocks.

Fluid Catalytic Cracking Unit: uses heat and catalyst to break or crack large gas oil molecules into a
range of smaller ones, specifically gasoline, low quality diesel stocks, and a residual oil called slurry (fuel
oil).

Desulfurization Unit: a device used to remove sulfur from petroleum oil.

Hydrotreating: removes impurities by using hydrogen to bind with sulfur and nitrogen.

Hydrocracking: breaks or cracks diesel stock material into gasoline blending stocks using heat, catalyst
and hydrogen under very high pressure.

Isomerization: rearranges the atoms in a molecule so that the product has the same chemical formula
but has a different structure, such as converting normal butane to isobutane.

mol`bpp
Excellence in Applied Chemical
Engineering

Gasoline
Diesel
Jet Fuel
Renewables
Asphalt

Propane
Sulfur
Naphthenic Oils
Solvents
Aromatics
Natural Gas Liquids
Petroleum Coke
(all information is for
ValeroRefining)

Gasoline Products:

Conventional gasoline
Reformulated gasoline (RFG)
o Non-VOC Winter gasoline
o VOC Summer gasoline

o
Arizona RBOB Reformulated Blendstock
for Oxygenate
Blending, with ethanol as
the oxygenate for use in the
state of Arizona
o
California RBOB Reformulated
Blendstock for Oxygenate Blending, with ethanol
as the oxygenate used to manufacture California
Air Resources Board (CARB)
gasoline.

o
Ultra-low-sulfur gasoline, specially blended
for the state
of Georgia
Additives, used to clean fuel injectors and
other engine
components

Ultra-low-sulfur diesel (ULSD), for


motor vehicle use across the country

CARB (California Air Resource Board)


diesel, for motor vehicle use in California

Low-sulfur diesel, primarily for offroad use in construction and agricultural


applications

Off-road diesel, primarily for railroad


locomotive and marine uses

Additives
o Dye - blended with diesel to indicate offroad use only
o CFI - Cold Flow Inhibitor, which improves
fuel performance in low temperatures
o TXLED - Texas Low Emission Diesel
additive
o Cetane - increases the performance of
diesel in certain conditions

Valero supplies approximately 12


percent of the U.S. jet fuel demand,
providing commercial jet fuel to airlines,
re-sellers and fixed-base operators.

fuel
Military jet

Approximately 12 percent of
Valero's fuel production is sold as JP-5
and JP-8 to the U.S. military.

Commercial jet fuel

Defense Standard

Defense Standard 91-91 is the


standard for aviation turbine fuel
consumed outside the U.S.

Sunray Wind
The company built a wind farm outside its McKee Refinery in the Texas Panhandle,
with 33 turbines capable of generating 50 megawatts of electricity.

Renewable Resources

Valero acquired 10 state-of-the-art ethanol plants, making it the first
traditional refiner to enter production of ethanol, under subsidiary Valero Renewable
Fuels Company LLC, or Valero Renewables for short.

Ethanol is an environmentally friendly source of high-octane renewable fuel


produced by fermenting converted corn starch with yeast. It is used as a blending
agent for gasoline.

The co-product left after the ethanol is removed from fermented corn mash,
called distillers grains, is sold as high-protein livestock feed.

Valero Energy additionally has investments in several companies working to


commercialize emerging alternative biofuels such as green diesel and valuable coproducts from algae, renewable green gasoline from low-cost biomass such as
municipal-landfill solid waste or energy crops, ethanol from cellulosic materials
and renewable diesel fuel from animal-fat grease and used cooking oil.

The entire kernel of corn is converted to ethanol or distillers grains.

Often referred to as the bottom of the


barrel, it is easy to overlook asphalt as one
of the many products derived from a barrel
of crude oil. In reality, there are many more
applications for asphalt than just paving.
Asphalt can also be used for roofing,
batteries, automotive parts, and other
materials used for building and
construction.

As the second-largest asphalt producer in the


United States, Valero strives to be a reliable
supplier offering a variety of different
grades. In addition to performance-grade
paving asphalt, Valero also offers quality
roofing asphalt, specialty grade industrial
asphalt and polymer modified asphalt.
Valero is a member of the Asphalt Institute,
the National Asphalt Paving Association
(NAPA), and numerous other state industry
associations. For more education on asphalt
including its different uses and applications,
please visit the links provided below.

Propane Products:
Valero is always seeking new ways to improve operations and use its
refinery network synergies for the benefit of the consumer. The company's
propane marketing department is here to help achieve that purpose.
Propane serves a variety of functions both in everyday life and in industry -whether used in home heating, backyard barbecue grills, water heaters,
crop drying, petrochemical feedstocks, forklift fuel, taxi fleets or even city
bus motor fuels. In addition, propane is a clean-burning fuel. Because of
propane's low-carbon content, users can
help cut greenhouse-gas
emissions, improve air quality and protect the environment.

For more information on propane and educational material on its uses visit
http://www.propanecouncil.org/.

Sulfur Products:
Molten sulfur
The refineries produce molten sulfur that can be loaded into trucks or rail cars.

Prilled sulfur

The international market trades sulfur in a solid form called prilled. Valero has
the ability to produce molten sulfur into prilled at an annual rate of 400,000 tons per
year. Beginning in 2010, Valeros capacity to produce prilled sulfur will
increase to
900,000 tons per year.

Naphthenic Oils:

Valero
produces a complete line of naphthenic base oil products at

the Three Rivers Refinery (Texas). Valero has an exclusive


agreement with NYNAS, USA to market naphthenic oils.

Naphthenic

These products are used as transformer oils, coolants, solvents,


cutting fluids and some lubricants.

The Solvents Valero Makes:

Toluene

Toluene solvent is a high-purity form of toluene


which is sold in truck and rail-car lots from the Valero
Three Rivers Refinery.

Mixed xylenes

Mixed xylenes solvent is a high-purity form of


xylene which is sold in truck and rail-car lots from the
Three Rivers Refinery.

MSO feedstock

MSO is a distillation fraction between kerosene and


gas oil, widely used as a solvent oil in gas adsorption
processes, as a lubricant for the rolling of metal foil and
as a base oil in many specialty formulations. In addition,
it has applications in fuels testing and oil drilling.

he Products Valero Offers:

Benzene
Produced from the extraction process
and is used in basic materials from plywood
to Styrofoam.

Toluene

Produced from the same process as


benzene and is used as an octane booster for
motor gasoline. It can be processed into
benzene and mixed xylene or used in the
process of making polyurethane foam.

Mixed xylenes

Produced from the extraction process


and fractionation. Mixed xylenes are
converted into para-xylene, which is used to
make polyester PET a solid plastic.

What Valero's Products Are Used For:

Propane (bulk) is sold for petrochemical feed.


Normal butane is sold for petrochemical feed, and refinery-grade butane is sold and
purchased for gasoline blending.
Iso-butane is purchased as feed for alkylation units.
Natural gasoline is sold and purchased for petrochemical feed and gasoline
blending.
Propylene is sold for petrochemical feed.

Delayed coke

Valero produces 8 million tons


annually, including 7 million tons in
the U.S. Gulf Coast and Caribbean
regions. This product is mainly used
in power and cement plants
worldwide.

Fluid coke

Valero produces 1 million tons


annually of fluid coke, with roughly
half apiece on the West and East
coasts.

Code of Federal Regulations

Safety
Customers
Methods
Instruments/Softwares
Specifications
Personnel
Training
Process
Special projects
Quality
Control/Documentation
Audits

ATTENTION CHEMIST!!!

All methods should follow:


QC schedule
PM schedule
Calibration curve with STDV
C of A of STDS
QC chart of D 6299
Incident Investigations records
Maintenance records
Training records
SOP updates
% R & % r and other statistics
Quality control protocols
Method parameters
Round Robins comparison ( ASTM)
Online data vs lab data charts
Detection limits
Interferences with matrix or elements

GASOLINE METHODS

ASTM D3606 - 10 Standard Test Method for Determination


of Benzene and Toluene in Finished Motor and Aviation
Gasoline by Gas Chromatography

Significance and Use

Benzene is classed as a toxic material. A knowledge of the concentration of this compound can be an aid in
evaluating the possible health hazard to persons handling and using the gasoline. This test method is not
intended to evaluate such hazards.

1. Scope

1.1 This test method covers the determination of benzene and toluene in finished motor and aviation
gasolines by gas chromatography.

1.2 Benzene can be determined between the levels of 0.1 and 5 volume % and toluene can be determined
between the levels of 2 and 20 volume %.

1.3 The precision for this test method was determined using conventional gasoline as well as gasolines
containing oxygenates (ethers such as methyl tert-butyl ether, ethyl tert-butyl ether and tert-amyl methyl
ether).

1.4 Methanol may cause interference. Appendix X1 provides an option for modifying the test method for
analyzing samples containing ethanol.

1.5 The values stated in SI units are to be regarded as standard. The values given in parentheses are for
information only.

1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is
the responsibility of the user of this standard to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use.

Analyzer Description
Configuration:
1-valve, 2-column (capillary),
TCD
Sample type:
Finished motor and aviation
gasoline
Components separated:
Benzene, toluene
Concentration range:
0.1 to 5 vol% for benzene
2 to 20 vol% for toluene
Quality Protocol: Ref std ,sx, sx
dup and Ref std.

Typical Chromatogram

Significance and Use

In gasoline blending, the determination of organic


oxygenated compounds is important. Alcohols,
ethers, and other oxygenates are added to
gasoline to increase the octane number and to
reduce tailpipe emissions of carbon monoxide.
They must be added in the proper concentration
and ratios to meet regulatory limitations and to
avoid phase separation and problems with engine
performance or efficiency.

This test method provides sufficient oxygen-tohydro-carbon selectivity and sensitivity to allow
determination of oxygenates in gasoline samples
without interference from the bulk hydrocarbon
matrix.

1. Scope

1.1 This test method covers a gas chromatographic


procedure for the quantitative determination of
organic oxygenated compounds in gasoline
having a final boiling point not greater than
220C and oxygenates having a boiling point limit
of 130C. It is applicable when oxygenates are
present in the 0.1 to 20 % by mass range.

1.2 This test method is intended to determine the mass concentration of


each oxygenate compound present in a gasoline. This requires knowledge
of the identity of each oxygenate being determined (for calibration
purposes). However, the oxygen-selective detector used in this test
method exhibits a response that is proportional to the mass of oxygen. It
is, therefore, possible to determine the mass concentration of oxygen
contributed by any oxygenate compound in the sample, whether or not it
is identified. Total oxygen content in a gasoline may be determined from
the summation of the accurately determined individual oxygenated
compounds. The summed area of other, uncalibrated or unknown
oxygenated compounds present, may be converted to a mass
concentration of oxygen and summed with the oxygen concentration of
the known oxygenated compounds.
1.3 The values stated in SI units are to be regarded as standard. No other
units of measurement are included in this standard.

Analyzer Description
Configuration:
Capillary column, methanizer, oxygenate
flame ionization detector (O-FID)
Sample type:
Finished gasoline
Components separated:
Water, methanol, ethanol, isopropanol,
tert-butanol, n-propanol, MTBE, sec-butanol,
DIPE, isobutanol, ETBE, tert-pentanol, 1,2dimethoxyethane, n-butanol, TAME
Concentration range:
Oxygenated components from 0.1 to 20
mass%
Key Features and Benefits
Oxygen specific detector eliminates all
hydrocarbon interferences
Linear response over four orders of
magnitude
Easily replaced cracking reactor and
methanizer, limiting downtime

OFID QUALITY PROTOCOL

Blank
Quality std
Sx
Sx dup
Sx 10%
Sx 10% dup
Independent std
Quality std

Significance and Use

Test methods to determine benzene and the aromatic content of gasoline are
necessary to assess product quality and to meet fuel regulations.

This test method can be used for gasolines that contain oxygenates (alcohols
and ethers) as additives. It has been determined that the common oxygenates
found in finished gasoline do not interfere with the analysis of benzene and
other aromatics by this test method.
1. Scope
1.1 This test method covers the determination of benzene, toluene, other
specified individual aromatic compounds, and total aromatics in finished motor
gasoline, including gasolines containing oxygenated blending components, by
gas chromatography/mass spectrometry (GC/MS).

1.2 This test method has been tested for the following concentration ranges, in
liquid volume percent, for the following aromatics: benzene, 0.1 to 4 %; toluene,
1 to 13 %; and total (C6 to C12) aromatics, 10 to 42 %. The round-robin study
did not test the method for individual hydrocarbon process streams in a
refinery, such as reformates, fluid catalytic cracked naphthas, and so forth, used
in the blending of gasolines.
1.3 Results are reported to the nearest 0.01 % for benzene and 0.1 % for the
other aromatics by liquid volume.
1.4 The values stated in SI units are to be regarded as standard. No other units
of measurement are included in this standard.

GC 6890
GC Consumables:
60 m

0.25 mm ID, 1.0m HP-1


P/N 19091Z-236
Split/Splitless liner with glass wool
P/N 19251-60540
Merlin Microseal
P/N 5181-8833
ALS:
7673 with nanoliter adapter
MS:
5973A Mass Selective Detector
MSD ChemStation:
Aromatics in Gasoline mode
MSD Productivity ChemStation Software

GC Injection Port:
250C
Split 1100:1
GC Oven Ramp:
120C for 0.5 minutes
3C/minute to 140C
10C/minute to 250C
0 minutes hold at 250C
Carrier Gas:
Helium
GC Pressure Program:
0.3 mL/minute for 1.0 minutes
1.0 mL/min at 1.0 minutes
35 cm/second constant flow
Vacuum compensation ON
Gas saver ON after 1 minute
5L syringe
Nanoliter adapter, stop = 1 (0.1
(0.1L injection size)
MSD:
Transfer Line: 280C
Ion Source: 200C
Quadrupole: 150C
Solvent Delay: 3 minutes
Electron Energy: 70 eV
Emission current: 35 amps
Mass Range: 60 to 170 Daltons
Scan Speed: 2
A/D samples
Autotune: Standard
Multiplier Voltage: Autotune value (1153 volts) +200
volts after 6.0 minute

Most people are familiar with gasoline octane number. It's the number that you refer to when selecting the grade of
gasoline to use in your car. The number may be 87 or 89. The vehicle manufacturer recommends a certain type of fuel
to be used. In most cars this is 87 octane unleaded gasoline. This octane rating is actually the average of two tests that
are run on the finished gasoline - the Research Octane and the Motor Octane. The average is the Road Octane or
(R+M)/2 which is posted on the pump. Some of you may remember when gasoline was sold with a Research number.
The difference between Research and Motor Octane is around eight with Research being higher.

Gasoline is blended to meet the following specifications:


Reid Vapor Pressure (RVP) which is a measure of hydrocarbon vapors and is needed for starting engines.

Octane which is a measure of anti-knock level of gasoline and is important because knocking lowers engine efficiency
and wastes power.

Toxics which are measures of the harmful components in gasoline and refiners are required to benzene, olefins and
sulfur levels.

Oxygen content in reformulated gasolines to reduce the level of green house gas emissions.

Jet fuel is blended to meet the following specifications:

Freeze Point is the temperature at which the fuel forms ice crystals which could clog engine fuel filters.

Viscosity is a measure of how easily the jet fuel flows.

Diesel engines are different than gasoline engines, and, as result, have different specifications:

Cetane Index is a measure of engine performance.

Sulfur content determines the level of sulfur oxides in the exhaust.

Pour Point is the temperature at which the diesel fuel flows.

Viscosity is a measure of how easily the diesel fuel flows.

Performance
Fuel efficiency

Combustion properties
Engine fuel deposits
Environmental cleanliness

Compatibility with engine materials

Storage facilities
Miscellaneous

Specification
D2700,D2699 Octanes
D86 Distillation
D 5188 Vapor to liquid ratio
Lead content
D 5191 Vapor Pressure
D 381 Washed gum
D 5599 Oxygen content
D 3606 Benzene content
D 5769Aromatics content
D 1319 Olefin content
D 130 Corrosion
D 2622 Sulfur
D 4871 Oxidation stability
Additives

OCTANE ROOM

ASTM D2699 - 12a Standard Test Method for Research Octane Number of
Spark-Ignition Engine Fuel
Significance and Use
5.1 Research O.N. correlates with commercial automotive spark-ignition
engine antiknock performance under mild conditions of operation.
5.2 Research O.N. is used by engine manufacturers, petroleum refiners and
marketers, and in commerce as a primary specification measurement
related to the matching of fuels and engines.
5.2.1 Empirical correlations that permit calculation of automotive antiknock
performance are based on the general equation:
Equation D2699-12A_1
Values of k1, k2, and k3 vary with vehicles and vehicle populations and are
based on road-O.N. determinations.
5.2.2 Research O.N., in conjunction with Motor O.N., defines the antiknock
index of automotive spark-ignition engine fuels, in accordance with
Specification D4814. The antiknock index of a fuel approximates the Road
octane ratings for many vehicles, is posted on retail dispensing pumps in
the U.S., and is referred to in vehicle manuals.
Equation D2699-12A_2
This is more commonly presented as:
Equation D2699-12A_3
5.2.3 Research O.N. is also used either alone or in conjunction with other
factors to define the Road O.N. capabilities of spark-ignition engine fuels
for vehicles operating in areas of the world other than the United States.
5.3 Research O.N. is used for measuring the antiknock performance of
spark-ignition engine fuels that contain oxygenates.
5.4 Research O.N. is important in relation to the specifications for sparkignition engine fuels used in stationary and other nonautomotive engine
applications.

1. Scope
1.1 This laboratory test method covers the quantitative determination of the knock rating
of liquid spark-ignition engine fuel in terms of Research O.N., including fuels that contain
up to 25% v/v of ethanol. However, this test method may not be applicable to fuel and
fuel components that are primarily oxygenates.2 The sample fuel is tested using a
standardized single cylinder, four-stroke cycle, variable compression ratio, carbureted,
CFR engine run in accordance with a defined set of operating conditions. The O.N. scale is
defined by the volumetric composition of PRF blends. The sample fuel knock intensity is
compared to that of one or more PRF blends. The O.N. of the PRF blend that matches the
K.I. of the sample fuel establishes the Research O.N.
1.2 The O.N. scale covers the range from 0 to 120 octane number but this test method has
a working range from 40 to 120 Research O.N. Typical commercial fuels produced for
spark-ignition engines rate in the 88 to 101 Research O.N. range. Testing of gasoline
blend stocks or other process stream materials can produce ratings at various levels
throughout the Research O.N. range.
1.3 The values of operating conditions are stated in SI units and are considered standard.
The values in parentheses are the historical inch-pound units. The standardized CFR
engine measurements continue to be in inch-pound units only because of the extensive
and expensive tooling that has been created for this equipment.

ASTM D2700 - 12a Standard Test Method for Motor Octane Number of Spark-Ignition Engine Fuel
Significance and Use
5.1 Motor O.N. correlates with commercial automotive spark-ignition engine antiknock performance under severe conditions of
operation.
5.2 Motor O.N. is used by engine manufacturers, petroleum refiners and marketers, and in commerce as a primary specification
measurement related to the matching of fuels and engines
5.2.1 Empirical correlations that permit calculation of automotive antiknock performance are based on the general equation:
Equation D2700-12A_1
Values of k1, k2, and k3 vary with vehicles and vehicle populations and are based on road-octane number determinations.
5.2.2 Motor O.N., in conjunction with Research O.N., defines the antiknock index of automotive spark-ignition engine fuels, in accordance
with Specification D4814. The antiknock index of a fuel approximates the road octane ratings for many vehicles, is posted on retail
dispensing pumps in the United States, and is referred to in vehicle manuals.
Equation D2700-12A_2
This is more commonly presented as:
Equation D2700-12A_3
5.3 Motor O.N. is used for measuring the antiknock performance of spark-ignition engine fuels that contain oxygenates.
5.4 Motor O.N. is important in relation to the specifications for spark-ignition engine fuels used in stationary and other nonautomotive
engine applications.
5.5 Motor O.N. is utilized to determine, by correlation equation, the Aviation method O.N. or performance number (lean-mixture aviation
rating) of aviation spark-ignition engine fuel.6

1. Scope

1.1This laboratory test method covers the quantitative determination of the knock rating of
liquid spark-ignition engine fuel in terms of Motor octane number, including fuels that contain
up to 25% v/v of ethanol. However, this test method may not be applicable to fuel and fuel
components that are primarily oxygenates.2 The sample fuel is tested in a standardized single
cylinder, four-stroke cycle, variable compression ratio, carbureted, CFR engine run in
accordance with a defined set of operating conditions. The octane number scale is defined by
the volumetric composition of primary reference fuel blends. The sample fuel knock intensity
is compared to that of one or more primary reference fuel blends. The octane number of the
primary reference fuel blend that matches the knock intensity of the sample fuel establishes
the Motor octane number.
1.2The octane number scale covers the range from 0 to 120 octane number, but this test
method has a working range from 40 to 120 octane number. Typical commercial fuels
produced for automotive spark-ignition engines rate in the 80 to 90 Motor octane number
range. Typical commercial fuels produced for aviation spark-ignition engines rate in the 98 to
102 Motor octane number range. Testing of gasoline blend stocks or other process stream
materials can produce ratings at various levels throughout the Motor octane number range.
1.3The values of operating conditions are stated in SI units and are considered standard. The
values in parentheses are the historical inch-pounds units. The standardized CFR engine
measurements continue to be in inch-pound units only because of the extensive and
expensive tooling that has been created for this equipment.

All methods should follow:


QC schedule
PM schedule
Calibration curve with STDV
C of A of STDS
QC chart of D 6299
Incident Investigations
records
Maintenance records
Training records
SOP updates
% R & % r and other statistics
Quality control protocols
Method parameters
Round Robins comparison
( ASTM)
Online data vs lab data
charts.

RVP

600

500

400
SDV = 0.187
300

200

100

0
-0.8
RVP

-0.6 -0.4 -0.2


0
0.2 0.4 0.6
LAB VALUE - RAMAN PREDICTION

16

Y = M0 + M1*X
M0=0.036024
M1=0.99639
R=0.99817

14

12

10
SDV = 0.187
8

6
6

10

12

LABORATORY VALUE

14

16

0.8

AREAS OF LAB
Analytical Area
Titrations: Acid content,
H2S,Mercaptans, Amines,
Caustic, Bromine number, Basic
nitrogen,
Viscosity
NACE
Concarbon
Particles
GUMS
Aniline
Wisdom
Asphaltenes

GC area
Purity of stream samples and final
products
DHA
Benzene
Oxygenados
SFC Olefins
GC MS: Aromatics

Specialty testing
Amine
Arsenic

Control area ( pipelines/ transportation)


Flash Point
Color instrument
Cooper corrosion
Doctor test
RVP
TV/L
Cloud, Freeze, Pour point

CONTROL AREA

D 56Flash point, D 86 Automatic distillation


RVP D 5191, D 4052 Density and API

NACE TM0172

AD Systems CT10 for NACE Spindle Corrosion Test

The corrosivity of petroleum products (gasoline and other distillates) must be


determined before transportation through pipelines in order to control the internal
corrosion of pipelines. The NACE TM01721 test for Determining Corrosive Properties
of Cargoes in Petroleum Product Pipelines is considered a reference test and is the
most widely used laboratory test for this purpose.
The CT10 performs an objective and accurate rating of the test specimen
A new instrumental approach for measurement of corroded surface area has been
developed by AD Systems in which the exact percentage of corroded area is
accurately determined by an automatic instrument reducing test subjectivity. The
innovative CT10 instrument images the whole surface of the specimen. Operation is
based on a homogeneous lighting source, CCD camera, specimen rotation system,
and specially designed Windows CE application software. The test can now be run
unattended which reduces labor costs.
The CT10 test is simple and straightforward. The specimen is prepared according to
the NACE TM0172 test procedure and is placed in the test chamber of the CT10. The
operator enters sample information, using an intuitive graphical interface with touch
screen panel, and starts a specimen scan. Specific light is emitted onto the surface
of the specimen. The specimen is rotated and several images are taken. The
software builds a flat image of the specimen surface, calculates the percentage of

Applications
The CT10 is a versatile instrument for both research and routine applications at
locations where NACE corrosion performance is evaluated:
Refineries
Independent Laboratories
Pipelines and Terminals
Corrosion Inhibitor Producers
Research and Development
Benefits
Quick, accurate and objective rating
Automatic specimen diameter verification
Compact design, robust construction, installed in minutes
The results are saved in an internal database and can be printed, transferred to a
USB memory stick and/or sent to a LIMS
Every test is fully documented and traceable
The CT10 strictly follows the test method removing the subjectivity inherent to
the manual test and significantly improving repeatability and reproducibility
with a final evaluation which eliminates disputes between the shipper and
receiver of the product.

SULFUR D 2622,D 5453, D


7039

S4 PIONEER BRUKER

The S4 PIONEER - the most compact


wavelength dispersive X-ray fluorescence
spectrometer (WDXRF) is dedicated to serve
all applications with need for high
performance and high sample throughput:
Whenever reliable trace analysis, high
analyzing speed for accurate process control
or robustness for industrial use is demanded the S4 PIONEER is the right choice for
industry as well as for research and
development.

Combustion IC
Chlorides
Sulfur
Halogens
Amines
Heat stable salts
Sulfides
Na,Ca,Ma,NH3,Li,K.

ICP.-Inductively Coupled Plasma - Optical


Emission Spectroscopy is a method for Metals
Analysis.

ICP

Inductively coupled plasma optical emission spectrometry (ICPOES), is an analytical technique used for the detection of trace
metals. It is a type of emission spectroscopy that uses the
inductively coupled plasma to produce excited atoms and ions
that emit electromagnetic radiation at wavelengths characteristic
of a particular element.[1][2] The intensity of this emission is
indicative of the concentration of the element within the sample.

Optical emission spectrometers determine analyte concentration via a quantitative measurement of the
optical emission from excited atoms.
When a material is heated sufficiently it will emit visible light in a discrete spectrum, characteristic of
the elements in the material. Each element has its unique atomic emission spectrum (both visible light
and x-rays)

Detection Limits for ICP-OES


The detection limits that ICP analysis can be performed to is determined by the
equipment, and LSMs recent investment in state of the art technology allows
detection limits in ppb parts per billion to be achieved.

AMINE TESTING

UIC .-CO2/CO analyzer.


T-90 Titration for H2S,CO2,and amine determination

Ion Chromatography for amines and heat stable salts.


Column : metrosep 4/250 Conductivity detector, high pressure pump

RAMAN Technology/Modeling for gasoline


blending

ASTM D3241-09 Standard Test Method for Thermal Oxidation Stability of


Aviation Turbine Fuels (JFTOT Procedure)
This test method covers the procedure for rating the tendencies of gas turbine fuels to deposit
decomposition products within the fuel system.
The final result from this test method is a tube color rating based on an arbitrary scale established for
this test method plus two additional yes/no criteria that indicate the presence of an apparent large
excess of deposit or an unusual deposit, or both.

GC AREA SAMPLE CYLINDER

REFINERY GAS ANALYZER ppm to % level mol/mol

*Low Detection Limits for metals below 5 ppm


*New crudes testing for better handling
*New EPA regulations/Emissions
*Equipment/software compatibility to LIMS
*Process Technology changes
*High demand for more sample points testing
*High expectations from Lab Technicians.

http://www.bruker.com/
http://www.home.agilent.com
http://www.astm.org/
http://www.paclp.com/
http://www.metrohmusa.com
http://us.mt.com
http://www.perkinelmer.com/
http://www.xos.com
http://www.horiba.com/
http://dcglass.com/
http://wasson-ece.com/

Remember, that a Laboratory is a Dynamic


department and every day represents a
new opportunity for a Chemist to apply all
the skills and knowledge acquired from the
University.
In the laboratory is not always necessary to
be the smartest, it is the one that cares who
accomplished the most.
Go for the challenges and enjoy the
wonderful world of Chemistry.
Take care and thank you for your time .
Marisa Werner.