Refining 101

Dennis Sutton
March 2012

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 The Petroleum Industry

Exploration
 The Petroleum Industry

Exploration
Production &
Supply
 The Petroleum Industry

Exploration
Production &
Supply
REFINING
 The Petroleum Industry

Exploration
Production &
Supply
REFINING
Distribution &
Marketing
Crude Oil Petroleum Products
Other Feedstocks Refinery
Safely, and efficiently transform crude oil and other raw
materials into on-spec finished products.
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Crude Oil
 To the consuming public, crude oil is the raw material that will
ultimately power our vehicles, provide heating, pave our roads,
and become the building blocks for many of the plastics we use.

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What is Crude Oil?
 Usually naturally occurring
 Not a single compound, but a
complex mixture of thousands
of compounds
 Wide boiling range
 Mostly hydrocarbons
(compounds with carbon and
hydrogen) but traces of other
compounds are present, such
as sulfur, nitrogen, oxygen, and
metals

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What is Crude Oil?
 Usually naturally occurring- but
what about synthetic crude?

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What are Synthetic Crudes?
 The oil sands of Canada and Venezuela are the source of the
synthetic crudes.

 Using refinery units, the heavy bitumen is upgraded to yield

products from the oil sands.

 So, the term “synthetic crudes” refers to partially processed,

hydrocarbon blends suitable for processing in a crude unit.
Classifying Crude Oil
 Location
 Density (light, heavy) - the scale most commonly used in API
Gravity. The higher the number the lighter the crude oil.
 Generally, the lighter crudes are more valuable since they’ll
produce more of the higher valued products.
 Sulfur content (sweet, sour)
 Low sulfur is sweet
 High sulfur is sour
 Sweet is usually defined as less than 0.5% sulfur
 Sweet crudes are more valuable as the sulfur is an undesirable
component that must be removed in the refining process.

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Are Crude oils all pretty
much the same ?

Definitely not.
No more than people
are all the same.

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Crude Oil Assay Program
 Crude oils are characterized utilizing a very comprehensive
testing slate
 Typical full crude assay cost:
 $10,000 - $20,000 per crude
 Information is used for:
 Purchase decisions
 Refining planning and optimization
 Capital project decisions

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Crude Oil Assay Program
Analytical Testing
 A representative sample of the crude is distilled in the laboratory
under similar conditions as the refinery.
 Ten or more boiling range fractions are obtained.
 Very extensive testing is conducted on the whole crude and the
various fractions.
 Tests performed are selected based on the products.

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Crude Assay Laboratory

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Crude Oil Assay Program
Converting Information to Intelligence
 Following the analytical testing, special software programs are
used to put the raw analytical data into a form that conclusions,
comparisons, and correlations can be made.
 Sophisticated computer models use the crude assay data
together with operational data and price information to allow for
optimal planning and operation.

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Other Non-Crude Refinery Feedstocks
 Gas oil, feed to the cat cracker
 Gasoline blendstocks - intermediate materials to be blended into
the finished gasoline
 Butane(s)
 Raw materials for specialty units

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REFINERIES are
like snowflakes…

no two are the same!!

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Refinery Configuration Factors
 Process Units (Type & Size)  Transportation Options
 Location  Tankage

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 A Very Simple Refinery
Light Naphtha RBOB
PBOB

BTX Naphtha GASOLINE Premium

REFORMER
BLENDING Regular
D
I Blend Grade
S
T
Ethylene, Propylene, Propane
Crude I
Heavy Naphtha Heavy Naphtha
L
L LCO and Slurry

A
Kerosene
T
Kero/Jet
I Distillate
O
DISTILLATE
N Reduced Crude BLENDING Low S Diesel
ALKYLATION
FCCU

High S Diesel

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Refining Process

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Refining Crude Into Useful Products

Physical Processes
Separate hydrocarbon compounds based on
physical characteristics without causing chemical
reactions
–Boiling point
–Solubility in selected solvent
No change to hydrocarbon structures
–Distillation

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Refining Crude Into Useful Products
 Chemical Processes
 Alter chemical structure of
hydrocarbon molecules
– Example: rearrange molecules into
ones with more desirable properties

 Change the size of hydrocarbon

molecules
– Example: break large molecules into
several smaller ones

– Example: combine several small

molecules into larger ones

 Remove impurities such as sulfur

and nitrogen

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Desalting
 Prior to introducing the crude to the main units, it must be
“cleaned.”
 By using chemicals, heat, and electrical fields, the sediment, salts,
and water are removed.

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Distillation

 Primary physical separation

process within the refinery
 Separates hydrocarbon
mixtures according to
boiling point
 Used in various places in
the refinery

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Refining Processes Involving
Chemical Reactions
Reforming
Cracking
Hydrotreating
Alkylation
Coking

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Catalytic Reforming
 Function is to chemically alter
“naturally-occurring” gasoline-
like material (naphtha) to
boost its octane
 Converts low octane paraffins
and naphthenes into high
octane aromatics

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Catalytic Reforming –
Primary Process Chemistry
 Dehydrogenation of naphthenes to aromatics
H H H H
H H

H H
H H
H H + 3H2
H H
H H H H

C6H12 Benzene- C6H6

RON 80 115
(an example)

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Catalytic Cracking
 Function is to “crack” the gas oil
(650°F- 1000 °F) fraction of the
crude oil to produce more
gasoline and distillate fuels
 Usually uses a fluidized catalyst
- thus Fluidized Catalytic
Cracking Unit (FCCU)
 FCC was developed since the
amount of naphtha in crude oil
is insufficient to meet the
demand for gasoline per barrel
of crude

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Hydrotreating
 Removes sulfur (and nitrogen) compounds from intermediate
feedstocks
 Hydrotreating is necessary to meet low sulfur product quality
specifications
 Uses hydrogen produced by reformers

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Alkylation

“Links” small molecules together to yield high octane,

low vapor pressure gasoline blendstock
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Alkylate Product
An Ideal “Green” Gasoline Blendstock
Very high octane
NO sulfur
NO aromatics
NO olefins
NO benzene
Can be low vapor pressure

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Coking
 A method of bottoms
upgrading
 Feedstock:
 Vacuum resid – heaviest
 Highest boiling crude
fraction
 High sulfur
 High metals

 Products:
 6-10% gas
 15-20% naphtha
 35-60% gas oil
 20-40% coke

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What Products do
we make?

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Petroleum Refinery Products
 Propane and Propylene  Jet Fuel
 Butane(s)  Diesel Fuel - various grades
 Specialty Solvents  Heavy Fuel Oils
 Specialty Products  No. 4, No. 6, etc.
 Benzene
 Roofing Flux
 Toluene
 Cumene…  Road Asphalt - various grades
 Gasoline - various grades  Petroleum Coke
 Kerosene

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Gasoline Blending (at the Refinery)
Natural Gasoline
(purchased) Blendgrade
N-Butane
Unleaded
LSR
Isomerate Mid- Grade
Reformate Unleaded
Cat Naphtha
Premium
Coker Naphtha
Unleaded
Hydrocrackate
Alkylate RBOB
Raffinate
PBOB
Additives

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 Typical Gasoline Specifications
87 Regular Conventional
Specification Test Method Unit Minimum Maximum Text
Workmanship N/A Clear, Bright, Particulate Free
ASTM D4052; Calculation;
Gravity - API degrees API Report Only
D1298; D287
Copper Strip Corrosion ASTM D130 1 Test conducted at 122deg F for 3hrs
Silver Strip Corrosion D4814 Annex 1 Test conducted at 122deg F for 3hrs
NACE NACE TM0172 B+ min
Oxidation Stability ASTM D525 minutes 240
Washed Gum ASTM D381 mg/100 ml 4
D7039; D5453;
Sulfur w/ethanol wt.ppm Report Only
ASTM D2622
Sulfur D2622; D7039; D5453 wt.ppm 80
Lead D3237; ASTM D3341 g/Gallon 0.05
Phosphorous ASTM D3231 g/Gallon 0.005
Doctor ASTM D4952 Negative
Mercaptan Sulfur ASTM D3227 wt.ppm 20
Oxygenates D5599 wt% 0.100
End Point w/ethanol ASTM D86 °F 430
End Point ASTM D86 °F 430
Residue w/ethanol ASTM D86 percent 2
Residue ASTM D86 percent 2.0
ASTM D2885; NIR;
RON Report
ASTM D2699
ASTM D2885; NIR;
MON 82.0
ASTM D2700
ASTM D2885; NIR;
(R+M)/2 87.0
ASTM D2700

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 Products
Propane 2711

Crude Oil Gasoline 2710.12

<25° API 2709.00.10 Kerosene 2710.19

>25° API 2709.00.20 Diesel 2710.19

Asphalt 2713.20
Petroleum Coke 2713.90
Other
Feedstocks Specialty
Butane 2711 Petroleum Products
Gas Oil and Other
Blend Stocks
2710 Refinery Benzene &
Toluene
2707
2902
Cumene 2902

Safely, and efficiently transform crude oil and other raw

materials into on-spec finished products.
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Refining Resources
 Marathon Petroleum “The Basics of Refining”
multi-media program

 “Petroleum Refining in Nontechnical Language,”

by William L. Leffler

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Questions?

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