Documente Academic
Documente Profesional
Documente Cultură
Petroleum Refining
Industry
Presented by
Michelle Dunbar
Sr. Planning Engineer
Agenda
Part 1
Petroleum Industry Segments
Refinery Feedstocks
Refinery Products
Part 2
Refining Processes
Refineries
Part 3
Refinery Profitability
People
Hydrocarbon production maps
HFC Refinery
El Dorado, KS
Tulsa, OK
Navajo (NM)
Cheyenne, WY
Woods Cross, UT
MBPD Capacity
TOTAL
135
125
100
52
31
443
HollyFrontier Refineries
US Refining Overview
US Refineries vs. Crude Throughput
(EIA data 2012)
# Refineries
Crude Throughput
16
180
15
160
14
140
13
120
12
100
11
19
8
19 5
8
19 6
8
19 7
8
19 8
8
19 9
90
19
9
19 1
9
19 2
9
19 3
9
19 4
9
19 5
9
19 6
9
19 7
9
19 8
9
20 9
0
20 0
0
20 1
0
20 2
03
20
0
20 4
0
20 5
0
20 6
0
20 7
0
20 8
0
20 9
1
20 0
1
20 1
12
# Refineries
200
17
Crude Throughput
MMBPD
220
Key Properties
API Gravity - Heavy or Light (% of large
HC molecules vs. small)
Sulfur Content - Sour or Sweet (contains
high sulfur or low)
Other Properties
Pour Point deg F ( % straight chain / waxy
vs. ring compounds)
Distillation Range - % fractions boiled off
at specified temperatures
Carbon Residue solids after distillation,
asphalt content
TAN or Total Acid Number (corrosive
acids present)
Contamination levels (sodium, metals,
chlorides)
7
0.5%
Crude Value
or Price
1.5%
Function of Crude
Quality and Location
Relative to Refinery
2.0%
2.5%
Low Cost $
Sour
Heavy
10
20
API Gravity
30
40
Light
API 40.8
0.30% Sulfur
$88.25 / BBL
API 20.3
3.4 % Sulfur
$57.87 / BBL
API 32.1
1.9 % Sulfur
$81.41 / BBL
These margins
have a large impact
on Refinery Crude
Selection and can
change drastically
from month to
month
API Gravity
Heavy
15
Sweet
20
25
30
Light
35
40
45
0
$6.84 differential
0.5
WTI
$88.25
Sulfur %
1.5
$23.54 differential
WTS
$81.41
2.5
3
WCS
$57.87
3.5
Sour
Hydrocarbon Chemistry
The chemistry of crude oil is
hydrocarbon chemistry
Understanding the molecule
types and their properties is
key to understanding the
refining process
Although it can be very
complex, we will focus on
the essential basics!
10
Properties vary by the number of C and H atoms and the way they hold hands!
Boiling
Temperature
C
H
# of Carbon Atoms
11
Hydrocarbon Names
Names
Commonly
used in our
industry
Carbons
Prefix
Examples
Meth
Methane
Eth
Prop
But
Butane, isobutane
Pent
Pentane, cyclopentane
Hex
Hexane, cyclohexane
Hept
Normal hepatne
Oct
Octane, isooctane
Non
Nonane
10
Dec
Decane
11
Undec
Undecane
12
Dodec
13
Tridec
Tridecalene
14
Tetradec
Tetradecane
15
Pentadec
Pantadecane
Ethane, Ehtylene
Propane, Propylene
12
Contaminants
Sulfur
Nitrogen
Oxygen
Metals (iron, zinc, etc.)
Salts (Na, Mg, Ca)
Acids
Silt, Sediment
H
H
H
H
H
N
H
Naphtenic acid
Refined Products
PRIMARY PRODUCTS
Gasoline automobile, light truck, small engine fuel
Diesel automobile, heavy trucks, trains, heavy equipment
Jet Fuel Commercial and military aircraft
SECONDARY PRODUCTS
Kerosene Home heating, charcoal fluid
Liquified Petroleum Gas (LPG) Chemical feed, heating, commercial applications
Fuel Oil Home Heating, Ships, boilers, furnaces (1 through 6 Oil)
Asphalt Roads, roofing material, sealants
Carbon Black Oil Carbon black manufacture, carbon composites, tires
Lubricating Oil Engine & machinery lubrication
Waxes Candles, industrial sealants
Petroleum Coke Coal fired boilers, metals manufacture (anodes, fuel)
Sulfur Chemical and fertilizer manufacture
NaHS (sodium hydrosulfide) paper, copper mining, leather industries (Holly
emphasis)
14
Refinery Products
800
Kerosene
300-540
500
400
300
200
100
600
Diesel
350-680
700
Distillation
Curve
900
Gasoline
90-435
Temperature
1000
RESIDUUM
Boiling Points
LPG
Hydrocarbon Fractions
Product Specifications
Every refinery product has numerous specifications that
must be met
Specifications are determined by end user requirements,
regulatory agencies, and pipeline / terminal operators
Products are tested and certified by Refinery
Laboratories prior to shipment
Testing protocols are standardized for all products by
ASTM ( American Society for Testing and Materials)
16
Gasoline Specifications
A number that indicates the tendency for a gasoline to pre-ignite and cause engine
knocking
All engines have an optimum octane rating for efficient and safe operation (ideal
firing, no engine damage)
Higher altitude allows lower octane gasoline (lower atmospheric pressure results in
less absolute cylinder pressure upon compression)
The Octane number is equal to the percent of iso-octane (100) in the isooctane / normal heptane (0) blend that knocks at the same compression
ratio as the gasoline or component being measured
Research and Motor Octane averaged to give Anti-Knock Index seen on gas pumps
R+M = Road Octane or AKI
18
2
Diesel Specifications
Lubricity
Fuel injection equipment lubricated by fuel
19
An indicator of the time period between the start of injection and start of combustion. The higher
the cetane, the quicker the fuel burns. n-cetane (C16H34) molecule ignites quickly, assigned
cetane number of 100. Alpha-methyl naphthalene is the 0 cetane reference fuel.
Cetane Number can be determined on a test engine with reference fuels similar to knock engine
for gasoline with reference fuels, but is not normally done. Increase compression ratio until time
between injection and ignition = 2.4 ms.
Calculated Cetane Index (CI) is a substitute for Cetane Number, and is based on density and
distillation properties of the fuel
C.I.
=
-420.34
+ 0.016 (API Gravity)2
+ 0.192 (API Gravity)(log of 50% point in degrees)
+ 65.01 (log of 50% point in degrees)2
- 0.0001809 (log of 50% point in degrees)2
Low cetane fuel leads to poor combustion, power loss and high emissions
Higher cetane fuel provides easier starting, lower temperature starting and smoother operation
Cetane Improver (combustion promoter) can be used, but cetane number improvement must be
proven on engine
20
Stability: storage stability (oxidation), thermal stability (gum) JFTOT (jet fuel thermal
oxidiation test)
Lubricity: Jet Fuel provides lubrication for some injection system moving parts
Volatility: Tendency to vaporize for ignition (flash point), tendency to vaporize in fuel
system / vapor lock
Corrosivity organic acids (total acidity) and mercaptan sulfur (sulfur containing
hydrocarbons) content
Water Separability Ability for water to drop out of fuel (WISM test)
Asphalt Properties
Refinery Processes
Gas
100 F
Carbons
4
Cooled Reflux
Naphtha
200 F
Cooled Reflux
Crude
Oil
Gasoline
8
300 F
Cooled Reflux
Kerosene
12
400 F
Vapor
500 F
Liquid
Cooled Reflux
Diesel
16
Lubricating Oil
Crude
Furnace
36
600 F
Heavy Gas Oil
44
Residue
700 F
70+
Distillation Column
24
Molecules separated by
boiling ranges, but not
chemically altered
25
26
Charge Heater
and Stack
Atmospheric
Column
27
FCC Unit
FCC Catalyst
Hydrotreater
Purpose
Remove sulfur (and nitrogen if required) from molecules in process unit feed with minimal
cracking of hydrocarbons
Hydrotreating Reactions
Heat
Catalyst
+
Thiopene
H
R S
R = parent
hydrocarbon
Hydrogen
+
N-Butane
Hydrogen Sulfide
Heat
Catalyst
Hydrogen
R H
H S
Hydrogen Sulfide
Hydrotreater Unit
Reactor
Catalyst
32
Hydrocracker
Purpose
Catalytic Cracking in the presence of hydrogen
Convert heavy material into lighter product
Can crack molecules that FCC cannot
Makes iso-butane for alkylation process
High temperature
(600-800 degF), high
pressure (1,500
3,000 psig) process
Unlike FCC, no
olefins produced (H2
rich cracking
environment)
C4 and lighter
Hydrogen
Recycle Hydrogen
Compressor
Light
Hydrocrackate
Feed
Fractionator
H2
Seperator
Heavy
Hydrocrackate
Distillate
Second Stage
Reactor
First Stage
Reactor
Heater
Gas Oil
Heater
33
Hydrocracking Reactions
H
C
H13C6
H
C
H
C
H
C
CH
C
H
C
H
2H2
H13C6
C2H5
H
C
C
C
H
C
H
H
C
C
CH
C
H
C2H5
C
H
Partial Saturation
4H2
H
C
H
C
CH3
C3H7
CH3
Isohexane
HC
HC
CH
C2H5
H2
C
H
Ethylbenzene
H13C6
H2
C
C
HC
CH
C
H
C2H5
C H2
H2C
H2C
C
C
H2
C2H5
H
Ethylcyclohexane
Hydrocracker
Fractionator
Catalyst
Reactors
Charge
Furnace
Heat Exchangers
35
Delayed Coker
Purpose
Convert heavy residuum into gas oil feed for FCC / Hydrocracker and
light products
36
Little Steam
Big Steam
Little Water
Big Water
Water Drain
COKING CYCLE OF A
COKE DRUM
DECOKING CYCLE
OF A COKE DRUM
Unhead
Coke Drilling
Drum Heading
Coking
Steam Purge
Preheat
Pressure Test
Types of Coke
Green (used for fuel). Has
residual HC, perhaps high
metals, Sulfur
Anode (used for aluminum
manufacture), calcined at 2500
F to remove HC
Needle (crystalline) used as
annodes in electric arc furnaces
37
Delayed Coker
Main
Fractionator
Drill
Derricks
Coke Drums
Furnaces
Petroleum Coke
Solvent De-asphalting
Purpose
Maximize recovery of Gas Oil from Residual streams after atmospheric or vacuum distillation (up to
2/3 of feed to gas oil)
Extract paraffinic / naphthenic DAO from ashpaltenic pitch
A method to separate molecules of different configurations that are in the same boiling range
Condenser
Light paraffinic
solvent (butane
or propane)
extracts
paraffinic rich
gas oil DAO
Solvent
Solvent
Recycle
Extractor
Condenser
Furnace
Gas
Oil
Furnace
DAO Stripper
Pitch with
solvent
Pitch Stripper
Vac
Resid
Charge
DAO
Separator
Gas Oil
and Solvent
Pitch
Asphaltenes
Solvent
Receiver
39
Gas oil
Heavy Paraffin
Pitch
Solvent (Butane)
Heavy
Asphaltene
Paraffinic solvent has affinity for heavy paraffinic molecules (Gas Oil) and effectively
attach to them
Paraffinic molecules effectively become lighter and rise in the solution (DAO)
Asphaltenic molecules drop in the solution solution (Pitch)
40
Solvent Deasphalter
Extractor
Feed
Pitch
Convert low octane (55-65) naphtha into high octane (90 -100+) gasoline component
Straight chain C7-C8 and unsaturated rings converted to aromatic compounds and isomers
Increased popularity in 1970s to produce unleaded gasoline with tetraethyl lead phase out
Creates Benzene, mainly from any cyclohexane and normal hexane in feeds (precursors)
Reactor
Reactor
Reactor
Treated
Naphtha
Feed
Furnace
H2
Recycle
H2 to Hydrotreaters
Reformate
90-102 RONC
Stabilizer
C4 and lighter
4th Reactor
sometimes added
to make semi-regen
unit
Furnace
Furnace
H2
Seperator
42
Convert low octane / value naphtha into high octane gasoline component (C7-C8) range
Creates Benzene, mainly from any cyclohexane and normal hexane in feeds (precursors)
43
Toluene (111)
Methylcyclohexane
Octane = 83
+
aromatization
N-Heptane
Octane = 0
Toluene (111)
Hydrogen
isomerization
2,5 Dimethylhexane (95)
N-Octane
Octane = -10
+
N-Heptane
Octane = 0
Hydrogen
cracking
Isopentane (93)
methane
44
45
Combines FCC olefinic material with isobutane to form high octane (up to 95) blending component
Acid
Settler
Dryer
Acid
DeC3
Acid
Rerun
Tower
Acid
Cooler
C3
Acid
Stripper
Olefin Feed
Polymers
HF Recycle
Recycle iC4
Dryer
De
iC4
Alkylate, nC4
De
C4
C4
treater
C3
treater
iC4 Feed
n-Propane
n-Butane
Alkylate
46
Combines FCC olefin material with iso-butane to form high octane blending component
47
Alkylation Unit
Reactor
Acid Settler
Reactors
(Contactors)
48
FCC
Gasoline
Gasoline Blending
89 Octane
7.5 RVP
Recipe Input
Blend Engineer
Reformate
92-100 Octane
6.5 RVP
On Line
Blend
Computer
Alkylate
94 Octane
9.0 RVP
To Pipeline
Controls
Isomerate
80 Octane
12.0 RVP
Analyzer
Butane
Subgrade
<87 Octane
Samples
Refinery
Laboratory
Straight
Run
Gasoline
Ethanol
113 Octane
Premium
91-93 Octane
Results
55 Octane
11.0 RVP
Regular
87 Octane
Terminal
Additives:
Detergents
Anti-Rust
Gum Inhibitors
Color Dye
Location Specific
and seasonal RVP
7.0 - 10.0
93 Octane
51.7 RVP
Gasoline Blending
Gasoline Blend recipes are developed using computer
optimization model
Balances all factors to meet product demand and
specifications in the most cost effective way
Component Considerations
Inventory
Component
Properties
Future Shipments
Refinery
Production
Blend Recipe
RVP
Octane
Sulfur
Volume
Distillation
Benzene
Shipment Considerations
50
Gasoline Blending
51
52
Sulfur Recovery
Purpose
Converts H2S gas into elemental sulfur, Claus Unit
1/3 of H2S burned in Reaction Furnace to produce SO2 (sulfur dioxide) 1.5 O2 + H2S SO2 + H2O
Zinc Oxide catalyst beds convert SO2 and H2S into elemental sulfur and water SO2 + 2H2S 3S +
2H2O
Sulfur is collected in pit or tank and trucked / railed. Used in chemical manufacture.
Process is about 96% efficient, so Tail Gas Treating (SCOT Unit or other) required to purify off gas
53
Sulfur Recovery
Truck
Rail
54
Steam Production
Purpose
Provide steam for process heating, steam stripping in distillation, and steam turbine
drivers
Vent
Makeup Water
Boiler
Steam Drum
Deaerator
Tube Firebox
Superheater
Mud Drum
Condensate
Refinery Users / Producers
- Turbines
- Exchangers
- Process
- Boilers
Blow dow n
Boiler Feed
Water Pum ps
High Pressure Steam
Excess Steam
to Vent
Condensate
Desuperheat
Steam Production
Steam Drum
Boiler Tubes
56
ph Control
Waste Water
Streams
Equalization
Basin
Dependant upon
where water is discharged
and environmental
permit requirements
API
Seperator
Advanced
Treatment
(chemical,
bilogical)
Oil
Water
Water
Activated
Sludge
Treatment
Sludge
Water
Water Reuse
Filtration
Carbon or
other
Underground Injection
Water Way
or Municipal Treament Plant
Many processes combined to meet specific refinery waste characteristics and discharge
requirements
Oil removal and biological treatment are 1st steps
Can be re-used, injected underground or sent to waterrway
57
API Separator
Carbon
Filters
API Separator
DAF
Unit
59
Amine
Treater
Propane
Steam
Butane
High RVP Season
Light
Naphtha
Hydrotreater
Isomerization
Unit
Isomerate
Hydrotreater
Merox
Treater
Jet Fuel
Kerosene
Sour
Waters
Steam
Catalytic
Reformer
Sweet
Naphtha
Stripped
Water
Reformate
Jet Fuel
Diesel
Hydrotreater
Diesel
Diesel
Hydrocracked Gasoline
Hydrocracker
Distillate
Alkylation
Unit
Isobutane
Gas Oil
Alkylate
Olefins
Light Cycle Oil
Distillation
Vaccum
Gasoline
Atmospheric
Bottoms
Crude
Oil
Atmospheric Distillation
Heavy
Naphtha
H2
Natural Gas
Merox
Treater
Gas
Processing
H2 Synthesis
Sulfur
Gasoline Blending
Other Gasses
Claus Sulfur
Plant
Sour H2O
Stripper
Model Refinery
FCC
Unit
FCC
Hydrotreater
Light
Gas Oil
Heavy
Gas Oil
Fuel Oil
Gas Oil
Gas Oil
Naphtha (after hydrotreating)
Pitch
PDA
Coker
Vacuum
Resid
60
Tulsa Refinery
Crude
3 Sunoco Pipelines
85KBPD
Barnsdall OK
Little Farm OK
Bad Creek OK
Magellan Cimmaron
40KBPD
(Cushing OK)
Tulsa
Refinery
Local Rack
61
62
Crude Oil
Balance
Intermediate
Feed availability
Natural Gas /
Electricity costs
Refinery
Configuration
Complexity
Crude flexibility
Highest value
products
Liquid Volume
Gain and Yield
Unit limitations
Reliability &
Efficiency
Size
Uptime & Capacity
Utilization
Turnaround
frequency and
duration
Operating
Expenses
Capital Investment
Product Value
Product Balance
Location
Competition
Inventory Value /
Risk
Seasonal factors
63
Variable
Fixed
Operating Expenses
Refinery
Complexity
Gross Margin
$$ / BBL
$$
Refinery
Complexity
Refined product
value
Crack Spread
Shorthand method to estimate refinery gross
margin (product value minus crude oil cost in
proportion to product production vs. crude)
Stated in $$ / BBL
Common Refinery Crack Spreads ($$ / BBL)
3-2-1.( 2 x Gasoline + 1 x Diesel - 3 x Crude) / 3
3 BBLs of Crude makes 2 BBLs gasoline, 1 BBL Diesel
65
Maximizing Profitability
Linear Program (LP) - Computer simulation tool that
helps to optimize refinery operation
Inputs include:
Maintenance
Technical
Administrative
-
67
Maintenance
Technical
Administrative
-
Pipefitters / Boilermakers
Instrumentation & Electrical
Rotating Equipment
Equipment Operators
Scaffold, Insulators,
Carpenters
Contract Services
Turnaround contractors
Maintenance Planners
Chemical, Mechanical,
Electrical, Control Engineers
Safety, Health, Environmental
Engineers / Specialists
Equipment Inspectors
Laboratory Technicians,
Chemists
Project Engineers, Designers
Technical Trainers
Outside consultants, technical
experts
Management
Purchasing agents
Warehouse workers
Accountants
Office assistants
68
69
70
71
72
73