Refining Fundamentals

Michael D. Morris
September 2007
 Outline

‰ Crude Oil Supply & Demand

‰ Composition of Crude

‰ Products from a modern refinery

‰ Petroleum refining objectives

‰ Process Overview
ƒ Refinery flowsheet ƒ Alkylation
ƒ Crude Distillation ƒ Reforming
ƒ Coking ƒ Hydroprocessing
ƒ Catalytic Cracking ƒ Sulfur Recovery
 Proved Oil Reserves – End of 2006

BP Statistical Review of World Energy -2007

Major Crude Oil Consuming Areas

BP Statistical Review of World Energy -2007

Crude is Like Wine ......
Really Bad Wine.....

Sulfur Cadmium

Nitrogen Selenium

Nickel Arsenic

Vanadium Organic Acids

What’s in Crude Oil ?
Products Made from Crude Oil

Transportation Fuels Chemical Feedstocks

Š Gasolines Š C2/C3/C4 - olefins
Š Diesel fuels Š Olefins…polyethylene,
polypropylene
Commercial Fuels
Š Aromatics -polyesthers,
Š Fuel oils polystyrene
Š Heating oils
Š Jet fuels Specialty Products
Š Propane
Š Coke……...coal substitute
Š Butane
Š Asphalt…..road paving
Lubricants Š Sulfur…….fertilizer, roads
Š Motor Oils Š Waxes…….candles, sealants
Š Greases
Š White Oils/petrolatums
Why Crude Needs Processing
Petroleum Refining Objectives

Adjust the fuel yields to match the market

Increase gasoline
Decrease kerosene, gas oil, and resid

Remove contaminants & catalyst poisons

Sulfur
Nitrogen
Heavy metals

Improve fuel quality and meet specifications

Octane (gasoline)
Cetane (diesel)
Flow characteristics (especially jet!)
Gasoline Specifications

Federal and State regulations

Š Reid vapor pressure
Š Octane (R+M)/2
Š No Tetraethyl Lead
Š Aromatics (Benzene)
Š Oxygenates
Š Olefins
Š Sulfur

Customer Satisfaction/Preference
Š Octane (R+M)/2
Š Reid vapor pressure
Š Volatility - Gasoline distillation curve
Š Additives - Anti-oxidants, detergents
 Typical Fuels Refinery Configuration

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
 Step One – Crude Oil Distillation

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
Crude Oil Distillation
Pipestill Fractions
 Pipestill Stream Dispositions

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
Atmospheric Distillation Tower
Vacuum Distillation Tower
Compressor Applications – Crude Units

Liquid Ring Vacuum Pumps

0 psig suction pressure

20-40 psig discharge pressure
<100 o F
Wet, Corrosive, Hydrogen sulfide
Low but variable flow
Variable molecular weight
Oxygen contamination
 Coking – The Bottom of the Barrel

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
 Petroleum Coking Process

Light Ends

Naphtha

Coke
Drums Raw Diesel

Gas Oil
Resid
Feed

Fractionator
Furnace Heavy
Gas Oil
Recycle
Petroleum Coking Process
Petroleum Coking Process
Petroleum Coking Product
 Compressor Applications – Cokers

Variable Speed Centrifugal Compressors

10-20 psig suction pressure
40-120 psig discharge pressure
Highly variable flow - cyclic
Wet, corrosive, reactive
H2S - Highly Toxic
100 – 200 o F
Variable molecular wt.
 Fluidized Catalytic Cracking

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
 Fluid Catalytic Cracking

Hydrocarbon to
Fractionation

FCCU Reactor
Flue Gas to
Energy
Recovery
Reactor Stripping
Section

Regenerator
1000+ F

Reactor Riser

Air
Feed
Catalyst Deactivation

Electron micrograph of carbon

deposit on catalyst surface
Fluid Catalytic Cracker
 Compressor Applications – Fluid Catalytic Crackers

Turbo Expanders
Combustion gases nitrogen +CO2
25-35 psig inlet pressure
Atmospheric discharge pressure
High flow, variable but gradual
Wet, but above dew point
1200 -1250 o F inlet temperature
Abrasive particulates

Constant Speed Variable Speed

Centrifugal Compressors
Air Blowers
30-50 psig discharge
Gradual changes in flow
High volume
Multiple machines
Centrifugal Compressors
15-30 psig suction pressure
80-120 psig discharge pressure
Gradual changes in flow
Gradual changes in MW
Wet, reactive gases
100 -150 o F
 Alkylation Process

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
 Alkylation Process – Sulfuric Acid

Isobutane Recycle Critical Variables

Temperature
Acid and Olefin
Caustic concentration
Treater
Reactor
Feed
Olefin +
Isobutane
De-isobutaniser

Acid
Settler

Fresh Acid Spent Acid Alkylate Product

 Alkylation Reaction

Butylene
Isobutane

Double Bond

Catalytic cracking produces unmarketable light

olefins which must be reassembled with
isobutane into gasoline components
Olefin Alkylation

Tri-methylpentane

Result
Highly branched,
high octane
gasoline blending
component
Typical Sulfuric Acid Alkylation Unit
 Compressor Applications – Sulfuric Acid Alkylation

Variable Speed
Centrifugal Compressors
Propane + butane refrigeration
refrigeration
5-10 psig suction pressure
50-70 psig discharge press.
Limited flow variability
Wet, highly corrosive, reactive
40-50 o F suction temperature
Low molecular wt. variability
 Typical Fuels Refinery Configuration

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
 Catalytic Naphtha Reforming - Cyclic

Reformer Reactors Hydrogen

Light Ends

Separator

Naphtha Feed
65 Octane

De-butanizer
Furnaces

Reformate
 Catalytic Naphtha Reforming - Cyclic

Reformer Reactors Hydrogen

Flue Gas
Light Ends

Air

Regeneration
Furnace
Separator

Naphtha Feed
65 Octane

De-butanizer
Furnaces

Reformate
 Catalytic Naphtha Reforming - Cyclic

Hydrogen
Reformer Reactors
Light Ends

Air

Regeneration
Furnace
Separator

Naphtha Feed
65 Octane

De-butanizer
Furnaces

Reformate
“Ultraformer” Design Reformer
Compressor Applications – Naphtha Reforming

Variable Speed Centrifugal Centrifugal or Reciprocating

Compressors Compressors
Recycle Gas Compressor Regeneration Gas Compressor
80-100 psig suction pressure
160-180 psig suction pressure
150-250 psig discharge pressure
320-380 psig discharge Highly variable flow - cyclic
pressure
High nitrogen content
Highly variable flow - cyclic 100-200 o F
High hydrogen content
Low level chlorides
100 -140 o F
Variable molecular wt.

Combustion Air Compressor

Regeneration Gas Compressor – Compressor type Application Specific
Atmospheric suction pressure
50-250 psig discharge pressure
Variable flow demand – multiple services
 Hydrotreating

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
 Hydrotreating Process

Fuel Gas

Compressor
Naphtha

Separator

Feed

Furnace Heat
Desulfurized
Product
Typical Desulfurization Units
 Compressor Applications – Hydrotreating
Reciprocating Compressors
Make-up gas service
High compression ratio 4 - 18
300-3000 psig discharge press.
Limited flow variability
High hydrogen concentration
0
Suction temperatures < 150 F

Centrifugal Compressors
Recycle gas service
Low compression ratio
Low temperature100-200 0 F
Limited flow variability
High hydrogen concentration
0
Suction temperatures < 150 F
 Sulfur Recovery Process

Fuel Gas

Alkylation

Separation
Reforming Gasoline

Crude
Hydro-
treating
Diesel

Catalytic
Cracking
Sulfur
Sulfur
Recovery

Coking Coke
Asphalt
Sulfur Recovery - Claus Process
Sulfur Recovery - Claus Process
 Compressor Applications – Sulfur Recovery Units

Centrifugal or Positive Displacement Compressors

Combustion air
Atmospheric suction pressure
< 25 psig discharge pressure
Low flow variability - dependent on plant turndown
Refining Process Overview

™Separation (getting started)

ŠCrude Distillation

™Boiling Range Adjustment (matching the market)

ŠDelayed Coking
ŠCatalytic Cracking
ŠAlkylation

™Heteroatom Removal
Š Catalytic Hydrotreating

™ Fuel quality improvement

ŠCatalytic Reforming
 Refining Industry Business Context

• A margin business, subject to cyclicality

• Capital intensive, combined with high cash costs

• High entry/exit barriers

• Politically sensitive/state-owned companies

• Long lead times on investment

• Mainly commodity products and very competitive

• Mature industry in most regions