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Delaware City Refinery Tour
       August 27, 2007




                              1
Agenda

Basics of Refining
Desulfurization
Hydrocracking
Delaware City Refinery Operations
Gasification Overview
Q&A
Plant Tour
Concluding Remarks
                                    2
Crude Oil Characteristics
Crudes are classified and priced by density and sulfur content
Crude density is commonly measured by API gravity
 • API gravity provides a relative measure of crude oil density
 • The higher the API number, the lighter the crude
    − Light crudes are easier to process
    − Heavy crudes are more difficult to process
Crude sulfur content is measured as a percentage
 • Less than 0.7% sulfur content = sweet
 • Greater than 0.7% sulfur content = sour
 • High sulfur crudes require additional processing to meet regulatory specs
Acid content is measured by Total Acid Number (TAN)
 • Acidic crudes highly corrosive to refinery equipment
 • High acid crudes are those with TAN greater than 0.7


                                                                               3
Crude Oil Basics
                                               Crude Quality by Types                                                            Estimated Quality of Reserves (2006)
                 4.0%
SOUR




                                            Cold Lake
                          Cerro Negro
                 3.5%
                                             Maya
                                          WCS
                 3.0%
                                                                                                                                                      Sweet
                                                                  Arab Heavy
                          M-100 (resid)
SULFUR CONTENT




                                                                                                                                High Acid
                 2.5%                                                          Arab Medium
                                                                                                                                                          20%
                                                                                                                                 (Sweet)
                                                                                                                                                                         Light/Medium
                                                                         Dubai
                                        Napo                                                                                        2%
                 2.0%                                                   Mars
                                                                                                                                                                             Sour
                                                                                 Arab Light
                                                         Iran Heavy
                                                                        2010                                                                          13%
                                  Ameriven-Hamaca
                                                                                                                                                                              66%
                 1.5%
                                                                                                                                   Heavy
                                                                2000            Urals
                                                                               1990
                                                                                                                                   Sour
                                               Alaskan North Slope
                 1.0%
SWEET




                                                                                        1980

                 0.5%                                                                             WTI
                                                                                          Brent
                                                                                                        Tapis
                                                                  Cabinda          Bonny Light
                 0.0%
                        15         20               25                30        35                40    45              50
                                                                                                                             Source: Oil & Gas Journal, Company Information
                          HEAVY                                         API GRAVITY                             LIGHT
                    Source: Industry reports
                    NOTE: Red line represents the average crude quality by decade (actual and projected)


                        Majority of global reserves are light/medium sour
                        Most quoted benchmark prices are light sweet crudes
                          • WTI (West Texas Intermediate), Western Hemisphere
                          • Brent (North Sea Crude), Europe
                        Historical trend shows global crude supply becoming heavier and more sour
                                                                                                                                                                                        4
What’s in a Barrel of Crude Oil?
    Crude Types                  Characteristics       Yields
                                                                              2005 U.S.
                                                        3%
                                                                             Production
                                 > 34 API Gravity
                                                       30%
   Light Sweet Crude             < 0.7 % Sulfur
                                                                                  Propane/
   (e.g. WTI, Brent, Saharan                                                      Refinery
                                                                      8%
                                                       34%                        Butane
                                                                     7%           Gases
                                 35% Demand
             Blend)
                                                       33%
                                 Most Expensive
                                                                                  Gasoline
                                                                                  RFG
                                                                     50%          Conventional
                                                        3%                        CARB
                                 24 – 34 API Gravity                              Premium
                                                       21%
  Medium Sour Crude              > 0.7 % Sulfur
    (e.g. Mars, Arab Light,                            26%
     Arab Medium, Urals)         50% Demand
                                                                                  Distillate
                                                                     33%
                                                       50%
                                                                                  Jet Fuel
                                 Less Expensive
                                                                                  Diesel
                                                                                  Heating Oil
                                                        1%
                                 < 24 API Gravity
                                                        14%
                                                                                 Heavy
                                                                   10%
                                 > 0.7 % Sulfur                                  Fuel Oil &
                                                        22%
   Heavy Sour Crude                                                              Other
                                 15% Demand
 (e.g. Maya, Cerro Negro, Cold
Lake, Western Canadian Select)                                  Source: EIA Refiner Production
                                                        63%
                                 Least Expensive




                Refineries upgrade crude oil to higher value products
                                                                                                 5
Basic Refining Concepts
                                       Intermediates                   Final Products
                           < 90°F      Propane, Butane                • Refinery fuel gas
                                          and lighter                 • Propane
                                                                      • NGLs
                                         Straight Run
                           90–220°F                      More
                                                                      • Gasoline (high octane)
                                         Gasoline (low
                                                         processing
                                            octane)
Crude oil
                                                         More
                           220–315°F                                  • Gasoline (high octane)
                                           Naphtha
                                                                      • Jet fuel
            Distillation                                 processing
               Tower
                                                                      • Kerosene
              (Crude
                                                         More
                           315–450°F                                  • Jet fuel
               Unit)                      Kerosene
                                                                      • Diesel
                                                         processing
                                                                      • Fuel oil

                                                                      • Gasoline (high octane)
                                                         More
                           450–650°F     Light Gas Oil                • Diesel
Furnace                                                  processing
                                                                      • Fuel oil

                                                                      • Gasoline (high octane)
                                                         More
                           650–800°F     Heavy Gas Oil                • Diesel
             Vacuum                                      processing   • Fuel oil
               Unit
                                                                      • Gasoline (high octane)
                                         Residual Fuel   More
                           800+°F                                     • Diesel
                                          Oil/Asphalt                 • Fuel oil
                                                         processing
                                                                      • Lube stocks
                                                                                                 6
Hydroskimming/Topping Refinery
          Crude
           Unit
                                                                                                                Propane/
                                                                                                          4%
                                                                         Propane/Butane
                                                                                                                Butane


                                                                                                               Gasoline
                                                       Reformer       High Octane Gasoline
                                 Low Octane Gasoline                                                           RFG
            Distillation Tower



                                                                                                         30%
                                 and Naphtha                                                                   Conventional
                                                                                                               CARB
                                                          Hydrogen
                                                                                                               Premium
Light
                                                                 Distillate
                                  HS Kerosene/Jet Fuel
Sweet                                                                           LS Kerosene/Jet Fuel
                                                                                                               Distillate
                                                                                                        34%
                                                                 Desulfurizer
                                                                                                               Jet Fuel
Crude                                                                                                          Diesel
                                                                                LS Diesel/Heating Oil
                                  HS Diesel/Heating Oil
                                                                                                               Heating Oil




                                                                                                               Heavy
                                                               Gas Oil
         Vacuum                                                                                                Fuel Oil &
                                                                                                        32%
           Unit                                                                                                Other

                                                          Heavy Fuel Oil

                                                                                                        100% Total Yield
   Simple, low upgrading capability refineries run sweet crude
                                                                                                                              7
Crude and Vacuum Towers
                                         Reactor




                                                        Heater


Crude Atmospheric Tower   Vacuum Tower             Reformer

                                                                 8
Medium Conversion: Catalytic
                                            Cracking
           Crude
                                                                                                                    Propane/
            Unit
                                                                                                              8%    Butane
                                                                             Propane/Butane

                                                                                                                     Gasoline
                                                                                                                     RFG
                                                        Reformer           High Octane Gasoline
                                  Low Octane Gasoline                                                         45%    Conventional
                                  and Naphtha
             Distillation Tower



                                                                                                                     CARB
                                                                                                                     Premium
                                                            Hydrogen


                                                                       Distillate
Light                                                                                  LS Kerosene/Jet Fuel
                                   HS Kerosene/Jet Fuel
                                                                       Desulfurizer                                 Distillate
                                                                                                              27%
Sour                                                                                                                Jet Fuel
                                    HS Diesel/Heating Oil                             LS Diesel/Heating Oil         Diesel
Crude                                                                                                               Heating Oil


                                          Light Cycle Oil
                                               (LCO)

                                                                               Alkylation
                                                                                                Alkylate
                                                                               Unit
                                                    Fluid Catalytic
                                    Gas Oil
          Vacuum                                    Cracker
            Unit                                                                      FCC Gasoline
                                                    (FCC)                                                           Heavy
                                                                                                                    Fuel Oil &
                                                                                                              24%   Other
                                                            Heavy Fuel Oil


                                                            104% Total Yield
   Moderate upgrading capability refineries tend to run more sour crudes
   while achieving increased higher value product yields and volume gain
                                                                                                                                    9
High Conversion: Coking/Resid
                                            Destruction
                                                       Hydrogen Plant
           Crude
                                       Gas
            Unit
                                                                                                                   Propane/
                                                                                                             7%    Butane
                                                       Propane/Butane

                                                                                                                    Gasoline
                                                                                                                    RFG
              Distillation Tower



                                                                                                             58%
                                                                        Reformer     High Octane Gasoline           Conventional
                                   Low Octane Gasoline
                                                                                                                    CARB
                                   and Naphtha
Medium/                                                                                                             Premium
                                                                             Hydrogen

 Heavy                                                                                                             Distillate
                                                              Distillate                                     28%
                                   HS Kerosene/Jet Fuel                        LS Kerosene/Jet Fuel
 Sour                                                         Desulfurizer                                         Jet Fuel
                                                                                                                   Diesel
 Crude                                                                                                             Heating Oil
                                                                               LS Diesel/Heating Oil
                                   HS Diesel/Heating Oil



                                                           Hydrocracker         Hydrocrackate Gasoline
                                     Light Gas Oil
                                                                              Ultra Low Sulfur Jet/Diesel
                                                         LCO                 Alkylation
                                                                                             Alky Gasoline
                                                                             Unit
                                                         Fluid Catalytic
                                                         Cracker (FCC)
                                   Medium Gas Oil
           Vacuum
                                                                                        FCC Gasoline
             Unit
                                                                                                                   Heavy
                                                                                                                   Fuel Oil &
                                                                                                             15%   Other
                                                               Delayed
                                      Heavy Fuel Oil                                      Coke
                                                               Coker
                                                                                                             108% Total Yield
   Complex refineries can run heavier and more sour crudes while achieving the
   highest light product yields and volume gain                                                                                    10
FCC and Hydrocracker Reactors
     Fluidized Catalytic Cracker
                               Reactor   Hydrocracker Reactors




Main Column              Regenerator

                                                                 11
Cokers
              Delayed Coker
Superstructure holds the drill and drill stem
                                                     Fluid Coker - Benicia
  while the coke is forming in the drum




                                                                             12
Conversion Economics
                                                       U.S. Gulf Coast Refinery Margins
            30

            25

            20

            15
US $/ Bbl




            10

              5

              0

             (5)

            (10)
              Jan-00          Jan-01           Jan-02          Jan-03         Jan-04     Jan-05     Jan-06      Jan-07

                       Arab Medium Hydroskimming                          LLS Cracking            Maya Coking


                  Need conversion capacity to capitalize on sour crude discounts
                   •   Hydroskim – Breakeven or moderate margins; High resid yield
                        −   When margins are positive – increase crude runs
                        −   When margins are negative – decrease crude runs
                   •   Cracking – Better margins; Lower resid yield
                   •   Coking – Best margins; Lowest resid yield
                        −   Maximize heavy crudes

                                                                                                                         13
Desulfurization Basics
   Objective
    Remove sulfur from light products (gasoline or diesel) to meet air quality
    requirements for clean burning fuels



                              Desulfurization Unit
                                                                 Desulfurized Light Products
                                                           HC
                                          H2
High Sulfur                                     HC-S
                               HC-S
                   HC-S
   Light                                              H2
                                                                             Elemental
                               H2
 Products                             Catalyst
                                                                 Sulfur Plant Sulfur
  (HC-S)                                                                                    • Agricultural
                                                  HC-S
                              HC-S                         H2S                        S
                                                                 S           S              • Pharmaceutical
                                     H2                                  S
                                               HC-S
                                                                     S       S
                          2
                          H
      Hydrogen Unit
                                                                                 LEGEND
        H2                                                                        LEGEND
              H2 H2                                                              HC : : Hydrocarbon
                                                                                  HC Hydrocarbon
       H2                       1000 or less PSI;                                H2 : : Hydrogen
                   H2
              H2                                                                  H2 Hydrogen
                                 700 F or less
                                                                                 S : : Sulfur
                                                                                  S      Sulfur
                                                                                                         14
Hydrocracking Basics
    Objective
        Value added upgrading of high sulfur distillates to low sulfur gasoline and ultra
        low sulfur jet/diesel to meet air quality requirements for clean burning fuels



                              Hydrocracking Unit          Desulfurized Hydrocrackate Gasoline
                                                    HC
                                       H2
High Sulfur                                  HC-S
                              HC-S
                   HC-S                 H2
 Distillate                       H2                      Desulfurized Ultra Low Sulfur Jet/Diesel
                                                    HC
                                            H2
                               H2
  (HC-S)                          Catalysts H2                        Elemental
                              H2
                                                          Sulfur Plant Sulfur
                              HC-S H2 H2 HC-S
                                                                                • Agricultural
                                                    H2S                   S
                                  H2                      S       S             • Pharmaceutical
                                       HC-S                   S
                                                            S   S
                          2
                          H
      Hydrogen Unit
                                                                    LEGEND
        H2                                                           LEGEND
              H2 H2                                                 HC : : Hydrocarbon
                                                                     HC Hydrocarbon
                                 1300+ PSI;
       H2                                                           H2 : : Hydrogen
                   H2
              H2                                                     H2 Hydrogen
                               725 to 780 F
                                                                    S : : Sulfur
                                                                     S      Sulfur
                                                                                               15
Andrew Kenner
Vice President and General Manager
       Delaware City Refinery



                                 16
Valero Delaware City Refinery

Built by Tidewater Oil Company in 1957
Acquired by Valero in 2005
Since commissioning, Valero and previous
owners have made significant modifications
and environmental upgrades
Total throughput of 191,000 bpd
High conversion operation
  • 60%+ gasoline yield
Staffed by more than 700 full-time
employees
Located on 5,000 acres, some of which is
leased to local farmers, preserving our
buffer zone
Seeking OSHA VPP Star Status

                                             17
Delaware City Products and
                            Crude Slate
      Typical Product Slate                        Typical Crude Slate
  Product      BPD       %                 Crude          S % / API      BPD       %
 Gasoline       85,000        50   Arab Heavy              2.7 / 29       75,000   45
 Distillates    65,000        38   M-100                   2.7 / 16       45,000   26
 Propane         7,500        4    Hamaca                  1.6 / 26       35,000   20
 Alkylate        5,000        3    Opportunity Crudes                     15,000       9
 6 Oils          4,500        3    Total                                 170,000   100
 Benzene         1,500        1
 Pet coke        1,900        1
 Sulfur           300     <1
 Total         170,700   100


Provides approximately 70% of all gasoline sold in Delaware

Flexible light-ends system

Produces petrochemical grade Benzene for sales into local market.
                                                                                           18
Delaware City Capital
                    Investments
$456 MM invested in capital improvements and $97 MM for turnaround maintenance
at Delaware City since Valero’s acquisition
 • Major plant turnaround completed in 4Q05
Fluid Coker Flue Gas Scrubber - $200 MM
Fluid Catalytic Cracking Unit Flue Gas Scrubber - $200 MM
Cracked Naphtha Hydrotreating Unit expansion project commissioned in 4Q05
Sulfur Plant O2 enrichment and reliability projects - $25 MM
Took over operations of Gasifier/Power Plant and have improved on-stream reliability
and throughput dramatically

                           Petcoke Destruction (TPD)
                                                     1,100

                                     650

                     300
                   Motiva          Premcor          Valero

                                                                                       19
Gasification Overview
                                                                                                                  File: GASIF03.vsd
                                                                                                                  by: MEL 5/15/98




                                       Delaware City Plant
  Air Separation
                               Coke Gasification Repowering Project
       Plant
                                                                                         Electric
                                                                          Gas Turbine
                                                                                         Power
                    Oxygen
                                                       Clean Syngas

                                                                                                        To
                                                                                                        Refinery
                                                        Sulfur
                                  Steam To
     Coke
                                                        Removal
                                  Refinery
Fluxant Water                                                                   Boiler
                                                                                              To
                                                                                Feed
                                                                                              Utility
                                                                                Water
                               Raw      Syngas                 Exhaust Gas
                               Syngas   Cooler
                    Gasifier




                                                                  Heat Recovery
                                   Boiler                         Steam Generator
                                   Feed
                                   Water
         Slurry                                              High Pressure Steam
                                            Acid Gas
                      Slag                                                                              To
                                                                                         Electric
                                                                                                        Utility
                                                                                         Power

                                                                                                        To
                   Sulfur
                                   Sulfur                                                               Refinery
                                Recovery Unit
                                                               Existing Steam
                                                                                                        Steam To
                                                               Turbine
                                                                                                        Refinery

                                                                                                                                      20
Appendix




           21
Delaware City Refinery
    Flow Diagram




                         22
Map of Valero Refineries
                                                                                                                Quebec, Canada
                                                                                                                • 215,000 bpd capacity




Benicia, California
• 170,000 bpd capacity
                                                                                                                                              Paulsboro, New Jersey
                                                                                                                                              • 195,000 bpd capacity




                                                                                                                                              Delaware City, Delaware
Wilmington, California                                                                                                                        • 210,000 bpd capacity
• 135,000 bpd capacity




McKee, Texas
• 170,000 bpd capacity

                                                                                                                                              Memphis, Tennessee
                                                                                                                                              • 195,000 bpd capacity
Three Rivers, Texas
• 100,000 bpd capacity
                                                                                                                                               Ardmore, Oklahoma
                                                                                                                                               • 90,000 bpd capacity

                                Corpus Christi, Texas
                                • 340,000 bpd capacity
     Valero Marketing                                                                              Krotz Springs, Louisiana
                                                                                                   • 85,000 bpd capacity
     Presence                                                                                                                                 St. Charles, Louisiana
                                                                                                                                              • 250,000 bpd capacity

                                                                  Houston, Texas
                                                                  • 130,000 bpd capacity   Port Arthur, Texas
                                Texas City, Texas
                                                                                           • 325,000 bpd capacity                        San Nicholas, Aruba
                                • 245,000 bpd capacity
                                                                                                                                         • 275,000 bpd capacity
            Capacity shown in terms of crude and feedstock throughput
                                                                                                                                                                        23
Major Refining Processes – Crude
                     Processing
Definition
• Separating crude oil into different hydrocarbon groups
• The most common means is through distillation
Process
• Desalting – Prior to distillation, crude oil is often desalted to remove
  corrosive salts as well as metals and other suspended solids.
• Atmospheric Distillation – Used to separate the desalted crude into specific
  hydrocarbon groups (straight run gasoline, naphtha, light gas oil, etc.) or
  fractions.
• Vacuum Distillation – Heavy crude residue (“bottoms”) from the atmospheric
  column is further separated using a lower–pressure distillation process.
  Means to lower the boiling points of the fractions and permit separation at
  lower temperatures, without decomposition and excessive coke formation.




                                                                                 24
Major Refining Processes – Cracking
Definition
• “Cracking” or breaking down large, heavy hydrocarbon molecules into
  smaller hydrocarbon molecules thru application of heat (thermal) or through
  the use of catalysts
Process
• Coking – Thermal non–catalytic cracking process that converts low value oils to
  higher value gasoline, gas oils and marketable coke. Residual fuel oil from vacuum
  distillation column is typical feedstock.
• Visbreaking – Thermal non–catalytic process used to convert large hydrocarbon
  molecules in heavy feedstocks to lighter products such as fuel gas, gasoline, naphtha
  and gas oil. Produces sufficient middle distillates to reduce the viscosity of the heavy
  feed.
• Catalytic Cracking – A central process in refining where heavy gas oil range feeds are
  subjected to heat in the presence of catalyst and large molecules crack into smaller
  molecules in the gasoline and surrounding ranges.
• Catalytic Hydrocracking – Like cracking, used to produce blending stocks for gasoline
  and other fuels from heavy feedstocks. Introduction of hydrogen in addition to a
  catalyst allows the cracking reaction to proceed at lower temperatures than in
  catalytic cracking, although pressures are much higher.


                                                                                             25
Major Refining Processes –
                      Combination
Definition
• Linking two or more hydrocarbon molecules together to form a large
  molecule (e.g. converting gases to liquids) or rearranging to improve the
  quality of the molecule
Process
• Alkylation – Important process to upgrade light olefins to high–value
  gasoline components. Used to combine small molecules into large
  molecules to produce a higher octane product for blending with gasoline.
• Catalytic Reforming – The process whereby naphthas are changed
  chemically to increase their octane numbers. Octane numbers are
  measures of whether a gasoline will knock in an engine. The higher the
  octane number, the more resistance to pre or self–ignition.
• Polymerization – Process that combines smaller molecules to produce high
  octane blending stock.
• Isomerization – Process used to produce compounds with high octane for
  blending into the gasoline pool. Also used to produce isobutene, an
  important feedstock for alkylation.


                                                                              26
Major Refining Processes – Treating
Definition
• Processing of petroleum products to remove some of the sulfur, nitrogen,
  heavy metals, and other impurities
Process
• Catalytic Hydrotreating, Hydroprocessing, sulfur/metals removal – Used to
  remove impurities (e.g. sulfur, nitrogen, oxygen and halides) from petroleum
  fractions. Hydrotreating further “upgrades” heavy feeds by converting
  olefins and diolefins to parafins, which reduces gum formation in fuels.
  Hydroprocessing also cracks heavier products to lighter, more saleable
  products.




                                                                                 27
List of Refining Acronyms
AGO – Atmospheric Gas Oil                kVA – Kilovolt Amp
ATB – Atmospheric Tower Bottoms          LCO – Light Cycle Oil
B–B – Butane–Butylene Fraction           LGO – Light Gas Oil
BBLS – Barrels                           LPG – Liquefied Petroleum Gas
BPD – Barrels Per Day                    LSD – Low Sulfur Diesel
BTX – Benzene, Toluene, Xylene           LSR – Light Straight Run (Gasoline)
CARB – California Air Resource Board     MON – Motor Octane Number
CCR – Continuous Catalytic Regenerator   MTBE – Methyl Tertiary–Butyl Ether
DAO – De–Asphalted Oil                   MW – Megawatt
DCS – Distributed Control Systems        NGL – Natural Gas Liquids
DHT – Diesel Hydrotreater                NOX – Nitrogen Oxides
DSU – Desulfurization Unit               P–P – Propane–Propylene
EPA – Environmental Protection Agency    PSI – Pounds per Square Inch
ESP – Electrostatic Precipitator         RBOB – Reformulated Blendstock for Oxygen Blending
FCC – Fluid Catalytic Cracker            RDS – Resid Desulfurization
GDU – Gasoline Desulfurization Unit      RFG – Reformulated Gasoline
GHT – Gasoline Hydrotreater              RON – Research Octane Number
GOHT – Gas Oil Hydrotreater              RVP – Reid Vapor Pressure
GPM – Gallon Per Minute                  SMR – Steam Methane Reformer (Hydrogen Plant)
HAGO – Heavy Atmospheric Gas Oil         SOX – Sulfur Oxides
HCU – Hydrocracker Unit                  SRU – Sulfur Recovery Unit
HDS – Hydrodesulfurization               TAME – Tertiary Amyl Methyl Ether
HDT – Hydrotreating                      TAN – Total Acid Number
HGO – Heavy Gas Oil                      ULSD – Ultra–low Sulfur Diesel
HOC – Heavy Oil Cracker (FCC)            VGO – Vacuum Gas Oil
H2 – Hydrogen                            VOC – Volatile Organic Compound
H2S – Hydrogen Sulfide                   VPP – Voluntary Protection Program
HF – Hydroflouric (adic)                 VTB – Vacuum Tower Bottoms
HVGO – Heavy Vacuum Gas Oil              WTI – West Texas Intermediate
kV – Kilovolt                            WWTP – Waste Water Treatment Plant
                                                                                         28
Safe Harbor Statement
Statements contained in this presentation that state the
Company's or management's expectations or predictions
of the future are forward–looking statements intended to
be covered by the safe harbor provisions of the Securities
Act of 1933 and the Securities Exchange Act of 1934. The
words quot;believe,quot; quot;expect,quot; quot;should,quot; quot;estimates,quot; and
other similar expressions identify forward–looking
statements. It is important to note that actual results could
differ materially from those projected in such forward–
looking statements. For more information concerning
factors that could cause actual results to differ from those
expressed or forecasted, see Valero’s annual reports on
Form 10-K and quarterly reports on Form 10-Q, filed with
the Securities and Exchange Commission, and available
on Valero’s website at www.valero.com.
                                                                29

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  • 1. Delaware City Refinery Tour August 27, 2007 1
  • 2. Agenda Basics of Refining Desulfurization Hydrocracking Delaware City Refinery Operations Gasification Overview Q&A Plant Tour Concluding Remarks 2
  • 3. Crude Oil Characteristics Crudes are classified and priced by density and sulfur content Crude density is commonly measured by API gravity • API gravity provides a relative measure of crude oil density • The higher the API number, the lighter the crude − Light crudes are easier to process − Heavy crudes are more difficult to process Crude sulfur content is measured as a percentage • Less than 0.7% sulfur content = sweet • Greater than 0.7% sulfur content = sour • High sulfur crudes require additional processing to meet regulatory specs Acid content is measured by Total Acid Number (TAN) • Acidic crudes highly corrosive to refinery equipment • High acid crudes are those with TAN greater than 0.7 3
  • 4. Crude Oil Basics Crude Quality by Types Estimated Quality of Reserves (2006) 4.0% SOUR Cold Lake Cerro Negro 3.5% Maya WCS 3.0% Sweet Arab Heavy M-100 (resid) SULFUR CONTENT High Acid 2.5% Arab Medium 20% (Sweet) Light/Medium Dubai Napo 2% 2.0% Mars Sour Arab Light Iran Heavy 2010 13% Ameriven-Hamaca 66% 1.5% Heavy 2000 Urals 1990 Sour Alaskan North Slope 1.0% SWEET 1980 0.5% WTI Brent Tapis Cabinda Bonny Light 0.0% 15 20 25 30 35 40 45 50 Source: Oil & Gas Journal, Company Information HEAVY API GRAVITY LIGHT Source: Industry reports NOTE: Red line represents the average crude quality by decade (actual and projected) Majority of global reserves are light/medium sour Most quoted benchmark prices are light sweet crudes • WTI (West Texas Intermediate), Western Hemisphere • Brent (North Sea Crude), Europe Historical trend shows global crude supply becoming heavier and more sour 4
  • 5. What’s in a Barrel of Crude Oil? Crude Types Characteristics Yields 2005 U.S. 3% Production > 34 API Gravity 30% Light Sweet Crude < 0.7 % Sulfur Propane/ (e.g. WTI, Brent, Saharan Refinery 8% 34% Butane 7% Gases 35% Demand Blend) 33% Most Expensive Gasoline RFG 50% Conventional 3% CARB 24 – 34 API Gravity Premium 21% Medium Sour Crude > 0.7 % Sulfur (e.g. Mars, Arab Light, 26% Arab Medium, Urals) 50% Demand Distillate 33% 50% Jet Fuel Less Expensive Diesel Heating Oil 1% < 24 API Gravity 14% Heavy 10% > 0.7 % Sulfur Fuel Oil & 22% Heavy Sour Crude Other 15% Demand (e.g. Maya, Cerro Negro, Cold Lake, Western Canadian Select) Source: EIA Refiner Production 63% Least Expensive Refineries upgrade crude oil to higher value products 5
  • 6. Basic Refining Concepts Intermediates Final Products < 90°F Propane, Butane • Refinery fuel gas and lighter • Propane • NGLs Straight Run 90–220°F More • Gasoline (high octane) Gasoline (low processing octane) Crude oil More 220–315°F • Gasoline (high octane) Naphtha • Jet fuel Distillation processing Tower • Kerosene (Crude More 315–450°F • Jet fuel Unit) Kerosene • Diesel processing • Fuel oil • Gasoline (high octane) More 450–650°F Light Gas Oil • Diesel Furnace processing • Fuel oil • Gasoline (high octane) More 650–800°F Heavy Gas Oil • Diesel Vacuum processing • Fuel oil Unit • Gasoline (high octane) Residual Fuel More 800+°F • Diesel Oil/Asphalt • Fuel oil processing • Lube stocks 6
  • 7. Hydroskimming/Topping Refinery Crude Unit Propane/ 4% Propane/Butane Butane Gasoline Reformer High Octane Gasoline Low Octane Gasoline RFG Distillation Tower 30% and Naphtha Conventional CARB Hydrogen Premium Light Distillate HS Kerosene/Jet Fuel Sweet LS Kerosene/Jet Fuel Distillate 34% Desulfurizer Jet Fuel Crude Diesel LS Diesel/Heating Oil HS Diesel/Heating Oil Heating Oil Heavy Gas Oil Vacuum Fuel Oil & 32% Unit Other Heavy Fuel Oil 100% Total Yield Simple, low upgrading capability refineries run sweet crude 7
  • 8. Crude and Vacuum Towers Reactor Heater Crude Atmospheric Tower Vacuum Tower Reformer 8
  • 9. Medium Conversion: Catalytic Cracking Crude Propane/ Unit 8% Butane Propane/Butane Gasoline RFG Reformer High Octane Gasoline Low Octane Gasoline 45% Conventional and Naphtha Distillation Tower CARB Premium Hydrogen Distillate Light LS Kerosene/Jet Fuel HS Kerosene/Jet Fuel Desulfurizer Distillate 27% Sour Jet Fuel HS Diesel/Heating Oil LS Diesel/Heating Oil Diesel Crude Heating Oil Light Cycle Oil (LCO) Alkylation Alkylate Unit Fluid Catalytic Gas Oil Vacuum Cracker Unit FCC Gasoline (FCC) Heavy Fuel Oil & 24% Other Heavy Fuel Oil 104% Total Yield Moderate upgrading capability refineries tend to run more sour crudes while achieving increased higher value product yields and volume gain 9
  • 10. High Conversion: Coking/Resid Destruction Hydrogen Plant Crude Gas Unit Propane/ 7% Butane Propane/Butane Gasoline RFG Distillation Tower 58% Reformer High Octane Gasoline Conventional Low Octane Gasoline CARB and Naphtha Medium/ Premium Hydrogen Heavy Distillate Distillate 28% HS Kerosene/Jet Fuel LS Kerosene/Jet Fuel Sour Desulfurizer Jet Fuel Diesel Crude Heating Oil LS Diesel/Heating Oil HS Diesel/Heating Oil Hydrocracker Hydrocrackate Gasoline Light Gas Oil Ultra Low Sulfur Jet/Diesel LCO Alkylation Alky Gasoline Unit Fluid Catalytic Cracker (FCC) Medium Gas Oil Vacuum FCC Gasoline Unit Heavy Fuel Oil & 15% Other Delayed Heavy Fuel Oil Coke Coker 108% Total Yield Complex refineries can run heavier and more sour crudes while achieving the highest light product yields and volume gain 10
  • 11. FCC and Hydrocracker Reactors Fluidized Catalytic Cracker Reactor Hydrocracker Reactors Main Column Regenerator 11
  • 12. Cokers Delayed Coker Superstructure holds the drill and drill stem Fluid Coker - Benicia while the coke is forming in the drum 12
  • 13. Conversion Economics U.S. Gulf Coast Refinery Margins 30 25 20 15 US $/ Bbl 10 5 0 (5) (10) Jan-00 Jan-01 Jan-02 Jan-03 Jan-04 Jan-05 Jan-06 Jan-07 Arab Medium Hydroskimming LLS Cracking Maya Coking Need conversion capacity to capitalize on sour crude discounts • Hydroskim – Breakeven or moderate margins; High resid yield − When margins are positive – increase crude runs − When margins are negative – decrease crude runs • Cracking – Better margins; Lower resid yield • Coking – Best margins; Lowest resid yield − Maximize heavy crudes 13
  • 14. Desulfurization Basics Objective Remove sulfur from light products (gasoline or diesel) to meet air quality requirements for clean burning fuels Desulfurization Unit Desulfurized Light Products HC H2 High Sulfur HC-S HC-S HC-S Light H2 Elemental H2 Products Catalyst Sulfur Plant Sulfur (HC-S) • Agricultural HC-S HC-S H2S S S S • Pharmaceutical H2 S HC-S S S 2 H Hydrogen Unit LEGEND H2 LEGEND H2 H2 HC : : Hydrocarbon HC Hydrocarbon H2 1000 or less PSI; H2 : : Hydrogen H2 H2 H2 Hydrogen 700 F or less S : : Sulfur S Sulfur 14
  • 15. Hydrocracking Basics Objective Value added upgrading of high sulfur distillates to low sulfur gasoline and ultra low sulfur jet/diesel to meet air quality requirements for clean burning fuels Hydrocracking Unit Desulfurized Hydrocrackate Gasoline HC H2 High Sulfur HC-S HC-S HC-S H2 Distillate H2 Desulfurized Ultra Low Sulfur Jet/Diesel HC H2 H2 (HC-S) Catalysts H2 Elemental H2 Sulfur Plant Sulfur HC-S H2 H2 HC-S • Agricultural H2S S H2 S S • Pharmaceutical HC-S S S S 2 H Hydrogen Unit LEGEND H2 LEGEND H2 H2 HC : : Hydrocarbon HC Hydrocarbon 1300+ PSI; H2 H2 : : Hydrogen H2 H2 H2 Hydrogen 725 to 780 F S : : Sulfur S Sulfur 15
  • 16. Andrew Kenner Vice President and General Manager Delaware City Refinery 16
  • 17. Valero Delaware City Refinery Built by Tidewater Oil Company in 1957 Acquired by Valero in 2005 Since commissioning, Valero and previous owners have made significant modifications and environmental upgrades Total throughput of 191,000 bpd High conversion operation • 60%+ gasoline yield Staffed by more than 700 full-time employees Located on 5,000 acres, some of which is leased to local farmers, preserving our buffer zone Seeking OSHA VPP Star Status 17
  • 18. Delaware City Products and Crude Slate Typical Product Slate Typical Crude Slate Product BPD % Crude S % / API BPD % Gasoline 85,000 50 Arab Heavy 2.7 / 29 75,000 45 Distillates 65,000 38 M-100 2.7 / 16 45,000 26 Propane 7,500 4 Hamaca 1.6 / 26 35,000 20 Alkylate 5,000 3 Opportunity Crudes 15,000 9 6 Oils 4,500 3 Total 170,000 100 Benzene 1,500 1 Pet coke 1,900 1 Sulfur 300 <1 Total 170,700 100 Provides approximately 70% of all gasoline sold in Delaware Flexible light-ends system Produces petrochemical grade Benzene for sales into local market. 18
  • 19. Delaware City Capital Investments $456 MM invested in capital improvements and $97 MM for turnaround maintenance at Delaware City since Valero’s acquisition • Major plant turnaround completed in 4Q05 Fluid Coker Flue Gas Scrubber - $200 MM Fluid Catalytic Cracking Unit Flue Gas Scrubber - $200 MM Cracked Naphtha Hydrotreating Unit expansion project commissioned in 4Q05 Sulfur Plant O2 enrichment and reliability projects - $25 MM Took over operations of Gasifier/Power Plant and have improved on-stream reliability and throughput dramatically Petcoke Destruction (TPD) 1,100 650 300 Motiva Premcor Valero 19
  • 20. Gasification Overview File: GASIF03.vsd by: MEL 5/15/98 Delaware City Plant Air Separation Coke Gasification Repowering Project Plant Electric Gas Turbine Power Oxygen Clean Syngas To Refinery Sulfur Steam To Coke Removal Refinery Fluxant Water Boiler To Feed Utility Water Raw Syngas Exhaust Gas Syngas Cooler Gasifier Heat Recovery Boiler Steam Generator Feed Water Slurry High Pressure Steam Acid Gas Slag To Electric Utility Power To Sulfur Sulfur Refinery Recovery Unit Existing Steam Steam To Turbine Refinery 20
  • 21. Appendix 21
  • 22. Delaware City Refinery Flow Diagram 22
  • 23. Map of Valero Refineries Quebec, Canada • 215,000 bpd capacity Benicia, California • 170,000 bpd capacity Paulsboro, New Jersey • 195,000 bpd capacity Delaware City, Delaware Wilmington, California • 210,000 bpd capacity • 135,000 bpd capacity McKee, Texas • 170,000 bpd capacity Memphis, Tennessee • 195,000 bpd capacity Three Rivers, Texas • 100,000 bpd capacity Ardmore, Oklahoma • 90,000 bpd capacity Corpus Christi, Texas • 340,000 bpd capacity Valero Marketing Krotz Springs, Louisiana • 85,000 bpd capacity Presence St. Charles, Louisiana • 250,000 bpd capacity Houston, Texas • 130,000 bpd capacity Port Arthur, Texas Texas City, Texas • 325,000 bpd capacity San Nicholas, Aruba • 245,000 bpd capacity • 275,000 bpd capacity Capacity shown in terms of crude and feedstock throughput 23
  • 24. Major Refining Processes – Crude Processing Definition • Separating crude oil into different hydrocarbon groups • The most common means is through distillation Process • Desalting – Prior to distillation, crude oil is often desalted to remove corrosive salts as well as metals and other suspended solids. • Atmospheric Distillation – Used to separate the desalted crude into specific hydrocarbon groups (straight run gasoline, naphtha, light gas oil, etc.) or fractions. • Vacuum Distillation – Heavy crude residue (“bottoms”) from the atmospheric column is further separated using a lower–pressure distillation process. Means to lower the boiling points of the fractions and permit separation at lower temperatures, without decomposition and excessive coke formation. 24
  • 25. Major Refining Processes – Cracking Definition • “Cracking” or breaking down large, heavy hydrocarbon molecules into smaller hydrocarbon molecules thru application of heat (thermal) or through the use of catalysts Process • Coking – Thermal non–catalytic cracking process that converts low value oils to higher value gasoline, gas oils and marketable coke. Residual fuel oil from vacuum distillation column is typical feedstock. • Visbreaking – Thermal non–catalytic process used to convert large hydrocarbon molecules in heavy feedstocks to lighter products such as fuel gas, gasoline, naphtha and gas oil. Produces sufficient middle distillates to reduce the viscosity of the heavy feed. • Catalytic Cracking – A central process in refining where heavy gas oil range feeds are subjected to heat in the presence of catalyst and large molecules crack into smaller molecules in the gasoline and surrounding ranges. • Catalytic Hydrocracking – Like cracking, used to produce blending stocks for gasoline and other fuels from heavy feedstocks. Introduction of hydrogen in addition to a catalyst allows the cracking reaction to proceed at lower temperatures than in catalytic cracking, although pressures are much higher. 25
  • 26. Major Refining Processes – Combination Definition • Linking two or more hydrocarbon molecules together to form a large molecule (e.g. converting gases to liquids) or rearranging to improve the quality of the molecule Process • Alkylation – Important process to upgrade light olefins to high–value gasoline components. Used to combine small molecules into large molecules to produce a higher octane product for blending with gasoline. • Catalytic Reforming – The process whereby naphthas are changed chemically to increase their octane numbers. Octane numbers are measures of whether a gasoline will knock in an engine. The higher the octane number, the more resistance to pre or self–ignition. • Polymerization – Process that combines smaller molecules to produce high octane blending stock. • Isomerization – Process used to produce compounds with high octane for blending into the gasoline pool. Also used to produce isobutene, an important feedstock for alkylation. 26
  • 27. Major Refining Processes – Treating Definition • Processing of petroleum products to remove some of the sulfur, nitrogen, heavy metals, and other impurities Process • Catalytic Hydrotreating, Hydroprocessing, sulfur/metals removal – Used to remove impurities (e.g. sulfur, nitrogen, oxygen and halides) from petroleum fractions. Hydrotreating further “upgrades” heavy feeds by converting olefins and diolefins to parafins, which reduces gum formation in fuels. Hydroprocessing also cracks heavier products to lighter, more saleable products. 27
  • 28. List of Refining Acronyms AGO – Atmospheric Gas Oil kVA – Kilovolt Amp ATB – Atmospheric Tower Bottoms LCO – Light Cycle Oil B–B – Butane–Butylene Fraction LGO – Light Gas Oil BBLS – Barrels LPG – Liquefied Petroleum Gas BPD – Barrels Per Day LSD – Low Sulfur Diesel BTX – Benzene, Toluene, Xylene LSR – Light Straight Run (Gasoline) CARB – California Air Resource Board MON – Motor Octane Number CCR – Continuous Catalytic Regenerator MTBE – Methyl Tertiary–Butyl Ether DAO – De–Asphalted Oil MW – Megawatt DCS – Distributed Control Systems NGL – Natural Gas Liquids DHT – Diesel Hydrotreater NOX – Nitrogen Oxides DSU – Desulfurization Unit P–P – Propane–Propylene EPA – Environmental Protection Agency PSI – Pounds per Square Inch ESP – Electrostatic Precipitator RBOB – Reformulated Blendstock for Oxygen Blending FCC – Fluid Catalytic Cracker RDS – Resid Desulfurization GDU – Gasoline Desulfurization Unit RFG – Reformulated Gasoline GHT – Gasoline Hydrotreater RON – Research Octane Number GOHT – Gas Oil Hydrotreater RVP – Reid Vapor Pressure GPM – Gallon Per Minute SMR – Steam Methane Reformer (Hydrogen Plant) HAGO – Heavy Atmospheric Gas Oil SOX – Sulfur Oxides HCU – Hydrocracker Unit SRU – Sulfur Recovery Unit HDS – Hydrodesulfurization TAME – Tertiary Amyl Methyl Ether HDT – Hydrotreating TAN – Total Acid Number HGO – Heavy Gas Oil ULSD – Ultra–low Sulfur Diesel HOC – Heavy Oil Cracker (FCC) VGO – Vacuum Gas Oil H2 – Hydrogen VOC – Volatile Organic Compound H2S – Hydrogen Sulfide VPP – Voluntary Protection Program HF – Hydroflouric (adic) VTB – Vacuum Tower Bottoms HVGO – Heavy Vacuum Gas Oil WTI – West Texas Intermediate kV – Kilovolt WWTP – Waste Water Treatment Plant 28
  • 29. Safe Harbor Statement Statements contained in this presentation that state the Company's or management's expectations or predictions of the future are forward–looking statements intended to be covered by the safe harbor provisions of the Securities Act of 1933 and the Securities Exchange Act of 1934. The words quot;believe,quot; quot;expect,quot; quot;should,quot; quot;estimates,quot; and other similar expressions identify forward–looking statements. It is important to note that actual results could differ materially from those projected in such forward– looking statements. For more information concerning factors that could cause actual results to differ from those expressed or forecasted, see Valero’s annual reports on Form 10-K and quarterly reports on Form 10-Q, filed with the Securities and Exchange Commission, and available on Valero’s website at www.valero.com. 29