developing coal tar/ petroleum pitches melvin d. kiser - marathon ashland petroleum company robert...
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Developing Coal Tar/Developing Coal Tar/Petroleum PitchesPetroleum Pitches
Melvin D. Kiser -
Marathon Ashland Petroleum Company
Robert H. Wombles -
Koppers Industries, Inc.
Discussion TopicsDiscussion Topics
IntroductionCoal Tar and Petroleum SuppliesCoal Tar and Petroleum Pitch
ManufacturingCoal Tar/Petroleum Pitch Product
Development
IntroductionIntroduction
First Coal Chemical Recovery Ovens Installed in the US in 1893
By 1915, By-product Ovens Accounted for 97% of Metallurgical Coke Produced in US
Since Then Coal Tar Pitch Has Been Binder of Choice for Aluminum, Commercial Carbon, and Graphite Industries
Introduction, Introduction, cont.cont.
Late 1980’s and 1990’s Closing of US Coke Ovens Accelerated Due to Economic and Environmental Pressures
Coke Oven Closures Resulted in Concern for Supply of Coal Tar Pitch and Strategies to Deal with Anticipated Shortage Being Sought
Introduction, Introduction, cont.cont.
Oil Industry As It Is known Today Began with the Discovery of Crude Oil in Ontario and Western Pennsylvania in 1850’s
Refineries Have Concentrated on Producing Transportation and Heating Fuel with Little Interest in Heavy Products Such as Pitch
Introduction, Introduction, cont.cont.
During 1960’s Some Refineries Began to Show Interest in Producing Petroleum Pitch and Some Were Successful in Producing High Aromaticity and Specific Gravity Pitches
Evaluation of These Pitches As Binder Pitches Has Given Mixed Results with Most Often Reported Shortcoming Being Higher Than Desired Carbon Consumption
Introduction, Introduction, cont.cont.
Future Use of Petroleum Pitches Will Probably Not Be Driven By Economics But Raw Material Availability and Regulations
Introduction, Introduction, cont.cont.
Strategies to Deal with Shrinking Coal Tar Supply Importing Coal Tar Importing Coal Tar Pitch Developing Processes to Improve Pitch Yield
and Upgrade Non-conventional Coal Tars Using Petroleum Pitches to Supplement Coal
Tar Pitch Supply
Coal Tar and Petroleum Coal Tar and Petroleum SuppliesSupplies
1997 1998 1999 2000 2001 2002 2003 2004 2005
Mexico
Canada
United States
North America
0
50
100
150
200
250
300
North American coal tar supplies to fall by 18% by 2005
North American Binder Pitch DemandNorth American Binder Pitch Demand
‘000 Metric Tonnes1997 1998 1999 2000 2001 2003
Aluminum Industry 627 654 649 657 678 696Commercial Carbon 108 112 95 100 108 115Miscellaneous 170 160 159 140 127 100
Total 905 926 903 897 913 911
Coal Tar Required 1442 1555 1514 1517 1555 1570Coal Tar Available 1302 1141 1141 1141 1027 1027 Tar Deficit 140 414 373 376 528 543
Petroleum SuppliesPetroleum Supplies
Yearly Supply of Coal Tar Is 6 MM Barrels (Less Than the Volume of Crude Oil Processed Each Day)
Yearly Supply of Potential Pitch Feedstocks Is 326 MM Barrels
Assuming Only 10% Available and Acceptable Results in Petroleum Pitch Yearly Feedstock Supply of 32.6 MM Barrels
Coal Tar and Petroleum Coal Tar and Petroleum Pitch Manufacturing Pitch Manufacturing
Coke Flow DiagramCoke Flow Diagram
One Metric Ton of Coal Yields:One Metric Ton of Coal Yields:
Blast Furnace Coke: 600 - 700 kg
Coke Breeze: 50 - 100 kg Coke OvenCoke Oven70%
Solids
70%
Solids
30% Gas + Liquid30% Gas + Liquid
Tar 35 - 50 LAmmonium Sulphate 10 - 15 kgAmmonia Liquor 60 - 145 LLight Oil 10 - 15 L
Coke Oven Gas300 - 360 m3
FlushingLiquor
Steam
2000°F
Coke Oven Liquor
Tar
DecanterSludgeDecanter
Tar FeedTank
Heater
Pitch
DistillateStream
DistillationTower
Steam
PRODUCTION OF COAL TAR PITCHPRODUCTION OF COAL TAR PITCH
gas
200°F
Coal
Coke Oven Thermal CrackingCoke Oven Thermal Cracking
1,095°CNo catalyst + C4
CH2 CH2 CH2 CH3
Petroleum Pitch ManufacturingPetroleum Pitch Manufacturing
Many Petroleum Products Referred to as Pitch (Causes Confusion Among Non-Refiners)
Different Pitches Share Only Commonality of Being Black Solids at Room Temperature
Characteristics of Petroleum Pitches Determined by Feedstock and Processing to Produce
Reaction Step Used to Generate or Concentrate the High Molecular Weight Molecules
Common Petroleum Pitch Producing ProcessesCommon Petroleum Pitch Producing Processes
Solvent Deasphalting Precipitation of High Molecular Weight and Aromaticity
Molecules Specific Gravity of 1.0 g/cc Contains Non-aromatic Molecules and High Metals Levels
Oxidation Little Incorporation of Oxygen in Product Oxygen Generates Free Radicals Which Cause Polymerization Products Typically Have Low Coking Values and High Viscosities
Thermal Processing Thermal Processing Temperatures of 300°C to 480°C Produces High Specific Gravity and Aromaticity Product
Desalting & Dewatering
Atmospheric Distillation
Pitch Feed Preparation
Fluid Catalytic Cracking
Vacuum Distillation
Primary Reaction Processes
Secondary Reaction Processes
Liquid Storage
Solidification
Crude Oil to Petroleum PitchCrude Oil to Petroleum Pitch
Other ComponentsOther Components
Crude OilCrude Oil
1. Feed preparation can consist of any one or a combination of blending, distillation, desulfurization and solids removal.
2. Primary reaction processes may consist of any one or a combination of solvent deasphalting, thermal processing, oxidation or catalytic reactions.
3. Secondary reaction processes may include distillation, desulfurization, oxidation or thermal soaking.
1. Feed preparation can consist of any one or a combination of blending, distillation, desulfurization and solids removal.
2. Primary reaction processes may consist of any one or a combination of solvent deasphalting, thermal processing, oxidation or catalytic reactions.
3. Secondary reaction processes may include distillation, desulfurization, oxidation or thermal soaking.
Petroleum Refinery Catalytic CrackingPetroleum Refinery Catalytic Cracking
540°CCracking catalyst + C3
CH2 CH2 CH2 CH3 CH3
Coal Tar/Petroleum PitchCoal Tar/Petroleum PitchAluminum Industry Experience with 100% Petroleum
Pitch Not AcceptableSuitable Petroleum Materials Must Be Identified (100
Materials Evaluated)Commercial Testing Began in 1994Small Performance Disadvantages IdentifiedEfforts to Improve Performance SuccessfulMost Economical Solution with Potential Plentiful
Supply
Property Coal Tar
Pitch Type A
Pitch Type BPitch
PetroleumPitch
Softening Point, °C 109.4 108.5 112.9 108.7
Toluene Insolubles, wt. % 27.5 25.8 29.6 3.5
Quinoline Insolubles, wt% 13.1 12.6 13.9 0
Beta Resins, wt. % 14.4 13.2 15.7 3.5
Coking Value, wt. % 57.8 56.3 58.4 47.1
Ash, wt. % 0.17 0.14 0.11 0.03
Specific Gravity 1.336 1.32 1.31 1.225
Sulfur, wt. % 0.64 0.68 0.78 1.30
PAH, wt. ppm 108,800 96,000 65,300 23,400
Properties of Typical PitchesProperties of Typical Pitches
ConclusionsConclusionsSupply of Coal Tar in North America Is Declining
Because of Environmental and Financial PressuresOne Strategy for Dealing with Declining Coal Tar
Supply Is Coal Tar/Petroleum PitchBecause the Refining Industry Uses Pitch to
Describe a Number of Products with Varying Properties, Care Must Be Taken in Selecting the Petroleum Component of a Coal Tar/Petroleum Pitch
Conclusions, Conclusions, cont.cont.
Coal Tar/Petroleum Pitch Is the Preferred Long Range Solution to the Tar Shortage Because: 1) It Is Economical, 2) Its Performance Has Been Proven, 3) Potential Feedstock Supply Is Plentiful and 4) Product Quality Is Consistent
Coal Tar/Petroleum Pitches with Significantly Reduced PNA Contents Have Been Developed
Coal Tar/Petroleum Pitch Product Development Efforts Will Continue