Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert...

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Developing Coal Tar/ Developing Coal Tar/ Petroleum Pitches Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Transcript of Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert...

Page 1: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Developing Coal Tar/Developing Coal Tar/Petroleum PitchesPetroleum Pitches

Melvin D. Kiser -

Marathon Ashland Petroleum Company

Robert H. Wombles -

Koppers Industries, Inc.

Page 2: Developing Coal Tar/ Petroleum 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

Page 3: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 4: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 5: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 6: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 7: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Introduction, Introduction, cont.cont.

Future Use of Petroleum Pitches Will Probably Not Be Driven By Economics But Raw Material Availability and Regulations

Page 8: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 9: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Coal Tar and Petroleum Coal Tar and Petroleum SuppliesSupplies

Page 10: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 11: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 12: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 13: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Coal Tar and Petroleum Coal Tar and Petroleum Pitch Manufacturing Pitch Manufacturing

Page 14: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 15: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 16: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Coke Oven Thermal CrackingCoke Oven Thermal Cracking

1,095°CNo catalyst + C4

CH2 CH2 CH2 CH3

Page 17: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 18: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 19: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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.

Page 20: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

Petroleum Refinery Catalytic CrackingPetroleum Refinery Catalytic Cracking

540°CCracking catalyst + C3

CH2 CH2 CH2 CH3 CH3

Page 21: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 22: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 23: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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

Page 24: Developing Coal Tar/ Petroleum Pitches Melvin D. Kiser - Marathon Ashland Petroleum Company Robert H. Wombles - Koppers Industries, Inc.

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