New Technology Controls High Temperature Coker Heater Fouling

AIChE Chicago Symposium 2007

September 25, 2007 Presented by: Bruce Wright
2007 Baker Hughes Incorporated. AllAll Rights Reserved. 2007 Baker Hughes Incorporated. Rights Reserved.

Discussion Topics
1. Coker economics and impact of fouling on DCU and refinery operations 2. Coker heater fouling mechanisms 3. Stages of fouling 4. Design of custom MILESTONE additive programs 5. Coking Stability Index (CSI) 6. Case histories 7. Summary
TM

MILESTONE is a trademark of Baker Hughes Incorporated

2007 Baker Hughes Incorporated. All Rights Reserved.

Delayed Coker Economics

Coker Economic Drivers
Primary driver is the differential value of light distillates (gasoline, kerosene, diesel) versus heavy fuel oils
P roduct Prices: 1998-2005
80 70 60 50 40 30 20 10 0 A vg 1998 A vg 1999 A vg 2000 Reg Gaso A vg 2001 A vg 2002 HS Dist A vg 2003 A vg 2004 A vg 2005

$/Bbl

Resid Fuel

US Gulf Coast (Harts Downstream Energy Services)

2007 Baker Hughes Incorporated. All Rights Reserved.

Delayed Coker Economics

Global market conditions have caused a great increase in coker margins since 2003:
C a lc u la t e d C o k in g M a r g in
16 14 12 $/Bbl 10 8 6 4 2 0 1998 1999 2000 2001 2002 2003 2004 2005

Cokers are making a lot of money, and refiners want new ways to increase unit throughput!
US Gulf Coast (Harts Downstream Energy Services)
2007 Baker Hughes Incorporated. All Rights Reserved.

Economic Impacts of Coker Heater Fouling

Throughput Losses
2-5% ~ $5 MM

Conversion Losses
1% ~ $3 MM

De-coking Costs
$25 50 M/coil

Increased Fuel Usage

2% > $200,000

Reduced Flexibility
Can be > $5 MM

(All Values Based on Typical 40,000 B/D Unit)

E, H & S Concerns

Coker Heater Design & Operation

Operating Parameters Affecting Coking Rates
Fluid velocity Continuous throughput

Continuous Flow and Adequate Velocities are Critical to Good Operations!

2007 Baker Hughes Incorporated. All Rights Reserved.

Coker Heater Design & Operation

Operating Parameters Affecting Coking Rate
Heater Outlet Temperatures Uneven Heat Distribution - Hot Spots Poor Flow Distribution
C
732 704 677 649 621 593 568 538 510

Feed Factors Impacting Fouling

Asphaltene content and stability
Higher asphaltene content leads to more coke generation in the coils Low stability feeds result in increased fouling

Content of solids/inorganics
Corrosion by-products Filterable solids and salts Sodium concentration

2007 Baker Hughes Incorporated. All Rights Reserved.

Sources of Inorganic Materials

Iron sulfide, rust (corrosion by-products)
Crude oil storage and transmission Upstream process units

Salts: sodium, calcium, and magnesium chlorides

From crude oil producing formation Brine contamination from transportation

Caustic
NaOH injections into desalted crude

Clay, dirt, sand, catalyst fines

From producing formation or bitumen deposit From upstream process units

Asphaltene Micelle In Solution

Resins Asphaltene Core

2007 Baker Hughes Incorporated. All Rights Reserved.

Asphaltene Destabilization

Asphaltenes readily destabilize when subjected to stress

Changes in pressure, temperature, pH and solution environment can cause destabilization Can occur when oils are blended and processed

Disruption of asphaltene resin interaction Thermal cracking conditions (>750F) cause progressive loss of asphaltene solubility in the bulk oil phase Asphaltenes lose paraffinic side-chains and naphthenic portions are de-hydrogenated to aromatic rings

2007 Baker Hughes Incorporated. All Rights Reserved.

Thermal Decomposition of Oil

Concentration of paraffin compounds increases Resins are lost from conversion to asphaltenes Naphthenes become aromatic Aromatics condense to form asphaltenes lose solubility in bulk oil
Heat
H

+
Solubility Loss, Precipitation, Dehydrogenation, Coke Formation

N-

Heat

Coke Formation
High temperature destabilizes asphaltenes They become more aromatic and less soluble in the bulk liquid

Destabilized asphaltenes aggregate to

become particle-like

The agglomerated phase precipitates,

adheres to the hot tube surfaces and dehydrogenates to form coke

At the unit start-up cleaned coils have a

catalytic effect on asphaltene deposition

2007 Baker Hughes Incorporated. All Rights Reserved.

Asphaltene Precipitation
Stress Asphaltene Destabilization & Disruption of Resins

Aggregation
Deposition Degradation

Hot Tube Surface

Stages of Fouling
Initial layer formed on tube surface
Metal catalyzed coking Fast - at the startup of the unit when coils are clean and metal is exposed

Secondary layer of deposition

Decreased asphaltene solubility in bulk oil Thermal breakdown of asphaltenes Precipitation of thermally converted asphaltenes or coke Slower

2007 Baker Hughes Incorporated. All Rights Reserved.

Catalysis of Coke Formation

Initial rapid coking due to tube surface metals
Cu >> Ni ~ Cr > Fe, but Many Fe sites available The activation energy needed to crack and dehydrogenate is decreased

Continued catalytic effects from metals cracked out of resid

Contributes to steady state coking of the furnace tubes

2007 Baker Hughes Incorporated. All Rights Reserved.

Stages of Fouling
Initial Fouling S teady State Fouling Bulk Fouling B u lk Pressure Drop Heat Transfer Coefficient U

Initial

Time

S h u tdow n Shutdow

Stages of Fouling Heater Tubes

Delayed Coker Heater Skin Temperatures
1250

Skin Temperature (F)

1200

Slope for first 30 days is 3.9 degrees F / day Slope for day 31 until end is 1.3 degrees F / day

1150

1100

1050

With Successful Treatment

1000 0 10 20 30 40 50 60 70 80 90 100

Days on Line

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Fouling Control Additives

Stabilize Asphaltenes Withstand High Temperatures

Polar functionality to adsorb on active metal sites

Program Success Requirements

Disperse Inorganic & Organic Particles

2007 Baker Hughes Incorporated. All Rights Reserved.

Research Program Design

Feedstock characterization test protocols Deposit characterizations Property ratios, correlations with fouling tendency Development of the Coking Stability Index Benchmark fluid characteristics with others in data base

2007 Baker Hughes Incorporated. All Rights Reserved.

Coking Stability Index (CSI)

Predictive tool for determining fouling potential and rate of fouling Uses an NIR laser to detect the onset of asphaltene precipitation Titration technique with non-solvent Used in conjunction with oil characterizations to determine stability of coker feed Chemical additive screening

2007 Baker Hughes Incorporated. All Rights Reserved.

Coker Feed

Furnace Run Length 2.4 Months 5.0 months 9.0 Months

CSI

Asphaltene/Resin Ratio 0.348 0.325 0.458

Saturate/Aromatic Ratio 2.63 3.85 2.94

Canadian Midwest West Coast

99.5 137.1 192.0

CSI Coker Stability Index Furnace Feed Stability

1200

West Coast Refiner Midwest Refiner Furnace Feed Canadian Refiner Furnace Feed

1000

800

INTENSITY

More Stable

600

400

200

0 0 50 100 150 200 250 300

CSI

MILESTONE Heater Fouling Control

Advanced Process Heater Fouling Control Technology A new fouling control program developed for high severity thermal conversion unit heaters Involves proprietary testing to understand the fouling mechanisms, and chemical program effectiveness Novel, multi-component fouling control solutions
Custom designed based on feedstock characterizations and comprehensive root cause investigations Specialized feedstock characterization methodologies Utilizes new high temperature chemistries

2007 Baker Hughes Incorporated. All Rights Reserved.

MILESTONE Additive Technology

Multi-Component Program

Interacts with metal surfaces to reduce catalytic effects on surface coking reactions Stabilizes asphaltenic compounds in the feedstock to inhibit their precipitation Disperses organic & inorganic particles

MILESTONE Technology: Pilot Scale Demonstrations

JIP Joint Industry Project, Using Department of Energy (DOE) Pilot Delayed Coking Unit at the University of Tulsa, OK
Investment by major refiners to study coker operating variables, including coker heater fouling Pilot unit studies confirmed suspected heater fouling mechanisms Pilot unit tests also confirmed efficacy of Baker Petrolite fouling control technology

2007 Baker Hughes Incorporated. All Rights Reserved.

Case History Summary

MILESTONE Program Performance
Refinery A B C Reduction in Fouling Rate 9X 3X Throughput Improvement 5% Returned to Normal 20% Return on Program >6:1 >3:1 >10:1

2007 Baker Hughes Incorporated. All Rights Reserved.

Summary
Delayed coker furnace fouling is a complex phenomenon involving heavy hydrocarbon compounds and inorganic materials Two stages of fouling: initial catalytic stage and thermal or steady-state stage Costs of delayed coker furnace fouling can be significant especially when throughput is restricted either during operation or during de-coking cycles

2007 Baker Hughes Incorporated. All Rights Reserved.

Summary
The Baker Petrolite research group has developed a successful mitigation program for delayed coker furnace fouling A new, multi-component program is utilized to combat the various mechanisms of heater fouling Treatment programs have been used in several applications with significant economic benefits

2007 Baker Hughes Incorporated. All Rights Reserved.

Thank You for Your Attention!

2007 Baker Hughes Incorporated. All Rights Reserved.