2010NPRASeminarFundamentalsofDesalterOperation PDF

Fundamentals of Desalter Operation
Baltimore Marriott Waterfront Hotel

October 13, 2010
Presenters:
Kerlin Lobo
Larry Kremer
Simon Cornelius
Baker Hughes Incorporated
2010 Baker Hughes Incorporated. All Rights Reserved.Confidential. No portion of this material may be copied, reproduced, transferred or stored without the express written permission of Baker Hughes Incorporated.
Outline
Process overview
Common designs
Design variables and performance expectations
Operating variables
Chemical treatment programs
Performance monitoring
Desalting system troubleshooting
Crude oil quality issues
Crude storage tank issues
Slop oil reprocessing
Wastewater treatment
2010 Baker Hughes Incorporated. All Rights Reserved. Confidential. No portion of this material may be copied, reproduced, transferred or stored without the express written permission of Baker Hughes Incorporated.
Process Overview
How Does the Desalter Process Work?

Mix crude oil with water
Use mix valve to agitate
Use an electrical field and chemical
to help break the emulsion
Wash contaminants out of oil (into
the water)
Clean oil is pulled off the top Using the right
equipment for the
Water is drawn off the bottom right job
4 2010 Baker Hughes Incorporated. All Rights Reserved. Confidential. No portion of this material may be copied, reproduced, transferred or stored without the express written permission of Baker Hughes Incorporated.
Refinery Crude Oil Handling System
Refinery
Tank Farm
Crude
Offloading Tank 1
Pipeline
Crude Oil
Tank 2
Pipeline Crude Tank Farm

Storage Crude Crude Pump
Terminal Booster Tank 3
Pump
To Hot Crude
Preheat Exchangers
Emulsion
Breaking
Crude Oil Desalter Cold Crude Chemical
Preheat Exchangers
Mix Crude
Valve Charge Pump
Interface Desalter
Level Effluent Desalter
Controller Water Pump Wash Water
Typical Crude Oil Contaminants & Effects

Dissolved salts:
NaCl (~70 - 75%)
MgCl2 (~15 -20%)
CaCl2 (~10%)
Crude preheat fouling
Crude unit corrosion
Downstream catalyst deactivation
Product quality concerns (coke, heavy fuel oils)
Metals (Fe, V, Ni)
Downstream catalyst deactivation
Typical Crude Oil Contaminants & Effects
Solids
Sand/silt/clays/scale
Corrosion products (iron sulfides, iron oxides)
Emulsion stabilization
Downstream unit fouling (coker, visbreaker, RHDS, RFCC)
Organics (asphaltenes, paraffins)
Desalting Purpose and Benefits

Remove excess water, contaminants from crude oils
Reduce:
Fouling in crude unit preheat exchangers, furnaces,
distillation columns
Corrosion in crude unit distillation columns and overhead
condensing systems
Potential unit damage, excessive energy costs due to
presence of water in crude
Impact of contaminants on downstream processes
Impact on product (coke, heavy fuel oil) quality
Bottom Line Refineries Desalt to Decrease Operating and

Maintenance Costs
Reduce crude preheat system fouling
Salts and solid particles can deposit in crude unit preheat
exchangers or furnace tubes
These deposits reduce heat transfer rates and/or cause
plugging of the tubes
Sodium also acts as a catalyst for coke formation in heat
exchangers, furnace tubes and transfer lines
A good desalting operation will reduce fouling potential by

removing a high percentage of crude oil salts and solids,
and by minimizing the amount of sodium in desalted
crude.

Reduce crude unit corrosion
Salt hydrolyze at temperatures found in crude unit
atmospheric and vacuum furnaces:
Heat
MgCl2 + 2H2O Mg(OH)2 + 2HCl

Heat
CaCl2 + 2H2O Ca(OH)2 + 2HCl
HCl gas dissolves in condensing water to form highly

corrosive hydrochloric acid
Found in overhead condensing systems of distillation
towers
Proper desalting will minimize the HCl generated and will
greatly reduce corrosion potential in the crude unit
Examples of Crude Unit Corrosion Damage
Overhead Vapor Condensing

System Pipe Damaged by Liquid
Hydrochloride Salts
Stainless Steel Distillation Tray

Damage from Exposure to Amine
Hydrochloride Salts
Refinery Corrosion Costs
50% of plant maintenance costs
4% of plant revenue
Desalting is the 1st defense for

refinery corrosion control for the crude
unit and downstream processing units.
Poor desalting will impact refinery

reliability and costs
Reduce the amount of water in crude oil
Excessive water in crude (water slugs) can cause
damage in the crude distillation tower
Pressure surges when water is vaporized to steam often
damage tower internals
Excess water in the desalted crude oil also requires more

fuel to heat crude oil to the desired atmospheric column
approach temperature
A good desalting operation will reduce the impact of

water slugs from the tank farm on crude unit operations
and improve energy efficiency

Reduce impact of contaminants on downstream
processes
Catalyst deactivation, especially if residual materials are
fed to the RHDS, RFCC or FCCU
Increased slagging in furnaces burning refinery fuel oil
Improve market value of refinery products
Contaminants can increase coke conductivity, making it
unsuitable for anode grade
Contaminants can increase metals, ash content of heavy
fuel oils
New ISO-8217 specs includes maximum Ca levels in HFO
Common Designs
Petreco Low Velocity Desalter

END VIEW SIDE VIEW
DESALTED
CRUDE
DESALTED
CRUDE
TRANSFORMER
GROUND
GRID CRUDE OUTLET
HEADER
( _)
(+)
MUD WASH
HEADER
HOT
H2O LEVEL GRID
CRUDE
MUD
H2O LEVEL INLET EFFLUENT
WASH DISTRIBUTOR WATER HEADER
EFFLUENT
MIX VALVE
WATER MUD WASH
RAW
RAW CRUDE
CRUDE EFFLUENT WATER
MIX VALVE WASH WATER

WASH
WATER
Optimum interface level: 6 (15 cm) above inlet
Howe Baker Low Velocity Desalter
DESALTED
DESALTED CRUDE
CRUDE SIDE VIEW
END VIEW TRANSFORMER
HOT CRUDE OUTLET

GRID HEADER
(_)
(+)
MUD WASH
HEADER
H2O CRUDE
LEVEL INLET EFFLUENT WATER
MUD
WASH HEADER HEADER
EFFLUENT WATER
MIX VALVE
MUD WASH
RAW
RAW CRUDE EFFLUENT WATER
CRUDE
WASH WATER
WASH
Optimum interface level: 6-12 (15-30 cm) below crude inlet
Cameron-Petreco Cylectric Desalter
Cameron-Petreco
Upper Grid
Bilectric Desalter
Middle Grid
Orifice Plate
Lower Grid
SIDE VIEW END VIEW
DESALTED CRUDE Crude oil
Transformer Transformer Emulsion
Transformer
Transformer
LC
Flow Baffle hot grids
DESALTED
Flow Baffle
LC CRUDE
Crude Outlet Header
Three
distributors are
typically used to
Mud
meter crude oil
Distributor Header Distributor Header Wash into the two
electrical fields
Mudwash MIX of the desalter
Header VALVE
Raw Mud Wash vessel.
Mudwash
Pump Crude Header
EFFLUENT
WASH WATER
Raw WATER
Crude EFFLUENT WATER
Mix Valve
Wash Water Optimum level: 12-24 (30-60 cm) below grids
BILECTRIC is a registered trademark of Cameron - Petreco


Design Variables and Performance Expectations
Desalter Design Variables
Each desalter has a design basis
Crude rate
Gravity
Viscosity
Temperature
Raw crude BS&W (basic sediment and water) and salt
Internal Dimensions:
Center line
1500
Tri-cock spacing and location Lower Electrode
250
Electrode position 290

CL
690
Levels
200
1750
4
200
1500
3
200
2
125
Manifolds
1
Desalter Performance Expectations
Performance predicted for design conditions

90 95% salt removal for single stage desalting
98% for two stage desalting
If raw crude salts <10 PTB, desalted crude salts <1 PTB
If operations are outside of design conditions,
performance may be affected
Desalter Design & Capacity
Desalter Size
Oil Residence Time affects emulsion resolution and
dehydration
Water Residence Time affects brine quality
Desalter diameters range from 10 to 14
Spherical desalters provide more residence time
Higher capital costs
Typical residence times
Crude Gravity Oil Residence Water Res

Time (min) Time (min)
15-18o API 30 - 60 120 140
18-22o API 20 30 80 120
22+o API 15 - 20 60 - 80
Desalter Design & Capacity

Grid design and voltage
Petreco claims Bilectric design has about 1.75 times the
treating capacity as low-velocity desalters of the same size
In Bilectric desalters residence time between the grids is the
critical variable
Grid voltage
Function of grid area and transformer size
Step up transformer voltage can be adjusted based on
operation SIDE VIEW
DESALTED CRUDE
END VIEW
Transformer Transformer Transformer
Transformer
LC
Flow Baffle hot grids
DESALTED
Flow Baffle
LC CRUDE
Crude Outlet Header
Mud
Distributor Header Distributor Header Wash
Mudwash MIX
Header VALVE
Raw Mud Wash
Mudwash
Pump Crude Header
EFFLUENT
WASH WATER
Raw WATER
Crude EFFLUENT WATER
Mix Valve
Wash Water
Operating Variables
Desalter Operating Variables
Desalter type
Wash Water System
Level control
Mix valve setting
Temperature
Mud wash
Desalter Wash Water
Common Sources
Process water
Preflash overhead water
Atmospheric column overhead water
Vacuum condensate
Stripped sour water
Municipal, well or filtered surface water
Boiler blowdown
Cooling water blowdown (scale, bio)
Brine recycle
Desalter Wash Water: Injection Location

Crude Oil Crude Oil to Hot Crude
Storage Tank Preheat Exchangers
Emulsion Breaker
Mix Valve
Wash Water
to Mix Valve Desalter
Wash Water
Wash Water to Cold
Desalter Effluent Water to
Crude Preheat Exchangers
Waste Water Treatment Plant
Normal injection is prior to mixing device

Can inject some water prior to preheat exchangers (10-100%)
Longer contact to dissolve salt crystals
Reduce exchanger fouling
Do not inject to suction of pump (can make difficult emulsion)
Desalter Wash Water
Best Practice Water Rate
Target:
4 6% (Light to Medium Crude Oil)
6 9% (Heavy Crude Oil)
Lower crude oil gravity = higher wash water rates for
optimum performance
Wash Water Impact on % BS&W
Settling
3% Water 5% Water 7% Water 9% Water
Time
20 min 1.2% 3.4% 4.5% 8.0%
30 min 1.7% 3.7% 5.5% 8.0%
Desalted
1.2% 0.8% 0.8% 0.2%
Crude BS&W
Heavy Canadian crude oil

Wash Water Quality
Best Practice Water Quality

pH (5 - 8)
Hardness (< 175 ppm as CaCO3)
Scale in brine effluent/wash water feed exchangers
Suspended solids (< 30 ppm)
Ammonia (< 50 ppm)
Phenols and organic acids (< 1 ppm)
Wash Water Source Concerns

High pH (normal 5 - 8)
Best practice pH around 7
High pH can stabilize
emulsion
Potential sources of high pH
Spent caustic
Caustic added at SWS to
improve stripping
Tramp amine/ammonia
Is it the desalter effluent pH
that is critical?
Desalter Operational Variables
Desalter type
Wash water system
Level control
Mix valve setting
Temperature
Mud wash
Interface Level Settings
Determined by desalter design:
Howe-Baker
5-30 cm (6-12) below crude inlet
Petreco Low Velocity

15 cm (6) above inlet
Petreco Bilectric & Cylectric

30-60 cm (12-24) below bottom grid
Interface Level Monitoring
Tri-cocks, trylines and/or swing arms
DESALTERLEVELSAMPLINGDEVICES
OIL
bottomgrid
EMULSION
5
EMULSION 2 1/4
4
2
3 1
2 "Arm" swings or rotates 180 degrees
0
1 straight up and down
1
2
WATER 2 1/4
SwingArm:
samplingpiperotates180degrees,
Tricocks:
enablingsamplecollectionatanypoint
separatelinesandvalves
<-----OR ----> {MUSTDETERMINESWINGARMSETTING
samplesvessel(desalter)typicallyat
vs.ACTUALHEIGHTINUNIT}
five(5)heights
Thesenumbersareonlyguides
bottom#1,top#5
Interface Level Monitoring
Use tryline or swing arm to establish level

Use instrumentation to monitor (not absolute)
Collect samples in centrifuge tubes from swing arm or
trylines
Centrifuge samples to determine BS&W at various levels
Interface Level Controllers
Floats/Displacers
Based on density differential
Less effective with higher density/low gravity crudes
Ineffective with emulsion pad
Capacitance probe
Measure differences in electrical capacitance
Agar probes
Measure differences in energy absorption
TRACERCO
Gamma ray technology
Level Control Capacitance Probe

Low Level Safety Float Switch Will cut power
to the middle grid if the float & Oil level drops
Desalted crude
4TH & 5th Tricock -

Upper Grounded Electrode Emulsion
8
Middle Energized Electrode 123%
8
Lower Grounded Electrode 20.8mA
105 %
20 Ma = 100% @ 66
Rag layer
18mA 87.5 %
Water Level
16 Ma = 75% @ 52 69.4%
15.1mA
12.288mA 79
12 Ma = 50% @ 38 Inlet 51.8%
Active Area 56
Distributor
69
72 Mud Wash
8 Ma = 25% @ 24 59
Capacitance Probe
49
4 Ma = 0% @ 10
39
10 Effluent Water
Desalter type
Wash Water System
Level control
Mix valve setting
Temperature
Mud wash
Mix Valve Setting

No absolute best setting
Will vary with type of crude, throughput, and type of
chemical used
For most efficient salt and solids removal
Increase mixing energy until BS&W begins to increase
Changing chemical can improve dehydration and allow
more mixing
Adjust the Mix Valve to Optimize
Salt and BS&W Removal
Desalter mix valve P vs. desalted crude salt and BS&W
100
% SALT IN DESALTED CRUDE
% BS&W IN DESALTED CRUDE

80
60
1.0
SALT CONTENT
40 0.8
OPTIMUM
MIXING 0.6
PRESSURE
}
20 0.4
BS & W 0.2
0 0
INCREASING MIXING PRESSURE


Desalter type
Wash water system
Level control
Mix valve setting
Temperature
Mud wash
Desalter Temperature
Typical range 165 295F
Higher temperatures decrease crude oil viscosity
Emulsion breaks more easily
Water more soluble at higher temperatures
Conductivity increases with temperature
Crude Oil Typical

Deg API Temperature
>36 220-250
36-30 235-265
30-24 250-280
24-18 265-295
18-12 280-310
Characteristic Temperature Viscosity

Relationship for Crude Oils
5000 1200
VISCOSITY - SAYBOLT SECONDS
2000 450
VISCOSITY - CENTISTOKES
10 API
1000
500 12 API 120
200
16 API
100 20.0
22 API
60.0
45.0 5.5
30 API
36 API
2.5
35.0
80.0 100 130 210 300
TEMPERATURE - F
Desalter type
Wash Water System
Level control
Mix valve setting
Temperature
Mud wash
Desalter Components - Mud Wash

Purpose: solids
accumulate in the bottom
of the vessel - forming
INTERFACE
LEVEL MUDWASH HEADER mud or oily sludge. The
&
IN VESSEL NOZZLES sludge may plug parts of
the effluent water header
or significantly decreases
water phase residence
LEVEL
time in the vessel.
CONTROLLER
DESALTER EFFLUENT
WATER HEADER
TO WWTP
MUD WASH PUMP
ALTERNATE
WATER SOURCE
Howe-Baker recommends mud washing a minimum of three minutes per day

for a typical mud washing system, while Petreco suggests mud washing for
one hour once per week. However, the frequency and duration of mud
washing is best determined through operating experience. [ALL DEPENDENT
ON SOLIDS LOADING]
Mud Wash Practices
Nozzles placed 0.3 0.5 m off bottom
Velocity and time are critical parameters
Mud wash until brine turns clear
Best to use recycled effluent water
Need mud wash pump
Dont starve wash water

Chemical Treatment Programs
Chemical Treatment Program Types
Conventional emulsion breaking chemicals (demulsifiers)
Injected into the suction of crude unit crude pump
Used to control interface growth and improve effluent water
quality
Can also have an effect on dehydration efficiency
Sole chemical used in majority of desalter operations
Adjunct chemical applications
Solids wetting agents
Used to improve solids handling capability
Typically injected into desalter wash water
Polymers
Used to shrink interface size, reduce effluent water oil content
In many cases used for upset recovery only
Typically injected into desalter wash water
Chemical Treatment Program Design

Feedstock evaluations
Service companies can pre-screen blends and/or individual
crudes in the lab to assess and predict:
Asphaltene stability
Feedstock compatibility
Emulsion resolution speed, efficiency
Best chemical treatment regimes
Chemical treatment program development
Based on feedstock pre-screening results
May be modified based on prior field experience
Adjust/optimize program on site
Good data collection, optimization protocols are key
Desalter Operating Variables: Summary
To optimize desalter operations:

Use an adequate amount of a good quality wash water
Maintain good level control
Use proper mix valve pressure drop settings
Use an effective chemical treatment program
Monitor desalting performance on a regular basis

Performance Monitoring
Monitoring to Ensure Performance
Major KPIs are measurable and reflect true performance

Some KPIs may be tied to the contract as performance
conditions

Suggested minimum KPIs for
desalter operations
Raw & desalted crude analyses
Salt, BS&W and Filterable Solids
Calculated % salt removal and %
solids removal efficiencies
Brine quality measures
pH
O&G in refinery lab or TD500 (or
other method)
Visual
Percentage oil by graduated cylinder
TD500 Oil in Water Meter
Basic process data monitoring recommendations
Crude rate
Crude type
Crude tankage operational status
Water slugs
Crude tank levels
Individual crude tank BS&W or filterable solids contents
Slop oil addition
Addition rate and quality (BS&W, solids content)

Special application KPI monitoring
Calcium removal efficiency
Tramp amine or ammonia removal
Iron removal efficiency
Additional Process Monitoring
Monitoring of operational variables that impact
performance but are not KPIs
Temperature & pressure
Mix valve P
Level; tri-cock analyses
Grid volts/amps
Sludge levels
Mud wash frequency, duration & efficacy
Wash water rate and quality
Flash drum bottoms temperature
Atmospheric column overhead accumulator water make

Other KPIs related to desalting
Crude column overhead condensate chloride content
Monitor caustic strength and addition rates, if used
Best practice: 5 Baume strength, 5 ptb addition rate
Chemical dosage and consumption history
Slop oil generation
Downstream unit specific KPIs
Benzene stripper
Coke sodium content (anode grade coke)
Desalting System Troubleshooting

Agenda
Common causes of
Poor performance
Upsets
Crude oil quality and its impact on desalter operations
Solids
Asphaltenes
Calcium naphthenates
Crude oil storage tank condition and operation
Slop oil reprocessing
What are the most common causes of desalter
performance problems?
Equipment problems
Operating conditions
Crude unit feedstock characteristics
Identifying and correcting performance problems
Operational and mechanical solutions
Chemical treatment programs
Combinations

Typical equipment problems
Treatment chemical pump malfunction
Level control indication or control system malfunction
Loss of electrical grid(s)
Sludge buildup in vessel/plugged effluent water header
Typical operating condition deficiencies
Wrong interface level setting
Low desalter temperature
Insufficient wash water rate
Incorrect mix valve setting
Ineffective chemical treatment program
Desalter feedstock characteristics
Most common cause of desalter upsets
Most desalter upsets related to desalter feedstock
characteristics
Crude oil quality
Individual crudes
Properties of crude blends
Impact of crude storage tank operating practices
Slop oil re-processing
Characteristics of re-processed slop
Slop injection practices
Wash water quality
pH
Solids content

Crude Oil Quality Issues
Crude Quality Issues
Crude oil characteristics
BS&W of raw crude
Filterable solids content of raw crude
Stability of asphaltenes in crude blends
Other crude oil contaminants
Surfactants
Ammonia, tramp amines
Naphthenic acids
Calcium naphthenates
Crude Oil Supply System

MARINE
OFFSHORE
Marine
BARGE Terminal
Tankage
TANKER
Pipeline
Tankage Refinery
Tankage
Lease
Tankage
ONSHORE
COQG Salt Dome

Storage
REFINERY
66
Filterable Solids
Inorganic solids, > 0.45m in diameter
ASTM D-4807-88 (using toluene wash step)
Not typically included in assays
Wide variation in solids content
What is high?
Systems vary in their tolerance to solids
Typical solids levels where emulsion stabilize >80 PTB
Desalter problems caused
Stabilized emulsions
Oil in brine
Specialty surfactants can help
Solids / Asphaltene Stabilized Emulsion

(5% Wash Water Added)
100 X
Filterable Solids Variations (Three Months)
Filterable S olids(P TB) 300

250
200
150
100
50
0
For some crudes oils there can be substantial daily filterable solids variation
Filterable Solids: Individual Lease Samples

Blended and Sold as Single Crude Oil
FilterableSolids -Lease Samples
900.0
800.0
700.0
600.0
500.0
400.0
300.0
200.0
100.0
0.0
Solids in crude oil blend vary depending on which wells are producing
Combined Raw Crude Filterable Solids
Wetting Agents can Mitigate Problems
Solid shading indicates
Wetting Agent
140 desalter upset
120
pounds per 1000 bbls
100
80
60
40
20
0
3/8/2000 3/16/2000 3/25/2000 4/15/2000 4/25/2000 5/8/2000 5/15/2000 5/26/2000 6/3/2000 6/9/2000
Asphaltenes
Stressing asphaltenes causes agglomeration
Paraffinic vs. asphaltenic crude oil
Temperature
pH
Can cause multiple problems
Sludge precipitation in tankage
Fouling
Foaming
Emulsion stability desalter problems
Effluent water quality
Wastewater treatment plant upsets
Theoretical Asphaltene Structure
Gray, M. R., Energy & Fuels 17(6), 2003, 1566
Asphaltene Micelle
Bulk oil
Resins
Asphaltene Core
Asphaltene Destabilization
Stress
(destabilizes resins)
Disruption of resins Agglomeration

(stacking of Asphaltenes)
ASIT Asphaltene Stability Index Test

Intensity
Onset Flocculation
Point of Asphaltenes
Titrant
Light
source
1 3
ASI
ASIT TM Principle
Measures the onset of the flocculation of the asphaltenes
with high accuracy by inducing the asphaltene precipitation
via titration with a paraffinic solvent
ASIT is a trademark of Baker Hughes Incorporated
ASIT Test Case History 1
Introduction of Crude 2 caused formation of rag layer
shorting out bottom grids
Oils were found to be incompatible
Blend had ASI in unstable region
# Oil / Blend ASI % Asphaltenes % Resins Asph/Res

1 Crude 1 1.75 3.4 7 0.49
2 Crude 2 0.96 5.4 10.8 0.50
3 Crude 3 1.5 6.53 27 0.24
4 55% (1) 20% (2) 25% (3) 1.24 - - -
ASIT Test Case History 1

120
100
80
Intensity
60 Asphaltene stabilizer
#1
increases stability of
40 #2 blend
#3
20 #4
# 4 & Additive
0
0 0.5 1 1.5 2 2.5
ASI
EDDA Demulsification Test % Water Drop % Water Drop % Water Drop BS&W
5 min 10 min 15 min
#4 0 0 0 0.6
# 4, Stabilizer & Demulsifier 3.3 3.8 4.5 0.14
Mitigation Strategy for Case History 1
Crude oil blending aid added to crude 2 as it was

transferred to storage tanks
Wash water rate increased from 4% to 5.3%
Increases droplet population
Increases oil-water interfacial area, effectively diluting
asphaltene surface concentration
Wetting agent added
Control solids that increase asphaltene destabilization
Crude Oil Blending Aid Case History 2

Refinerys ability to process heavy Canadian crude limited
Poor dehydration
Poor brine quality
Asphaltene stabilization determined to be the problem
Tested crude blend samples to select best chemical
treatment program
Crude oil blending aid (new)
Oil-soluble emulsion-breaking chemical (already in use)
Solids wetting agent in wash water (already in use)
Crude Oil Blending Aid Case History 2
Results:
More than doubled the amount of heavy Canadian crude
being processed
7.5 KBPD to 17.5 KBPD
Maintained salt removal efficiency

Dehydration performance maintained
Field ASIT ServicesTM Technology
Field ASIT ServicesTM is a trademark of Baker Hughes Incorporated
Other Contaminants: Calcium Naphthenates
Tank Farm problems
Calcium naphthenates are natural emulsion stabilizers
High BS&Ws in oil charged to crude unit
Desalting problems, when metals are present as
naphthenate salts or fine particulates
High conductivity causes voltage loss
Water carryover
Poor effluent water quality (high O&G)
Desalter effluent water exchanger scaling
Calcium deposits
Chemical Treatment Programs To Mitigate

Calcium Naphthenate Problems
TreatedCrudeOil
toHotPreheatTrain
CrudeOil
Desalter
Storage
MixValve
WashWaterto
Desalter
BakerPetroliteEmulsion
BreakingChemical Desalter
EffluentWater
toWasteWater
TreatmentPlant
EXCALIBUR Contaminant
RemovalAdditive
BakerPetrolite
CalciumScaleInhibitor
84
Case History 1: Refiner Processing 20%
High Ca Naphthenate Doba Crude Oil
Contaminant removal additive application reduced desalter
effluent water oil content vs. previous, non-Doba
operations
Doba processing had no significant effect on effluent water
COD levels
Phenol levels also reduced
Oil in Effluent Chemical Oxygen

Water, mg/L Demand, mg/L Phenol, mg/L
Before Doba
Processing 243 2,002 12.3
Average Values
During Doba
Run 34 2,870 2.3
Case History 1: Calcium Removal

Efficiency Over 90%
Case History 2: Desalter Contaminant Removal
Background:
Refinery processing up to 20% high Ca naphthenate Doba crude
Concerns with Ca impact on FCCU catalyst
Two stage desalting with minimal (2.5%) wash water
Results:
Limited metals removal without contaminant removal program
Metal Raw Crude Desalted Crude % Removal

(ppm) (ppm)
Calcium 46.1 45.0 2
Iron 7.4 7.2 3
Barium 1.4 0.6 57
Magnesium 1.0 0.6 40
Manganese 1.0 1.0 0
Case History 2: Desalter Contaminant Removal

Results:
Metals content of desalted crude monitored daily
Contaminant removal program showed much greater
calcium, iron and other metals removal performance
Metal Raw Crude Desalted Crude % Removal
Calcium (ppm) 53 4 92
Iron (ppm) 8 2 75
Barium (ppm) 2 0.1 95
Magnesium (ppm) 2 0.1 95
Manganese (ppm) 1.0 0.34 66
Contaminant Removal Program Benefits
Metals removal from crude oil

Reduces downstream catalyst deactivation
Improves coke, heavy fuel oil quality
Improves desalter stability
Reduces effluent brine downstream impacts (WWTP)
Provides a key tool for overhead salt formation and
corrosion strategy
Also removes alkaline materials (ammonia, amines)
Minimizes crude preheat fouling
89
89 2010
2010 Baker
Baker Hughes
Hughes Incorporated.
Incorporated. AllAll Rights
Rights Reserved. Confidential. No portion of this material may be copied, reproduced, transferred or stored without the express written permission of Baker Hughes Incorporated.
Reserved.

Crude Storage Tank Issues
Crude Storage Tank Issues
Crude oil handling impacts
Tank stratification
Tank switches
Tank sludge issues
Water slugs
Crude Storage Tank Handling Practices

Storage tank stratification
Salts and water content vary as function of height
Can form water lenses
Results in varying crude quality to crude unit
Can result in abrupt quality change during tank switch
Can result in water slugs to crude unit
Desalter cannot drain water fast enough
High salt levels in and out of desalter
Loss of grids
Operators cannot respond fast enough
Mitigation Plan for Tank Switches
Many desalter upsets occur during tank switch
Switch from best of old tank to worst of new tank
Improve communication between Oil Movements and
Crude Unit
Slow transition during switch
In line water sensor to alert operators of problems
Chemical pre-treatment can reduce impact
Crude Oil Pretreatment

Treat crude oil in the tank farm
Long contact time between surfactants and solids, sludge
Improves solids control
Stabilizes asphaltenes
Helps resolve desalter emulsions
Reduces oil under-carry
Pretreatment
Chemical
PIER
Crude Oil
Storage Tanks
COMPOSITE SAMPLER
Crude Oil Pretreatment Case History 1
Marlim Crude Tank Treatment Trial - Total Drain Water(Bbl)

600 Untreated T-41
Drained Water (Barrels)
500 Baker Petrolite Treated T43 500

460
400 Untreated Water Draw 420
Treated Water Draw
339
300
231
200
100
0 12 3 6 8 9 12
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Settling Time (Hrs)
Untreated Tank Settling
120
100
80
Top
Salt (PTB)
Middle
Bottom
60
Top
Middle
Bottom
40
20
0
0 24 30 48 72 96
Hours
Treated Tank Settling
120
100
80
Top
Salt (PTB)
Middle
Bottom
60
Top
Bottom
Series7
40
20
0
0 24 30 48 72 96
Hours
Crude Oil Pretreatment Case History 2:

Improve Heavy Oil Handling Capabilities
Desalter upsets when processing heavy oil sands crude oil
Up to 3,000 ppm oil in desalter effluent water
Caused problems in WWTP
Implemented crude oil pretreatment program
With pretreatment, effluent water oil content decreased to
an average of 140 ppm
Improved WWTP operation
Odor emissions reduced
Filterable solids removal efficiency increased from 27% to
42%
Heavy Oil Pretreatment Case History 2
Desalter Effluent Water Quality Before and After Pretreatment Program
In Line Water Sensors

Measure water in crude oil
Give operators 10 to 30 minutes to react to water slug
Reduce wash water
Drop level in desalter
Reduce mix valve P
Crude Oil Crude Oil to
Storage Tank Hot Crude
Preheat
Exchangers
Transformer
Emulsion Breaker
Interface
Level
Controller
Crude Mix Valve

Charge
Pump
Wash Water
Wash Water to Cold to Mix Valve
Crude Preheat Exchangers
Desalter
Wash Water
Desalter Effluent Water to
Waste Water Treatment Plant
Sludge in Crude Tank
Visible Light Micrograph of

Sludge From Tank I
102
Schematic of a Complex Emulsion
Oil
Water
Water
Problems - Solution
Problems
Sludge can lead to water slugs
Complex emulsion difficult to resolve in desalter
Solution
Water slug alarm
Chemical treatment to reduce sludge
Average Sludge Depth in Tank Farm
with 3 Years Chemical Treatment
40
35
30
DEPTH (cm)
25
20
15
10
5
0
0 10 20 30 40
MONTHS OF TREATMENT

Slop Oil Reprocessing
Why is slop oil a problem?
Should all slop go into the desalter?
What can be done to manage slop oil?
Why is Slop Oil a Problem?

High water content
Inconsistent quality
Can destabilize crude oil
Solids can stabilize emulsions
Coke fines causes desalter upsets
Sand, clay, dirt
Iron sulfide can affect product quality
Problems Associated with
Cost of reprocessing Corrosion
Direct costs Fouling
Opportunity costs Inorganic solids
Desalter upsets Organic materials
Stable emulsions
Pressure surges
Grid loss
Tray damage
High BS&W
Throughput reductions
Effluent water quality
Catalyst poisons Environmental releases
Heavy metals Waste water system
Alkali metals Hazardous gases
Nuisance odors
Should All Slop Go To The Desalter?

No-Nos
Coke fines
Catalyst fines
Biological waste
Cleaning waste
Paraffinic material
If no water and salt, it does not need to be desalted
Some slop should be treated before desalting
What Can Be Done?
Segregate slop oil to better recycle
Continuous feed versus batch feed
Enable operators to back out slop
Chemically treat slop oil
Drops out oil and water
Improves quality and consistency
This slide contains

2010 the proprietary
Baker Hughes information
Incorporated. of Reserved
All Rights Baker Petrolite Corporation.
. Confidential. No portion of this material may be copied, reproduced, transferred or stored without the express written permission of Baker Hughes Incorporated.
By reading this Slide the reader agrees not to disclose any information
Troubleshooting Crude Quality Issues:

Summary
Understand factors affecting quality of feed to desalter
Minimize variations in quality
Alert operators to problems and enable them to respond
Consider chemical treatment to solve some problems
Wet crude oils
High solids crude oils
Incompatible crude oils
High metals crude oils
Emulsions and sludge in storage tanks
Slop re-processing
Wastewater Treatment
Agenda
Introduction
Wastewater treatment overview
Chemical treatment strategies
Examples
Post desalter strategies
Brine Treatments
Today, more and more emphasis is being put on brine

quality (solids and oil content) and its effects on
downstream processes (e.g. NESHAP, BRU Benzene
Reduction Units ) and the WWTP
Many sites processing heavier crudes see desalter
emulsions (and possible upsets, mudwashings)
contributing to brine quality problems, plus potentially the
accumulation of sludge in BRU tanks
Filtration or Lime Softening
Refinery
Corrugated Plate Interceptor (CPI)

American Petroleum Institute (API)
Separators
Equalization Basin
Sludge
Digester Solids Dissolved Air Flotation (DAF)
Induced Air Flotation (IAF)
Thickener Aeration
Basin
Clarifiers
Dewatering Filtrate
Filtration/Activated
Carbon Adsorption
Landfill
River/Sewer
Wastewater Treatment Process Overview
Primary
Secondary
Tertiary
Dewatering
Primary Treatment
Removal of relatively large, heavy suspended solids
and/or free oil
Process involved:
Equalization
pH adjustment
Chemical oxidation
Precipitation
Equipment involved:
API Separators
Corrugated Plate Interceptors (CPI)
Parallel Plate Separators (PPS)
Induced Air/Gas Flotation Units (IAF)
Dissolved Air/Gas Flotation Units (DAF)
Steam strippers
Clarifiers
Filtration units (sand, gravel, nutshell media)
Secondary Treatment
Removal of colloidal and dissolved organics by a biological
system
Equipment involved:
Equalization Basin
Aeration Basin
Waste Activated Sludge
Rotating Biological Contactors (RBCs)
Secondary Digesters (aerobic or anaerobic)
Fixed Film Bioreactors
Secondary Clarifiers
Biosludge Thickeners
Thickened Sludge DAFs
Tertiary Treatment
Any form of advanced treatment of secondary effluent,
such as media filtration, nitrogen removal, carbon
adsorption, etc.
Produces high quality water for reuse or discharge
Equipment involved:
Oxidation systems:
Chlorine dioxide, ozone generators
Hydrogen peroxide (possibly catalyzed)
Sodium hypochlorite, gaseous chlorine
Powdered activated carbon adsorption
Granular activated carbon
Nutrient removal (nitrogen, phosphorus)
Ultra filtration
Sludge Dewatering
The removal of water from sludge to further concentrate
solids
Equipment involved:
Plate and frame press
Rotary vacuum filtration
High speed centrifuge
Vacuum belt filter
Belt filter press
Dewatering box
Heavy Oils Present Operating Challenges

Crude quality issues
Filterable solids
Asphaltenes
Non desaltable chlorides
Observed problems
Stable emulsions
Water carryover
Oil and solids in effluent water
Mud build up in desalters and brine separators
WWTP performance problems
Typical Desalter Effluent Brine Quality Variations
Based On Filterable Solids Estimates in Raw Crude Slate
2 3 4 5
1
30 - 60 PTB 60 - 100 PTB 100 - 130 PTB 130 - 150 PTB 150 + PTB
Brine Treatment Unit

Brine Quality Cycle
Pre mud wash 15 minutes after 1 hour after 2 hour after 15 minutes after 2 hours after
starting mud wash starting mud wash starting mud wash stopping mud wash mud wash
O&G- 127 mg/l O&G- 40,441 mg/l O&G- 11,640 mg/l O&G- 2,031 mg/l O&G- 343 mg/l O&G- 22 mg/l
TSS- 43 mg/l TSS- 10,382 mg/l TSS- 2849 mg/l TSS- 658 mg/l TSS- 92 mg/l TSS- 16 mg/l
Heavy Oil Case History 1
Refinery upgraded desalter for heavy Canadian crudes
Poor desalter effluent water quality
Low dissolved oxygen in WWTP
Pre-screened crude blend samples to select chemical
treatment program
Oil soluble emulsion breaking chemical
Solids wetting agent in wash water
Polymer when needed
Desalter operating variables optimized in the field
Heavy Oil Program Results: D.O. in WWTP

Waste Water Treatment Plant Dissolved Oxygen
Before Baker Petrol ite After Baker Petroli te

7.0
6.0 dissolved O2
Competitive average
Dissolved Oxygen, ppm
5.0 Baker Petrolite Average
4.0
3.0
2.0
1.0
0.0
Daily
Heavy Oil Program Case History 1: Results
Can run 250 PTB solids in crude charge
Salt removal and dehydration maintained
Filterable solids removal remains at 80%
WWTP operation improved
COD reduced
DO increased
No longer affected by oily brine
Overall chemical usage dropped nearly 50%
Polymer Use Reduces

Desalter Effluent Water Oil Content
Single stage BILECTRIC high velocity desalter
Heavy Canadian crude
0.91 Kg/L (24API)
200 to 450 ppm solids
2 5% oil in desalter effluent water
Injected dispersion polymer into wash water
Oil and grease dropped to < 100 ppm
Solids removal remained 66 73%
Dehydration improved
Dispersion Polymer Application
Improves Desalter Effluent Water Quality
This is Not Good Enough

Still have solids to contend with
High levels of oily solids during mud wash
Upsets can send oil to WWTP
Solids and oil tend to accumulate in Equalization Tanks
The solution is to treat the effluent brine!
Advanced Separation Technologies
Gas Flotation
Hydrocyclones
Centrifuges (2 and 3 Phase)
Membranes
Desalter Effluent Brine Treatment

Recommended Flow Scheme
Desalter
Cone Bottom Tank

Or
API
Induced Static Floatation

Dissolved Nitrogen Floatation
Induced Gas Floatation
Equalization Tanks
Primary Refinery API
Waste Water Treatment

Plant
Primary Treatment Equipment
Designated desalter effluent API or heated cone bottom
break tank advantages
Provides for initial three phase separation of oil, solids and
water prior to chemical addition
Enhances recovered free oil quality by not tying solid and
oil together with a polymer or flocculant into one phase
Reduces overall slop oil production
Breaks the internal refinery solids cycle

Heated Cone Bottom Tank Operation
Desalter
Free Oil to API or Slop

Max BSW: 0.5%
Optional
Emulsion Breaker
Or Wetting Agent Effluent Brine OIL
if needed or treat To Deoiler ISF, DNF or IGF
only during mud wash
Emulsion
Max Oil: 500 ppm
Solids
Centrifuge Note: Agar Probes can be installed in tank

Solids to better monitor oil/emulsion interface
Solids to Roll off box Cationic Flocculant

Or Coker (Spectrafloc Product)
(ISF, DNF, or IGF)
Skim oil to Oily Sludge Thickener
Cationic Coagulant then Centrifuge Feed Tank
Blend Anionic Flocculant
BPW 76030 (Spectrafloc Product)
Effluent to API
or Equalization
Reverse Emulsion Max Oil: 25 ppm
from Cone Bottom Tank
Solids to Centrifuge

Designated desalter brine effluent flotation vessel
advantages
Effluent can the be sent to benzene stripper for NESHAP
conformance with little to no fouling potential
Reduces insoluble COD/BOD
Reduces overall organic loading to wastewater treatment
plant
Excellent point source control measure
Treats only the emulsified portion of the desalter brine
Desalter # 3 Brine Testing
3 minutes Rapid Mix

5 Minutes 40 RPM
5 Minutes Settle
Blank BPW 76030 BPW 76091 BPW 76453

O&G 776 ppm @ 20 ppm @ 20 ppm @ 20 ppm
O&G 32 ppm
Note: 1.0 ppm SPC-880 added

.
@ start of slow mix
2010 Baker Hughes Incorporated. All Rights Reserved Confidential. No portion of this material may be copied, reproduced, transferred or stored without the express written permission of Baker Hughes Incorporated.
Typical Refinery
Wastewater Treatment Layout
Process/Storm
Water
EQ
CPS ISF AERATION CLARIFIER WASTE
TO SLUDGE
A THICKENER
AERATION CLARIFIER
B
EQ CPS ISF
AERATION CLARIFIER
C
Reroute PST
supernatant PST
Deoiler Deoiler SKIM

Break
ISF Tank
Flocculant
@ 3.0 ppm
Desalter Effluent
Coagulant OILY WATER ( 400 gpm)
@ 30 - 50 ppm
WEST COAST REFINERY
WWT JAR TESTING
DEOILER ISF
3 MINUTES @ 100 RPM

5 MIN. 40 RPM
5 MIN. SETTLE
BLANK BPW 76030 BPW 76030 BPW 76030

@ 20 ppm @ 30 ppm @ 40 ppm
Note:All jars treated with 0.5 ppm SPC-880 during slow mix
WEST COAST REFINERY

Brine and WWT ISF Trial Samples
Polymer Treatment Level Polymer Treatment Level
BPW 76030 @ 120 ppm BPW 76030 @ 50 ppm
Spectrafloc 880 @ 7.0 ppm Spectrafloc 880 @ 5.0 ppm
5600 NTU 337 NTU 125 NTU 7.6 NTU
Break Tank Desalter ISF Equalization WWT ISF

Effluent Effluent Effluent Effluent To Bioreactors
BRINE DE-OILER AND WWT ISF
Polymer Dosage Model
WASH WATER TARGETS

KPI's DESALTED CRUDE TARGETS
#N/A BPD BPD KPI's
#N/A % % SALT: #N/A PTB PTB
#N/A pH: pH: BS&W: #N/A % %
SALT REMOVAL: #N/A % %
DESALTER
Process
& Storm water
1200 GPM EQ
CRUDE RATE CHARGE
KPI's MIXED CPS ISF
CHARGE RATE: #N/A BPD
API GRAVITY: #N/A
SALT: #N/A PTB
FILT SOLIDS: #N/A PTB
BS&W: #N/A %
EQ
MIXED CPS ISF EFFLUENT TO BIOREACTORS TARGETS
KPI's
EFFLUENT BRINE TURBIDITY #N/A NTU's NTU's
KPI's O&G #N/A ppm ppm
Visual Quality Index #N/A 1-5 PST TSS #N/A ppm ppm
O&G #N/A ppm COD #N/A ppm ppm
TSS #N/A ppm SKIM
Deoiler Deoiler
Brine Effluent Visual Quality Index ISF CPS
3 4 5
1 2
DE-OILER EFFLUENT TARGETS
KPI's
TURBIDITY #N/A NTU's NTU's
O&G #N/A ppm ppm
TSS #N/A ppm ppm
#REF!
Desalter Brine Effluent 400 gpm
Advanced Brine Treatment Unit

Oil to slop
Three Phase
Centrifuge
Floatation Units
Solids to thermal
Desalted Crude
desorption
BPW 75850
Spectrafloc 875
(Metals Removal)
Water to API
Raw Crude BPW 76001
During mud wash BPW 76453
Float
Fresh Washwater
Spectrafloc 875
Effluent Brine
2nd stage effluent brine to 1st stage
Dirty Brine
3000-4000 mg/l O&G BPW 76001 Effluent to API
250-500 mg/l TSS
Target
> 500 mg/l O&G
Mud Wash Brine
1.5 2.0 % O&G > 500 mg/l TSS
2000 - 3000 mg/l TSS
Off Spec Off Spec

Tank Tank
Brine Treatment Unit Metals Removal Test Results
D200 Brine Vanadium Removal Testing
0.045
Raw Data
0.04 Dose of Metals Total Dissolved
Sample Products Precipitant Vanadium Vanadium
Numbers Samples mg/L mg/L mg/L
0.035
1 Blank 0 0.041 0.027
Blank 2 Polymer 0 0.0092 0.0074
0.03 3 TR6 50 0.0013 0.0016
4 TR6 100 0.0018 0.0012
0.025 5 TR6 200 ND ND
6 75850 50 0.0011 ND
mg/L
7 75850 100 0.0058 0.0039

0.02 8 75823 50 0.0029 0.0023
9 75823 200 0.0018 ND
0.015
Polymer
Only
0.01
Polymer Polymer
Polymer
& BPW 75850 & BPW 75823
& TR6
0.005
0
0 1 2 3 4 5 6 7 8 9 10
Samples
Total V Dissolved V
Conclusions
Heavy crude oils typically produce poorer quality brine
Solids and asphaltenes affect

Emulsions in desalter
Oil carryunder
Optimize desalter to improve effluent quality
Chemical treatment to minimize oil carryunder
Brine requires treatment prior to equalization
Baltimore Marriott Waterfront Hotel
October 13, 2010
Presenters:
Kerlin Lobo
Larry Kremer
Simon Cornelius
Baker Petrolite Desalter Operating Guidelines
Feedstock flexibility equals refining profitability
Our Baker Petrolite XERIC heavy oil program enables you to process
higher rates of heavy, high solids and high asphaltene crude oil blends
for improved feedstock flexibility and plant profitability.
Maintains desalter operational stability while providing desired

dehydration and salt/solids removal efficiency
Reduces oil recovery costs by reducing the amount of oil loss from
desalter operations
Prevents wastewater treatment plant upsets by lowering desalter
effluent water oil content
Controls expenses related to wastewater plant chemical treatment
by improving influent water quality
High Salt High Salt

High BS&W
High Oil Wide High Amps, Carryover with Carryover with Typical
in Desalted Items to Check
Undercarry Interface Low Volts High Water Normal Water Range
Crude
Carryover Carryover
Crude change/crude tank switch?
Poor wash water quality/high pH? pH 6.0-7.5
Low wash water rate? 4-8%, typ. 5%
Poor quality/high quantity of slop oil?
Desalter mix valve DP high? 2-25 psig
Desalter mix valve DP low? 2-25 psig
Demulsifier rate high?
Demulsifier rate low?
Water level high? *
Water level low? 125-165

Water residence time low? minutes
Desalter level controller operating OK?
Desalter back pressure fluctuating?
Cycletric desalter distributor DP OK? 3-7 psig
Desalter temperature OK? 240-300F
Desalter pressure low?
Crude rate increased?
Electrical system OK?
= check first = check second

*Water level should be kept as high as practical, generally 1-2 ft below the bottom grid for PETRECO desalters.
XERIC is a trademark of Baker Hughes Incorporated.
2010 Baker Hughes Incorporated. All Rights Reserved. 28888
77-80 30/9/04 8:52 Page 77
Crude Oil Tank

Sludge Treatment
Mark Preston, Paul Martin and Scott Bieber, Baker Petrolite, USA, discuss a chemical
treatment program for reducing the amount of sludge accumulation in tank storage.
s an oil refinery repeatedly fills and empties crude stor- crudes produced in the world today. The distillation character-
A age tanks, over time paraffin wax, asphaltenes, emul-

sified water and solids settle in the storage tank as
sludge. Depending on the quality of the crude oils and the
istics and contaminant levels vary from crude to crude.
Crude oil is most often produced as a water-in-oil emul-
sion containing large quantities of dissolved salts and sus-
length of time the tank has been in storage, this sludge accu- pended solids. The salts are mostly chloride, sulfate and car-
mulation can be from several centimetres to over one metre bonate salts of calcium, magnesium and sodium. The solids
deep. are typically silt, sand, clay, iron oxides, and iron sulfides.
Baker Petrolite has developed crude oil tank pretreatment Crystalline salts may also be present.
programs that recover trapped oil in These contaminants frequently
the accumulated sludge and reduce arise from several sources:
the sludge volume by as much as Brine contamination as a result
90%. The treatment program can of the brine associated with the oil in
reduce a refinerys total cost of oper- the formation.
ation by several millions dollars, pro- Most minerals, clay, silt, and
viding the following benefits: sand found in the formation around
Reduced tank turnaround time the oil well bore.
for inspection and maintenance. Iron sulfides and oxides as a
Increased usable storage capac- result of corrosion during produc-
ity. tion, transport and storage.
Recovery of unusable hydrocar- Polar molecules in the oil can
bon inventory. act as emulsifiers, adsorbing to the
Reduced storage tank cleaning oil/water interface. These polar
Figure 1. Graphical depiction of an
and maintenance costs. compounds may include
emulsified water droplet in crude oil.
Reduced sludge disposal costs. asphaltenes, resins, oxygenated
Fewer crude unit desalter sulphur and nitrogen compounds,
upsets. porphyrins, waxes, organo-metallic salts and organic acids.
These chemical treatment programs are conducted while They have a lipophilic (oil loving) portion which tends to be
the crude storage tanks are in use, so no service interruptions soluble in hydrocarbons such as crude oil, and a hydrophilic
are necessary to achieve reductions in tank sludge levels. (water loving) portion that tends to be soluble in water.
These stabilisers, when concentrated, have a mutual
Crude characteristics and tank farm attraction, which results in an elastic and sometimes tough
sludge formation and viscous film around the water drop. Figure 1 shows how
Crude oil is a mixture of hydrocarbons with boiling points rang- the polar molecules are oriented in the interfacial area sur-
ing from -100 C to 800 C. There are hundreds of different rounding a water droplet suspended in a continuous oil
Reprinted from HYDROCARBON ENGINEERING AUGUST 2004

77-80 30/9/04 8:52 Page 78
phase. Finely divided solids also collect at the liquid-liquid mixers.

interface leading to a minimum interfacial area and further Tank water draining practices.
stabilisation of emulsions. Sludge profiles of crude tanks show sludge levels from
Crude can also become contaminated during shipping. several centimeters to over a metre in depth. This translates
For example, solids can be picked up in pipelines and termi- into hundreds and thousands of tonnes of sludge. Over time
nal storage facilities or the oil can become the trapped hydrocarbon can undergo oxida-
contaminated with sea water ballast in tion and polymerisation reactions, forming
ocean-going vessels. Waste oils and other very viscous tank bottom deposits.
unknown chemicals can also be added to During receipt of a new crude some of the
the crude at the production site or during sludge sloughs off and is suspended into the
transportation without the refinerys knowl- crude phase. If the tank is fed to the crude unit
edge. without sufficient settling time, the suspended
As crude oil is pumped into refinery stor- tank bottom sludge is also fed to the crude
age facilities emulsified water, solids, paraf- unit. This disturbance of the sludge layer can
fin wax and destabilised asphaltenes start to cause desalter upsets and can even con-
settle to the bottom of the crude tanks. Even tribute to episodes of water carryover out of
if crude oil is low in BS&W (basic sediment the desalters.
and water), large amounts of sludge can be Figure 2 shows untreated crude oil, high in
formed. For example, 1 million bbls of crude Figure 2. Untreated crude emulsified water and solids. Solids can be
containing only 0.01% BS&W could repre- oil containing dispersed- seen adhering to the sample bottle surface
sent over 10 t of potential sludge. above the crude oil.
solids and water droplets.
The final composition of
storage tank sludges varies Tank sludge
widely, but typically contains reduction
tightly emulsified oil and water, Sludge reduction involves
stabilised by solids. Sludges chemical treatment of the
can contain both oil in water sludge to achieve removal,
and water in oil emulsions. rupture, or counteraction of the
Solids that stabilise such emul- emulsifiers, coalescence of the
sions include inorganic materi- emulsified water droplets, and
als such as sand, silt, clay, gravitational separation of the
metal oxides, metal sulfides oil and water phases. Figure 3
and organic materials such as shows a crude oil sample
precipitated asphaltenes and viewed through a microscope
insoluble paraffins. with water droplets emulsified
The amount of sludge that into oil. Notice the solids
accumulates in the tank bot- adhered to the water droplets
tom depends on several fac- surface.
tors: Figure 3. Photomicrograph of solids-stabilised Baker Petrolite has devel-
Amount and nature of
water droplets in crude oil. oped a range of chemistries
solids in the crude. that water wets the solids and
adsorb at the oil-water interface, where the chemicals spread
Compatibility of crudes blended in the storage tank.
with sufficient pressure to displace the natural emulsifying
Degree of emulsification of water in the crude oil. agents from the interfacial area. This leaves an interface cov-
Transfer activity and residence time of crude oil in the tank. ered or partially covered with a very thin film which offers little
Number, condition and operational practices for any tank resistance to coalescence and break out of free water and
Figure 4. Typical sludge reduction chemical injection system.

77-80 30/9/04 8:52 Page 79
release of trapped hydrocarbon. The zeta potential on the vice for maintenance. It was found that the quantity of sludge
water droplets is reduced, allowing the water droplets to coa- had been reduced from 322 to 46 t. Treatment was via injec-
lesce and eventually separate from the oil phase. tion of chemical into crude receipts charged to T-1.
The application of a Baker Petrolite chemical program for
tank sludge reduction is very straightforward. Sludge reduc- Results
tion chemical is typically injected into the crude being dis- In the past, sludge removal took up to 30 days per tank. By
charged into the refinery crude (Figure 4). Several different treating the tank with Baker Petrolite demulsifier, the quantity
additive injection methods have been of sludge that needed to be removed
implemented that automate the control of from the tank, treated and disposed of
chemical dosing into the crude oil being was reduced by 86%. The cost savings
transferred. for this treatment are broken down as
As the treated crude enters the tanks, follows:
sludge is picked up by the shearing force Cost to remove sludge from the tank:
of the incoming crude and is mixed with US$ 500/t
the chemically treated crude oil. Cost for disposal:
Figure 5 shows a crude sample taken US$ 90/t
from the bottom of a refinery tank Total cost of sludge removal:
untreated in the left hand tube and treated US$ 590/t
in the right hand tube. The sludge content Untreated tank sludge removal/dis-
of the untreated sample was 12%. posal:
Chemical treatment separated approxi- 322 t x US$ 590/t =$US 189 980
mately 6% hydrocarbon, 6% water and Treated tank sludge removal/disposal:
0.05% solids from the crude oil. 46 t x US$ 590/t = $US 27 140
When incoming crude oils are treated Cost savings to refinery by chemically
to reduce tank sludge levels, the sepa- treating tank T-1:
rated water and mostly inorganic solids US$ 162 840
settle to the bottom of the tank. The
The total cost of chemical treatment
released water and some of the solids Figure 5. Untreated (left) and
was less than 10% of the cost savings
are then removed via the tank bottom treated crude tank bottom sludge.
due to sludge reduction. Additionally,
drains. Recovered hydrocarbon is
the time required to remove the remain-
absorbed into the crude oil. Exposure of
ing solids from the bottom of the tank
tank bottom sludge to this treated crude
after treatment was reduced from
oil slowly reduces the level of sludge in
approximately 30 days to 5 days.
the tank. Over a period of weeks to
months, significant reductions in sludge Other benefits within the tank
volume can be achieved. farm area
Economic benefits Reduced oil loss from tank
Proper management of the crude oil stor- draining operations
age system, including the use of a crude When water is drained from an
oil pretreatment program, can have sig- Figure 6a. Crude tank water draw, untreated crude tank there can be large
nificant impact on refinery profitability and untreated. oil losses, as the oil/water interface can
the efficiency of downstream operations. be very indistinct, with water emulsified
Reduced tank bottoms sludge into the crude oil phase and oil emulsified
accumulation into the water phase. Tank farm pre-
Reducing the amount of sludge in the treatment resolves these emulsions pro-
bottom of crude oil tanks provides sev- ducing a sharp oil/water interface and
eral direct benefits for tank farm man- relatively oil free water. This reduces the
agers: hydrocarbon loading in the refinery
waste water treatment system.
Reduced tank turnaround time for
Figure 6 shows water drained from
inspection and maintenance.
storage tanks containing the same ship-
Increased usable storage capacity. ment of crude oil, with one crude tank
Recovery of unusable hydrocarbon Figure 6b. Crude tank water draw, untreated and the other treated with a
inventory. treated. Baker Petrolite crude treatment chemical
Reduced storage tank cleaning and program (Figure 4).
maintenance costs.
Reduced sludge disposal costs. Improved custody transfer measurements
Crude pretreatment programs provide faster and more com-
Case history one: Asia Pacific plete separation of oil and brine in the crude storage tanks. As
refinery a result, crude pretreatment has been used successfully to pro-
vide more accurate gaugings of tank inventories when custody
Application transfer volume measurements are made. This program fea-
Baker Petrolite conducted a trial using a chemical surfactant ture can significantly reduce the refinerys payments for crude
to pretreat the sludge in tank T-1 prior to this tank being taken receipts that are based on these measurements, since emulsi-
out of service for maintenance. Tank sludge level measure- fied water that can be separated in tankage will not be counted
ments were made on 8th November prior to treatment and as oil.
then measured again on 25th May prior to coming out of ser- For example, if an extra 0.05% of crude oil water

77-80 30/9/04 8:52 Page 80
content can be released from a receipts going to the storage tanks,

1 million bbl shipment of crude and by providing continuous mixing
oil valued at US$ 35.00 per bbl, on the tanks, the solids could be
the price for this shipment would preconditioned so that they could
be decreased by 1 000 000 x be more easily removed in the
35.00 x 0.0005, or US$ 17 500. desalter, without causing oil carry
under.
Improved crude unit
operations Results
Proper crude oil pretreatment pro- The reduction in oil carry under
grams can also reduce the fre- achieved with the tank pretreat-
quency of water slugs in the feed ment program was dramatic. The
to the crude unit. These applica- improvement in tail water quality
tions will also help reduce the raw Figure 7. Pretreatment of SJV crude oil was immediately apparent by
crude salt, solids and sludge con- reduces desalter effluent water oil content. visual comparison of brine samples
tent. This enables the crude unit from the desalter. Without treat-
desalter to be run at optimum con- ment the desalter tailwater typically
ditions with higher mix valve settings, reduced desalter chemi- had 2 - 5% oil. When the tank farm pretreatment program was
cal dosage and higher interface levels. The end result is often in use, the brine typically had a trace to 0.5% oil. Results are
improved system salt removal efficiency, less oil in the desalter shown in Figure 7.
effluent and reduced desalter chemical costs. This treatment program greatly reduced the loading on the
refinery waste water treatment system and slop oil recovery
Case history two: system. In addition, it has also reduced the demand for chem-
ical emulsion breaker used at the desalter.
Tank pretreatment improves
desalter operation Conclusions
Chemical treatment programs have been developed that
Application reduce sludge levels in crude oil storage tanks while they
A US refinery processing 16 API San Joaquin Valley (SJV) are in service. Chief economic benefits include reduced
crude was experiencing several percent oil under-carry in the time for tank maintenance, lower sludge disposal costs
crude unit desalter operation. It was determined that solids and better quality raw crude charged to the crude unit.
coming in from the crude oil storage tanks were insufficiently Crude tank pretreatment provides many potential sec-
water wetted, so that the oil laden solids in the emulsion were ondary benefits, including fewer crude unit upsets, better
being carried into the desalter effluent water. It was determined desalter operation, less crude unit preheat system fouling
that by injecting a tank pretreatment chemical into the SJV and improved crude unit corrosion control.____________
World Headquarters Eastern Division

12645 West Airport Blvd. Kirkby Bank Road
Sugar Land, TX 77478 Knowsley Industrial Park
P.O. Box 5050 Liverpool L33 7SY
Sugar Land, TX 77487-5050 United Kingdom
Tel: +1-281-276-5400 Tel: +44-151-546-2855
Toll: +1-800-231-3606 Fax: +44-151-549-1858
Fax: +1-281-275-7395
Crude Oil article4.qxd 9/15/05 8:01 AM Page 1
REFINING
Crude oil and quality

variations
An assessment of the impact of crudes on operational and product quality, with
an explanation of the way in which the crude oil supply chain, combined with
the sources of many crude constituents, affects production
Larry N Kremer
Baker Petrolite Corporation
T
he biggest variable input into the fouling tendency, corrosivity, emulsion on crude oil that it transports. To meet
refinery process is the variation in forming tendency, or environmental these specifications, producers will cut
crude oil quality. Variations in impact. the crude oil with diluents to lower the
crude oil quality can affect finished viscosity and density of the crude oil.
product quality, environmental dis- Crude oil supply chain Condensate is a commonly used dilu-
charges, corrosion, heat balance on the There are many parties involved in the ent. However, in some regions, conden-
units, catalyst performance, potential supply of crude oil to the refining sate has become so scarce that other
safety issues, and the time before industry. Producers are primarily inter- diluents such as refinery cracked stock
required maintenance. Yet, most crude ested in minimising their exploration and butane have been used. The cracked
oil is bought and sold on the basis of and production (E&P) costs and maxi- stock can contain olefins that could
density (API gravity), sulphur content, mising their production. They are not cause fouling or quality problems with
and water content (BS&W, or basic sedi- primarily interested in meeting the straight-run products. The butane pro-
ment and water), which are insufficient quality expectations of the refinery. duces so-called dumbbell crudes that
to predict most of these problems. Rather, they must meet the quality stan- have larger-than-expected light ends
The definition of what constitutes dards set by the shipper and the trader and residual material and lower-than-
crude oil can vary widely. Crude quality who purchases the crude oil. Crude expected middle cuts.
refers to the properties and components quality issues are often negative for
of the crude oil that affect processing crude oil traders, who may have to Changes during transportation
and the products that can be refined reduce the price of the crude oil to the Several factors can change crude oil
from the crude oil. Numerous standard refinery because of quality issues, or in quality during transportation. For this
and non-standard tests have been devel- some cases fix" the crude oil before a reason the quality of the crude oil
oped to measure various aspects of crude suitable buyer can be found. received by the refinery may differ from
oil quality. The impact of these quality The shipper often finds itself in the the quality of the oil produced in the
characteristics can vary widely depend- middle of disputes between producer field. Degradation during normal hand-
ing on the design of the units and the and refinery. For this reason it often has ling can affect quality. As previously
robustness of the processes. For example, extensive quality control (QC) pro- mentioned, tank heels from previous
some but not all crude units are grammes to protect itself. Shippers also cargoes can contaminate new crude oil
designed to handle sour crude oil. It is set specifications on crude oil that they placed in a tank. Small amounts of
important to identify crude oil quality will accept. For example, ships and material are left on the walls of
standards suitable for a specific refinery, barges often set limits to the amount of pipelines, and subsequent cargoes can
monitor these characteristics and design hydrogen sulphide (H2S) in the crude oil pick up these contaminations.
and implement strategies to handle vari- and pipelines often set specifications on Pipelines transport crude oil in batches.
ations from the quality standards. viscosity, pour point and water content Some mixing at the interface between
While it is critical to fully characterise (BS&W). In any case, refineries need to two pipeline shipments is inevitable.
any new crude oil brought into the set quality expectations suitable to their One estimate of the interface size is
refinery, the discussion of the oil supply operation. 1500 barrels, provided there are no
chain will show that there are many fac- The crude oil processed by the refin- problems with the shipment. To min-
tors introducing variation into the crude ery is necessarily a blend of crude oils imise this cross contamination,
oil that the refiner may have been pur- from different wells, from different for- pipelines prefer to schedule large vol-
chasing for years. For example, gravity mations, and often different geographic ume shipments and try to keep similar
may vary by one or two API units from locations. Many production facilities cargoes back-to-back.
the last published assay. Published have such low rates that they must Some corrosion is inevitable in the
assays may be based on pilot plant data blend their crude oil with production handling of crude oil and this too can
or test well samples. With time, the from other areas to form a marketable be incorporated into shipments, pri-
quality of oil flowing from a well may crude oil with a name recognisable by a marily as particulate iron oxide and
deteriorate. In addition new producing refinery. As crude oil is transported it iron sulphide. Crude transported by
oil wells may be put on line, which are may be placed in temporary storage in ships or barges can become contaminat-
then blended into the currently pur- tanks at terminals in the supply chain. ed with various brines and slops. Ship-
chased crude oil. There is always a heel in the tanks from pers try to minimise all these forms of
The published assays should be previous cargoes that is then blended in degradations.
viewed as typical properties. In addition, with the current batch.
the standard assays do not list many of For handling purposes, a shipper may Altering crude before receipt
the operational characteristics, such as have gravity or viscosity specifications There are many additives that are used
1
P T Q AUTUMN 2004
w w w. e p t q . c o m
REFINING
occurrence in various sources of crude oil corrosive in many of the units in the
Naturally occurring impurities are discussed in the publication Impuri- refinery. Cyanide can also contribute to
ties in Petroleum. This book also describes corrosion in the form of hydrogen blis-
Impurity General range several problems that these species cause tering and hydrogen stress corrosion
in refineries. Table 2 lists several of these cracking.
Salts 101000ptb
Water 0.12 vol%
contaminants and the potential prob- These secondary nitrogen com-
Sediment 1500ptb lems they can cause in refineries. pounds are water-soluble and can nega-
Sulphur compounds 0.15 wt% Most crude oil is co-produced with tively impact the wastewater treatment
as sulphur large amounts of water in the form of facility. Many refinery waste water sys-
Organo-metallic compounds brine that can be a larger fraction of the tems are limited by the amount of nitro-
(nickel, vanadium, iron, 5400ppm well production than the hydrocarbon gen compounds they can handle.
arsenic, etc) as the metal content. Extensive facilities exist at pro- Filterable solids or sediment are inor-
Naphthenic acids 0.030.4 vol% ductions sites to remove most of the ganic solids that are co-produced with
Nitrogen compounds 0.0515 vol% brine to a level acceptable to the shipper the crude oil and can be sand, silt, clay,
Non-acidic oxygen compounds and buyer. Typically, water in the form scale, etc. Corrosion products such as
(resins, cresols, etc) 02 wt% of BS&W ranges from 0.5 to 2% depend- iron oxide and iron sulphide can also be
ing on the local specifications. Salts in included in the filterable solids. The fil-
Table taken from Impurities in Petroleum, rare cases can be in excess of 1000ptb terable solids are known to stabilise
published by Petrolite Corporation, 1958 (2860ppm), but typically are consider- emulsions and can cause oil under-carry
ably below 100ptb as NaCl. in the desalter, thus putting a load on
Table 1 Because of the downstream problems the wastewater handling system. If not
of corrosion, fouling, catalyst poisoning, removed in the desalting process, they
in the oil field to enhance production, and product quality, most refineries can cause fouling. Since they are not
improve reliability, control corrosion, have electrostatic desalters to remove as volatile, they tend to concentrate in the
meet environmental requirements, and much of the brine salt as possible before bottoms streams where they can be a
improve handling characteristics. Pro- further processing. source of ash and metals in the residual
duction facilities often add corrosion Crude oil naturally contains numer- products.
inhibitors, emulsion breakers, scale con- ous sulphur-containing compounds that Organic acids include both naph-
trol agents, hydrate inhibitors, wax and must be reduced to very low levels in thenic acids and low molecular weight
paraffin inhibitors, and defoamers to finished products to meet increasingly carboxylic acids such as acetic and pro-
improve the operation of their facilities. severe environmental standards. Tech- pionic acid. Many of the new fields com-
Pipelines often add flow improvers to nology to remove sulphur is so exten- ing into production are high in organic
increase the throughput of the pipelines sive in refineries that it will not be acids. It is expected that crude oils with
and minimise pumping costs. Pour discussed further in this article. increasingly high TAN will make up an
point additives are added to many high Crude oil likewise contains numerous increasingly larger fraction of the oils
pour point crude oils, either at the pro- nitrogen-containing molecules. Nitro- available on the market. The naphthenic
duction facility or at terminals. Hydro- gen is often present in asphaltenes, but acids tend to concentrate in certain frac-
gen sulphide scavengers are added to also exists in many smaller molecules tions, such as gas oil, and can cause cor-
provide worker safety and control such as pyrroles, indoles, and pyridines. rosion rates of several hundred MPY.
odours. These are all added purposely Some of these nitrogen-containing Mitigation strategies can be quite
and in many cases the refinery can molecules are associated with fuel quality costly. The low molecular weight acids
become informed if it asks. issues including colour and gum forma- tend to distil overhead in the atmos-
Crude oil can be contaminated either tion. Many of the problems with nitro- pheric tower. While they are weak acids
with naturally occurring materials or by gen arise from secondary molecules that compared with HCl, they require large
unauthorised additions of non-naturally are generated by thermal stress and amounts of neutraliser to raise the pH
occurring materials. Each of these classi- hydrotreating. Such problem molecules and make pH control in the atmospher-
fications will be discussed separately. It include ammonia, volatile amines, ic tower more difficult. All of the organ-
should be pointed out that there usually cyanide, and NOx. The ammonia and ic acids have some limited solubility in
is shipment-to-shipment variation in amines can form salts that can be very the desalter effluent brine. The organic
the concentration of each of these
species for any given crude oil. Naturally occurring impurities
Table 1 lists several impurities in
crude oil and typical ranges for each.
Contaminant Problem areas
Most crude oils received by the refinery
Brine salts Corrosion, fouling, catalyst poison, product quality
will have measurable amounts of the (primarily NaCl, MgCl2, CaCl2)
impurities listed in the table. Recently
Water Corrosion, product quality
discovered crude oils push the upper
Filterable solids Fouling, environmental, product quality
limits for some of these impurities. Sulphur compounds Product quality, corrosion, environmental
Some of the recently discovered crude Organic acids Corrosion, product quality, environmental
oils have naphthenic acid concentra- Nitrogen compounds Product quality, fouling, environmental, corrosion
tions greater than 2%. It should be Transition metals Product quality, catalyst poison, environmental
pointed out that the nitrogen com- (Fe, Ni, V, Cu, Zn, etc)
pounds, naphthenic acids, and non- Mercury Environmental, health
acidic oxygen species percentages are NORM (Naturally Occurring Environmental, health
based on the total molecule, which con- Radioactive Material)
tains them, whereas the sulphur and Calcium naphthenates Fouling, environmental, product quality, catalyst poison
metals are expressed as a percentage of Arsenic Environmental, health, catalyst poison
the element. A detailed discussion of the Selenium Environmental
types of molecules represented by the
various species listed in Table 1 and their Table 2
2
P T Q AUTUMN 2004
REFINING
molecular weight that it goes with the

Additive contaminants bottoms. However, when thermally
stressed, the silicone oil breaks down
Contaminant Source Potential problem into volatile oligomers that distil into
naphtha and mid-distillate cuts. The sili-
Nitrogen compounds Corrosion control, Corrosion, environmental,
biocides, H2S scavengers product quality cone oligomers have been implicated in
Sulphur compounds Corrosion control, wax Environmental
poisoning of hydrotreater catalyst, thus
and asphaltene control greatly shortening the beds useful life.
Phosphorous Well stimulation Fouling Catalyst change outs are costly and limit
Silicone Defoamers Catalyst poison the production of marketable products.
Methanol Hydrate inhibitor Environmental In more than one case it has been found
Glycols Hydrate inhibitor Environmental that the amount of silicone coming in
Surfactants Many uses including Environmental with the crude oil is greater than all the
deposit control silicone being added in the refinery.
Mineral acids Environmental, well Environmental, corrosion Methanol and glycol are used in the
stimulation oilfield as gas hydrate inhibitors. Gas
hydrates are clatherate compounds of
Table 3 water and light hydrocarbons, such as
methane and ethane. These hydrates are
acids dissolved in the water add to the levels of calcium naphthenate (20 to solids, which can plug flow lines, thus
COD load on the wastewater treatment over 200ppm). In high concentrations, stopping production. Hydrate formation
plant. Some refineries have special ves- calcium naphthenate can cause rapid is a particular problem in the deep-water
sels to remove the organic acids from fouling of equipment, stabilise emul- offshore production facilities.
the desalter effluent, before it is dis- sions in desalters, poison FCC catalyst, Since these fields are a recent devel-
charged. and exceed limits for some product opment in the industry, methanol and
Transition metals, such as iron, nickel, specifications. Methods have been glycol hydrate inhibitors are only now
vanadium, zinc, and copper, can be nat- developed to remove sufficient amounts being used in significant quantity. These
urally occurring in the oil. Since many of the calcium naphthenate in the compounds are water soluble and are
of these same metals can be present in desalter to mitigate the negative impact often not uniformly distributed in a
used lubricating fluids, the presence of of this crude oil constituent. shipment of crude oil. When the crude
much higher than normal levels may be oil reaches the desalter, they are washed
an indication that the crude oil has been Additive contaminants out and sent to the wastewater treat-
adulterated with waste motor oil. Most There are many chemicals that have been ment plant. While they can cause
of these heavy metals are FCC catalyst used in the oil field and in pipelines for desalter operational problems, the main
poisons. In addition, any of these many decades without noticeable affect. impact is on the waste treatment plant,
species, which are dissolved into the However, in large enough concentration, which can see huge spikes in COD that
water will have a negative impact on some of these materials have the poten- send the refinery out of compliance
wastewater treatment. In extreme cases tial to cause problems. Table 3 lists their with its discharge permits.
specialised water treatment programs source and potential problems that they There are many types of surfactants,
have been implemented to remove these might cause. such as emulsion breakers, that have
metals from the water before discharge Many of the additives listed in Table 3 been used in the oil field for many
from the refinery. as used in the oil field are also used for decades without causing problems in
Mercury and naturally occurring much the same purpose in refineries. the refinery. Some oil is produced by
radioactive material (NORM) are a spe- For example, nitrogen compounds such generating foam in the well with surfac-
cial case of the heavy metals in that they as imidazoline corrosion inhibitors and tants in order to lift the hydrocarbon
are usually not in crude oil to a measur- neutralising amines are used for corro- out of the ground. However, there have
able extent. When they do occur, it is sion control by both refineries and the been occasions when the level of certain
often discovered after the fact when oil field. Nitrogen-based compounds are undesirable surfactants is sufficiently
units are opened at turnarounds. Thus, also added to crude oil as hydrogen sul- high to cause problems in the refinery.
they have the potential for environmen- phide scavengers to limit worker expo- Some of these surfactants partition into
tal release and worker exposure to toxic sure and environmental release. Many the water and can contribute to COD
material. Mercury is the only metal that of these additives have been used in loading of the waste treatment plants.
is liquid at room temperature, so it tends crude oil for decades without causing Some refineries have restrictions on the
to distil in the atmospheric tower and noticeable affect. level of surfactants in their out-fall due
condense in pools in the equipment. Recently, many refineries have experi- to toxic affects they can have on fish.
Compounds of arsenic and selenium enced problems, such as corrosion Phosphorous compounds have been
can be toxic. Luckily, most crude oils do under amine salts in the atmospheric studied by the Canadian Crude Quality
not contain these elements in sufficient tower trays and overhead system, when Technical Association (CCQTA). Several
quantity to warrant action. Elaborate unexpectedly high levels of amines of their refinery members experienced
treatment schemes have been developed arrived in the crude oil. The source of crude unit tower fouling that showed
to remove selenium form wastewater in these amines may be internal rather phosphorous in the deposit analysis.
cases where stringent discharge limits than from the received crude oil. For Since phosphorous is not naturally in
must be met. example the wash water and slop oil are crude oil, the search was begun. The
Small amounts of calcium naphthen- vehicles that can transfer amine con- source was eventually traced back to an
ate have probably been present in many tamination into the crude oil from other additive used in well stimulation. The
crude oils, but have not existed in quan- locations in the refinery. refineries went to the oil producers to
tities to cause noticeable problems. Silicone oil based defoamers are used try to have them change to more benign
Recently, some crude oils from the both in the refinery and oil field (partic- chemistry, but the phosphorous com-
North Sea, West Africa and Indonesia ularly offshore production). The silicone pounds have not yet been phased out of
have been reported to have very high in both locations is of high enough oil filed use.
3
P T Q AUTUMN 2004
REFINING
ing in some crude oils. The source can

Rogue contaminants be incompletely hydrotreated synthetic
crude oils and solvents added to crude
Contaminant Source Problem oil by producers or pipelines to reduce
the viscosity.
Organic halides Cleaning and lab waste Extreme corrosion
Transition metals Used lubricating fluids Environmental, catalyst poison
Drilling waste Oil field drilling Environmental, catalyst poison, fouling
What can a refinery do?
Cleaning waste Various Fouling, environmental Oilfield operations and shippers con-
Olefins Upgraded crude oil, solvents Fouling, product quality duct quality testing on crude oil on a
regular basis primarily for their own
Table 4 needs. For example, producers monitor
BS&W continuously so they can meet
Rogue contaminants that cannot be removed by water wash- their shipping specifications. The refin-
Many of the rogue contaminants listed ing. These species include the ery needs to set quality standards that fit
in Table 4 are from external sources. organohalides, but also amine halide their specific operation, monitor the
They have been designated rogue con- salts, and even salt crystals. When wells crude receipts to ensure conformance,
taminants because they should never be are acidised, strong mineral acids, such and develop strategies to handle quality
added to crude oil. When they are as HCl, are pumped into the well to dis- deviations from what is expected.
added, they are often difficult to detect, solve material that is plugging the for- Refiners should be able to find out in
because they are unexpected and there- mation, thus increasing the production general what types of treatments, if any,
fore not monitored. Because of the of the well. Some of this HCl can react the shipper has added to the crude oil.
severe damage that some of these con- with naturally occurring nitrogen com- Producers can tell the refiner what
taminants have caused, refineries have pounds in the crude oil to form amine materials have been added to the crude
traced down the source of these addi- chloride salts. oil at the production site. As an exam-
tives and implemented corrective Other oilfield practices, including ple, the synthetic crude suppliers can
actions. various upgraders, have the potential to reveal what types of materials are in the
The presence of organic halides is rare drive all of the water out of the hydro- crude blend to be purchased and if the
and is generally used to refer to carbon, so that any salt from the brine is cracked materials blended into the crude
molecules such as perchlorethylene and left as salt crystals. Often, these salt crys- oil have been hydrotreated.
methylene chloride. These compounds tals can be coated with a water insoluble Producers and shippers cannot be
are not typically removed in the crust such as paraffin or asphaltene. All expected to alert refiners to every poten-
desalter, but they can hydrolyse to some of these species are difficult to remove in tial issue, which possibly could cause a
extent. Thus, increasing the level of the desalter, but can release HCl down- problem. However, if the refiner has spe-
chlorides in the atmospheric overhead stream if the conditions are favourable. cific concerns, they can work with the
and contributing to corrosion. More of a As has been seen, many transition refiner on these concerns. If the poten-
problem is that some of these organic metals, such as Fe, V and Ni, can be nat- tial risks and problems are known up
chlorides are not destroyed in the crude urally occurring in the crude oil. They are front, there are often steps that can be
unit but rather distil into straight-run also present in high levels in waste lubri- taken. Monitoring schemes can be
products. cating and cutting oils. Such waste oils implemented to insure that the problem
When these products are then should not be added to virgin crude oil. is under control.
hydrotreated, the chlorinate organic Waste drilling mud can be very high As discussed previously, the supply
compounds are converted into HCl. The in solid material as well as halide salts, chain for the crude oil results in some
HCl can then react to form salts with and transition metals such as zinc (Zn) drift in the quality of the crude oil. The
ammonia or amines that are present. and chromium (Cr). All of these mater- crude assay as shipped can be somewhat
There have been several reports of catas- ials can adversely affect the waste treat- different than the assay for the crude oil
trophic failure of new heat exchangers ment plant. In addition they can be as received by the refinery. With time,
in a matter of weeks or months due to catalyst poisons, and contribute to foul- the crude characteristics vary from those
the formation of these salts after the ing and corrosion. Most drilling sites stated in published assays. Several sys-
hydrotreater reactor. dispose of drilling waste separately and tems have been developed to use meas-
In some of the severe cases that have do not allow it into the crude oil they ured properties for a specific batch of
been reported, investigation has produce. crude oil to extrapolate qualities from
revealed several sources of the chlori- Cleaning waste can contain high lev- existing crude assays. This can work well
nate organic compounds. In one case, els of solids and surfactants that can sta- for yields and product qualities, but may
an overzealous pipeline lab was washing bilise emulsions in the desalter, not exactly predict some operational
down equipment with chlorinated sol- contribute to fouling and negatively problems. Crude assays tend not to
vent before collecting crude oil samples. impact the waste treatment plant. Oil include information that would predict
The waste was dumped in the pipelines. producers and pipelines should not add corrosion, fouling, desalter perfor-
In more sinister cases, people have been this material to the crude oil. One of the mance, and impact on the wastewater
illegally disposing of chlorinated clean- sources of this contamination is the treatment plant. There are some tests
ing waste in crude oil collection tanks refinery. Improper disposal of that can be run to predict these proper-
and pipelines. The refinery may also be turnaround cleaning waste can result in ties. However, many are time consum-
the source of chlorinated laboratory sol- the solids that the refinery paid to ing and not practical as a routine quality
vents that are dumped into the refiner- remove from the equipment being added control test. They are, however, useful in
ies waste oil system. Such chlorinated back to the crude oil being processed. screening candidate crude oils that the
solvents should be disposed of properly Proper disposal techniques should be refinery is evaluating for purchase. Some
and removed from the refinery. part of the plan for any cleaning job. of these tests will be further described.
A more general term for these prob- Olefins are not naturally occurring in When evaluating a new crude oil, it is
lem chloride sources is non-extractable crude oil. Olefins can potentially cause often helpful to discuss operational
chlorides. The non-extractable species fouling and straight-run product quality issues with other refineries that have
are any chlorine source in the crude oil issues. Recently, they have been appear- already processed the crude oil. This can
4
P T Q AUTUMN 2004
REFINING
be helpful in spotting potential prob- stability index test

lems. However, there are limits to the (ASIT) has been used to Evaluation of new crude oils
usefulness. Different refineries may have measure the stability of
different perceptions of the same phe- asphaltenes in a crude Property Possible tests
nomenon. For example, a refinery that oil blend.
Desalting EDDA, ASIT Index,BS&W, salt,
normally uses 15ppm of a desalting There are several filterable solids
chemical on its normal crude would tests that can be run in Waste water treatment Extraction, EcoTox, COD, BOD,
consider a crude oil that only requires a few hours to evaluate metals
10ppm to be easy, whereas a refinery a crude oil for poten- Fouling ALCOR, ASIT Index, spot test, SARA
used to crudes that only require 5ppm, tial desalter problems. Catalyst Metals, sulphur, nitrogen
would view the crude as difficult. However, Baker Petro- Product quality Distillation, various tests
The problems may manifest them- lite has found that Corrosion Salt, TAN, sulphur, amines,
selves differently depending on equip- more extensive organic acids
ment and operating conditions. It has desalter simulation
been reported that two crude units run- using the EDDA gives Table 5
ning identical crude slates have seen high better prediction of
temperature naphthenic acid corrosion in how a crude oil will perform in the ing, but also is implicated in foaming
different sections of the crude unit. refinery. The BS&W can vary for many issues and desalter emulsion stability
Refineries buying crude oil under the reasons, but excessively high BS&W in a and oil under-carry problems.
same generic name may be purchasing crude may indicate the tendency to In extreme cases of blending of
slightly different blends of crude oil. For form stable emulsions. It has also been incompatible crude oils, there has been
example, refiners in California that Baker found that filterable solids in crude oil catastrophic precipitation of asphaltenes
Petrolite has worked with have seen often correlate with desalter problems. in tankage and transfer lines. More com-
higher levels of amines in one particular The desalter operation also impacts monly, the crude blend is on the edge of
crude oil, compared to refineries buying on wastewater treatment as the desalter asphaltene stability. Many tests have
the same crude oil on the Gulf Coast. is typically the largest source of wastew- been developed to try to predict the
Thus, other refinerys experience can ater in the refinery. Various methods fouling and other problems associated
highlight some areas of concern, but can be used to extract the water-soluble with asphaltenes. There have been
should not be relied on completely. One components from crude oil to simulate attempts to simulate the fouling of
specific refiner may have a problem that the quality of water that a candidate exchangers using devices such as the
other refiners have never seen. crude oil might send to the wastewater Alcor. Baker Petrolite has used such
facilities. Once this simulated waste- Alcor rigs for 20 years to simulate heat
Evaluating new crude oils water is obtained, numerous tests of exchangers, but they have the limita-
Bringing a new crude oil into a refinery varying complexity can be run. Perhaps tion that the fluid must be stressed far
introduces many unknowns into the simplest is analysis of inorganic species beyond actual operating conditions to
operation of the refinery. Much more by ICP which can analyse for several get fouling to occur in the time scale
effort is expended vetting a new crude elements simultaneously. This will typ- suitable for a lab test. Others have artifi-
than is expended on old stand by crudes ically identify problem species such as cially doctored the fluid with high levels
that the refinery has run many times Zn, Cd, Cr, Cu, Se, As, Pb, etc. COD is of asphaltenes to force precipitation in a
before. Often, more in depth testing can another quick test to estimate the organ- laboratory time scale.
be conducted that would not be possible ic loading on the water treatment plant. Because of the limitations of the sim-
for a routine quality control test. If a It is important to note that this testing ulation testing, researchers have tried to
current crude assay is not available, one generally assumes that there will be no measure more fundamental properties
should be conducted on the whole oil under-carry from the desalter, so it is of the crude oil to predict fouling and
crude oil and the various product frac- only focused on the water-soluble asphaltene stability. Saturates, aromat-
tions. There are several evaluations in organics in the extracted water. More ics, resins and asphaltenes (SARA) is an
Table 5 that should be considered in time consuming tests such as BOD, or in extensive series of solvent extractions to
addition to the assay information. some cases, full simulation of the waste break crude oil into the four categories
The desalter is the refinerys main activated sludge system using sludge suggested by the name of the test. It pro-
tool to remove many of the contami- from the refinerys plants have been vides useful information regarding the
nants from the crude oil, before further conducted. composition of the crude oil, but is only
processing. Problems with the desalter Some of this testing, such as the lat- suggestive of potential asphaltene stabil-
operation can lead to increased corro- ter, can take weeks to conduct and is ity problems.
sion, increased fouling, catalyst poison- very expensive. The decision of the level There are crude oils with high levels of
ing, product quality issues, and negative of detail to pursue for a candidate crude asphaltenes that are not particularly
impacts on the wastewater treatment is typically made on a case-by-case basis, unstable and there are crude oils with low
facility. It is therefore important to eval- depending on the sensitivity of the levels of asphaltenes, but are very un-
uate a new crude to determine if any refinerys wastewater treatment plant to stable to asphaltene precipitation. Several
problems might occur on the desalter. upsets, and how different the candidate tests have been developed to try to pre-
It has been found that the electrostat- crude oil is from the normal crude slate dict the asphaltene precipitation using
ic desalting and dehydration apparatus run by the refinery. addition of paraffinic solvent to desta-
(EDDA) laboratory testing is the best way Fouling can relate to many phe- bilise the crude oil. Some of these tests,
to evaluate how difficult a crude oil is to nomenon and multiple chemical factors such as the P test and the spot test can
desalt. However, the test is time consum- can affect fouling. While metal ions, be run in the field, but rely on the ana-
ing and specialised, so may not be prac- such as Cu and filterable solids are lysts eyeball to determine the endpoint.
tical for every potential crude purchase. implicated in many fouling mechan- Baker Petrolite has developed the ASIT to
It has also been found that with heavy isms, the focus here is on asphaltenes. accurately measure the asphaltene stabili-
crude oils, asphaltene stability can be a Asphaltene instability and precipitation ty and eliminate the operators estimation
predictor of desalter problems. For this, has not only been found to occur in of the endpoint. It has been found that
Baker Petrolites proprietary asphaltene crude unit exchanger and furnace foul- this test correlates with both potential
5
P T Q AUTUMN 2004
REFINING
fouling and desalter issues. ferent distributions of these molecules. severe and catastrophic corrosion with
Impacts of crude quality on product The high temperature corrosion is also rates of many hundred mpy. Rules of
quality are an important consideration. known to be velocity-dependent. Natur- thumb based on TAN and sulphur in the
Some of the affects on crude quality can ally occurring inhibitors as well as those crude oil provide only rough guidelines.
be estimated by distillation of the crude supplied by chemical vendors can A comprehensive corrosion manage-
oil and performing tests on the various reduce the corrosivity of various ment programme includes assessing
fractions. Often, full crude oil assays will streams. equipment constraints, monitoring and
contain many of these test such as yield, When deciding to bring in a new managing the impact of naphthenic
API gravity, viscosity, sulphur, nitrogen, crude with potential corrosion issues, it acid corrosion. Monitoring can include
paraffin, aromatics, naphthenes, ben- is important to develop a comprehen- fixed corrosion probes and coupons,
zene, metals, TAN, pour point, cloud sive corrosion management plan. This non-invasive corrosion monitoring and
point, flash point, RVP, smoke point, plan should start with a risk assessment analysis of stream qualities such as TAN
RON, MON, CCR etc for various stan- survey of all the sections of equipment and metals content. Mitigation may
dard fractions. In some cases pilot plant that may be affected by corrosion from involve retrofitting units with more
tests (such as pilot FCC units) are used this new crude oil. Developing a moni- resistant metallurgies and treatment
to predict the product quality when a toring plan for the key areas and devel- with naphthenic acid corrosion
significant change in crude oil quality is oping mitigation strategies in case inhibitors when needed.
anticipated. These tests are very expen- corrosion exceeds expectations in the
sive and involved, so it is not practical affected sections are very important. Monitoring
to run for each shipment of crude oil. This mitigation may involve metallurgi- No crude oil management program
There are several parameters, such as cal enhancements or the use of corro- would be complete without continuing
salt, sulphur, and TAN, which are related sion inhibiting additives. monitoring of crude oil quality. Standards
to corrosion in the refinery. Unfortu- must be set to meet the refinerys require-
nately there is no equation that can be Crude oil management ments and incoming crude oil must be
plugged in that predicts corrosion Once the decision to introduce a new tested to determine conformance. If the
throughout the refinery. Crude units crude oil into a refinery has been made quality deviates from expectation, correc-
running the same crude blend can a crude oil management programme tive actions should be taken. Each refin-
experience corrosion in different areas needs to be implemented to evaluate the ery has its own testing protocol to meet
due to variations in equipment and critical areas in the refinery process, its specific needs. Often, refineries moni-
operating conditions. For example, the establish monitoring programmes, tor little more than gravity, sulphur, and
pH and the corrosion in the overhead is develop mitigation strategies, and BS&W. If naphthenic acid is a concern,
related to the amount of salt in the implement corrective actions if moni- then TAN is usually measured.
crude oil leaving the desalter. toring indicates. Refineries often rely on suppliers to
While the salt is usually expressed as A detailed description of mitigation measure salt and filterable solids in the
NaCl (common table salt), since that is strategies is beyond the scope of this crude oil. Salt content and filterable
the most common, it is actually a blend discussion, so only a few strategies will solids can vary widely for each shipment
of other salt species including calcium be mentioned and not in any detail. In of a particular crude oil, so it is impor-
and magnesium halides, sulphates, car- many cases, the desalter is the unit tant to monitor them frequently. If a
bonates etc. These do not all hydrolyse that is used to remove contaminants crude oil is known to have a particular
the same to produce acid species in the from the crude oil. This water wash- problem, then routine testing to moni-
overhead. The hydrolysis is also depen- ing process readily removes water-sol- tor that quality should be instituted.
dent on many factors such as the tempera- uble constituents such as salt. Various There are several contaminants that
ture profiles and residence times in the optimisation programmes and spe- the refinery should check on a regular
furnaces and the acidity or the crude oil. cialised chemistries have been devel- basis because the consequence of their
Two other species that Baker Petrolite oped to increase solids removal in the presence is potentially rapid and drastic.
is finding with increasing frequency are desalter. Recently, programmes have Chlorinated organic compounds and
volatile amines and volatile organic been developed to remove some water- methanol occur infrequently and can
acids, such as acetic and propionic acid. insoluble constituents such as calcium sometimes be found in a crude that
These volatile amines distil in the naphthenate. never contained them before. Both
atmospheric tower and combine with New technologies are emerging in the volatile amines and volatile acids are
HCl to form salt deposits in the tower wastewater treatment field. Baker Petro- becoming more common. They can
top, trays, and top pumparound. Severe lite has conducted field evaluation of cause problems with corrosion control
under-deposit corrosion occurs in a new membrane technology, which programs on crude units. It can be diffi-
localised fashion where these salts reduced selenium (Se) in the effluent cult to locate the source of these volatile
deposit. The organic acids, distil into the water from average of 2.5ppm to below compounds, since they can come in
overhead where they act as buffers that 5ppb in the outfall. Using this same with the crude oil, or form as thermal
make it difficult to control the overhead technology in lab tests, it was possible to degradation products, or derive from
pH properly. Some of these species can convert desalter effluent into boiler feed other sources in the refinery though the
result from thermal cracking but others water quality. slop oil system.
can be present in the raw crude oil. In some cases the contaminants are
Analysis of these species can be difficult. not easily removed, so the mitigation Larry N Kremer is senior technical consul-
High temperature corrosion is related strategy may involve operational tant, industrial technology, at Baker Petro-
to the presence of sulphur and naph- changes, metallurgical changes, blend- lite Corporation, Houston, Texas, USA. He a
thenic acids (as indicated by TAN). How- ing, and or chemical treatment. One technology fellow at Baker Petrolite and has
ever, no magic formula has been example that is becoming increasingly worked on crude quality issues, desalting,
published. The TAN and the sulphur are common is the processing of high TAN foaming, cleaning, and other surface-
made up of hundreds of different crude oils. It is known that under certain active phenomenon. He holds a PhD in
molecules with different corrosive char- operating conditions, the naphthenic physical chemistry.
acteristics. Different crude oils have dif- acids in high TAN crudes can cause E-mail: larry.kremer@bakerpetrolite.com
6
P T Q AUTUMN 2004
Calcium articlev.qxd 9/14/05 7:51 PM Page 1
REFINING
Calcium removal from high

TAN crudes
Crude oils high in calcium naphthenate content are being processed using
technology developed to remove calcium in crude unit desalting operations,
with calcium removal efficiencies averaging 70% on Doba blends
Jerry J Weers and Scott Bieber
Baker Petrolite
W
est African Doba crude oil is
an attractive refinery feed- Solubility of divalent calcium salts in water
stock due to its low sulphur
content, but presents some challenges Anion Carboxylic acid molecular Temperature, Water solubility,
to a refiner due to its high total acid weight, (g/mole) C g/100 cc
number (TAN) and high metals Chloride 20 74.5
1
(primarily calcium) content. The high Acetate 60 0 37.4
TAN value is an indicator of potential Valerate 102 20 8.28
high-temperature corrosion problems Laurate 200 15 0.004
and, if not removed, calcium (Ca) can Palmitate 256 25 0.003
Stearate 284 15 0.0014
promote catalyst deactivation when
reduced crudes are upgraded in Taken from Handbook of Chemistry & Physics, 56th Edition
2-5
downstream FCCU operations. High
Ca levels in coke and heavy fuel oils can Table 1
also result in reduced product value
and/or marketability. refinery process, as they would create crude oil dehydration in the refinerys
In many crude oils, metals such as Ca, too many downstream problems. For desalter operation.
sodium and potassium are present in example, acetic acid is too soluble in To screen demulsifier chemistries on
forms such as chlorides, which are very crude oil, as a large amount of the acid Doba crude oil blends, laboratory
water soluble and thus relatively easy to stays with the hydrocarbon, where it electrostatic demulsification and
remove from the hydrocarbon by water distills to the overhead system, causing dehydration apparatus (EDDA) equip-
washing in a desalter. However, in high high corrosion rates. Other materials are ment was used to simulate the desalting
TAN crudes such as Doba, the chloride too toxic to the refinery wastewater process. This equipment reproduces the
salts are mixed with salts formed by the treatment facility. Thus, a new conditions present in a desalter,
interaction of the metals with technology needed to be developed to including the presence of an electric
carboxylic acids (naphthenates). Studies overcome these obstacles. field to help break the emulsions formed
have shown great variability in the The invention of a process to remove in the process. The procedure allows the
naphthenates present in crude oils, but Ca from Doba crude oil involved several user to vary the wash water rate and
metals in high TAN crude oils typically steps. In addition to identifying a cost- quality, mixing energy, oil residence
associate with acids that have a effective metals complexing agent, time, temperature, and grid voltage to
molecular weight of between 300 and treatment programs had to be developed determine the impact of these variables
400 grains/mole. Even higher molecular that addressed the emulsion stability of on desalting performance. The
weight acid salts can be formed if the the Doba crude blends, controlled the equipment also provides samples of
pHs of the produced fluids are allowed scaling problems created by the high desalted oil and effluent water for
6,7
to increase into the basic pH range. levels of Ca in the desalter effluent analysis of metals content.
The naphthenate portion of the water, and minimised the desalter wash Many of the demulsifiers evaluated in
complex gives the salt much lower water water and effluent water removal system the EDDA testing did not break the
solubility (Table 1) than the correspond- corrosion potential created by the low emulsions quickly enough to be used in
ing chlorides, making them difficult to pH of the Ca-removal additive. crude units with short desalter residence
remove by simple water washing. times. Calculated oil residence times for
A review of the referenced literature Demulsification studies the desalters can be as low as ten
shows that a variety of chelation and The first step in developing the new minutes, which requires rapid resolution
acidification agents have been evaluated metals-removal process was an of any emulsions present in the system.
to improve metals removal in the water- evaluation of demulsification chemistry. Thus, a new demulsifier formulation
washing process. These include scale The amount of Ca being removed from (demulsifier 3) had to be designed to
inhibitors, dispersants, Ca chelants and Doba would result in a desalter effluent meet the quick resolution requirement at
inorganic or organic acids of various water Ca content of nearly 1000ppm. If many refineries. In addition to rapid
8-12
types. Of the methods tried, additions even small amounts of this metal-laden water settling, the demulsifier provided
of hydrochloric or acetic acid are usually water were left in the desalted crude, it good dehydration of the crude to
the most successful. Many of the agents would increase its metal content minimise any contribution of the water-
employed in the references were applied significantly. Thus, an effective metals- soluble metals to the overall desalted
in the oilfield but cannot be used in a removal program necessitated very good crude metals content (Table 2).
1
P T Q Q3 2005
w w w. e p t q . c o m
REFINING
Laboratory demulsification test results on Doba crude oil Ca to the aqueous phase from the
hydrocarbon, and to prevent Ca
Water separation (mLs) % BS&W deposition in the desalter equipment.
Additive @ 5 minutes @ 10 minutes @ 15 minutes @ 15 minutes The choice of a scale-control product
settling time settling time settling time settling time was difficult, as many inhibitors are
Demulsifier 1 2.6 2.6 2.6 0.15 incompatible with high TAN crude oils.
Demulsifier 2 2.6 2.6 2.6 0.15 In addition, the inhibitor chosen had to
Demulsifier 3 2.6 2.8 3.0 0.05 withstand the high temperatures found
3% wash water rate
in a typical desalter and could not
negatively impact any downstream
Table 2 processes. After screening a variety of
inhibitors, a product was chosen, which
Removal of Ca from Ekofisk/Doba (70/30 blend) using organic acids prevented the formation of the residue
on the test equipment and consistently
Additive Dose rate in ppm Ca in crude ppm Fe in crude improved Ca balances to the 8095%
crude, ppm after desalting after desalting range, at dosage rates as low as 1ppm in
Raw crude 100.0 11.0 the emulsions tested.
CRA 50 14.9 5.0
Acetic acid 50 21.5 3.5 Corrosion inhibitor testing
Lactic acid 50 32.2 2.4 The low pH values produced by the
Oxalic acid 50 80.0 11.0 complexing agent in the crude oil wash
water samples raised concerns that high
Table 3 corrosion rates would be observed in
crude unit desalter water-injection
Two-stage desalting simulation with Ekofisk/Doba (70/30 blend) systems. A series of 48-hour kettle tests
were conducted using stainless and mild
steel coupons and desalter wash water
CRA dose in crude Test conditions Ca content, ppm % Ca removal
samples from a European refinery.
oil, ppm
40 1st stage desalted crude 12.7 83
Coupon data suggested corrosion rates
12 2nd stage desalted crude 0.7 99 of 140 MPY or higher could occur with
use of the complexing agent. Corrosion
Raw crude Ca content = 74.8 ppm, using demulsifier 3 with 4% wash water used in all tests. inhibitor combinations were screened
for corrosion protection as well as for
Table 4 compatibility with the CRA chemistry. A
multi-component inhibitor package was
Calcium removal/scale were noted during this series of tests. For identified, which provided protection in
inhibitor studies example, all of the materials that worked both water and oil/water systems.
The initial EDDA test results indicated well had excellent water solubility and Subsequent tests showed the inhibitor
that the simple water washing of the formed water-soluble complexes. The pH was compatible with the CRA chemistry,
Doba crude oil only removed metals of the solution used to wash the and commercial products are now
such as sodium and potassium. High hydrocarbon was important in formulated with this corrosion inhibitor
concentrations of Ca and iron were still achieving good metals removal. to provide wash water-injection system
present in the desalted oil, suggesting Many refineries use two-stage corrosion protection.
these metals were present in desalting, so the screening tests were
naphthenate form. It appeared that designed to simulate this condition. It Wastewater impact testing
additional metal chelants and/or was also anticipated that contacting the A wastewater toxicity study was
acidification agents would be needed to crude twice with the CRA would conducted in a European refinerys
lower the concentration of these metals. improve metals-removal efficiency. laboratory to determine the impact of
The development of an effective Water and crude oil samples were the metals-removal program on its
demulsifier for Doba crude blends generated in the same sequence as they wastewater treatment plant. It was
allowed potential Ca-removal additives to are in a desalting operation. The results expected that the CRA chemistry might
be evaluated. Crude blends containing indicate that very high levels of Ca increase chemical oxygen demand
30% Doba and 70% Ekofisk were used in removal from Doba/Ekofisk blends can (COD) values in the desalter effluent
the evaluation to represent typical be achieved with relatively low dose water, in addition to lowering the pH. It
Doba/North Sea blends. After running rates of additive. Excellent Ca was also expected that the metals
over 100 lab tests, a mixture of organic accounting was also achieved (Table 4). removed from the Doba crude could
acids designated calcium removal During these tests, it was observed have some toxicity to a plants biological
additive (CRA) was identified as giving that the Ca balance (sum of the amounts system.
the best overall performance. A of Ca found in the oil and water phases In the study, shaking the Doba crude
performance comparison between the as compared to the original oil Ca oil with water containing the CRA
CRA and some of the acids found in the content) varied. In some samples where chemistry in a separatory funnel
reference material is shown in Table 3. Ca-removal efficiency from the oil was generated samples of water. The water
The CRA was found to give better Ca- high, the Ca recovered represented only was then separated from the oil and
reduction values compared to other 7080% of the Ca in the original sample. tested for relative toxicity with a
common acidification/chelation agents. Further investigation showed a cream- proprietary Hach ToxTrak test kit. The
Iron removal by the CRA was also coloured solid was visible in some of the COD values and metals contents of the
acceptable, although some other agents test equipment. This led to the separated waters were also measured.
gave lower desalted crude concentrations. development of scale inhibitors as co- The test results indicated that the extract
Several performance characteristics additives to improve the transfer of the water samples containing the CRA
2
P T Q Q3 2005
REFINING
Ca speciation test results
Crude blend components Raw crude Filtered crude Filtered & water Filtered & acid
% % % % % % % Ca content, Ca content, washed crude washed crude Ca
1 2 3 4 5 6 7 ppm ppm Ca content content, ppm
19 42 19 0 19 0 1 74.4 76.2 54.6 0.1
15 26 36 0 22 0 1 54.0 57.3 29.1 2.0
15 26 24 22 3 7 3 70.3 64.1 50.0 11.4
15 8 45 29 2 0 1 83.3 69.6 53.8 2.2
15 8 45 29 3 0 0 68.4 69.7 53.8 23.0
15 8 45 29 3 0 0 76.6 77.5 56.0 7.0
1 = Doba, 2 = Ekofisk, 3 = Gulfaks, 4 = Njord, 5 = Saharan, 6 = Wytch Farm, 7 = Other.
Table 5
chemistry were actually lower in COD refinery crude oil blends were evaluated compared to the period before crude oil
than the extract water containing no (Table 5). pretreatment. Grid amperage decreased
additive. A theory developed to explain The results showed that the amounts while maintaining excellent salt
this observation was that the low pH of water/acid-extractable Ca varied, removal, crude oil dehydration and good
values generated by the additive depending on the crude slate. With effluent water quality. These results
prevented naturally occurring acidic some of the blends, the Ca is in a form suggest that an effective crude oil
materials such as phenols, naphthenic that is difficult to extract. Processing pretreatment program can enhance the
acids and naphthenic acid salts from these blends would make it more performance of the Excalibur process.
partitioning into the water. By reducing difficult to achieve the low metals
the concentration of these extracts, the contents desired by the refinery. Wastewater treatment
CRA chemistry actually decreased the However, it did not appear that the Doba operations
COD of the effluent water. The crude contained the less extractable The waste treatment plant conditions
conclusions from this study were that forms of Ca. The blend with the highest observed during Doba crude processing
the use of the complexing agent should level of Doba produced the lowest were similar to the results predicted by
have minimal impact on a refinerys concentration of Ca in the washed oil. the laboratory tests described earlier. The
wastewater treatment plant. These observations reinforced the initial concerns about the potential for
importance of testing to determine the increased desalter effluent water toxicity
Metals removal in a European results that can be expected by a refinery and high COD levels created by the
refinery on a specific crude oil blend. metals-removal process were not
The metals-removal process described up observed during the evaluations of the
to this point was commercialised and Emulsion breaking Excalibur technology.
implemented at a European refinery in evaluations The other concern was the possibility
May 2004. This refinery processed Doba The demulsifier and scale inhibitor of toxicity to the biological system due
crude oil at a rate of about one million formulations identified in the laboratory to low desalter effluent water pH values.
barrels per month, averaging approxi- studies were applied to the desalters The observed effluent pH ranged from
mately 15% of crude slate, with the when the Doba first arrived at the 5.08.3 (6.5 pH average). However, these
balance comprised primarily of North refinery. The demulsification results pH ranges were not low enough to cause
Sea crudes such as Ekofisk, Gulfaks, were excellent, with low desalted crude problems in the wastewater treatment
Captain and Njord. BS&W (trace average) and salt contents system after the effluent water was
(1ppm average). Good desalter effluent diluted with other wastewater streams
Speciation studies water quality and minimal emulsion from the refinery.
Due to the variety of crudes blended layer thickness at the oil/water interface The refinery effluent water contained
with Doba at this refinery, there was a in the desalter vessel were also observed very high levels of Ca during the
concern that these other crudes could throughout the evaluation. evaluation period. There were some
contain metals that would not be in the Doba is a highly conductive crude oil, concerns that scaling could occur
form of extractable chlorides or which causes high amperage draws on downstream of the desalter, especially if
naphthenates and might not respond to the desalters. One approach to dealing water pH was increased by dilution or
the CRA technology as well as predicted with this problem is to pretreat the crude intentional pH adjustment. Also, a
by the laboratory studies. A test protocol oil with a specially designed demulsifier desalter feed/effluent exchanger between
was developed to determine if a as it is unloaded into tankage from the the first- and second-stage desalters had
representative mixture of crude slates transport ship. The addition of a some previous fouling history. However,
would still produce a feedstock pretreatment demulsifier at this point no indications of any scale formation in
responsive to the Excalibur technology. starts to break up any emulsions present the desalter effluent water system were
In the protocol, the crude oil samples and helps drop some material (water, observed during application of the
were first filtered through a 0.45 micron solids) out of the crude oil in tankage Excalibur technology, which included
filter to remove any particulate before it goes to the desalters. the use of the scale inhibitor developed
naphthenates. The filtered samples were Pretreatment also helps destabilise the for this process.
then water washed to remove the water- emulsions that are created in the Corrosion rates in this system were
soluble metals species. Finally, the desalting process. This allows better measured both upstream and down-
samples were washed with a solution of dehydration of the crude oil, reducing stream of the injection point of the CRA
aqueous hydrochloric acid to convert the conductivity of the oil in the desalter into the wash water. The CRA was
any oil-soluble metal naphthenates into grid area.
formulated with the corrosion inhibitor
metal chlorides, which could then be Pretreatment of crude oil receipts
package developed for the Excalibur
extracted into water. A number of typical improved the desalter operation,
3
P T Q Q3 2005
REFINING
process. Rates were measured using an Metals removal in a US 3 Thakur D S, Thomas M G, Catalyst
electrical resistance probe. Probe data deactivation in heavy petroleum and
refinery
synthetic crude processing: a review, Applied
showed the corrosion rates in the wash A US refiner introduced Doba crude into Catalysis, 15, 197, 1985.
water system were 2 mils per year (mpy) its blend, with Ca levels averaging 4 Connor J E, Rothrock J J, Birkhimer E R,
or less, and no operational problems 30ppm. The Excalibur metals-removal Leum L N, Fluid cracking catalyst
have been observed to date. technology was initiated when Doba contamination. Some fundamental aspects
crude entered the system. of metal contamination, Industrial &
Calcium removal results Engineering Chemistry, 49, 2, 276, 1957.
Many of the observations made at the
5 Yung K Y, OConnor P, Yanik S J, Bruno K,
Ca levels in the Doba crude shipments European refinery have been repeated at Catalytic challenges, Hydrocarbon Engineer-
ranged from 250435ppm. Crude blends this location. Over 750 000 barrels of ing, January 2004.
charged to the crude unit ranged from Doba crude have been processed, with 6 Rousseau G, Zhou Z, Hurtevent C, Calcium
28119ppm Ca. Ca removal efficiencies no reported impact on the wastewater carbonate and naphthenate mixed scale in
ranged from a low of 24% to a high of treatment plant operation. Desalter deep-offshore fields, SPE Paper 68307
99% as conditions on the unit were presented at the 3rd International
performance has been excellent, with
Symposium on Oilfield Scale, January 2003.
varied. Ca removal efficiency over five trace BS&W values and low salt contents 7 Dyer S J, Graham G M, Arnott C,
cargos of Doba processed averaged 70%. measured in the desalted crude. No Naphthenate scale formation
A statistical analysis of the data was desalter effluent system scaling problems examination of molecular controls in
performed to determine which factors have been observed. There are also no idealised systems, SPE Paper 80395
most influenced Ca removal efficiency. presented at the SPE 5th Symposium on
indications of any desalter wash water
Variables that favoured increased Ca Oilfield Scale, January 2002.
line corrosion activity. Ca removal
8 Gallup D, Smith P C, Chipponeri J, Abuyazid
removal included a higher desalter wash efficiencies have averaged 70%, with an A, Mulyono D, Formation & mitigation of
water rate, higher CRA dosage and lower average of 9ppm Ca in the desalted metallic soap, Attaka, Indonesia Field, SPE
desalter effluent water pH. Ca removal crude. Paper 73960 prepared for presentation at
efficiency averaged 78% when the pH of the SPE International Conference on Health
the desalter effluent water was Conclusions Safety and the Environment in Oil and Gas
The metals-removal technology dis- Exploration and Production, March 2002.
controlled to 6 or less. Desalter wash
cussed throughout can be used to allow 9 Garwood W E, Denton W I, Bishop R B,
water rates averaged only 3.8% during Lukasiewicz S J, Miale J N, Cleaning up
the evaluation period. Ca removal refiners to process high Ca naphthenate
petroleum stocks with hydriodic acid,
efficiency averaged 89% when desalter content Doba crude oils. Key
Industrial & Engineering Chemistry, 51, 11,
components of this technology include 1377, 1959.
wash water rates were 5% or above. By
the use of a proprietary complexing 10 Vindstad J E, Bye A S, Grande K V, Hustad
effectively removing Ca from the crude
agent that can increase the solubility of B M, Hustvedt E, Nergard B, Fighting
oil, this refiner was able to continue Ca naphthenate salts, and the naphthenate deposition at the Heidrun
processing atmospheric resid at the implementation of appropriate demulsi- Field, SPE Paper 80375 presented at the 5th
FCCU at rates that would not have been fier chemistries and desalter optimisa- International Symposium on Oilfield Scale,
economically viable without application tion strategies to minimise the emulsion- January 2003.
of the Excalibur technology. stabilising effects of Ca naphthenates. 11 Guiling L, Xinru X, Jinsheng G, Study on
An important observation made Doba crude blends can be processed the deferrization and desalting for crude
without experiencing fouling in desalter oils, Energy & Fuels, 18, 918, 2004.
during this evaluation was the effect of
effluent water exchangers and without 12 Kremer L, Nguyen J, Weers J, Removal of
alkaline contaminants in the Doba calcium and other metal species from crude
significant impacts on wastewater
crude on CRA usage. Many high TAN oil in the desalting process, presented at the
treatment plant operations. With proper
crudes produced from limestone AIChE Spring National Meeting 2004, New
control of program variables, Ca removal
formations contain considerable Orleans, LA, 2529 April 2004.
efficiencies averaging over 85% can be
amounts of carbonates and bicarbonates achieved.
in the produced water. These materials
will increase acid demand if not
Jerry J Weers is senior technical manager,
ToxTrak is a trademark of Hach Company. R&D, industrial division, Baker Petrolite in
removed from the crude oil prior to Sugar Land, Texas, USA. Weers earned a
Excalibur (EXCALIBUR) is a service mark of
desalting. The effects of these Baker Hughes. PhD in organometallic chemistry from the
contaminants can be mitigated to some University of Iowa in 1984.
degree by pretreatment of the crude oil Email: jerry.weers@bakerpetrolite.com
References Scott Bieber is marketing manager for
to promote separation and removal of
this alkaline water in crude storage 1 Doba Crude Oil Analysis, ExxonMobil Baker Petrolites industrial division in Sugar
Research & Engineering, 27 March 2003. Land, Texas, USA. Bieber earned a BS in
tanks, as described earlier. Use of
2 Yaluris G, Cheng W C, Peters M, McDowell, biochemistry from the University of Illinois,
mineral acid injections can help Hunt L, Mechanism of FCC catalyst and an MBA (international business) from
neutralise these alkaline contaminants deactivation by Fe, Prepr. Pap. Am. Chem. the University of Houston.
while minimising CRA usage and cost. Soc., Div. Pet. Chem. 48, 3, 183, 2003. Email: scott.bieber@bakerpetrolite.com
4
P T Q Q3 2005
Originally appeared in:
September 2008.
Used with permission.
Refining Developments SpecialReport
Rethink desalting strategies when

handling heavy feedstocks
Oil sands based crudes bring extra processing challenges
for crude units and wastewater treatment plants
L. Kremer and S. Bieber, Baker Petrolite Corp., Sugar Land, Texas
R
efiners are accepting challenge feedstocks as part of their Challenging feedstocks. The most challenging WCSB
crude slates to improve margins. Such crude oils may have feedstocks, from the standpoint of desalting, are the heavier crudes
a lower cost, but require more processing to yield end that contain high levels of filterable solids, unstable asphaltenes
products. Challenging Canadian feedstocks are lower in API or difficult-to-remove chloride salts. Since the filterable solids,
and contain high levels of filterable solids, unstable asphaltenes asphaltenes and salts are concentrated in the bottoms fractions,
or difficult-to-remove chloride salts. These feeds are especially the more difficult feedstocks tend to be:
problematic to desalter operations. Several case histories discuss Heavy, conventionally produced crude oils
operating practices that can be used to improve the processing of Oil sands bitumens diluted with lighter hydrocarbons or syn-
challenge crudes. thetic crudes to meet pipeline gravity and viscosity specifications.
Most heavy feedstocks exported from this region range from
New crudes. Refineries in Canada and the US process a vari- 19API to 22API, which tends to create desalter challenges
ety of crude feedstocks from Alberta and Saskatchewan, often due to the resulting higher crude blend viscosities. However,
denoted as Western Canadian sedimentary basin (WCSB) feed- there are also lower density crudes coming from this region
stocks. These include conventionally produced Western Canadian that can be problematic, owing to their high filterable solids
crudes and synthetic crude oils (SCOs) from the oil sands bitu- contents. The large and growing number of different WCSB
men upgraders in Alberta and Saskatchewan. Other feedstocks feedstocks produced, and the variability in quality observed,
contain WCSB bitumens produced in situ, which are diluted with requires increased vigilance by refiners and service companies
condensates, naphthas and SCOs. seeking to understand and to overcome the impact of these
According to the Canadian Association of Petroleum Pro- feedstocks on desalter operations.
ducers, incremental production of these WCSB feedstocks is
estimated to grow to 2.1 MMbpd by 2015, with more than half Inorganic solids in WCSB feedstocks. As with any crude
of this volume representing heavier crudes.1 Current and future oil, the solids present in WCSB feedstocks originate in the forma-
pipeline projects will allow this increased WCSB production to tion from which they are produced, plus any sediment or corro-
reach refineries on the US Gulf Coast, in Southern Illinois, Ohio, sion scale picked up during transportation. There is considerable
Oklahoma and Kansas and terminals in British Columbia. Several variation of the solids contents of individual WCSB feedstocks.
refineries have already initiated or announced projects designed As a result, very large day to day swings in the level of filterable
to increase WCSB processing capabilities. solids of crude oil blends processed are common. Some refineries
The specific processing challenges posed by these feedstocks processing these feedstocks typically have between 50 and 100
depend on the physical and chemical characteristics of the feeds, pounds per thousand barrels (PTB) of solids, whereas others
their behavior when blended with other crudes, and the configu- have seen crudes with over 300 PTB. Fig. 1 shows the variability
rations and capabilities of the refinerys process units. This article in raw crude blend filterable solids content at a Midwest US
will focus on the characteristics of feedstocks that are most prob- refinery processing predominantly heavy WCSB crudes, over a
lematic relative to crude unit desalter operations. For example, three month period.
many feedstocks with residual bitumen content may have high These solids can stabilize desalter emulsions. Samples of
asphaltene and inorganic solids contents, or difficult to remove desalter emulsions collected during upset conditions have been
salts, due to thermal stressing of the hydrocarbon during the found to contain high concentrations of the same solids materials
production or upgrading process. These contaminants can have a that are found in raw crude samples.2 Crude blend filterable solids
negative impact on refinery desalter performance, and can lead to levels significantly above 100 PTB (using a 0.45 filter pad) can
additional operating problems in downstream process units and cause high desalter electrode current draw, high desalted crude
wastewater treatment facilities. oil basic sediment and water (BS&W) content, emulsion layer
Several key strategies can be used by refiners purchasing these build-up and oily desalter effluent water.
feedstocks to overcome desalting challenges and improve the X-ray diffraction (XRD) analysis of the filterable solids depos-
refinerys flexibility when selecting heavy WCSB crudes for their its typically reveals the presence of iron oxides, iron sulfides,
operations. silicon oxide (sand) and silicates of aluminum, magnesium and
HYDROCARBONPROCESSING september 2008

SpecialReport Refining Developments
potassium (clays). Many WCSB crudes also contain salt crystals result in higher crude unit atmospheric column overhead system
such as sodium chloride. chloride loadings, increased overhead neutralizer demand and
higher overhead condensing system corrosion potential.
Asphaltenes increase emulsion stability. Several refin-
eries processing high percentages of WCSB feedstocks have expe- WCSB Desalting Strategies
rienced desalter problems related to asphaltenes instability in the Maintaining desalter performance while processing these chal-
crude oil blends. Asphaltenes are known to stabilize water-in-oil lenging feedstocks requires careful attention to proper equipment
emulsions, perhaps due to their concentration from the oil phase design and operating conditions, use of innovative chemical treat-
to the oil/water interface. The result can be an increased current ment approaches, and implementation of comprehensive perfor-
draw, BS&W carryover into desalted crude oil and the appearance mance monitoring programs.
of asphaltene particulates in the desalter effluent water. Asphaltene
instability can also promote sludge accumulation in crude storage Typical operating conditions for WCSB crude oils.
tanks, and can cause accelerated crude preheat exchanger fouling Here is a summary of the desalting practices used by many refin-
and pre-flash or atmospheric column foaming. ers who successfully process heavy WCSB feedstocks. However,
The instability of asphaltenes in certain WCSB blends is due most every unit has unique crude blends, plus significant dif-
in part to adding relatively paraffinic diluents to heavy oils and ferences in desalting equipment and operating conditions. A
bitumens to meet crude oil pipeline specifications. For example, significant amount of hands-on field work is usually required
one producer adds up to 26% gas-well condensate into its ther- to derive the optimal settings for a specific crude blend and
mally produced oil sands bitumen for this purpose. Asphaltene operating environment.
stability can also be affected by blending WCSB crudes with other Wash water. Most refineries running WCSB crude oil use
hydrocarbon feedstocks in the refinery crude oil storage tanks or a blend of overhead condensate water, vacuum condensate and
in the charge to the crude unit. stripped sour water. More expensive to use is well water and clari-
Several methods have been used to assess crude blend incom- fied surface water, which can be high in hardness and suspended
patibility, including SARA (saturates, aromatics, resins and solids. While boiler feedwater has excellent quality for desalting,
asphaltenes) testing, asphaltene-to-aromatic ratio and various it is also relatively expensive and is only used in special circum-
precipitation tests. Proprietary screening tests also have been stances. Table 1 summarizes some key quality parameters and their
developed to better predict the asphaltene instability of hydro- typical target operating limits.
carbon feedstocks.3 Test results can be used to predict problem Water sources that exceed these limits have been used in desalt-
crude blends, as well as to set up crude blending schemes and to ing, but they should be investigated carefully to make sure that
select proper treatment programs to control problems associated there will be no problems. It is critical to maintain the wash water
with incompatible blends. pH below 8, preferably 56.5. Under alkaline conditions, soaps
can form from the naphthenic acids in the WCSB crude oils, thus
Non-desaltable chlorides in WCSB blends. Non-water stabilizing emulsions in the desalter.
extractable or non-desaltable chlorides can be defined as organic Increasing the wash water rate generally increases desalter
or inorganic chlorides that are not dissolved in emulsified water, performance, in terms of salt content and BS&W of the desalted
removed by desalters, or indicated in normal, extractable chlo- crude and desalter effluent water quality. One might expect that
ride measurement methods.4 Certain WCSB feedstocks have higher percentages of wash water would result in wetter crude oil
been shown to contain these materials. The exact identity of but the opposite is true. When the wash water rate is increased,
non-desaltable chlorides varies with the specific feedstock, but there are more water droplets. The droplets are closer together
potential sources include oil-wetted inorganic salt crystals, due and coalescing of small droplets into larger ones is facilitated.
to thermal stresses experienced in production or upgrading, and Increasing the wash water rate also dilutes the concentration of
asphaltene hydrochlorides. The presence of these materials can stabilizing molecules at the oil/water interface, which reduces the
coalescing of droplets.
A wash water study was done using a Western Canadian heavy
crude oil in a bench-top electrostatic demulsification and dehy-
300 dration apparatus. The data in Table 2 shows the improvement
in dehydration efficiency using higher wash water rates. It was
250 found that increasing the amount of wash water up to 9% not
only improved the speed of release of water from the crude oil,
Filterable solids, PTB
200 but it also resulted in better dehydration (measured as % BS&W),

which should translate into drier crude oil leaving the desalter.
150 In general, operators like to see at least 90% of the wash water
recovered as water drops in 15 to 20 minutes in these bench top
100 tests, as an indicator of good desalting in the field.
Mixing energy. To remove contaminants from the crude, it is
50 necessary to contact the wash water droplets with the contaminant
directly. If there is not enough mixing, then not all of the contami-
0 nants will be removed. If there is too much mixing, then very small
water droplets are formed, producing an emulsion which cannot
Fig. 1 WCSB crude blend filterable solids test results vs. time, be fully resolved in the desalter vessel. Over-mixing results in high
three-month period. BS&W in the desalted crude oil and in poor salt removal.

For refineries running heavy WCSB crude oil, the mixing If the mud accumulates, the working volume of the desalter is
energy (as measured in psi drop across the mixing device, or DP) reduced; water outlet manifolds can become partially blocked,
varies from a low of 1 psi up to one refinery that consistently runs and in desalters with inlet headers in the bottom of the vessel,
1922 psi. Most refineries running WCSB crudes use only a mix the inlet manifold can be partially plugged. The mud buildup
valve. One refinery installed an inline mixer but removed it when can lead to increased oil in the effluent brine and poor desalter
they found that the vanes had eroded away. performance.
During normal operation, the mixing setting typically is not It is critical for desalters running WCSB crude oils to have a
changed. If there is a significant increase in the crude charge rate, mud-wash system or sludge buster to remove mud from the bot-
then more shear and mixing will result. Also, there will be less tom of the desalter. A survey of about two-thirds of the refineries
residence time in the desalting vessel. Therefore, at higher charge running WCSB crudes indicates that they mud wash in a range
rates, it may be necessary to adjust the mixing device setting. from 15 minutes per shift at one location up to continuous mud
Some emulsion breaking chemicals produce a more rapid reso- wash at a second location. It is very important to mud wash at
lution of the emulsion in the desalter. When using such chemicals, least once per day. If the mud is allowed to accumulate for several
it is possible to increase mixing without increasing the BS&W weeks, it becomes compacted and can no longer be easily removed
in the desalted crude oil. This can result in improved desalting from the desalter.
efficiency, especially where the salts are particularly difficult to
extract. Chemical Treatment Programs
Temperature. While temperature is a variable that is not typi- Several chemical treatment programs have been developed to
cally changed much on the desalter, there are cases where favor- improve the overall desalting system performance while process-
able exchanger configurations can be used to increase desalter ing many types of opportunity crudes.5 Most programs have been
temperature. There are also cases in which changing the crude adapted for use with heavy WCSB feedstocks, beginning with the
slate will change the heat balance on the tower and, hence, affect earliest production of conventional heavy crudes, and continuing
the desalter temperature. In general, raising the temperature will on with the latest variations of Dilbits, Synbits and Syndilbits.
improve the oil/water separation in the desalter because the vis- The most common chemical treatment regime includes the
cosity of the hydrocarbon decreases as the temperature increases. familiar application of an oil-soluble emulsion breaking chemical
There are also naturally occurring materials at the oil/water inter- injected into the crude oil upstream of the desalter. For treating
face that stabilize the desalter emulsion. These materials are dis- heavy WCSB feedstocks, this first mode of treatment is often
solved in the oil or water phase at higher temperature, thus mak- supplemented by the application of water-based wetting agents
ing the emulsion easier to break. fed to the fresh wash-water stream, to improve a desalters solids
However, there are negative impacts to raising the desalter handling capabilities.
temperature. First, asphaltenes can become unstable as the tem-
perature is increased. Precipitated asphaltenes collect at the oil- WCSB case history 1. A Midwestern US refinery was expe-
water interface to stabilize the emulsion and cause oil undercarry. riencing severe brine quality problems while processing blends
Second, water is more soluble in oil at higher temperatures, reduc- of heavy Canadian crude oils, including those produced from
ing the ability to dehydrate the crude oil (high BS&W in the oil sands. The desalter had been recently upgraded to allow bet-
desalted crude). Third, the conductivity of crude oils increases ter processing of the heavier solids-laden Canadian crude oils.
with temperature. For some crude oils, high conductivity can lead The refinery had hoped to increase its feed of heavier crudes
to excessive current draw and potential loss of grids. and reduce the amount of light Canadian, Louisiana and Texas
For various practical reasons, the upper limit of the desalter crude oils being processed. This was not possible with the incon-
temperature is about 310F (154C). Most refineries processing sistent desalter performance. The poor quality of the desalter
WCSB crudes run at temperatures substantially below the 310F effluent water was negatively affecting wastewater treatment plant
maximum. Each refinery should determine the optimum operating (WWTP) operations, as evidenced by low dissolved oxygen levels.
temperature for the crude blends that they process. It is important A plan was developed to improve desalter operations.
to work with a knowledgeable service company when determining
optimal desalter temperatures for WCSB processing.
Mud-wash practices. The desalting process removes contami- Table 2. Dehydration speed and efficiency
nants such as sand, clay, iron sulfide, iron oxide and other solid vs. washwater rate
materials from the crude oil. These solids settle to the bottom of
the desalting vessel and form a mud or sludge. Since WCSB Water drop, %
crude oils often contain more filterable solids than lighter crude 3% 5% 7% 9%
oils and even heavy crude oils from California and Venezuela, EDDA settling Wash Wash Wash Wash
time, minutes water water water water
they tend to generate substantial mud volumes in the desalter.
5 0.4 1.0 3.5 5.0
10 1.0 2.9 4.0 6.0
Table 1. Good wash water quality parameters
15 1.2 3.0 4.5 7.0
Parameter Target range 20 1.2 3.4 4.5 8.0
pH 58 25 1.5 3.5 5.0 8.0
Hardness <150 ppm as CaCO3 30 1.7 3.7 5.5 8.0
Suspended solids <30 ppm BS&W, % 1.2 0.8 0.8 0.2
Ammonia <35 ppm BS, % 0.1 0.2 0.4 0.1

SpecialReport Refining Developments
Samples of crude blends and wash water were screened to CRUDE OIL PRETREATMENT
select a chemical treatment program that would improve solids Crude oil pretreatment programs were originally developed
removal, salt removal, dehydration and brine quality. The new to address desalting challenges presented by heavy West Coast
chemical treatment program used an oil-soluble emulsion breaker US crude oils in the 1980s. Crude pretreatment involves adding
and a water-based wetting agent. An emulsion polymer was used specially formulated chemicals to crude receipts entering refinery
on a temporary basis, most often for rapid effluent water cleanup crude storage tanks.6 When added ahead of tankage, these chemi-
after the completion of a mud-wash cycle. Within a few hours, cals have more time to diffuse to solids particles, asphaltenes and
electrical grid conditions stabilized, and, by the next day, the brine other emulsion stabilizing materials at the oil/water interface
quality had improved significantly. surrounding brine droplets. This provides more effective phase
Wash-water rates were optimized, and, with better control of the separation and solids removal in the desalting vessel.
emulsion in the vessel, the interface levels were adjusted to further These programs can provide several key benefits. For WCSB
improve desalter performance. A more comprehensive desalter desalting operations, the primary goals for crude pretreatment
performance monitoring program was also implemented. programs include reduced hydrocarbon contamination of desalter
Satisfied with the desalting operation, operations personnel effluent water, reduced emulsion layer buildup and better dehy-
increased the ratio of heavier WCSB crudes in their blends. Filter- dration.
able solids levels climbed as high as 250 PTB without a decrease
in the desalter performance. Typically, solids content in the crude WCSB case history 2crude oil pretreatment. A
blends are now two to three times higher than when the upgraded North American refinery experienced desalter upsets while pro-
desalter chemical treatment program was started. cessing heavy crudes, including one grade from oil sands deposits,
As the winter months approached, received crude oil tem- which is processed during plant asphalt runs. Increased buildup
peratures dropped to about 40F (4.4C), causing the desalter of stabilized emulsions while processing these crudes resulted in
temperature to fall significantly. In addition, a mechanical failure oily desalter effluent water. This hydrocarbon loss represented a
of the bushings caused the middle grid to go out. Also, wash-water significant cost and created problems with WWTP operations.
rates were low due to a separate mechanical issue. Even with these To improve the desalter operation, a crude oil pretreatment
less than optimal operating conditions, total chemical usage has program was recommended. A specially formulated emulsion
dropped nearly 50%, and the desalter performance reliability has breaking chemical is injected into crude oil receipts upstream
improved, without compromising brine quality. of crude storage tanks. The crude oil pretreatment program sig-
The upgraded desalter chemical treatment program produced nificantly improved desalter operations during crude unit asphalt
several benefits for the refiner: runs. The primary goal of reducing the oil undercarry was accom-
Heavier Canadian WCSB crude oils are being processed plished immediately. Fig. 3 illustrates the effectiveness of the crude
with no compromise in salt removal, dehydration efficiency or pretreatment during the asphalt runs. The water sample shown
brine quality on the left is the effluent sample before the pretreatment program
Wastewater plant operations are no longer being affected by commenced, and the effluent sample on the right was taken dur-
oily desalter brine ing the first run of the pre-treated crude.
Solids removal efficiency is typically 80% Prior to the pretreatment program, the desalter brine contained
A significant reduction in organic loading chemical oxy- as much as 3,000 ppm of oil and grease content. After the crude
gen demand (COD) to the wastewater treatment system was pretreatment program was initiated, the amount of oil in the
achieved desalter brine decreased to an average of 140 ppm. Furthermore,
Increased dissolved oxygen by more than a factor of two in the higher quality desalter brine improved the operations in the
the wastewater treatment biological reactors (see Fig. 2) WWTP. It was stated by an operator that the transition from light
Overall chemical usage has dropped nearly 50% fuels to asphalt runs has been more stable. Also, the amount of
Refinery employees no longer need to focus their efforts and gross oil removal in the dissolved air flotation unit has decreased,
limited resources on the desalting operation. as have odor emissions from this unit.
Waste water treatment plant dissolved oxygen

Before After
7.0
6.0 Dissolved O2
Before average
Dissolved oxygen, ppm
5.0 After average
4.0
3.0
2.0
1.0
0.0
Daily
Fig. 3 Desalter effluent water samples during a crude unit
Fig. 2 WWTP dissolved oxygen during transition to new desalter asphalt run: ARegular asphalt run without a pretreatment
treatment program. program and BAsphalt run with a pretreatment program.

Another benefit obtained after the crude pretreatment program washwater just upstream of the desalter mix valve. Due to ease of
was the increase in the desalters filterable solids removal efficiency use and avoidance of fisheyes or gels, it is usually best to use disper-
from 27% on average prior to the pretreatment to 42% during the sion polymers. If the wrong polymer is used, or if fed improperly,
pretreatment. Based on these results, the refinery decided to make polymers can cause problems in the desalter, such as a buildup in
the crude pretreatment program part of the ongoing operations. rag layer. In most cases, the polymer is injected on a short-term
basis to control effluent water quality during upset conditions, or
Emulsion problems. For some crude oil blends, destabiliza- to facilitate speed recovery from mud-washing operations.
tion of asphaltenes in the crude charge can cause excessive emul-
sion buildup, with eventual water carryover and oil carryunder DESALTER PERFORMANCE MONITORING
problems. Fig. 4 shows the typical appearance of desalter effluent Conventional analytical methods can be used on a day-to-day
water containing suspended asphaltenes. In cases such as this, basis to properly monitor desalter performance while processing
chemical pretreatment recommendations may include proprietary WCSB feedstocks. However, the variability seen in analytical
asphaltene stabilizers, which are used to prevent asphaltenes from characteristics of these crudes requires increased vigilance in the
accumulating in the emulsion, thus reducing their concentration frequency of desalter performance measurements, in order to
in the desalter effluent water. respond to upsets quickly.
Filterable solids levels are a key monitoring parameter with
WCSB case history 3asphaltene stabilizer. A Mid- WCSB crude oils. Most refineries running these crudes measure
western US refinery was plagued by a variety of desalter perfor- the filterable solids content frequently, sometimes even daily.
mance issues, including increased solids in Typically, desalter problems occur when the
the water draw, emulsion buildup, high cur- filterable solids are above the 90100 PTB
rent draw, water carryover and oily effluent range in the raw crude oil.
water. The oily effluent water was the most Contingency plans should be developed
problematic issue, as it overwhelmed the to respond to any upsets that might occur
capabilities of the WWTP and ultimately when solids levels are particularly high,
resulted in reduced crude charge rates. or when asphaltene instability becomes
In this case, the desalter upsets were deter- extreme. These plans include adjustments
mined to be caused in part by the destabiliza- of crude blends, changes in chemical treat-
tion of asphaltenes in the crude unit. This ment dosages, adjustment of mix valve DP,
resulted in stabilized emulsions in the desalt- or re-direction of desalter effluent water
ers, as well as other complications. These to dedicated secondary separation systems
problems were further exacerbated when sour upstream of the WWTP.
Canadian crudes, high in asphaltene content, The best defense against desalter upsets
were processed by the refinery. is to use crude compatibility and bench-top
For this refinery, a two-pronged chemi- desalter simulator screening tests to predict
cal treatment approach was implemented. Fig. 4 Asphaltenes suspended in the behavior of specific crude blends in the
First, the continuous injection of a crude desalter effluent water during desalter, and to select the best set of desalt-
WCSB processing.
pretreatment surfactant formulation into ing conditions and chemical treatment
the crude rundown line to tankage was ini- methods to handle various crude blends.
tiated. The second treatment approach was using a proprietary These screening tests also have been used successfully to develop
asphaltene stabilizer when heavy Canadian sour crude blends are blending rules that help prevent the blending of incompatible
being received by the refinery. feedstocks.
The refinery agreed to a trial of the crude pretreatment pro- The characteristics of many heavy WCSB feedstocks seen to
gram, and it was able to realize the benefits of the new program date can include high solids levels, unstable asphaltenes, non-
almost immediately. Within days, it was evident that using the extractable chlorides, and considerable variability in one or more
surfactant formulation resulted in effective preconditioning of of these parameters for a given grade of crude oil. While these
solids and asphaltenes at the tank farm as shown by the decrease factors present various desalting challenges, technologies have
in crude charge solids content. Additional use of the asphaltene been developed that can be used to process these feedstocks,
stabilizer helped control asphaltenes when more aggressive crude with minimal impact on desalter and wastewater treatment plant
blends were utilized, giving the refinery the increased flexibility operations and performance. Proper desalter operation, suitable
to handle unplanned crude mixing. The demand for emulsion- chemical treatment programs and enhanced desalter monitoring
breaking chemical at the desalter was cut by nearly 50%. Signifi- are all keys to successful WCSB crude processing. HP
cant reduction of oil undercarry was realized and the WWTP
was no longer overburdened by oily effluent water. Moreover, LITERATURE CITED
1 Crude Oil Forecast, Markets and Pipeline Expansions, Canadian Association
the refinery was able to increase throughput over design capacity.
of Crude Oil Producers, June 2007 Report.
The increase in throughput resulted in a return on investment 2 Kremer, L. N., Challenges to Desalting Heavy Crude Oil, International
of 34 times the cost of the increased chemical usage. Conference on Refinery Processing, 2000 AIChE Spring National Meeting,
March 59, 2000, Atlanta.
3 Stark, J. L., J. Nguyen and L. N. Kremer, Crude Stability as Related to
HIGH MOLECULAR-WEIGHT POLYMERS
Desalter Upsets, 5th International Conference on Refinery Processing, 2002
High molecular-weight emulsion or dispersion polymers are AIChE Spring National Meeting, March 1114, 2002, New Orleans.
sometimes used to reduce the amount of oily solids in the desalter 4 NACE International Technical Committee Report, Effect of Nonextractable
effluent water. These products are typically added into the fresh Chlorides on Refinery Corrosion and Fouling, Task Group 274, NACE

Bruce Horne,
Baker Hughes
Incorporated, USA,
discusses strategies and new chemical technologies to overcome desalting
challenges of heavy crudes.
R
efiners globally are under continuous pressure to reduce costs and do more with less, so the ability to process
discounted challenge crudes, such as heavy crudes, remains of interest. The majority of heavy oil comes from
North and South America, with significant quantities being produced in the US, Canada, Mexico, Venezuela
and Brazil. Global heavy oil production will increase with the development of new projects in the Middle East, China,
Russia, South America and Africa. Total projected global heavy oil production (<22 API), including bitumen and heavy
synthetic crude oil, is expected to increase to 15.4 million bpd by 2025, an increase of over 50% based on 2008
production levels.1
www.hydrocarbonengineering.com Reprinted from October2009 HydrocarbonEngineering

Processing of heavy crude oil is a consideration for Heavy crude oil processing
refiners throughout the world. In an effort to improve the challenges
nations energy security, the US plans to double the amount The specific processing challenges posed by heavy
of heavy oil imports from Canada by 2035. China is quickly feedstocks depend on the physical and chemical
moving to increase production of heavy oil to slow growing characteristics of the crudes, their behaviour when blended
oil import dependence as domestic reserves of lighter with other crudes, and the configurations and capabilities
crude grades become harder to recover. The Middle East is of the refinerys processing units. Heavy oils yield significant
undergoing an aggressive programme of refinery expansion, economic benefits to refineries, provided processing
which will increase heavy crude processing capacity 10 challenges can be moderated. Several case histories are
fold.2 provided that discuss operating practices of refineries
According to the Canadian Association of Petroleum worldwide, which can be used to improve the processing of
Producers, with moderate growth, the supply of heavy heavy crudes.
conventional and oil sands derived crudes from Western Heavy crudes present many challenging problems with
Canada is estimated to grow from 1.3 million bpd in 2008 respect to desalting. The higher viscosities of these crudes
to 1.8 million bpd by 2015 and to 2.3 million bpd by 2020.3 and the techniques used for production tend to pull more
Several North American refineries have already initiated or inorganic solids from the formations from which they are
announced projects designed to increase their Western produced. The inorganic solids present in many heavy
Canadian Sedimentary Basin (WCSB) feedstock processing feedstocks range from 90 to >400 lb/1000 bbls of crude. If
capabilities. the solids are not controlled, those left in the crude oil can
cause fouling downstream of the desalter and those in the
water, which are generally oil coated, can cause difficulty
in the wastewater treatment plants. The asphaltene levels
present in these heavier crudes are significantly higher than
in lighter feedstocks, sometimes reaching concentrations
of over 30 wt%. Blending of diluents and lighter crudes into
heavy oils to facilitate transportation of these crudes can
destabilise the asphaltenes to a greater degree. Both the
asphaltenes and inorganic solids can also cause fouling in
downstream process units, and the destabilised asphaltenes
and inorganic solids can stabilise emulsions and initiate rag
layer growth in the desalter. The high salt content in heavy
crudes is also a major concern for refinery operations.
During production, the heavy crudes normally have a higher
Figure 1. Percentage of Cold Lake crude in feedstock. water specification for pipeline shipment (approximately
1%), which reduces salt mitigation. In addition, some of the
production treating involves flash units, which can crystallise
salt within the crude oils. Additional problems associated
with processing heavy crudes affect the refinery downstream
of the desalter as well as in the desalter but are outside the
scope of this article. Some of the major issues include high
sulfur levels, high naphthenic acid content and high metals
content.4,5,6,7,8
Case study 1
A North American refinery wanted to increase the percentage
of lower cost Cold Lake crude in its crude slate, but high
levels of oil in the desalter effluent water prevented them
from doing so. When the refinery attempted to increase the
Figure 2. Effluent water quality. amount of Cold Lake crude, wastewater problems forced
them to return to the prior crude slate. After repeated
attempts, the previous supplier was not able to correct the
problem, so the refinery asked Baker Hughes to conduct a
trial programme on their desalters.
The field trial clearly demonstrated the ability of Baker
Petrolite desalting technology to provide effective salt
Table 1. Desalter field trial results

Previous Baker
supplier Hughes
Desalted crude salt content (lb/000 bbls 7.2 5.9
of crude)
Figure 3. Crude oil desalting. Effluent water quality Clear Clear
Reprinted from HydrocarbonEngineering October2009 www.hydrocarbonengineering.com

removal without sacrificing effluent water quality (Table1). As content in the inlet crude blends are now two to three times
a result of the trial, Baker Hughes was awarded the business. higher than when Baker Hughes began its desalter chemical
Since obtaining this business, Baker Hughes has treatment programme.
continuously optimised the system. The Baker Petrolite As the winter months approached, received crude
desalting programme has allowed the refiner to increase oil temperatures dropped to approximately 40 F (4.4 C),
Cold Lake crude (Figure 1) without increasing oil in the causing the desalter temperature to fall significantly. In
desalter effluent water (Figure 2), and equally important, addition, a mechanical failure caused the middle grid to
without suffering from increased salt content in the desalted stop functioning. Also, wash water rates were low due to
crude (Figure 3). In fact, salt content in the desalted crude a separate mechanical issue. Even with these less than
currently runs on average at 3.2 lb/1000 bbls of crude, a optimal operating conditions, total chemical usage dropped
significant improvement relative to the 5.9 lb/1000 bbls of nearly 50% and desalter performance reliability improved,
crude achieved during the trial period. without compromising brine quality.
The Baker Petrolite desalting programme has allowed The Baker Petrolite desalter chemical treatment
the refiner to increase the percentage of Cold Lake crude in programme produced the following benefits for the refiner:
the feedstock by 10%, for a net increase of 4000 bpd. The l Heavier WCSB crude oils are being processed with no
refinery increased operating profit by US$ 2/bbl of Cold Lake compromise in salt removal, dehydration efficiency, or
crude processed. Overall, the refinery increased its cash flow brine quality.
by approximately US$ 2.9 million/y. l Wastewater plant operations are no longer being
affected by high oil content in the desalter brine.
Case study 2 l Solids removal efficiency is typically 80%.
A large Midwestern refiner was experiencing severe brine
l A significant reduction in organic loading (COD) to the
quality problems while processing blends of heavy Canadian
wastewater treatment system was achieved.
crude oils, including those from oil sands. The desalter had
been recently upgraded to allow better processing of the l Dissolved oxygen levels were increased by more than a
heavier solids laden Canadian crude oils. The refinery had factor of two in the waste treatment biological reactors
hoped to increase its feed of heavier crudes and reduce (Figure 4).
the amount of light Canada, Louisiana and Texas crude oils l Overall chemical usage dropped nearly 50%.
being used in their crude slate. This was not possible with the l Refinery employees no longer need to focus their efforts
inconsistent desalter performance they were experiencing. and limited resources on the desalting operation.
Poor desalter effluent water quality was negatively
affecting wastewater plant operations, as evidenced by low
dissolved oxygen levels. The previous specialty chemical
supplier tried various chemical approaches, but could not
meet refinery expectations. Baker Hughes was asked to
immediately implement a plan to help improve desalter
operations.
Samples of the crude blends and wash water were
screened to select a chemical treatment programme that
would improve solids removal, salt removal, dehydration
and brine quality. Immediately following the delivery of the
chosen chemical additives, a Baker Hughes technology and
sales team initiated the proposed programme. The initial
programme used an oil soluble emulsion breaker and water
based wetting agent. An emulsion polymer was also used on
Figure 4. A significant reduction in organic loading to the wastewater
a temporary basis, most often for rapid effluent water clean
treatment system was achieved with the Baker Petrolite desalter
up after the completion of mud wash operations. Within a
programme.
few hours of the chemical implementation, electrical grid
conditions stabilised and by the next day the brine quality
had improved significantly. Case study 3
Working with the customer, wash water rates were A US refiner was processing heavy Mexican, Venezuelan
optimised, and with better control of the amount of emulsion and other imported crudes suitable as asphalt feedstock.
in the vessel, interface levels were adjusted to further Combined crude slate gravities ranged from 19 22 API,
improve desalter performance. A more comprehensive with some components as low as 13 API. The refiner was
desalter performance monitoring programme was also put significantly concerned about potential desalting problems.
into practice. Under the incumbent suppliers programme, the plant
Implementation of the Baker Petrolite demulsifier commonly encountered emulsion buildup, high current draw,
programme rapidly improved grid stability and interface level water carryover and oily effluent water. Crude rates were
control. Clean oil was lowered to below the top try line to frequently limited, either by water carryover or by concerns
improve grid operation while maintaining desired effluent from the wastewater treatment plant over handling oily
water quality. Satisfied with the desalter performance, effluent. The desalter chemical treatment strategy employed
operations personnel increased the ratio of heavier WCSB a primary demulsifier and relied heavily on the use of a
crudes in their blends. Filterable solids content present in cationic emulsion polymer injected into the wash water.
the inlet crude climbed as high as 250 lb/1000 bbls of crude The refinery decided to run a 30 day competitive trial
without a desalter performance decrease. On average, solids among the three primary chemical suppliers. Following a

complete system review by Baker Hughes, a comprehensive potential processing issues with Baker Hughes prior to
Baker Petrolite Crude Oil ManagementTM programme was the shipment. Based on its experience at other refineries
designed and implemented during the evaluation period. The processing heavy crudes, Baker Hughes proposed a tank
programme incorporated crude oil pretreatment, a single pretreatment regime to not only stabilise desalter operations,
product desalting programme, and an effective slop oil but also to allow the tank farm operators to drain free water
treatment and management strategy. from the crude tanks. The high salt content of the crude
Baker Hughes initiated the pretreatment programme (257 ppm in this case), combined with non-optimal desalter
on all crude receipts going to storage, initially at 24 ppm. A operations, could also have a negative impact on the
demulsifier was employed at the desalter, initially at 6ppm. corrosion control of the overhead system of the unit.
As the first pretreated crude arrived at the crude unit, Since there was not enough time to break the oil/
dramatic improvements were immediately observed at the water emulsion at the desalter with the traditional chemical
desalter. Grid voltages climbed to all time highs, while amps treatment programme, it was decided to add extra residence
dropped to unprecedented lows, as the wide emulsion band time by pretreating all the crude as it was transferred to
steadily dissipated over the first few hours. Correspondingly, storage. The Baker Petrolite pretreatment programme
water content in the desalted crude dropped from 0.7% to was put in place with an average dosage of 15 ppm under
0.3%. The programme enabled the refinery to increase their conditions of low ambient temperature. The water draining
mix valve pressure drop from their previous limit of 7 psi process at the tank farm started after only three days.
to 20 psi. Salt removal efficiencies increased from a prior During the following two weeks, clean and oil free water was
70to80% range to above 90%. drained daily from the storage tanks.
One area of significant improvement was the appearance The pretreated crude was processed at rates of 24, 34
of the desalter tail water during the initial introduction of and 36% of the total charge. To prevent unit upsets from
the pretreatment programme. Previously, the tail water occurring, a decision was made to inject 8 ppm of a heavy
commonly was a chocolate brown containing measurable crude oil demulsifier at the desalter. After a few days, due to
amounts of free oil. However, the appearance quickly the excellent results obtained, the dosage was decreased by
changed to that of inky black with high amounts of oil 50% and over time was no longer required.
free solids. Despite the dark appearance, there were no The pretreatment programme had an impressive effect
detectable levels of oil, and the solids settled rapidly to on the desalter operations. The electrical grid conditions
the bottom of the sample bottles. This observation is were kept stable and no upsets were registered in the unit.
characteristic of the pretreatment programmes effect in The overall performance of the desalting operation was very
breaking up tank sludge and interfacial material. As the high, with a desalting efficiency of 98% (from 257 ppm to
system cleaned up the solids that had accumulated in the 5ppm).
desalter, the effluent water transitioned from the black solids The trial clearly showed the effectiveness of the crude oil
laden water to a clear to cloudy white appearance by the pretreatment programme. The desalter operation was stable,
end of the first eight days. with high desalting efficiencies that minimised the corrosion
As a result of this evaluation, the pretreatment potential in the unit overhead systems. Pretreatment also
programme was adopted as standard practice by the allowed water drainage from crude oil storage tanks, with
refinery. The pretreatment chemical has since been clean water sent to the wastewater treatment plant. The
optimised to 14 ppm, and the demulsifier applied at the effectiveness of the pretreatment programme allowed the
desalter is no longer needed on a routine basis. refinery to reduce the desalter demulsifier to a minimum
The following benefits of the Baker Petrolite Crude Oil dosage. All these factors represented significant cost
Management programme have been realised at this refinery reductions to the refinery.
location:
l Fewer unit upsets and crude rate cuts due to desalter Innovation
problems. Baker Hughes scientists have developed a new range of
l Energy savings as a result of lower desalted crude water desalter demulsifiers for heavy crude oils, including WCSB
content. crudes. During the product development stage, XERIC
l Improved overhead system corrosion control.
l Elimination of demulsifier demand at the desalter.
l Elimination of polymer at the desalter (elimination of
difficult injection equipment and lower risk of fouling in
the desalter).
l Improved wastewater treatment plant operations.
l Reduced polymer demand at the wastewater treatment
unit due to the reduction of desalter oil under carry.
l Elimination of a major source of slop generation, slop
recovery, and rerun costs.
l Comprehensive system management by Baker Hughes
personnel from tank farm to wastewater treatment plant.
Case study 4
A Western European refinery was about to receive its first
shipment of Soroosh, a 20 API crude from Iran. As is typical Figure 5. Stabilised emulsion resolution by XERIC 7000 Heavy Oil
when facing a new crude receipt, the refinery discussed Demulsifier compared to industry leading desalter demulsifier.
Reprinted from HydrocarbonEngineering October2009 www.hydrocarbonengineering.com

7000 Heavy Oil Demulsifier displayed an improved ability to
reduce unresolved stabilised emulsions (Figure 5).
This is an important factor in the mechanics of the
desalter. The electrical grids present in desalters are
designed for the coalescence of dispersed water droplets;
they have little effect in resolving stabilised emulsions.
The characteristics of heavy crudes tend to promote the
formation of severe stabilised emulsions and creation
of large rag layers. Emulsions containing surface active
materials, such as asphaltenes, produce a physical barrier
or film that diminishes the coalescence of the water
droplets. This is one of many ways in which stabilised
emulsions differ from dispersed water in oil emulsions.
With the ability of heavy oil demulsifiers to resolve these
stabilised emulsions, the desalter becomes more efficient in
dehydration and helps expedite the treatment of the crude
by removing the entrained salts and inorganic solids held in
the rag layers.
Many desalter demulsifiers are deficient in their ability to
maintain low oil and grease levels in the effluent water. With
the high levels of asphaltenes and inorganic solids present
in heavier feedstocks, water quality has become a major
concern to refiners. In laboratory testing, XERIC 7000 Heavy
Oil Demulsifier showed the ability to resolve emulsions
while maintaining excellent effluent water quality (Figure6). Figure 6. The ability of the XERIC 7000 Heavy Oil Demulsifier to
Additional experimental demulsifiers have also shown a provide cleaner effluent water is significant to the treating capabilities
reduction in desalted crude water content by 50% in the of the wastewater treatment plant.
laboratory, while also providing improved effluent water
content. This reduction in desalted crude water content will
ultimately correlate to improved salt removal efficiencies
across the desalter.
XERIC 7000 Heavy Oil Demulsifier

field trial
A trial of this new chemical demulsifier was conducted on a
two stage desalting unit processing 17 20 API Canadian
crude. Two base case periods were established using the
incumbent demulsifier and a solids wetting agent at an
agreed upon dosage. These two base case periods were Figure 7. XERIC 7000 Heavy Oil Demulsifier averaged 72% better
followed by two tests of the new XERIC 7000 Heavy Oil effluent water quality than the incumbent desalter demulsifier.
Demulsifier lasting six and nine days, respectively. During
these evaluation periods, feedstock quality was stable and Conclusion
desalter operating conditions were held constant, in order to As crudes continue to decline in quality and as heavy crudes
be able to reliably measure the effects of the new demulsifier represent a larger percentage of the refinery feedstocks,
formulation on desalter performance. refiners face a relentless task of pushing their units
Trial data shows that use of this new XERIC Heavy harder for longer periods of time, while being expected to
Oil Demulsifier reduced desalter effluent oil content by reduce or limit operating and capital expenditures. Recent
6575%, compared to the previous treatment programme innovations in operating practices and specialty chemical
(Figure 7). Data collected during the new product evaluation treatment program technologies can help refiners meet such
confirmed that desalter operations remained very stable, challenges head on.
and that crude oil salt removal, dehydration and solids
removal efficiencies were maintained at slightly better levels References
than those achieved by the incumbent primary demulsifier. 1. 'Heavy Crude Oil: A Global Analysis and Outlook,' Hart Energy
Consulting, April 2008.
Salt removal efficiency remained at the 98% level, while 2. 'Growth in the Canadian Oil Sands: Finding a New Balance,' IHS
solids removal efficiency was maintained in the 75 85% Cambridge Energy Research Associates, May 2009.
range. 3. 'Crude Oil Forecast, Markets and Pipeline Expansions,' Canadian
Association of Crude Oil Producers, June 2009 report.
This level of reduction in desalter effluent water oil 4. GREEN, K., 'Improve processing of opportunity crudes,'
content can save refiners a significant amount of money in Hydrocarbon Processing, June 2004.
terms of reduced oil losses, reduced oil recovery costs and 5. WEERS, J. J., and BIEBER, S., 'Calcium removal from high TAN
crudes,' Petroleum Technology Quarterly, Q3, 2005.
reduced slop oil handling. Better quality desalter effluent 6. PALMA R., 'Processing acid crudes with confidence,' Hydrocarbon
water helps to prevent wastewater treatment plant upsets, Engineering, March 2007.
improves overall wastewater treatment plant performance, 7. GIESBRECHT, W., and DUGGAN, G. G., 'Controlling salt corrosion,'
Hydrocarbon Engineering, November 2007.
and helps control expenses related to wastewater plant 8. KREMER, L., and BIEBER, S., 'Rethink desalting strategies when
chemical treatment. handling heavy feedstocks,' Hydrocarbon Processing, September
2008.

Originally appeared in:
September 2010, pgs 67-73.
Used with permission.
REFINING DEVELOPMENTS SPECIALREPORT
Fine-tune processing heavy

crudes in your facility
A better understanding of asphaltene stability in crude oils
allows refiners to increase blending of opportunity feedstocks
T. FALKLER and C. SANDU, Baker Hughes, Sugar Land, Texas
H
eavy crude oils are often appealing feedstocks for refiner- imports are steadily increasing due to the pipeline infrastructure
ies, due to their lower cost. The availability of these heavy that has been recently developed and extended.13 To accom-
crudes is improving as production rates increase, particularly modate the growing influx of heavy crudes, several US refineries
in North and South America. Refiners want to keep certain key are revamping process configurations; such modifications involve
performance indicators (KPIs) such as heat transfer coefficients, more bottoms upgrading capability and greater consumption of
corrosion rates, pressure drop and throughput under control. How- steam, hydrogen and power.35 These measures require a signifi-
ever, asphaltenes present in heavy crudes can significantly affect cant capital investment, and due to present economic conditions,
these KPIs when they become their implementation is progress-
destabilized and agglomerate to ing at a slow rate.
the extent where precipitation The ability to measure crude blend stability
can occur. Asphaltene particles and compatibility quickly and accurately can Operational challenges.
can stabilize emulsions, caus- create a competitive advantage for refiners Heavy crude oils are commonly
ing desalter performance and oil wanting to improve feedstock flexibility and blended with lighter crudes and
carry-under problems, and can reduce feedstock costs by processing greater other feedstocks at terminals or
contribute to accelerated fouling quantities of heavy crude oils. A robust field in refinery crude tanks to facili-
in crude unit preheat exchang- testing instrument and analysis procedures tate transportation and process-
ers. have been developed that provide on-site ing. Each heavy crude oil has
This article reviews the prob- unique physical and chemical
measurements of crude blend asphaltene
lems associated with asphaltene characteristics that can represent
destabilization and discusses stability allowing more timely feedstock specific operational challenges.
new tools available to improve segregation and blend optimization decisions. Heavy crudes are usually
and control asphaltene behav- characterized by high levels of
ior. A laboratory asphaltene stability test has been successfully filterable solids, asphaltenes, water and salts, as compared to
used to determine heavy crude feedstock compatibility. Case lighter crude oils. Industry experience indicates that blending
histories show how new field techniques were used to develop heavy crudes with other crude oils or lighter feedstocks can form
appropriate blend ratios for specific sets of crude feedstocks, and unstable or incompatible crude blends that can lead to serious
how this information was used, together with a heavy oil blend- operational problems such as:
ing aid program, to improve the utilization of these crudes and Sludge buildup in crude storage tanks
avoid downstream operational problems. Stabilized emulsions
More frequent desalter upsets
Heavy feeds. Heavy crude oils are forecast to be more signifi- Increased desalter water and salt carryover
cant feedstocks for refineries due to increased production coupled Increased amounts of oil in the desalter effluent water
with growing global energy demand. The heavy feedstocks com- Increased fouling in crude-preheat exchangers, and in atmo-
monly processed in US refineries usually come from California, spheric and vacuum tower furnaces.
Canada (Alberta or the Western Canadian Sedimentary Basin), Greater salt carryover can also lead to increased corrosion activity
Venezuela, Mexico and Saudi Arabia. Canadian heavy crude in the atmospheric tower and the overhead condensing system.
HYDROCARBONPROCESSING SEPTEMBER 2010
SPECIALREPORT REFINING DEVELOPMENTS
Fouling impact. The economic impact from fouling is very ponents of refinery fouling deposits. Asphaltenes are defined as a
significant. It is estimated that billions of dollars are spent annu- class of hydrocarbons that are soluble in xylene and toluene, but not
ally to address this problem.6 Major areas affected by feedstock soluble in paraffinic solvents such as heptane or pentane. They are
asphaltene destabilization are: polar compounds that normally contain hetero-atoms like sulfur,
Crude storage tanks nitrogen and oxygen. When asphaltenes form aggregates, it is possi-
Crude unit preheat exchangers ble to generate sludge in storage tanks and fouling on equipment.
Crude unit atmospheric and vacuum furnaces Asphaltenes can also aggregate at oil/water interfaces, where
Resid hydroprocessing units they stabilize water-in-oil emulsions, or at oil/solid interfaces
Delayed coker furnaces where they can alter surface wetting properties. One area in
Visbreaker furnaces and preheat exchangers. the refinery where this phenomenon is frequently encountered
Fig. 1 illustrates the locations where fouling is observed in is around the crude unit desalter.9,10 In several cases where
crude distillation unit operations. These impacted areas all cre- heavy Canadian feedstocks were processed, it was observed that
ate significant operational problems by increasing energy costs, asphaltene destabilization resulted in either a stabilized water/
raising greenhouse gas emissions and limiting unit throughput. oil emulsion in the desalter, increasing basic sediment and water
Typical measures that refineries can use to mitigate fouling phe- (BS&W) carryover into desalted crude, or the appearance of
nomena include: asphaltenes in desalter effluent water.
Increasing the frequency of heat exchanger and furnace tube The stability of a feed is not directly proportional to the
cleaning operations asphaltene amount present. More important, is the stability of
Increasing furnace firing rates to compensate for furnace the asphaltenes that are present in the organic matrix, and the
inlet temperature losses quality of the solvent in the organic matrix of the feed. Light
Chemically treating the crude charge with heavy oil blend- oils with limited amounts of asphaltenes are more likely to cause
ing aids, to improve asphaltene stability in the blended feed. problems during production than heavy crude oils with larger
A combination of methods is often the most economical solu- amounts of material in the asphaltene fraction.11,12
tion for managing fouling.7, 8 Heavy crude oils, although they contain higher amounts of
Considering that new, more stringent environmental regula- asphaltenes vs. typical crudes, are also characterized by a rich
tions are anticipated, and rigorous control and lower levels of organic matrix of intermediate components such as resins,
carbon dioxide (CO2) and sulfur dioxide (SO2) emissions will be aromatics, polynuclear aromatics with 23 rings, and naph-
required, refineries are challenged to identify the best approaches thene-aromatics that are good asphaltene solvents. Light oils
to mitigate and control fouling phenomena with minimum capi- can consist principally of paraffinic materials in which, by
tal expenditures.58 definition, asphaltenes have very limited solubility. The key to
identifying feed stability lies in having a very accurate method
Role of asphaltenes. Asphaltenes are one of the major com- to measure the optimum ratio of the good solvent species vs.
the paraffinic components, thus preventing the destabilization
of asphaltenes by maintaining the optimum ratio throughout
Cold crude Hot crude
preheat preheat the entire refining process.
Desalters
Atmos. Impact of blending on asphaltene behavior. There is
crude no linear behavior in crude blending; only in specific cases may
Crude Crude tower
storage furnace the behavior be close to linear where crude blends might exhibit
stabilities between the two individual crude oil stabilities. These
Pipeline Vacuum
distillation
tower
Vacuum
furnace
FIG. 1 Crude unit locations impacted by asphaltene fouling

phenomena.
Decreased stability
0 10 20 30 40 50 60 70 80 90 100
Light crude oil in blend, %
FIG. 3 Example of crude incompatibility resulting in asphaltene
FIG. 2 Example of nonlinear stability behavior upon mixing light precipitation raw crude A (right); raw crude B (left); and
crude with heavy crude. 50/50 blend of crudes A/B (center).

cases are usually encountered when crudes with a similar amount predict and control the stability and compatibility of crudes and
of asphaltenes, as well as similar organic matrixes, are mixed (e.g., heavy crude oil blends. To obtain more valuable information, a
light crude with light crude, or heavy crude with heavy crude). versatile laboratory asphaltene stability technique was developed
In most real-life situations, the nonlinear behavior is frequently and is frequently used in laboratories.
seen where blends of light crude with heavy streams are used. Fig.
2 shows the stability trend obtained by mixing light crude with Laboratory asphaltene stability technique. The labo-
heavy crude. This example illustrates clearly that the crude blend ratory asphaltene stability test was developed to provide highly
obtained has lower stability vs. the initial stabilities of the blend sensitive information about the stability of crude oils as well as
components, and there is no linear behavior. their blends, and to detect very small changes in the blend sta-
It is imperative for the refiner to assess the compatibility/ bility. As little as a 2% change in the blend composition can be
stability of the feedstocks prior to their blending, and to iden- resolved with the method. The asphaltene stability test measures
tify the optimum mitigation solution. Crude compatibility is the stability of asphaltenes in crude oils via determination of
defined as the ability to blend two or more crude types without the onset of the asphaltene flocculation point using a solvent-
inducing asphaltene precipitation. Crude stability is an intrinsic titration method.
physical characteristic and refers to the capacity of the crude The test instrument is equipped with a coherent near-infra-
oil to keep all constituents, including the asphaltenes, well dis- red (NIR) source that transmits through a sample. The device
persed. Both parameters require evaluation prior to blending also has a solid-state detection system capable of measuring the
or processing. change in intensity upon a titration with an asphaltene precipi-
Fig. 3 shows an example of two crude oils that, upon mixing, tant (a nonsolvent such as pentane). An inflection point can be
become incompatible and asphaltene destabilization occurs. On observed in a plot of transmittance vs. the volume of added non-
the left side of Fig. 3 is the heavy crude oil that, by itself, is sta- solvent as flocculation begins. The point of inflection, expressed
ble; on the right side is the lighter asphaltenic containing crude as the asphaltene stability index (ASI), corresponds to the point
that is also stable. Both crudes show no evidence of asphaltenes of asphaltene precipitation and provides a relative measure of the
precipitated on the bottle walls. By creating a 50/50 blend of asphaltenes stability in the oil.
these two individual crudes, a very unstable mixture is produced A scale of ASI values was developed that can classify the feed-
that immediately displays asphaltenes precipitated on the walls stock with respect to its stability and fouling potential:
of the bottle, thus indicating the incompatibility of these two 0130 ASI: High fouling potential
selected feedstocks. In practice, refineries blend their feedstocks 130200 ASI: Medium fouling potential
by considering a series of factors such as storage-tank availability 200 and higher ASI: Low fouling potential.
and capacity, feedstock availability and inventory, targeted refin- This technique is used to measure the stability of crude,
ery throughput and yield characteristics of the blend. crude blends and the effects of chemical additives upon
asphaltene stability.13
Measuring asphaltene stability. A series of conventional
analytical tools are used to characterize and quantify the physical Asphaltene stability test case. A US West Coast refinery
and chemical properties of received feedstocks. The most typical displayed poor desalter dehydration and brine quality issues when
characterization performed measures the amount of saturates, processing a particular heavy Canadian crude. The refinery was
aromatics, resins and asphaltenes (called a SARA analysis) in the interested in improving the desalter operation; the emulsion or
oil sample. The asphaltene-to-resin ratio is usually used as a rough rag layer was building up and significant amounts of solids and
indication of the stability of the crude or crude oil blend (A/R > asphaltenes were present that diminished the salt-removal effi-
0.35 indicates unstable oil). Although these methods are useful ciency and affected the quality of the effluent brine. The refinery
directional indicators of feedstock stability and compatibility, was interested in solving these issues, but it also wanted to boost
these techniques are not always sensitive enough to measure, the amount of this heavy crude processed above 7,000 bpd.
Decreased fouling potential

Decreased fouling potential
1,400 1,400
Heavy crude
1,200 Standard refinery feed 1,200 90/10 crude blend
26 90/10 blend 90% 149 168 Additive 1 addition 149 171 192
1,000 standard feed and 1,000 Additive 2 addition
10% heavy crude
Intensity
800
Intensity
800
600
600
400
400
200
200
0
0 0 50 100 150 200 250 300
0 50 100 150 200 250 ASI
ASI
FIG. 4 Comparison of the asphaltene stability: heavy crude, FIG. 5 Chemical additives increase stability of crude blend with
standard refinery feed and crude blend of 90/10 standard 10% heavy feed: 90/10 crude blend, Additive 1 on crude
feed/heavy crude. blend and Additive 2 on crude blend.

REFINING DEVELOPMENTS SPECIALREPORT
Decreased fouling potential 100

1,400 85.76 94.84
90
Heavy crude feed
1,200 80/20 crude blend 80
45 146 172 Processed feed
1,000 Additive 2 applied 70
to 80/20 crude blend 57.92 62.17
Intensity
800 60
180
ASI
600 50
400 40
200 30
0 20
0 50 100 150 200 250 300
10
ASI
0
FIG. 6 Chemical additive increases stability of crude blend Untreated Current Proposed Experimental
with 20% heavy feed: heavy crude, 80/20 crude blend, crude treatment treatment heavy oil
blending aid
processed feed and Additive 2 on 80/20 crude blend.
FIG. 8 Improved asphaltene stability for crude blend No. 1 using
chemical additives.
Crude # 1 Field Based on these results, it was recommended that Additive 2 be

Laboratory applied in the field. Using this additive program, the refiner could
Crude # 2
increase the rate of heavy oil processed from 7,000 bpd to 15,000
Crude # 3 bpd, while maintaining desired salt-removal efficiency, as well as,
dehydration performance.
Crude # 4 After seeing this positive response from the heavy oil blending
aid, the refinery wanted to process more than 10% of the heavy
Crude # 5 crude oil component. Another round of testing was done on
the new heavy feed as well as on the currently processed feed. A
Crude # 6
blend of 80% processed feed with 20% heavy crude was made.
Crude # 7 Additive 2 was applied to this new crude blend; test results are
illustrated in Fig. 6.
Crude # 8 The 80/20 crude blend showed a 15% decrease in its stability
0 20 40 60 80 100 120 140 160 180 200 in comparison with the processed feed. Treating the heavy crude
with Additive 2 prior to mixing with the processed feed resulted
FIG. 7 Crude stability comparison on samples measured with in a 23% improvement in stability. Based on these laboratory data,
both laboratory and field techniques from a Texas Gulf the refinery more than doubled the amount of processed heavy
Coast refinery. Canadian crude from 7,500 bpd to 17,500 bpd and maintained
good desalter performance.
Laboratory tests were performed on the heavy crude, the refin- These results illustrate the importance of identifying the
ery blend and multiple synthetic blends to identify the optimum stability and/or compatibility of multiple crudes or crude mix-
ratios for processing. The laboratory asphaltene stability test was tures when heavy streams are part of the blending formulation.
used to perform this study. Fig. 4 shows the asphaltene stability Also important is determining the optimum blending ratio of
results obtained for the standard refinery blend, where no heavy the feeds prior to charging them to the processing units, and
blend component or heavy oil blending aids were present; the selecting the most cost-effective chemical treatment program
heavy crude oil alone; and a blend containing 90% of the standard to improve blend stability. By performing this exercise before
unit blend with 10% heavy crude. the blending step, refineries can avoid significant operational
The standard unit feed shows a moderate fouling potential. problems, reduce energy costs, and lower feedstock costs by
The heavy Canadian crude is severely unstable, with an ASI value increasing the amount of heavy crudes in the crude blend.
of 26. By adding only 10% of the heavy component into the stan- To obtain this information, refiners usually ship samples
dard crude blend, the asphaltene stability of the processed feed to testing laboratories and wait until results are returned,
decreased by about 11.3%. Thus, the heavy crude is expected to which can take from one week to one month. This approach
have detrimental effects on the desalter performance, reducing is not satisfactory in the refinery environment where deci-
dehydration efficiency and affecting effluent water quality. sions must be made in a matter of hours, or where infor-
A decision was made to evaluate several samples using chemical mation is needed onsite for a particular feed with specific
additives to improve the stability of the 90/10 crude blend. Fig. operating conditions.
5 shows the results obtained with two additives that displayed
the best asphaltene-stabilizing effect. Additive 1 increased the Field asphaltene stability testing. In response to refin-
stability of the 90/10 crude blend by 15%. Additive 2 showed an ers need to access valuable information onsite and to enable
improvement of 29% and shifted the stability to a range of values operators to screen feedstocks for asphaltene stability and blend
indicative of lower fouling potential. compatibility, a new portable field asphaltene stability monitor-
SPECIALREPORT REFINING DEVELOPMENTS
ing technique was developed. Having this technical capability blend optimization decisions, and it will provide more effective
available onsite can provide several advantages: heavy oil blending aid program optimization. This new capabil-
Greater flexibility in selecting feedstock types ity can help refiners increase their heavy crude processing while
More ability to optimize the blend feedstock ratios maintaining desired desalter operation and performance. HP
Capability to improve optimization of any heavy oil
blending aid program. ACKNOWLEDGMENTS
The new field asphaltene stability technique is similar in prin- The authors wish to thank several Baker Hughes employees, especially Jerry
ciple with the laboratory method now used. Weers, director of Industrial Technology; Lawrence N. Kremer, technical advisor;
and Marco Respini, technology development specialist, for contributing to the
This instrument is more rugged, self-contained and com- manuscript and Roger Metzler, technical support manager, and Bruce Wright,
pletely portable. As with the laboratory test, the technique itself technical field engineer, for supporting this work and reviewing the manuscript.
measures the stability and blend compatibility of refinery feed-
stocks, the impact of chemical additives on these parameters LITERATURE CITED
and the optimum amount of chemical needed to improve blend 1 Worrell, E. and C. Galitsky, California Industries of the Future Program,
stability. However, the field asphaltene stability test has improved Energy Analysis Department and Environmental Energy Technologies,
sensitivity and detection capabilities to make these measurements Lawrence Berkeley National Laboratory, July 2004.
2 Energy Efficiency Roadmap for Petroleum Refineries in California,
quickly and accurately.
Energetics Incorporated Report, April 2004.
3 Crude Oil Forecast, Markets and Pipeline Expansions, Canadian Association
Case study on crude-oil blend stability. A series of of Crude Oil Producers Report, June 2009.
crude feedstocks were obtained from a Texas Gulf Coast refinery. 4 Downstream industry struggles with fewer resources, Oil & Gas Journal,
The asphaltene stability was measured using both laboratory and pg. 52, 2008.
5 Gunaseelan, P., Changing US Crude Imports are Driving the Refinery
field techniques. Laboratory results were obtained on samples Upgrades, Oil & Gas Journal, August 2009.
received from the field and measured within 12 weeks. The 6 Fouling Minimization, Office of Industrial Technologies, US Department
results obtained with the field instrument were recorded in the of Energy, January 1999.
7 Wright, B. and T. Falkler, Fouling Control Programs Reduce Energy
field on samples provided by the refinery.
Consumption, CO2 Emissions, NPRA Annual Meeting, AM-09-52,
Fig. 7 illustrates the results from this experiment and shows the March 2224, 2009.
same stability trend obtained with both techniques: Crudes No. 8 Smali, F., V. S. Vassiliadis and D. I. Wilson, Mitigation of Fouling in
1 through No. 5 are very unstable and have a high potential for Refinery Heat Exchanger Networks by Optimal Management of Cleaning,
fouling, and Crudes No. 6 to No. 8 show medium stability and Energy & Fuels, 2001, 15, pp. 10381056.
9 Kremer, L. N., and S. Bieber, Rethink Strategies When Handling Heavy
have moderate fouling potential. Feedstocks, Hydrocarbon Processing, September 2008, pp. 113122.
Based on these results, Crude No. 1 was selected as the best 10 Horne, B., Homing in on Heavy Crudes, Hydrocarbon Engineering,
candidate to perform more in-depth studies on the effects of heavy October 2009.
11 De Boer, R. B., K. Leerlooyer, M. R. P. Eigner and A. R. D. van Bergen,
oil blending aids to improve crude stability vs the current chemi-
Screening of Crude Oils for Asphalt Precipitation: Theory, Practice and
cal treatment program. Initially, one additive dosage was tested the Selection of Inhibitors, SPE Production & Facilities, February 1995,
for all stability measurements. The results are illustrated in Fig. pp., 5561.
8. As shown, a slight increase in asphaltene stability is provided 12 Branco, V. A. M., G. A. Mansoori, L. C. De Almeida Xavier, S. J. Park,
with the current treatment program. These tests also suggest that and H. Manafi, Asphaltene flocculation and collapse from petroleum fluids,
Journal of Petroleum Science and Engineering, Vol. 32, pp. 217230, 2001.
using newly developed products can provide a 64% improvement 13 Stark, J., L. N. Kremer and J. M. Nguyen, New method prevents desalter
in asphaltene stability. upsets from blending incompatible crudes, Oil & Gas Journal, March 18,
Working with the refinery to optimize both the blend ratio 2002.
and cost performance, a proposed chemical solution was recom-
mended where a 48% stability improvement could be obtained.
This testing was performed in the test laboratory and in the field Thomas Falkler is a senior research scientist in Baker Hughes Fouling Control
at the refinery. A protocol to correlate these test results with field Group in Sugar Land, Texas. He has over 30 years of experience with Baker Hughes in
developing technologies to improve the stability of petroleum fluids and laboratory
experience is being planned for this refinery location. test methodologies to identify new mitigation and application strategies for refinery
fouling. Mr. Falkler has authored or co-authored papers and patents focusing on
Overview. The ability to measure crude blend stability and coker-furnace fouling, asphaltinic polymers in FCC slurries, oxidation polymerization
compatibility quickly and accurately is an important competitive in naphtha streams, and asphaltene stability in crude oil and heavy hydrocarbon
feedstocks.
advantage for refiners wanting to improve feedstock flexibility and
reduce feedstock costs by processing greater quantities of heavy
Dr. Corina Sandu is a project manager in Baker Hughes Commercial Develop-
crude oils. Suitable laboratory techniques have been developed ment Group, Industrial Technology, in Sugar Land, Texas. In her current position, Dr.
that can determine these measurements, but these techniques Sandu is responsible for leading the development of new technologies to enhance the
require long lead times to receive good results. A robust field test- performance of fireside additives for gas turbine applications. She is also responsible
ing instrument and analysis procedures have been developed that for Baker Hughes control/prediction programs for heavy fuel oil stability/compatibility.
Dr. Sandu holds a PhD in materials chemistry from the University of Houston, and a
allow onsite measurements of crude blend asphaltene stability. post-doctorate from Rice University in Houston. She is a member of ACS and SPE. Dr.
Based on results obtained, this new technology is a versatile Sandu has authored and co-authored 19 publications in peer-reviewed journals as well
tool that will allow more timely feedstock segregation and as many conference publications, and has two patents.
Article copyright 2010 by Gulf Publishing Company. All rights reserved. Printed in U.S.A.
Not to be distributed in electronic or printed form, or posted on a website, without express written permission of copyright holder.
Downstream Chemical Services
XERIC Heavy Oil Program

Process heavy crude oils while minimizing
operating cost and risk
Process heavy crudes
Processing low-cost, heavy crudes with high viscosity, high solids Cold Lake crude processed
content, and unstable asphaltenes is extremely challenging. Heavy while meeting the operational
crudes often cause significant problems: uncontrollable emulsions, targets of the wastewater
oil carryunder, and water and salt carryover. These problems result treatment plant and complying
in reduced throughput, wastewater treatment plant upsets, with regulated limits on
increased fouling and corrosion, and higher energy costs. treated water discharges. Effluent water quality - XERIC heavy oil
demulsifier (left) vs incumbent (right)
The Baker Petrolite XERIC heavy oil program helps you Reduce risks
reduce feedstock costs and improve feedstock flexibility while For many years, Baker Hughes has supplied premier demulsifier
maintaining throughput, minimizing operating costs, and improving products to the refining industry. Our latest XERIC chemical
environmental compliance. Using our well-established crude oil technologies have set a new standard for managing refinery
management concepts, the XERIC program provides your refinery desalter operations when processing heavy crudes.
with a comprehensive system-wide analysis, effective chemical
treatment technologies, and a broad-based design for mitigating A western Canadian crude oil upgrader processing 100% heavy
heavy oil processing problems. Canadian feedstocks used a new Baker Petrolite XERIC heavy oil
demulsifier to reduce oil losses by 70% while maintaining desalter
With proven Baker Petrolite chemical products and Baker Hughes operational stability and the desired salt, water, and solids
desalter optimization knowledge and expertise, heavy crude oils removal performance.
become opportunities to make money rather than opportunities
for lost profits. Maintain refinery reliability
Stable crude oil desalter operation is a critical factor for reducing
Increase feedstock flexibility crude unit fouling and controlling corrosion. Baker Petrolite XERIC
With the XERIC heavy oil program, your refinery can process a wider heavy oil programs ensure optimal desalter performance during
variety of heavy crude oils while decreasing the problems they cause. heavy crude oil processing campaigns.
A refinery wanted to increase the percentage of lower cost A U.S. refiner processing heavy Mexican and Venezuelan crudes
Cold Lake crude in its crude slate, but the resulting levels of oil experienced emulsion buildup, high current draw, water carryover,
in the desalter effluent water prevented them from doing so. The and oily effluent water. After a comprehensive refinery-wide system
refinery staff asked Baker Hughes to conduct an evaluation of a new analysis, Baker Hughes implemented a XERIC heavy oil treatment
XERIC heavy oil demulsifier. The success of the XERIC demulsifier program that reduced unit upsets, reduced energy costs, and
treatment program allowed the refinery to increase the amount of improved overhead system corrosion control.
2
Predict and control unstable crude blends A Gulf Coast refinery changing crude slates requested a stability
Baker Hughes can tell you before you start processing heavy crudes study using the Field ASIT services technology. In an extremely
what problems to anticipate. Whether it is difficulty desalting, short time, the onsite Field ASIT test analyzed 10 crude samples, six
asphaltene stabilization of desalter emulsions, or potential blending aids, three dosages, and five separate blends. The refinery
wastewater operating challenges, youll understand the problems quickly determined the most effective blend for the available
youre facing, and Baker Hughes personnel will be ready to help you feedstock and was able to control processing, maximize throughput,
solve them. and minimize desalter upsets and downstream problems.
With analytical tools like Baker Petrolite Field ASIT services, we If you want to increase refinery profitability and feedstock flexibility
analyze your feedstocks on site to provide fast measurements of by processing heavy crude oils, but want to minimize operating risks
crude blend asphaltene stability. This allows timelier feedstock and costs, call the opportunity crude experts at Baker Hughes and
segregation and blend optimization decisions, and better ask about the Baker Petrolite XERIC heavy oil program.
management of XERIC crude oil blending aid chemical applications.
Baker Hughes crude oil management approach
Better crude unit reliability, lower operating costs

XERIC heavy oil demulsifiers improve desalter salt and
solids removal, which means reduced fouling and better
corrosion control in the preheat and overhead exchangers.
Improve feedstock quality
Baker Petrolite XERIC heavy oil products
are added as crude is off loaded, Less o
il un
pre-conditioning solids, stabilizing derc
ng arry
salti
asphaltenes, and dropping BS&W e de to w
p rov ast
ew
im
in the storage tank before it ids Less salt, less sediment, ate
d sol rt
re
reaches the desalter. at e less fouling. Ensure wastewater
re
ret
at
treatment plant performance

me
p
nt
d
XERIC desalter brine treatment

pla
an
Cle
de
nt
aids are used to improve

cru
an
er
W
slo
wastewater plant operations.

BS&
po
Low
il to
desa
lter f
or sm
oother
ality compliance
operation
ry
cove
ater qu
d re
y an
ent w
alit
qu
efflu
Reduce wastewater treatment plant upsets

oil
te
ved
Slop oil treatment improves the quality of water

s
wa
d
ve
pro
returned to the wastewater plant. astewater plant pro

Im
rn to w tu Im
oil re
im um
Min
Improve slop oil processing

Baker Petrolite slop oil treatment minimizes solids returning
with recovered oil for more effective desalting.
3
XERIC and Field ASIT Services are trademarks of Baker Hughes Incorporated.
Disclaimer of Liability:
Baker Petrolite Corporation and its affiliates (BPC) disclaim all warranties or representations express or implied, including any implied warranties
of merchantability or fitness for a particular purpose or to the accuracy, correctness or completeness of such information herein or that reliance on
such information will accomplish any particular result. All such information is furnished as is and by using such information the user is assuming
all liabilities for the use or reliance on such information. BPC SHALL NOT BE LIABLE FOR ANY INDIRECT, SPECIAL, PUNITIVE, EXEMPLARY OR
CONSEQUENTIAL DAMAGES OR LOSSES FROM ANY CAUSE WHATSOEVER INCLUDING BUT NOT LIMITED TO ITS NEGLIGENCE.
www.bakerhughes.com/XERIC 2010 Baker Hughes Incorporated. All rights reserved. 29772

EXCALIBUR Contaminant
Removal Technology
Improve refinery profitability and feedstock flexibility
Baker Petrolite EXCALIBUR contaminant removal technology is a The EXCALIBUR technology solution
process for removing certain contaminants from crude oils in the The EXCALIBUR technology process involves injection of a water
crude unit desalting operation. Baker Hughes customers world soluble complexing agent into the crude unit desalter wash water
wide use EXCALIBUR technology to process higher rates to increase the solubility of contaminants in the aqueous phase.
of opportunity crudes, improving refinery feedstock flexibility Dissolved contaminants are removed from the desalter with the
and profitability. effluent water drained from the bottom of the vessel.
Contaminants can limit refinery feedstock selection The complexing agent formulation contains corrosion inhibitors
Crude unit feedstock contaminants such as calcium naphthenates, that allow its safe use in crude unit desalting equipment.
inorganic iron, caustics and other alkaline materials can cause Specially formulated Baker Petrolite emulsion breaking chemicals
several operating and product quality problems in a refinery: are also used to break stabilized emulsions and to maximize
Desalter emulsion stabilization crude oil dehydration, thereby minimizing carryover of dissolved
Desalter water carryover and oil carryunder contaminants into the desalted crude oil stream.
Desalter capacity constraints
Desalter vessel and effluent water system scaling A Baker Petrolite scale inhibitor can be applied to prevent
Crude unit preheat exchanger and heater tube fouling deposition of any metal carbonates or sulfates in the desalter
FCCU catalyst deactivation effluent water removal system.
High heavy fuel oil metals and ash content
High fuel and anode grade coke metals and ash content
These problems can reduce the number of feedstock sourcing

options for refiners. Also, many refinery feedstocks with high
levels of contaminants are available at a discount, so increasing
the amount of these feedstocks in the crude blend can be
economically attractive.
Example EXCALIBUR Technology Application Treated crude oil to

hot preheat train
Crude Oil Desalter

Storage
Mix valve
Wash water
to desalter
Baker Petrolite emulsion
breaking chemical
Effluent water
to wastewater
Baker Petrolite treatment plant
EXCALIBUR additive
Baker Petrolite
scale inhibitor
2
EXCALIBUR technology results and benefits What benefits can EXCALIBUR contaminant removal
EXCALIBUR technology allows refiners to significantly improve technology provide for your refinery?
plant profitability by processing higher rates of lower cost, Call your Baker Hughes representative to see what benefits
opportunity crude oils while continuing to produce on- EXCALIBUR technology can provide for you! Your representative
specification coke and heavy fuel oils. Refiners can also maintain can arrange laboratory pre-screening tests on representative
target rates of reduced crudes to their resid FCCUs while crude blend samples to demonstrate the level of calcium, iron
processing high metals crudes. and other contaminant removal achievable in your crude unit.
The results of these screening tests, plus a thorough unit survey
These benefits are delivered with minimal capital expense, while can be used to develop an EXCALIBUR technology program for
maintaining stable desalter and wastewater plant operation your particular crude blends, desalting equipment and desalter
and performance, and with no contaminant metal scaling or operating environment.
fouling problems.
EXCALIBUR Iron Removal Data in a Commercial Application

For example, calcium removal efficiencies as high as 95% have 18
Crude oil iron content, parts per million

been achieved in units processing crude oils high in calcium 16
Raw crude Fe Desalted crude Fe
14
naphthenate content, such as Doba, Shengli and various North
12
Sea crudes. Crude oil iron removal efficiencies greater than 10
% Iron removal
70% have also been achieved in commercial applications of 8
EXCALIBUR technology. 6
85% 75% 71% 81%
4
2
By providing a lower, more stable pH in the crude unit desalters,
0
use of EXCALIBUR additives can also provide: Blend 1 Blend 2 Blend 3 Blend 4
Crude blends (North Sea, West Africa)
Better control of desalter emulsions
Improved desalter effluent water quality
Better wastewater treatment plant operation
Improved capability to handle feedstocks contaminated with
caustics and other alkaline materials, such as ammonia or amines
EXCALIBUR Calcium Removal Data, 15-18% Doba in Crude Blend

100 100 %
90 90 %
Calcium in crude oil, mg/L
80 80 %
Calcium removal %
70 Raw crude Ca removal % Desalted crude 70 %

60 60 %
50 50 %
40 40 %
30 30 %
20 20 %
10 10 %
0 0%
2-July 7-July 12-July 17-July 22-July 27-July 1-Aug 6Aug 11-Aug 16-Aug
Date
3
EXCALIBUR is a trademark of Baker Hughes Incorporated.
all liabilities for the use or reliance on such information. BPC SHALL NOT BE LIABLE FOR ANY INDIRECT, SPECIAL, PUNITIVE, EXEMPLARY OR CON-
SEQUENTIAL DAMAGES OR LOSSES FROMANY CAUSE WHATSOEVER INCLUDING BUT NOT LIMITED TO ITS NEGLIGENCE.
www.bakerhughes.com/EXCALIBUR 2010 Baker Hughes Incorporated. All rights reserved. 30001t

Refinery Wastewater Treatment
Increasing Plant Reliability

Increase Plant Reliability with Dynamic Wastewater Treatment
What would it mean to your bottom line if you could improve plant reliability by making
your wastewater facility more efficient?
Todays increasingly complex crude oil blends and higher throughput rates are creating
an associated increase in contaminants and solids concentrations, adding new stresses
to aging wastewater treatment plants worldwide.
Increased concentrations of contaminants, such as oil-entrained solids, phenols,

sulfides and heavy metals are creating new operational bottlenecks. Many who could
achieve adequate liquids/solids separation five years ago are now threatened by
increased environmental regulatory fines, elevated costs from reduced wastewater
system performance, depressed revenue from lower plant throughput or even refinery
shut-downs.
Baker Hughes wastewater treatment experts, focused on the hydrocarbon-processing

industry, will help to keep you on track. Well not only optimize your wastewater
plants efficiency, well treat process effluent before it gets to the wastewater treat-
ment plant to derail potential upsets.
Through our predictive and proactive treatment approaches, expert equipment and
operational recommendations, you will increase your refinerys reliability by:
! removing profit-slashing wastewater treatment plant bottlenecks.

! preventing costly wastewater treatment plant upsets.
! achieving or maintaining environmental compliance.
Remove Profit-Slashing Wastewater Treatment Plant Bottlenecks
Many sources of organic and inorganic contaminants end up at the wastewater treatment plant: cooling tower blow-down; storm
water; and process stream effluent from coker blow-down, benzene removal units and wet-gas scrubbers, to name a few. If too many
oil-entrained solids from desalter effluent enter the wastewater treatment facility, effective oil and water separation processes cannot keep
up with the required pace. This bottleneck results in the wastewater treatment plant dictating throughput and profits. Baker Hughes
applies specific knowledge, experience and carefully considered treatment approaches so bottlenecks are either quickly eliminated
or avoided altogether.
Case History:
A large, independent refiner processing heavy Canadian crude oil was
challenged by insufficient primary treatment at their wastewater treatment
plant (WWTP). High oily water concentrations were entering the aeration
basin, where effluent ammonia levels, targeted for 1 ppm, had spiked to
23 ppm. Desalter wash-water rates and mix-valve settings were altered to
reduce oily water concentrations. This operational constraint quickly tran-
sitioned into costly crude unit reliability problems. To remove this WWTP
bottleneck, incumbent chemical program changes were made, especially at
the Dissolved Air Flotation (DAF) unit. New chemical treatment designed
specifically for DAF solids and oil removal immediately helped stabilize
aeration basin microbial activity. Ammonia concentration dropped to
below 1 ppm. Previous record-time ammonia breakthrough was 245 days.
With now well over 365 days since treatment began, there have been no
ammonia-level breakthroughs.
Prevent Costly Upsets at the Wastewater Treatment Plant

Every process crude oil slate change contributes a different set of con-
taminants and solids to your wastewater treatment facility. The key is to
be able to predict what impacts these changes may have on your waste-
water operations so you can prevent potential performance disruption. By
understanding and working with the various process streams, Baker Hughes
can troubleshoot existing equipment configurations, make operational
suggestions and deploy chemical treatment programs to help you achieve
maximum wastewater system performance.
Predictive Study:
A global, fully integrated energy company was having problems at one of its US
refineries with its crude oil blend iron concentrations. Baker Hughes developed
an innovative chemical solution to remove iron in the desalter process. A key
issue was whether or not this new chemistry, as part of desalter effluent, would
impair microbial activity at the WWTP. A respirometry laboratory study was
performed to help predict any negative impacts. Oxygen uptake was measured
by subjecting microbial samples, taken from the WWTP, to various
field-simulated conditions. Results showed no negative impact or reduction in
oxygen uptake. This predictive, screening study allowed the customer to move
forward with a field trial to resolve iron-concentration challenges in their crude
oil blends.
Achieve or Maintain Environmental Compliance

A wastewater treatment plant operates as a process unit. It is basically a
once-through application with fluctuating inputs. In order to achieve and then
maintain environmental compliance, you need rigorous monitoring and control.
You also need system flexibility that can respond effectively to changing
conditions. We offer dynamic wastewater treatment programs and expertise
that can minimize your environmental and liability risk, maximize system
performance and return cleaner water to the environment cost-effectively.
Case History:
Baker Hughes was asked to design a wastewater treatment program for a
large, independent refiner during a shut-down. During a previous turnaround,
the WWTP experienced significant oily solids overloading, resulting in effluent
permit violations and fines, and added operational and disposal costs to divert
wastewater to storage tanks. For this shut-down, Baker Hughes focused on two
waste streams, the API separator and the WWTP effluent. API effluent was
mixed with other difficult-to-treat water streams coming to the WWTP from the
turnaround. Therefore, API effluent had to be well below plant effluent targets
to ensure overall HSE compliance. Baker Hughes used a three-part treatment
regime consisting of: lab simulations to anticipate oil and grease concentrations
to determine the best chemical treatment ahead of time; equipment recommendations to optimize oil and grease removal; and 24/7
manpower coverage during the five-day turnaround to ensure optimum results. Oil and grease concentrations remained below the 100-
ppm target the entire time. The refiner saved from USD 300,000 to 500,000 in fines and anticipated wastewater re-processing charges.
From the API separator to final filtering and dewatering, we have the programs and expertise to help your wastewater treatment plant
operate the way it was designed, no matter how challenging the crude oil slate or throughput objective. Well also treat process unit
effluent before it becomes a problem at the WWTP.
Look forward to making a difference to your bottom line through increased plant reliability. Count on our dynamic team and wastewater
treatment initiatives to make your wastewater facility more efficient. Call Baker Hughes today.
12645 West Airport Boulevard
Houston, Texas 77478
U.S.A.
Tel +1 800 231 3606
Fax +1 281 275 7395
DEMANDTRAC, LEAKGUARD, BIOKLENZ,

SPECTRAFLOC, CHEMCROBE and GUARDION
are trademarks of Baker Hughes Incorporated.
Baker Petrolite Corporation and its affi liates (BPC)
disclaim all warranties or representations express
or implied, including any implied warranties of
merchantability or fi tness for a particular purpose
or to the accuracy, correctness or completeness
of such information herein or that reliance on
such information will accomplish any particular
result. All such information is furnished as is
and by using such information the user is assum- ISO 14001 ISO 9001
ing all liabilities for the use or reliance on such
information. BPC SHALL NOT BE LIABLE FOR ANY
INDIRECT, SPECIAL, PUNITIVE, EXEMPLARY OR
CONSEQUENTIAL DAMAGES OR LOSSES FROM
ANY CAUSE WHATSOEVER INCLUDING BUT NOT
LIMITED TO ITS NEGLIGENCE.
www.bakerhughes.com/WATERMANAGEMENT 2009 Baker Hughes Incorporated. All Rights Reserved. 27413 PGI 500 12/09
Wastewater Plant Treatment Areas within a Typical Refinery

Slop Oil
Flotation Demulsifiers
Flocculants (IAF, DAF)
Metals
Nutrients Antifoams Removal
Biological Agents
(Ponds, ASU)
Secondary
Clarifiers
Free Oil Settling

Separators Primary Aids
Emulsion
(CPI, API) Breakers Clarifiers Odor Microbial
Control Maintenance
Agents Aids
Tertiary /
Waste Effluent
Thickeners
Charge
Neutralizers Dewatering Dewatering
Hydrocarbon (Centrifuges) Aids
Oily Water
Water Thickening
Biological Solids
Program Application
Aids
2009 Baker Hughes Incorporated. All Rights Reserved. 27487 (12/09) PGI 500
Examples of Refinery Process Water Streams that Challenge Wastewater

Treatment Plants
Desalters Coker Blowdown Emulsion
Breakers
Water
Clarifiers
Water
Clarifiers
Water
Clarifiers
Emulsion
Stripping Breakers
(Benzene, H 2 S, NH 3 )
Wet Gas Clarifiers/PTU
Scrubber
Scale
Inhibitors
Settling
Aids
Emulsion Antifoulants
Breakers
Water
Water Settling Clarifiers
Unit Influent
Clarifiers Aids WWTP
Unit Water Effluent
Program Application
2009 Baker Hughes Incorporated. All Rights Reserved. 27487 (12/09) PGI 500
Conquer Heavy Canadian

Crude Oil Challenges
Improve profitability, reduce operating risk
Experience Required Defining the Challenges
How has Baker Hughes earned a majority share of specialty Typical desalter problems include effluent water with high oil
chemical programs in refinery crude units processing heavy and solids content, poor desalting efficiency, stable emulsions,
Canadian feedstocks? and basic sediment and water (BS&W) carryover into desalted
crude. Poor desalter effluent water quality can have a
Proven solutions for heavy Canadian crude processing significant impact on wastewater treatment plant operation
Industry leading desalter optimization and XERIC heavy and performance.
oil treatment program
Wastewater treatment plant optimization and XERIC The same feedstocks that cause desalter problems can also
desalter brine treatment aids cause crude unit distillation column overhead corrosion
SMARTGUARD naphthenic acid corrosion assessment problems, due to the higher chloride loadings caused by lower
and control technologies desalter performance.
TOPGUARD overhead system corrosion assessment and
control technologies Some oil sands deposits may also be high in TAN, which can
Crude oil blend stability-monitoring protocols using cause high temperature naphthenic acid corrosion problems.
proprietary ASIT technology High TAN feedstocks can also contribute to crude unit
Crude preheat exchanger and process heater fouling distillation tower overhead system corrosion problems, due
control programs to the generation of lower molecular weight organic acids.
Background The high solids contents and unstable asphaltenes in these

Higher volumes of heavy conventional and bitumen-based crudes can increase crude preheat exchanger and atmospheric
crudes from western Canada are becoming available to more and vacuum column heater fouling. Increased heater fouling
North American refineries, as production and transportation can also be experienced in downstream delayed coker units.
infrastructure is developed. However, this categorys wide
variety of feedstocks exhibit fundamentally different Assess the risks, plan your strategy
characteristics, and many refiners may not yet recognize the Successful processing can be achieved with an informed
complex processing challenges they can pose in terms of assessment of potential risks, and utilization of a combination of
desalting, corrosion, fouling, and wastewater operations. treatment best practices, which have already been developed
and proven on these feedstocks. Baker Hughes is the industry
leader in developing predictive tools and innovative specialty
chemical programs for processing heavy Canadian crudes!
Let Baker Hughes help develop your strategy

Planning ahead will pay major dividends to refiners who want
to maintain profitability by processing these crudes efficiently
from the outset. Effective crude unit desalting, corrosion
and fouling control programs, plus wastewater treatment
technologies, appropriately applied, will give processors
considerable power to increase feedstock flexibility without
disrupting plant operations.
With Baker Hughes as a partner, refiners can address these

complex challenges with already proven best practices, which
Asphaltenes suspended in desalter effluent water, heavy will improve refinery profitability and help maintain plant
Canadian crude processing integrity, reliability, and environmental compliance.
2
Wastewater Treatment Plant Dissolved Oxygen
40
Before Baker Hughes After Baker Hughes
35 Untreated - Lower TAN 7.0
Untreated - Higher TAN 6.0 Dissolved O2

30
Treated - Higher TAN Competitive Average
Dissolved Oxygen, ppm

5.0
Corrosion Index
25
Baker Hughes Average
20 4.0
15 Upper 3.0
Target
10 2.0
5 1.0
0 0.0
Preheat Train Distillate PA AGO PA AGO FV Reduced Crude Daily
SMARTGUARD corrosion inhibitor technology controls high temperature naphthenic WWTP dissolved oxygen during transition to Baker Hughes desalter treatment
acid corrosion. program on a heavy Canadian crude unit
3
XERIC, SMARTGUARD, TOPGUARD, and ASIT are trademarks of Baker Hughes Incorporated.
all liabilities for the use or reliance on such information. BPC SHALL NOT BE LIABLE FOR ANY INDIRECT, SPECIAL, PUNITIVE, EXEMPLARY OR
CONSEQUENTIAL DAMAGES OR LOSSES FROM ANY CAUSE WHATSOEVER INCLUDING BUT NOT LIMITED TO ITS NEGLIGENCE.
www.bakerhughes.com/OPPSCRUDES 2010 Baker Hughes Incorporated. All rights reserved. 29983T

Baker Hughes
Planning Ahead for Effective

Canadian Crude Processing
24699.White Paper template.indd 1 2/17/2009 11:45:19 AM

Baker Hughes
Executive Brief
Heavy conventional and bitumen-based crudes from Canada represent a significant volume increase in
feedstocks for North American refineries, as production and transportation infrastructure is developed. Some
shipments of these feedstocks have already been processed in Gulf Coast refineries. But aside from exist-
ing heavy Canadian crude processors, many refiners may not yet recognize the full scope of these feedstocks
or the complex processing challenges they pose in terms of desalting, corrosion, fouling and wastewater
operations. This paper, based on extensive Baker Petrolite experience, suggests that successful processing
will depend on implementing a combination of treatment best practices which have already been proven
on these feedstocks.
The Coming Boom in Production and Processing Market Demand for Western Canadian Crude Oil -
Actual 2007 vs 2015 Potential
Refineries in the US Midwest, the Great Lakes, the
Rockies and Canada already process a variety of
(613)
crude feedstocks from Alberta and Saskatchewan
(often denoted as Western Canadian Sedimentary Basin, or 720
WCSB, crudes). These include conventional heavy Canadian

578
crudes (e.g., Lloydminster, Cold Lake) and synthetic crudes
(385)
from the oil sands bitumen upgraders in Alberta.
371
PADD IV (3,622)
More recently, diluted bitumens (dilbit) from in-situ steam- PADD V (598) 247
2,378
assisted gravity drainage or cyclic steam stimulation (2,646) 286
production, and combinations of bitumens and synthetic ?

280 PADD II
122 1,098
crudes (synbit and syndilbit) are also being produced.
PADD I
(7,990)
(1,627)
Exceptional growth in these feed streams is antipated,world PADD III ?
63
oil prices notwithstanding. Production and transportation 59
71
strategies are driven by producers need for expanded
export capacity, economic sources of diluents, and US
refineries need to maintain diversified sources of supply.1 (Total 2008 refining capacity All crude)
In one Moderate Growth Case, total WCSB oil produc- 2015

Potential demand for
Western Canadian crude
Thousand Barrels Per Day
tion is projected to increase to almost 4.4 MMBPD in 2020 2007 Actual demand for
from about 2.4 MMBPD in 2008.2 Also, current and Western Canadian crude
future pipeline projects will allow this increased WCSB

production to reach the US Gulf Coast, the Atlantic Coast,
Southern Illinois/Ohio, Oklahoma/Kansas and ports in CAPP June 2008 Crude Oil Forecast,
Markets & Pipeline Expansions report
British Columbia.
2 2009 Baker Hughes Incorporated. All rights reserved. ASIT and SMARTGUARD are trademarks of Baker Hughes Incorporated.

Baker Hughes
This categorys wide variety of feedstocks exhibits funda- Several refineries have already initiated or announced
mentally different characteristics. In fact, the composition projects designed to increase WCSB processing capa-
and contaminant levels of bitumen-derived crudes does not bility but understanding which refineries are the best
make them an easy replacement for conventional crudes, candidates to receive these feedstocks is important. The
especially since most existing refineries have limited specific processing challenges posed by these feedstocks
capacity to accept poorer quality feedstocks.3 depend on the physical and chemical characteristics of the
feedstocks, their behavior when blended with other crudes,
The impacts of these streams on profitable refinery opera- and the configurations and capabilities of the refineries
tions will be significant. However, there is still considerable process units.4
industry uncertainty about exactly when and how these
feedstocks will find their way into the US and overseas WCSB Crudes: Direct Processing Challenges
markets.
To start with, Athabasca bitumens are high in sulfur,
nitrogen, CCR, metals and TAN.
Understanding the New Feedstreams
In the future, actual WCSB uptake will depend on many
Athabasca Arab
factors. Key variables include the rate of WCSB production Bitumen Heavy
increases, capacity and actual completion dates of pipeline
projects, competing crude pricing, diluent availability and API 8.0 27.4
pipeline tariffs imposed.
Gravity 1.015 0.891
Market acceptance of Canadian feedstocks is a function of
pricing, chemical and physical properties, and the speed Sulfur, wt% 4.9 2.8
and extent of refinery project investments to allow process-
Nitrogen, wt% 4000 1600
ing of these feedstocks. Most heavy, sour WCSB feedstocks
will be shipped to refineries already configured for these CCR, wt% 13.6 6.8
types of crudes, i.e., those with sour coking configurations.
Most of these facilities are on the Gulf Coast, which are Nickel, ppm 92 16
already processing heavy, sour and high-total acid number
(TAN) crudes from Venezuela, Brazil and Mexico. Vanadium, ppm 226 55
Asphaltenes, wt% 18.1 6.2

Most lighter, lower-sulfur feedstocks (synthetic crudes)
are expected to be shipped to the low- to medium-sulfur
refineries in the Mid-Continent, Midwest and Great Lakes
regions of the US. This assay suggests that heavy, sour, high-TAN diluted
bitumens and blends will present several processing prob-
Upon completion of pipeline projects to coastal British lems for refiners. Synthetic crudes tend to have high heavy
Colombia, higher volumes of WCSB crudes will be available vacuum gas oil yields; lighter distillates are high in aromat-
for the West Coast market. Heavy, sour feedstocks should ics, and produce straight run diesels with very low cetane
be processed at the refineries in California already config- numbers. The table below summarizes many of the chief
ured for heavy, sour, high-TAN crudes. Other WCSB grades considerations for each major set of feedstocks.
would be suitable for the low- to medium-sulfur crude units
in California and Puget Sound refineries.

Baker Hughes
Refinery Constraints and Modifications for Oil Sands Crude Processsing
Product Constraint(1) Modification

DilBit - % resid - Larger cokers, ancillaries
- % sulfur - More HDS, recovery (2)
- TAN (3) - Metallurgy
- Asphalt (4) - Blending
SynBit - % VGO - Larger FCC, ancillaries

- % sulfur - More HDS, recovery (2)
- TAN (3) - Metallurgy
- Asphalt (4) - Blending
SCO (Sweet, bottomless) - % VGO - Hydrocracking
- % Distillate - Hydrocracking
- Diesel aromatics - Aromatics saturation
Notes: (1) Refinery constraints may also include product blending and environmental emissions.
(2) Refineries must reduce the sulfur content of gasoline and diesel.
(3) High TAN for Athabasca, not Cold Lake.
(4) Asphalt from mined bitumen may be poor quality. SynBit asphalt quality uncertain.
Purvin & Gertz, Inc.

NPRA 2006 Annual Meeting
The most challenging WCSB feedstocks, from the stand- The same feedstocks that cause desalter problems can
point of crude unit operations, are the heavier crudes that also cause crude unit distillation column overhead corro-
contain high levels of filterable solids, unstable asphaltenes sion problems, due to the higher chloride loadings caused
or difficult-to-remove chloride salts due to thermal stressing by lower desalter performance.
of the hydrocarbon during production. Since the filterable
solids, asphaltenes and salts are concentrated in bottoms Thermally produced bitumens from the Athabasca oil sands
fractions, the more difficult feedstocks tend to be: deposits may also be high-TAN, which can cause upgrader
or refinery high temperature naphthenic acid corrosion prob-
Heavy, conventionally produced crude oils lems in the crude unit atmospheric and vacuum distillation
systems.5 They can also contribute to crude unit distillation
Thermally-produced oil sands bitumens diluted with
tower overhead corrosion problems, as high TANs promote
lighter hydrocarbons or synthetic crudes to meet pipeline
salt hydrolysis to hydrogen chloride, and can thermally de-
gravity and viscosity specifications.
grade to form lower molecular weight organic acids. These
acids can increase both unit neutralizer demand and over-
Most heavy feedstocks exported from West-
head system corrosion potential.
ern Canada range from 19-22 API, which creates
additional desalter challenges due to resulting high-
The high solids contents and unstable asphaltenes in these
er crude blend viscosities. However, there are also
crudes can increase crude preheat exchanger and atmo-
lower-density crudes coming from this region that
spheric and vacuum column heater fouling. Increased heat-
can be problematic, owing to their high filterable solids
er fouling can also be experienced in downstream delayed
contents.
coker units.
Typical desalter problems include effluent water with
Most 100% synthetic crudes will cause minimal crude unit
high oil and solids content (and subsequent prob-
processing problems, as they do not contain any uncon-
lems at the wastewater treating plant), poor desalt-
verted bottoms (bitumen) fractions. Their lower sulfur, nitro-
ing efficiency, uncontrollable emulsions and basic
gen and TAN contents also prevent most downstream unit
sediment and water (BS&W) carryover into desalted crude
problems.
effective wastewater treatment is another key factor in solv-
ing the complex treatment challenge.

Baker Hughes
Complex Challenges Demand Inclusive Solutions

It is suggested that the complicated challenges of treating oil sands-derived crudes are most effectively approached using
a best-practices combination of technical offerings and technical capabilities. These practices may already exist in-house.
However, the relatively recent advent of WCSB feedstocks may mean that such expertise may only be available from a
vendor-partner.
Based on long experience gained in WCSB and opportunity crude-processing refineries4, it is possible to plan ahead for
successful (efficient, cost-effective) processing treatments. Planning ahead ought to encompass:
Desalting. These Western Canadian feedstocks put a high demand on refinery crude oil desalting capabilities. Opti-
mizing these units for WCSB crudes involves effective desalting chemical combinations, including oil-soluble emulsion
breaking chemicals, asphaltene stabilizers, solids wetting agents and polymers.
Wastewater Treatment. Treatment chemicals and application methods are used to minimize the impact of high
solids-content desalter effluent water on wastewater treatment plants. Reducing wastewater plant upsets and improv-
ing performance are key factors in this regime.
Naphthenic Acid Corrosion (NAC) Control. Due to the high TAN levels of Athabasca bitumens, NAC control and
monitoring technologies can be usefully implemented where blended crude TAN is high enough and suitable alloy is
not in place.
Crude Unit Overhead Condensing System Corrosion Control. Higher loadings of corrosive materials in Western
Canadian crudes may also increase crude unit distillation tower and overhead system corrosion. Appropriate modeling
and chemical program technologies can mitigate increased corrosion risk.
Crude Oil Pretreatment. Some heavy Canadian and synthetic crudes are incompatible with other hydrocarbon
streams and may cause storage tank sludging or crude preheat exchanger fouling. Pretreating the WCSB feedstocks
as the crudes enter the refinery can minimize impacts.
Refinery Process Fouling Control. High solids contents and unstable asphaltenes in these crudes, along with their
atmospheric and vacuum resids, may cause accelerated fouling in crude preheat exchangers as well as coking in
atmospheric, vacuum and coker heaters. Crude preheat exchanger fouling control technologies and heater fouling
control applications are effective mitigation options.
In support of the refinery/vendor-partner experience, Baker Petrolite has demonstrated that the role of laboratory and
computer modeling in planning for WCSB processing is of significant assistance. For example:
ASIT Asphaltene Stability Index Testing helps parameterize the asphaltene stability of the feedstock and offers
qualitative information on prospective fouling rates.5
The Electrostatic Desalting Dehydration Apparatus, used to simulate crude oil desalting systems, has been success-
fully predicting field desalter and emulsion breaking chemical additive performance for more than 50 years. It contin-
ues to be an effective modeling tool.
SMARTGUARD predictive modeling helps recognize where in a given processing circuit the potential for NAC is
greatest, to more precisely identify high-risk areas. 6
Ionic modeling enables the prompt evaluation of and response to changes in overhead corrosion risk as refinery
conditions including the composition of the feedstocks change.7

Baker Hughes
Conclusion: Opportunities Enhanced with Best Practices

The production volume of heavy WCSB feedstocks is increasing. Its growing availability as well as expansion of the pipeline
transportation network will increase the number of refineries which can benefit from processing them. In effect, these feed-
stocks represent the perfect opportunity crudes.
There is already significant experience with such opportunity crudes not only in the Northern US and Canada but in the
Gulf Coast, too (WCSB feedstocks are expected to replace heavy, sour Venezuelan crudes in this region). Given appropri-
ate pipeline system new-builds and expansions, in fact, there is hardly any area of North America which will not be able to
accept WCSB crudes for processing.8
All Proposed WCSB Pipeline Projects
32
30
31 Edmonton
1
2
27 5B
Hardisty
28
Burnaby
Trans
5A
Anacortes
Mountain
3
26
Express 36 33
25 35
Montral
29 Superior
12
6 8
St. Paul Enbridge 11 Portland

7A
Platte Sarnia
Buffalo
Salt Lake City Guernsey
9 10 13
Chicago 14
15 Toledo
24 7B 16
23 Lima
17 Philadelphia
4
Wood Patoka
18 River
22
Cushing Mid Valley
21
34
Capline
20
19
Houston
St. James
CAPP June 2008 Crude Oil Forecast,

Markets & Pipeline Expansions report
Planning ahead will pay major dividends to refiners who want to maintain profitability by processing WCSB crudes efficiently
from the outset. Effective desalting, corrosion and fouling control programs, appropriately applied, will give processors
considerable power to increase feedstock flexibility without disrupting plant operations.
Addressing these challenges with already proven best practices will improve productivity, and help maintain refinery
reliability and environmental compliance.

Baker Hughes
References About Baker Hughes

1. Interim Report to Shareholders, 3rd Quarter 2008 Baker Hughes provides worldwide oil and natural gas
MD&A, Enbridge Inc. industry products and services for drilling, formation
evaluation, completion and production. We create value
2. CAPPs Crude Oil Forecast, December 2008 for oil and gas producers by providing advanced, reliable
Interim Update, December 11, 2008. technology to find, develop, produce and manage oil and
gas reservoirs. We also provide reservoir engineering
3. G
ary R Brierley, Visnja A Gembicki and Tim M Cow- and other consulting services. Baker Hughes operates in
an, Changing Refinery Configuration for Heavy and over 90 countries serving independent, international and
Synthetic Crude Processing, UOP LLC, Des Plaines, national oil companies.
IL 2006, NPRA Annual Meeting, AM-06-16.
Baker Petrolite, a Baker Hughes Company, is a world leader
4. L arry N Kremer and Scott A Bieber, Strategies for in providing chemical services, engineering and techno-
Desalting Heavy Western Canadian Feedstocks, Baker logical solutions to the global hydrocarbon recovery and
Petrolite, NPRA Annual Meeting, AM-08-36. processing industries. With significant core competen-
cies in multi-faceted treatment services and systems for
5. J oseph L Stark, Joe Nguyen and Larry N hydrocarbon processing, Baker Petrolite delivers value to
Kremer, Crude Stability as Related to Desalter customers in oil and gas production, pipeline transporta-
Upsets, Baker Petrolite, 2002 AIChE Spring National tion, refining and petrochemical production.
Meeting, New Orleans, LA, March 2002.
6. R ui De Palma, Smart Protection, Baker Petrolite,

Hydrocarbon Processing, March 2007.
7. R andy Rechtien, Crude unit corrosion-control

programme, Baker Petrolite, Petroleum
Technology Quarterly, Q4 2007.
8. Crude Oil Forecasts, Markets and Pipeline

Expansions, Canadian Association of Petroleum
Producers, June 2008.

Baker Hughes
Contact
For more information
Scott A Bieber
scott.bieber@bakerpetrolite.com
Baker Petrolite
12645 West Airport Boulevard
Sugar Land, TX 77478 USA
PO Box 5050
Sugar Land, TX 77487-5050 USA
2009 Baker Hughes Incorporated. All rights reserved. ASIT and SMARTGUARD are trademarks of Baker Hughes Incorporated. PET-09-24699 (2/09)

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Fundamentals of Desalter Operation

Baltimore Marriott Waterfront Hotel

Baker Hughes Incorporated

How Does the Desalter Process Work?

Pipeline Crude Tank Farm

Typical Crude Oil Contaminants & Effects

Desalting Purpose and Benefits

Bottom Line Refineries Desalt to Decrease Operating and

A good desalting operation will reduce fouling potential by

Desalting Purpose and Benefits

MgCl2 + 2H2O Mg(OH)2 + 2HCl

CaCl2 + 2H2O Ca(OH)2 + 2HCl

HCl gas dissolves in condensing water to form highly

Overhead Vapor Condensing

Stainless Steel Distillation Tray

Refinery Corrosion Costs

50% of plant maintenance costs

Desalting is the 1st defense for

Poor desalting will impact refinery

Excess water in the desalted crude oil also requires more

A good desalting operation will reduce the impact of

Desalting Purpose and Benefits

Petreco Low Velocity Desalter

MIX VALVE WASH WATER

Optimum interface level: 6 (15 cm) above inlet

END VIEW TRANSFORMER

HOT CRUDE OUTLET

Optimum interface level: 6-12 (15-30 cm) below crude inlet

Cameron-Petreco Cylectric Desalter

Wash Water Optimum level: 12-24 (30-60 cm) below grids

BILECTRIC is a registered trademark of Cameron - Petreco

Fundamentals of Desalter Operation

Electrode position 290

Desalter Performance Expectations

Performance predicted for design conditions

Crude Gravity Oil Residence Water Res

Desalter Design & Capacity

Desalter Operating Variables

Desalter Wash Water: Injection Location

Normal injection is prior to mixing device

Wash Water Impact on % BS&W

20 min 1.2% 3.4% 4.5% 8.0%

30 min 1.7% 3.7% 5.5% 8.0%

Heavy Canadian crude oil

Best Practice Water Quality

Wash Water Source Concerns

Interface Level Settings

Determined by desalter design:

Petreco Low Velocity

Petreco Bilectric & Cylectric

Interface Level Monitoring

Use tryline or swing arm to establish level

Level Control Capacitance Probe

4TH & 5th Tricock -

Mix Valve Setting

% BS&W IN DESALTED CRUDE

INCREASING MIXING PRESSURE

Desalter Operational Variables

Crude Oil Typical

Characteristic Temperature Viscosity

Desalter Components - Mud Wash

Howe-Baker recommends mud washing a minimum of three minutes per day

Fundamentals of Desalter Operation