Corrosion Laboratory-slides show

Honeywell Corrosion Solutions
Igor Kosacki
Engineering Manager – Corrosion
Honeywell Process Solution
igor.kosacki@honeywell.com

2 Honeywell Confidential
• Corrosion: A critical issues for industry
• Honeywell Portfolio:
- Laboratory based experimental simulation / testing
- Real Time Modeling and Monitoring
- New materials for Oil & Gas
- Comprehensive, industry specific consulting solutions
• Synergistic offerings for Plant Safety across multiple industry verticals
• Honeywell Technology: key differentiator in an integrated solution
• Recap
Overview
Corrosion cost in US - 276B$/year

Corrosion Value…….in Industry
• Global process control industries spend an average of US $50 billion
a year on corrosion problems
• Honeywell proprietary on-line corrosion technology can reduce
corrosion costs to process control customers in the range of 20-40%
• Increases plant uptime and availability due to improved Reliability of
assets
• Reduction in maintenance costs
• Through integration with Experion PKS, operators can transform raw
corrosion monitoring data into high-value process knowledge.
• Significant reduction in inhibitor / chemical costs

Corrosion Management
• Conventional methods utilize
- inspection
- coupons
- corrosion is not quantified as it happens, it is found after
it happens
• New concept of corrosion monitoring in-situ and real time
- SmartCET
- surface imaging
- nanosensors
Weight Loss Coupons
-50
-40
-30
-20
-10
0
10
20
30
40
50
60
70
80
Y(µm)
0 50 100
X (µm)
5 µm5 µm5 µm
FeCO3
Fe3O4
Fe2O3
Metal surface imaging
SmartCET
Corrosion sensor
Corrosion a consequence of surface/interface chemistry / interactions

Honeywell Corrosion Solutions
• Unique Honeywell
IP - based
Software Models
• State of the Art
Laboratory to provide
advanced experimental
simulation
• Industry leading real time
monitoring technology
Core expertise areas with
substantive synergy

Honeywell Corrosion Solutions - Scope of Service
Honeywell Corrosion Solutions portfolio includes:
- corrosion prediction / management software
- corrosion monitoring technology
- laboratory services
- consulting services
Honeywell Corrosion Solutions provides:
- help customers appropriate materials of construction
- realize significant reductions in cost of corrosion management
- enhanced asset management
Client base includes:
- leading upstream/Downstream/Midstream operators in energy sector
- global materials and services suppliers
- some of the largest chemical/hydrocarbon processing, chemical,
petrochemical, pharmaceutical companies
shouldn’t do business without science and
shouldn’t do science without a business

Honeywell Corrosion Laboratory
Mission:
• Solving materials and corrosion problems for oil and gas industry
• Develop new experimental techniques - optical spectroscopy,
electrochemical methods, nanotechnology
• Close the gap in basic understanding of materials and provide basis
for new technologies - new materials and experimentation
• Create fundamentally new knowledge and necessary tools to develop
and optimize oil /gas production / transmission / refining
Current lab activities:
• over 30 concurrent projects related to corrosion ($50K - $2M)
• JIP - Joint Industry Projects
- NAP - Naphtenic Acid Corrosion
- CDU - Crude Distillation Unit
- H2S - Serviceability Limits (2015)
- CUI - Corrosion Under Insulation (2015)

Honeywell Corrosion Laboratory

Honeywell Corrosion Solutions - Laboratory Services
HCS operates from a new, purpose-built facility
• A fully-equipped $25M, 17,500 sqft (1625 m2) corrosion and
materials research and engineering laboratory specifically designed
for HPHT testing with H2S.
High-pressure, high-temperature vessels
Mechanical testing
Custom-built equipment
Electrochemical testing

Autoclave testing
Laboratory has many autoclaves
(C276 wetted parts) for mimic real
extreme conditions and testing
materials
• (1) 22L capacity, 5000psi/600F
• (3) 2.7L capacity, 20000psi/600F
• (8) 0.7L capacity, 10000psi/550F -
rotoclave
• (5) 1.5L capacity, electrochemical
tests opportunity

Corrosion tests under applied stress
Material compatibility:
• determined for cracking and
corrosion resistance to
relevant environments
• TM0177 methods used to
evaluate cracking resistance;
tensiles, C-rings, bent beams,
double cantilever beam
specimens
• coupons used to evaluate
general and localized corrosion
resistance

Stirred Autoclave Options
Rotating Shaft ASTM G170 Rotating Cage

Laboratory Services
• Standardized and Modified Testing per ISO, ASTM, NACE,
EFC, methodologies
• Custom testing based on client needs
• Upstream
• Downstream
• Corrosion Evaluations
• Environmental Cracking Evaluations
• Simulated Service Environments
- High Temperature, High Pressure
 Up to 1100 F, 20,000 psi
- Corrosive Media
 Simulated with NaCl, H2S, CO2, etc.
 Client supplied chemicals

Pine RCE Apparatus
• Ambient pressure
• 80°C maximum
temperature
• 20,000 rpm maximum
speed
• Runs with Gamry
Potentiostat
- LPR
- Potentiostatic/Galvanostatic
Polarization
- CPP
- EIS

Electrochemical techniques in corrosion tests
Our Corrosion Laboratory provides:
• corrosion tests under high pressure, high temperature and different
ambient atmospheres - CO2, H2S, H2, H2O, O2
• corrosion rates determination
• materials selection and evaluation
• life prediction of components and structures
Electrochemical tests used
in our laboratory:
• Electrical Resistance
• Linear Polarization Resistance
• Electrochemical Cyclic
• Potentiodynamic Polarization
• Potentiostatic Polarization
• Electrochemical Noise
• Electrochemical Impedance
Spectroscopy

Linear Polarization Resistance (LPR)
• technique used to determine polarization resistance (Rp) and
corrosion rate
• Rp= E/I = B/icorr where B is Stern-Geary constant
• corrosion rate , CR can be calculated from relationship:
heat
bandCE WE RE
CR: corrosion rate in mpy
W: weight of metal
A: area of metal
D: density of metal

Electrochemical Cyclic Potentiodynamic Polarization
Electrochemical information:
• study of passive behavior
• evaluate localized corrosion
resistance of metal
• pitting potential (Ep)
• repassivation potential (Erp)
• passivation current (ipass)
• measure corrosion rate
OCP
Time
E 15-Cr SS in CO2 purged 100k ppm
Cl- brine solution containing acetate
or bicarbonate buffer (pH 4.5) at 25C
Pitting corrosion

Procedure:
• measure OCP of specimens
• apply a constant potential for ca. 1h
• monitor current at hold OCP
Electrochemical information:
• qualitative evaluation of
pitting resistance
OCP
Time
OCP+50mV
1 hour
E
10
-7
10
-6
10
-5
0 500 1000 1500 2000 2500 3000 3500 4000
CurrentDensity(A/cm
2
) Time (s)
11459-2F in ENV#2 @ 75 F
10K ppm Cl + 1.5 psi H
2
S
pH 3.5
hold at 50 mV OCP
(-266 mV Ag/AgCl)
Pitting
initiate
2.4 mil deep
longitudinal pitt
Potentiostatic Polarization

Electrochemical Noise Method (ENM)
• ENM simultaneously
measures fluctuation of
currents and potentials
that are related to kinetic
of corrosion reactions at
surface
• Monitor current between
two identical specimens
using a ZRA
Pitting
Passivation

Electrochemical Impedance Spectroscopy (EIS)
tUtU o  sin)(
)sin()(  tItI o 
Using the combinations of Rx and Rc= (iC)-1 elements, we can
model specimen response
1xx CR
Z’’
Z’
Rx
Rx
Cx
I(t)
U(t)
AC - 10-3 – 107Hz
Impedance Spectroscopy useful
to determine:
• material resistance, capacitance,
dielectric constant
• separate the response with
different relaxation times - bulk,
electrode and interfacial properties
• monitor the interaction between
material and ambient atmosphere
- O2, H2, H2O, H2S, CO2
500 1000 1500 2000
Sc:ZrO2
GB
Z''(ohms)
Z' (ohms)
electrodebulk
T = 700C
R1
C1
R2
C2
W
 sincos'''
iZiZZZ
)(
)(
)(
tI
tU
Z 

Corrosion observation of X65 pipeline steel
Three layer of thin film formed at the
metal surface after 25 days of exposure
Impedance Spectroscopy applications in corrosion study:
• corrosion mechanism - metal dissolution and passive film
formation mechanism
• measure corrosion rate of metal
• hydrogen permeation in metals
• evaluate corrosion inhibitor performance
• quantitatively assess coating performance

Localized Electrochemical Impedance Spectroscopy
• system allows spatially resolved impedance
measurements to be made with scanning
probe technique
• small electrochemical probe is scanned close
to the surface, measuring the local current in
the electrolyte
• useful technique for monitoring the time
dependent processes - corrosion observation,
coatings testing, material degradation, surface
reactions
Localized impedance map
of intact coating on mild steel
with sub-film chloride
contamination.
Next Generation of Surface Imaging Technique

0.0 5.0x10
4
1.0x10
5
1.5x10
5
2.0x10
5
2.5x10
5
3.0x10
5
 = 6.5*10
3
S/cm
 = 2.5S/cm
10%H2
O2
R = 52.4
R = 0.02
4 - probe meas.
I = 1.05mA
T = 950
o
C
72%NiO-CeO2
cermet
10
-1
10
-3
10
-2
10
-4
10
-5
Voltage-U(V)
Time - t (seconds)

 OHOOHV x
oo 22
OHNiHNiO 22 
eOHOgH x
o  .
2 )(2/1
Material interaction with ambient atmosphere
 = 2.6 10
3
S/cm
 = 2.8 10
3
S/cm
U/t = 9.1x10
-11
V/s
wet 0.9N2
+0.1H2
I = 0.01A
T = 950
o
C
72%NiO-CeO2
cermet
0.0 5.0x10
4
1.0x10
5
1.5x10
5
2.0x10
5
2.5x10
5
3.0x10
5
3.0x10
-4
4.0x10
-4
5.0x10
-4
6.0x10
-4
7.0x10
-4
8.0x10
-4
Voltage-U(V)
Time- t (seconds)
Impedance Spectroscopy
for monitoring materials and
processes:
• reduction of NiO to Ni
• materials stability in water
• containing atmosphere
inout
NiO-CeO2 composite Ni-CeO2 composite

0 100000 200000 300000 400000
3x10-4
4x10-4
5x10-4
6x10-4
7x10-4
8x10-4
dry (0.9N2+0.1H2)=>dry (0.9N2+0.1H2+30ppmH2S)
I = 10mA
T = 950o
C
72%NiO-CeO2 cermet
Voltage-U(V)
Time - t (seconds)
=2 103
S/cm
=2.5 103
S/cm
0.9N2+0.1H2
The development of materials
with tolerance to sulfur is the prime goal
for new composites for oil and gas
Ni reacts with sulfur forming
nonconductive Ni3S2. CeO2 can trap
sulfur when it is presented in the oil or
gas in small concentration.
0 50000 100000 150000
0
1
2
3
4
5
6
Time - t (seconds)
 = 2.9 10
3
S/cmR = 0.04
dry 0.1H2
=> wet (0.1H2
+0.1%H2
S)
I = 100mA
T = 950
o
C
72%NiO-CeO2
cermet
Voltage-U(V)
Sulfur poisoning of Ni-CeO2 composite
2232 223 HSNiSHNi 
22222 HSOCeSHCeO 

Experimental techniques for materials characterization
Access to research facility at UHD and Rice
University – collaboration with academia
• Scanning Electron Microscopy - EDS
• Raman Spectroscopy
• Atomic Force Microscopy - AFM
• X-ray Diffraction - XRD
• Thermogravimetry and Mass Spectroscopy
• Optical Spectroscopy

Process monitoring tools:
• Corrosion models
• Electrochemical sensors - SmartCET
• Optical spectroscopy and surface imaging

Process monitoring techniques
• Reservoir monitoring is a significant process issue for oil and gas
industry - exploration, production, reservoir management and safety
• Novel techniques to analyze in situ and real time the reservoir
chemistry are needed - monitor chemicals in EOR process, detect
hydrocarbons in reservoir fluids and gasses - H2S, CO2
• Proposed solution: develop “portable” Raman system integrated
with fiber optics for field operation
- key component of smart fields
- effective method for qualitative and quantitative analysis of solids,
fluids and gasses
- possible remote monitoring
- collected data can be used in reservoir modeling
• Important and possible applications in corrosion
• Challenges, opportunities

Integrated Real - Time Solution
• Real Time Models and Monitoring Systems
Assists in identification of critical processes that may cause damage
Enables problem resolution through Boundary and Deviation
management
Corrosion quantified as it happens, providing operator / management
ability to react quickly and appropriately
Ability to see ahead facilitates optimized functioning

29 Honeywell Confidential29
Delivering Operational Excellence
Human
Error
40%
Equipme
nt failure
40%
Other
20%
Causes of Process Upsets
76%
10%
5%
5% 2% 2%
Causes of Equipment Failure
Operating out of range
Improper design
Improper maintenance
No defect found
Improper installation
Improper material
Source: ASM Consortium
• ~80% of process upsets
attributed to equipment
failure / human error
• ~76% of equipment failure
related to managing
operations outside of
“boundaries”
PROBLEM: Operating Out of Range contributes to incidents

Integrated Solution for Asset Integrity
Process
Data
Risk Based Inspection
Manual Data
Reliability Centred Maint
Safeguarding
(Pressure Relief &
Level Limits)
Safety Systems
(Trip Settings)
HazOp / PHA Pressure
Temperature
Flow
Corrosion
Vibration
Current
Acceleration
pH
Limits
Real-Time
Corrosion
Operator Rounds &
Field Inspections
Deviation
Reporting
Console Operator
Alarms &
Alerts
Limit
Monitoring
Target Lo
Target Hi
Standard Lo
Standard Hi
Critical Lo
Critical Hi
Management
Reporting
Sources of Limits
Know Your Limits - Stay Within Them - All the Time!

Corrosion Value Proposal: Why should You Care?
Opportunity Value
Failure prevention/risk
reduction
$10 to $35 million (CDU overhead)
$60 million each (sour water system)
Reduce lost production ~$100,000 per day
Steel/alloy upgrade $1 to $10 million
Prioritize inspections $1M+ to postpone smart-pig runs /
20% reduction in inspection costs
Reduce Unplanned Shutdown
Costs
>$240,000 per day
Reduce Capital Materials
Costs
~$17million per plant
Optimize Inhibitor Dosage 20-60% Savings on $250K to $2M
contracts

Corrosion Models: Target Markets and Applications
Software Application Oil & Gas
(Upstream/G
as Plants)
Refining Transmission
Predict 6.0  
PredictPipe 3.0  
Socrates 9.0  
Strategy-A 4.0  
Strategy-B 4.0 
Predict-SW 3.0 
Predict-Amine 2.0  
Predict-SAA 
Predict-Crude 
Corrosion models are specialized and targeted specific industry
applications
Typical customers include O&G operating companies such as Chevron, Shell,
Aramco, Petrobras, CNPC, ONGC and Engineering companies such as IMV
Projects, KBR, WorleyParsons, Fluor, Black & Veatch

Example: Predictive Models for Refining
• Predict-SW: Corrosion prediction for NH4HS in sour water
systems (hydroprocessing, sour water strippers, amine units)
• Predict-Amine: Amine corrosion in Amine units (MEA, DEA,
DGA, MDEA)
• Predict-SAA: Corrosion in sulfuric acid alkylation systems
• Predict-Crude: Corrosivity of Crude oils due to Naphthenic
Acid Corrosion and Sulfidation

Real-Time Predictive Modeling Solutions
DCS LIMS
HISTORIAN (OPC COMPLIANT)
Configuration
Prediction
Engine
Visualization /
Trending
Custom Data
Store
Administrator
Operations
Personnel
Inspection
Personnel
Refinery
Management

Real Time Monitoring with SmartCET
Transmitter
Assembly
Insertion probe body
Probe electrodes
(consumable)
Principle of operation:
LPR (Linear Polarization Resistance)
HAD (Harmonic Distortion Analysis)
ECN (Electrochemical Noise)
• 4-20mA output is (LPR) - general corrosion
• Digital HART outputs - Pitting Factor
Provides four outputs
- Operator Level
* General Corrosion Rate (mpy/mmpy)
- The overall rate of metal loss (corrosion rate)
* Pitting Factor (localized Activity)
- Qualification of whether corrosion is likely uniform or localized
- Expert Level
* b value - Stern Geary constant
- b value is related to the activation energy of the corrosion process
* Corrosion Mechnism Indicator - Double Layer Capacitance
No other monitoring system provides a 30 second cycle time

Online, real-time corrosion monitoring….
0
100
* mpy - mils per year
mmpy - millimeters per year
Red Line
A “Tachometer” for the plant operator!

Novel optical methods for gas/fluid/solid detection
Benefits :
• develop new technology for in-situ and real
time monitoring of reservoirs
• enable for quick determination of natural
gas from shale formations and reservoir fluids
• obtained data will help to develop numerical
models of geological structures
• enable to monitor hydrocarbon recovery
Raman spectrometer
Measuring cell
miniature devices for special applications
Advantages of Raman spectroscopy:
• no samples preparation
• non-destructive and non-contact technique
• measurements can be taken continuously
• allows to identify compounds and determine
their concentration
• can measure fluids, gasses and solids

Wide range of applications of Raman spectroscopy
for reservoir monitoring
• Salinity
• Polymers
• Surfactants
• Gases: C1 – C3
• H2S
• CO2
• Contaminations of
reservoir fluids
• Rock chemistry
• Mineral composition
• Rock/surfactant/surface
interactions
1000 1200 1400 1600 1800
5000
10000
15000
20000
CO2
bending
CO2
stretching
H2
Obending
"Perrier" carbonated water - 390mg/l CO2
Tap water
ScatteringIntensity(arb.units)
Raman Shift (cm
-1
)
CO2
mode
stretching
bending mode

Raman spectroscopy for corrosion monitoring
Carbon steel exposed
for 3 months
for 1 month
for 2 months
g-FeOOH
g-FeOOH + a-FeOOH
g-FeOOH + a-FeOOH + Fe3O4
100
200
300
400
500
600
700
800
900
1 000
1 100
1 200
Intensity(cnt)
200 400 600 800 1 000 1 200 1 400 1 600 1 800 2 000
Raman Shift (cm-1
)
10oct0110FeBulk10d-H3S-01pc-sp1 dark spot
10oct0111FeBulk10d-H3S-01pc-hazy spot
Distribution of Fe2O3, FeCO3 and Fe3O4
compounds formed on Fe metal surface
Fe2O3
Fe3O4
-50
-40
-30
-20
-10
0
10
20
30
40
50
60
70
80
Y(µm)
0 50 100
X (µm)
5 µm5 µm5 µm
Fitting the Raman spectra as a
superposition of oxide signatures, it
is possible to determine the
corrosion rates
Localized Raman map - next generation
of surface imaging technique
FeCO3

Conclusions
• Honeywell Corrosion Team has over twenty years of experience in
modeling and developing solutions for problems related to corrosion
and material selection
• Solutions for Oil & Gas Industry - solving corrosion problems
- Corrosion laboratory for materials testing
- Corrosion Prediction Software Models
- Consulting Services
- Advanced Flow Modeling Tools
- Real-time Corrosion Monitoring for gas / liquids pipelines
• Honeywell offers advanced technologies for processes monitoring
- SmartCET - in-situ and real time corrosion monitoring sensor
- new monitoring methods - optical spectroscopy
• Materials challenge - new materials are key to major developments
in Oil & Gas
- Exceptional potential of nanocrystalline ceramics for corrosion protection
at high temperatures and aggressive environment
- Nanotechnology to improve oil and gas production

Customer Base
Leading Global Industrial Process operators and materials
suppliers - including Exxon, Shell, Chevron, BP, Sumitomo,
JFE, Petrobras, ONGC, Reliance, StatOil, Aramco, Total, Fluor,
Dow, Dupont, KBR, Worley Parsons, IMP, Ecopetrol,
Petrochina, CNPC, Hyundai, Samsung, Larsen&Toubro

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