corrosion laboratory-slides show

Honeywell Corrosion Solutions

Igor Kosacki Engineering Manager – Corrosion

Honeywell Process Solution

[email protected]

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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

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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)

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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 band CE 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

OC

P+

50

mV

1 hour

E

10-7

10-6

10-5

0 500 1000 1500 2000 2500 3000 3500 4000

Cu

rre

nt

De

ns

ity

(A

/cm

2)

Time (s)

11459-2F in ENV#2 @ 75 F

10K ppm Cl + 1.5 psi H2S

pH 3.5

hold at 50 mV OCP

(-266 mV Ag/AgCl)

Pitting

initiate

2.4 mil deep

longitudinal pitt

Potentiostatic Polarization

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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= (iC)-1 elements, we can

model specimen response

1xx 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''

(o

hm

s)

Z' (ohms)

electrode bulk

T = 700C

R1

C1

R2

C2

W

sincos''' iZiZZZ

)(

)()(

tI

tUZ


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 5.0x104

1.0x105

1.5x105

2.0x105

2.5x105

3.0x105

= 6.5*103S/cm

= 2.5S/cm

10%H2

O2

R = 52.4

R = 0.02

4 - probe meas.

I = 1.05mA

T = 950oC

72%NiO-CeO2 cermet

10-1

10-3

10-2

10-4

10-5

Vo

ltag

e -

U

(V

)

Time - t (seconds)

OHOOHV xoo 22

OHNiHNiO 22

eOHOgH xo .

2 )(2/1

Material interaction with ambient atmosphere

= 2.6 103S/cm

= 2.8 103S/cm

U/t = 9.1x10-11

V/s

wet 0.9N2+0.1H

2

I = 0.01A

T = 950oC

72%NiO-CeO2 cermet

0.0 5.0x104

1.0x105

1.5x105

2.0x105

2.5x105

3.0x105

3.0x10-4

4.0x10-4

5.0x10-4

6.0x10-4

7.0x10-4

8.0x10-4

Vo

ltag

e -

U (V

)

Time- t (seconds)

Impedance Spectroscopy

for monitoring materials and

processes:

• reduction of NiO to Ni

• materials stability in water

• containing atmosphere

in out

NiO-CeO2 composite Ni-CeO2 composite


0 100000 200000 300000 4000003x10-4

4x10-4

5x10-4

6x10-4

7x10-4

8x10-4

dry (0.9N2+0.1H

2) => dry (0.9N

2+0.1H

2+30ppmH

2S)

I = 10mA

T = 950oC

72%NiO-CeO2 cermet

Voltag

e -

U

(V)

Time - t (seconds)

= 2 103S/cm

= 2.5 103S/cm

0.9N2+0.1H

2

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 103S/cmR = 0.04

dry 0.1H2 => wet (0.1H

2+0.1%H

2S)

I = 100mA

T = 950oC

72%NiO-CeO2 cermet

Vo

ltag

e -

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

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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 Confidential 29

Delivering Operational Excellence

Human Error 40%

Equipment 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

CO

2 b

endin

g

CO

2 s

tretc

hin

g

H2O

be

nd

ing

"Perrier" carbonated water - 390mg/l CO2

Tap water

Sca

tterin

g In

ten

sity (

arb

. un

its)

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

Inte

nsi

ty (

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


Questions / Discussion

corrosion laboratory-slides show

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