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- 1. Honeywell Corrosion Solutions IgorKosacki Engineering Manager – Corrosion Honeywell Process Solution igor.kosacki@honeywell.com
- 2. 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
- 3. 3 Honeywell Confidential CorrosionValue…….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
- 4. 4 Honeywell Confidential CorrosionManagement • 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
- 5. 5 Honeywell Confidential HoneywellCorrosion 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
- 6. 6 Honeywell Confidential HoneywellCorrosion 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
- 7. 7 Honeywell Confidential HoneywellCorrosion 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)
- 8. 8 Honeywell Confidential HoneywellCorrosion Laboratory
- 9. 9 Honeywell Confidential HoneywellCorrosion 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
- 10. 10 Honeywell Confidential Autoclavetesting Laboratory has many autoclaves (C276 wetted parts) for mimic real extreme conditions and testing materials • (1) 22L capacity, 5000psi/600F • (13) 5L capacity, 5000psi/600F • (12) 6L capacity, 1000psi/600F • (3) 2.7L capacity, 20000psi/600F • (8) 0.7L capacity, 10000psi/550F - rotoclave • (5) 1.5L capacity, electrochemical tests opportunity
- 11. 11 Honeywell Confidential Corrosiontests 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
- 12. 12 Honeywell Confidential StirredAutoclave Options Rotating Shaft ASTM G170 Rotating Cage
- 13. 13 Honeywell Confidential LaboratoryServices • 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
- 14. 14 Honeywell Confidential PineRCE Apparatus • Ambient pressure • 80°C maximum temperature • 20,000 rpm maximum speed • Runs with Gamry Potentiostat - LPR - Potentiostatic/Galvanostatic Polarization - CPP - EIS
- 15. 15 Honeywell Confidential Electrochemicaltechniques 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
- 16. 16 Honeywell Confidential LinearPolarization 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
- 17. 17 Honeywell Confidential ElectrochemicalCyclic 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
- 18. 18 Honeywell Confidential 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
- 19. 19 Honeywell Confidential ElectrochemicalNoise 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
- 20. 20 Honeywell Confidential ElectrochemicalImpedance 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''(ohms) Z' (ohms) electrodebulk T = 700C R1 C1 R2 C2 W sincos''' iZiZZZ )( )( )( tI tU Z
- 21. 21 Honeywell Confidential Corrosionobservation 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
- 22. 22 Honeywell Confidential LocalizedElectrochemical 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
- 23. 23 Honeywell Confidential 0.05.0x10 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
- 24. 24 Honeywell Confidential 0100000 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
- 25. 25 Honeywell Confidential Experimentaltechniques 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
- 26. 26 Honeywell Confidential Processmonitoring tools: • Corrosion models • Electrochemical sensors - SmartCET • Optical spectroscopy and surface imaging
- 27. 27 Honeywell Confidential Processmonitoring 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
- 28. 28 Honeywell Confidential IntegratedReal - 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. 29 Honeywell Confidential29 DeliveringOperational 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
- 30. 30 Honeywell Confidential IntegratedSolution 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!
- 31. 31 Honeywell Confidential CorrosionValue 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
- 32. 32 Honeywell Confidential CorrosionModels: 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
- 33. 33 Honeywell Confidential 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
- 34. 34 Honeywell Confidential Real-TimePredictive Modeling Solutions DCS LIMS HISTORIAN (OPC COMPLIANT) Configuration Prediction Engine Visualization / Trending Custom Data Store Administrator Operations Personnel Inspection Personnel Refinery Management
- 35. 35 Honeywell Confidential RealTime 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
- 36. 36 Honeywell Confidential Online,real-time corrosion monitoring…. 0 100 * mpy - mils per year mmpy - millimeters per year Red Line A “Tachometer” for the plant operator!
- 37. 37 Honeywell Confidential Noveloptical 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
- 38. 38 Honeywell Confidential Widerange 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
- 39. 39 Honeywell Confidential Ramanspectroscopy for corrosion monitoring Carbon steel exposed for 3 months Carbon steel exposed for 1 month Carbon steel exposed 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
- 40. 40 Honeywell Confidential 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
- 41. 41 Honeywell Confidential CustomerBase 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
- 42. 42 Honeywell Confidential Questions/ Discussion