Appendices - EFC | European Federation of Corrosion
Transcription
Appendices - EFC | European Federation of Corrosion
Appendix 1 List of participants and excused persons Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Participants EFC WP15 meeting 6th September 2005 Lisbon Surname Name Company Country Martin Stuart Chris J Hennie Paul Alec Craig A. Joanna Russell Maarten Ellina David Andrew M John Roberto Francois Rob Günter Laszlo Nick Stefano Stefan Richez Bond Claesen de Bruyn Eaton Groysman Howard Hucinska Kane Lorenz Lunarska Owen Pritchard Pugh Riva Ropital Scanlan Schmitt Simor Smart Trasatti Winnik Total TWI Nalco Borealis AS Champion Technologies Inc Oil Refineries Ltd GE Infrastructure Gdansk Technical University Intercorr Shell Global Solutions Inetrnational B.V. Institute of Physical Chemistry GE Betz Corrosion & Fouling Consultancy Innovene Grangemouth Eni Tecnologie Institut Français du Pétrole Conoco Lab for Corrosion Protection Danube Refinery Serco Assurance F University of Milan Exxon Mobil Chemical FRANCE UK BELGIUM NORWAY USA ISRAEL AUSTRALIA POLAND USA NETHERLANDS POLAND UK UK UK ITALY FRANCE UK GERMANY HUNGARY UK ITALY UK Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Excuses received for the EFC WP15 meeting 6th September 2005 Lisbon Surname Name Company Country Curt André Michael Nicholas Charles Sebastien Carlo Tiina Martin Andrew Mario Morten Istvan Richard Kirsi Iris Liane Betrand John Alan Christensen Claus Davies Dowling Droz Duval Farina Hakonen Holmquist Kettle Lanciotti Langøy Lukovits Pargeter Rintamaki Rommerskirchen Smith Szymkowiak Thirkettle Turnbull Force Institutes GE Betz CARIAD Consultants Shell Global Solutions International B.V. Exxon Mobil Saipem Corrosion Consultant FORTUM Oil & Gas Oy AB Sandvik Steel Chevron Texaco Ltd Polimeri Europa S.p.A Bodycote Materials Testing AS Chemical Research Center TWI FORTUM Oil & Gas Oy Butting Edelstahlwerke GmbH&Co KG Intetech Ltd IFP Technology Group - AXENS Thor Corrosion National Physical Laboratory DENMARK BEGIUM GREECE NETHERLANDS FRANCE FRANCE ITALY FINLAND SWEDEN UK ITALY NORWAY HUNGARY UK FINLAND GERMANY UK FRANCE UK UK Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Appendix 2 EFC WP15 Activities Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Presentation of the activities of WP15 European Federation of Corrosion (EFC) • Federation of 32 National Associations • 19 Working Parties (WP) + 1 Task Force • Annual Corrosion congress « Eurocorr » « Eurocorr » • Thematic workshops and symposiums • Working Party meetings (for WP15 twice a year) • Publications • EFC - NACE agreement • for more information http://www.efcweb .org http://www.efcweb.org WP 15 meeting September 6th 2005 Lisbon EFC Working Parties • WP 1: Corrosion Inhibition • WP 3: High Temperature • WP 4: Nuclear Corrosion • WP 5: Environmental Sensitive Fracture • WP 6: Surface Science and Mechanisms of corrosion and protection • WP 7: Education • WP 8: Testing • WP 9: Marine Corrosion • WP 10: Microbial Corrosion • WP 11: Corrosion of reinforcement in concrete • WP 12: Computer based information systems • WP 13: Corrosion in oil and gas production • WP 14: Coatings • WP 15: Corrosion in the refinery industry • WP 16: Cathodic protection • WP 17: Automotive • WP 18: Tribocorrosion • WP 19: Corrosion of polymer materials • Task Force 2: Corrosion and Protection of steel structures WP 15 was created in sept. sept. 96 with J. Harston as first chairman WP 15 meeting September 6th 2005 Lisbon 1 EFC Working Party 15 « Corrosion in Refinery » Activities The following are the main areas being pursued by the Working Party: ·Information Exchange - Sharing of refinery materials /corrosion experiences by operating company representatives. ·Forum for Technology - Sharing materials/ corrosion/ protection/ monitoring information by providers Publications WP 15 meeting September 6th 2005 Lisbon EFC Working Party 15 « Corrosion in Refinery » Activities WP Meetings ·One WP 15 working party meeting in Spring, (this year on 17-18 March 2005 in Trondheim) ·One meeting at Eurocorr in conjunction with the conference, (this meeting during Eurocorr 2005 4-8 September in Lisbon) Eurocorr Conference sessions (September) Refinery Corrosion Session + Workshops or Joint Session with other EFC WP parties WP15 page in EFC Web site http://www.efcweb.org/WP_on_Corrosion_in_the_Refinery_Industry.html WP 15 meeting September 6th 2005 Lisbon 2 EFC Working Party 15 « Corrosion in Refinery » Activities http://www.efcweb.org/WP_on_Corrosion_in_the_Refinery_Industry.html WP 15 meeting September 6th 2005 Lisbon EFC Working Party 15 « Corrosion in Refinery » Activities http://www.efcweb.org/WP_on_Corrosion_in_the_Refinery_Industry.html WP 15 meeting September 6th 2005 Lisbon 3 Appendix 3 Proposal of a typical failure refinery corrosion cases atlas Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Typical refinery failure cases atlas ? Corrosion Atlas, Elsvier WP 15 meeting September 6th 2005 Lisbon API 571 Typical refinery failure cases atlas ? WP 15 meeting September 6th 2005 Lisbon 1 Appendix 4 Electrochemical noise in corrosion monitoring A. Cafissi and S. Trasatti (University of Milan) Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 “Electrochemical Noise in corrosion monitoring” A.Cafissi and S.P.Trasatti Departement of Physical Chemistry and ElectrochemistryUniversity of Milan- via Venezian, 21- 20133 MILAN (italy) EUROCORR 2005 4-8 September 2005 , Lisboa (P) Electrochemical Noise Noise Electrochemical Electrochemical technique entails with registration and analysis of potential and current fluctations associated with electrochemical phenomena at the electrode/solution interface. Current fluctations between two working electrodes involve in the process are in the range of 10-11-10-3 A Potential fluctuations between the working electrodes and the reference electrode are in the range 10-6-10-1 V Sketch of electric circuit Experimental set-up ZRA V Ia,t Current Fluctuations Measure of potential fluctuations ?I Working Electrodes 1 and 2 and their current i1 & i2 ?V Ia,t WE 2 WE 1 Ic,t Ic,t RE Impedance of the two working electrodes Circulating current Solution resistance 1 Applications of of Elettrochemical Elettrochemical Noise Noise Applications The EN has a wide range of appplications, i.e.: ¾ Determination of active/passive transition ¾ Study of the passive film breakdown (pitting, crevice corrosion, etc.) ¾ Growth and detachment of hydrogen bubbles (acid corrosion) ¾ Determination of fluctuations due to diffusive phenomena ¾ Coating failure on metallic substrate ¾ Biological corrosion phenomena ¾ Electrocrystallization associated with diffusion processes Analysis of of Electrochemical Electrochemical Noise Noise data data Analysis It can be performed as follows: First: ¾ Direct analysis of raw data Second Statistical analysis: dV ,dI, variance, kurtosis, skewness, ¾ skewness, average values, etc. ¾ Determination of Rn (Noise resistance ), a useful parameter for the corrosion rate: (Rn (Rn ≈ Rp) Rp) Rn = dV / dI ¾ Determination of localization index LI = dI /Irms Third ¾ Fourier Trasform analysis (power spectral density, PSD). PSD). 2 Experimental scope scope Experimental Evaluation of Electrochemical Noise tecnique for monitoring corrosion of industrial plants Study of different corrosion morphologies Study of the influence of physical and mechanical parameters (flow rate, bacteria, temperature, tensile load,etc) load,etc) Definition of statistical parameters (d (dV, dI, Rn, LI, PSD ) Development of a statistical metodology of the electrochemical signal by the use of neural networks Acquisitionset setup upfor forstatic staticexperiment experiment Acquisition -Potenziost/galvanostat in ZRA configuration potenziostat potenziostat -A reactor for electrochemistry reaction -A reference electrode (i.e. SCE saturated calomel electrode) Analisi dei dati -Two identical working electrodes THERMOMETER WORKING ELECTRODES Acquisitionset setup upfor fordynamic dynamicexperiment experiment Acquisition SALT SOLUTION - A flowdynamic reactor -Two working electrode of steel -A metallic (Pt,Ru) reference electrode potenziostat potenziostat Analisi dei dati 3 Informations available from different testing conditions Testing Experiment Purpose Study of different corrosion morphology Static test Applicability of EN in stress corrosion cracking Tensile test Monitoring the influence of SRB bacteria SRB corrosion test Flow dynamic test Monitoring the influence of dynamic conditions Materials Carbon steel - X65 Grade- Inox austenitic steel -304L and 316LInox Super Austenitic -Sanicro 28- Nickel alloy -Inconel 600- Gas pipeline – Oil pipeline Chemical reactor Heat exchanger Special devices 4 INFLENCE OF BACTERIA ACTIVITY ON STEEL CORROSION -increase of corrosion current - forms a biofilm on the metallic surface - metal depassivation - reduces the activity of inhibitors Bacterial activity Bacterial activity causes - forms corrosive H2S gas in solution - prevents oxygen diffusion in the solution - blistering in the steel - creates a differential areation on the substrate - decrease in pH solution 800 10 600 400 200 uA/cm2 uA7cm 2 5 0 -5 0 -200 -400 -10 -600 -800 -15 0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 Time (s) 500 600 700 800 Time (s) Current fluctations for steel pipe in a 3,5% NaCl solution in the presence of Bacteria SRB (temperature: 30 °C): current spike in the range of 600 µA/cm2 Current fluctations for a typical steel pipe in a 3,5% NaCl solution in the absence of SRB bacteria: current spike of 12 µA/cm2 Immersion Time (h) µA/cm2 X65 X65 + SRB µA/cm2 mm/y X65 mm/y X65+SRB 8 5 200 31.4 x 10-3 2.51 Surface appearance of carbon steel after SRB corrosion Super austenitic stainless steel : Sanicro 28 Typical Time record of current density for Sanicro 28 in a 3,5% NaCl solution at room temperature T im e r e c o r d o f c u r r e n t d e n s it y c h lo r id e a d d it io n a fte r ( s a n ic r o 2 h f r o m th e 2 8 ) 1 µ A/cm 2 0 ,5 0 - 0 ,5 - 1 - 1 ,5 0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 t im Immersion Time (h) Background Noise µA/cm2 Spike Charge (µ (µC/cm2) Background Noise 2 0,02 0,3 2,5 x 10-4 3 0,016 1,8 2,0 x 10-4 5 0,01 3,6 1,25 x10-4 3 0 0 e 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0 (s ) CR:mm/y M a g n if ic a t io n 0 ,4 o f th e p r e v io u s t im e r e c o r d 0 ,2 0 µ A/cm 2 - 0 ,2 - 0 ,4 - 0 ,6 - 0 ,8 -1 t im e (s ) - 1 ,2 2 2 5 Note: very good material , so very few spikes & low corrosion 2 3 5 2 4 5 2 5 5 2 6 5 T i m e r e c o r d o f c u r r e n t d e n s i ty a f t e r 3 h f r o m c l o r i d e a d d i ti o n ( s a n i c r o 2 8 ) Current density (uA/cm 2) 0 ,1 T i m e r e c o r d o f c u r r e n t d e n si ty a fte r 5 h fr o m c h l o r i d e a d d i ti o n J (uA/cm ) 2 ,0 E- 0 2 0 ,0 E+ 0 0 - 2 ,0 E- 0 2 - 4 ,0 E- 0 2 - 6 ,0 E- 0 2 - 8 ,0 E- 0 2 - 1 ,0 E- 0 1 - 1 ,2 E- 0 1 - 1 ,4 E- 0 1 - 1 ,6 E- 0 1 - 1 ,8 E- 0 1 - 2 ,0 E- 0 1 0 ,0 5 0 - 0 ,0 5 - 0 ,1 - 0 ,1 5 - 0 ,2 - 0 ,2 5 - 0 ,3 0 100 200 300 400 500 T im e ( s ) 600 700 800 900 0 1000 500 1000 T im e ( s ) 1500 2000 M a g n i fi c a ti o n o f a sp i k e i n th e p r e v i o u s sp e c tr a 0 ,0 2 o f p re v io u s tim e Cur r e n t d e ns ity (uA/cm 2) 0 M a g n ific a tio n r e c o r d 2 ,0 E - 0 2 0 ,0 E + 0 0 J (uA /cm 2) - 2 ,0 E - 0 2 - 4 ,0 E - 0 2 - 6 ,0 E - 0 2 - 8 ,0 E - 0 2 - 0 ,0 2 - 0 ,0 4 - 0 ,0 6 - 0 ,0 8 - 0 ,1 - 0 ,1 2 - 0 ,1 4 - 0 ,1 6 - 0 ,1 8 - 1 ,0 E - 0 1 - 0 ,2 - 1 ,2 E - 0 1 T im e ( s ) 570 620 670 720 770 - 1 ,4 E - 0 1 6 8 0 7 0 0 7 2 0 7 4 0 T im e 7 6 0 ( s ) 7 8 0 8 0 0 8 2 0 8 4 0 5 AISI 316 L Time record of current density for AISI 316L Steel in a 3,5% NaCl solution at room temperature and relative magnification of transient spike T i m e r e c o r d o f c u r e n t d e n si ty a fte r 2 h fr o m a d d i ti o n (a i si 3 1 6 ste e l ) c h lo rid e µA/cm2 Cur r e nt de ns ity (uA/cm 2) 15 CR: mm/y Immersion Time (h) background Spike Charge (µC/cm2) Height of Spike µA/cm2 Background-Noise 2 2,7 3 8 33,8 x 10-3 3 2 5,1 7 25,1 x 10-3 5 3 31,5 22 37,6 x 10-3 10 5 0 -5 -1 0 0 200 400 M a g n ific a tio n o f a T im e ( s ) sp ik e i n th e 600 800 1000 p r e v i o u s sp e c tr a 8 6 T im e re c o rd o f c u r r e n t d e n sity fo r A i s 3 1 6 L s o l u tio n a t r o o m te m p e r a tu r e in Cur r e nt de n s ity (uA/cm 2) Note :Grow of current spikes and localized corrosion as the test proceed 3 ,5 % N a C l 4 2 0 -2 -4 -6 Charge: 3 -8 1 0 µC/cm2 -1 0 C u r r e nt d e n s ity (u A/cm 2) 5 401 403 404 405 406 407 408 409 T im e ( s ) -5 T im e -1 0 re c o rd 1 5 -2 0 0 2 0 0 4 0 0 T im e (s ) 6 0 0 8 0 0 1 0 0 0 Cur r e nt de ns it y (uA/cm 2) -1 5 -2 5 o f c u r r e n t d e n sity fo r a is in 3 1 6 L so lu tio n a t r o o m te m p e r a tu r e 3 ,5 % N a C l 5 0 -5 -1 0 T im e M a g n i fi c a ti o n o f a sp i k e i n th e p r e v i o u s sp e c tr a in 1 0 (s ) -1 5 5 0 10 0 20 0 3 00 4 00 5 00 6 0 0 0 M a g n i fi c a ti o n o f a sp i k e i n th e p r e v i o u s sp e c tr a -5 6 4 -10 C ur r e nt de ns ity (u A/cm 2) Cu r r e nt d e n s ity (u A/cm 2) 402 0 -15 -20 -25 10 15 20 T im e ( s ) 25 30 35 40 2 0 -2 Charge: 5,1 Cµ/cm2 -4 -6 -8 130 135 T i m1 4 e 0( s ) 145 150 Charge: 31,5 µC/cm2 AISI 304 L in the loop Time record of current density for Aisi 304L in loop reactor in a 3,5% NaCl solution at room temperature and relative magnification of transient spikes Time record of current density for aisi 304L in loop cell, after 0,5 h from chloride addition Note :Very low current density due to high oxygen concentration caused by turbolence conditions (flow rate 6 l/min). Immersion Time (h) SpikeCharge (µC/cm2) Background Noise 2 0,067 CR: mm/y 0,7 1,5 Curren t density (u A/cm 2) µA/cm2 2 8,36 x 10-4 1 0,5 0 -0,5 Charge: 0,7 µC/cm2 -1 -1,5 -2 4 0,03 1 3,8 x 10-4 6 0,01 1,75 1,36 x10-4 0 100 Time (s) 200 300 400 500 600 T im e r e c o r d o f c u r r e n t d e n sity fo r a i si 3 0 4 L i n lo o p c e ll , a fte r 1 h fr o m c h l o r i d e a d d i ti o n Cur r e nt de ns ity (uA/cm 2) 0 ,2 Tim e re cord of curre nt de nsity for AIS I 304L in loop re a ctor, a fte r 2h from cloride a ddition 0,2 0,1 0,05 0 ,1 0 ,0 5 0 - 0 ,0 5 - 0 ,1 - 0 ,1 5 - 0 ,2 - 0 ,2 5 0 0 100 200 300 -0,05 400 500 600 T im e ( s ) -0,1 -0,15 Magnification of a spike in the previous spectra -0,2 200 400 Tim e (s) 600 800 1000 1200 0,1 Current density (uA/cm2) 0 M a g n i fi c a ti o n o f a p r e v i o u s sp e c tr a 0 ,0 5 C ur r e nt de n s ity (uA/cm 2) Current de nsity (uA/cm 2) 0,15 0 ,1 5 0 ,0 0 - 0 ,0 5 - 0 ,1 0 0 -0,05 -0,1 -0,15 Charge: 1,0 µC/cm2 -0,2 170 Charge: 1,75µC/cm2 - 0 ,1 5 0,05 180 190 200 210 220 230 240 Time (s) - 0 ,2 0 800 850 9 0 0 T im e ( s ) 950 1000 1050 6 SCC on AISI 304L Time record of current density after 1h from chloride addition on Aisi 304L in tensile stress Time record of current density for AISI 304L in a 3,5% NaCl solution at different time and with constant tensile stress. Relative magnification of transient spike Background Noise 1 7,7 Height spike Spike Charge µA/cm2 40 Curre nt de nsity (uA/cm 2) Immersion time Time (h) 60 CR:mm/y (µC/cm2) µA/cm2 µA/cm 20 0 -20 -40 -60 -80 -100 -120 -140 0 110 24 100 300 Time (s) 400 200 500 600 9,7x10-2 M a g n i fi c a ti o n o f a sp i k e i n th e p r e v i o u s sp e c tr a 8 3 120 27 0,1 4 0 ,0 0 Note : EN can be very helpful in monitoring the passive film break Cu r r e nt de n s ity (u A/cm 2) 2 0 ,0 0 0 ,0 0 - 2 0 ,0 0 - 4 0 ,0 0 - 6 0 ,0 0 Charge: 24 µC/cm2 - 8 0 ,0 0 - 1 0 0 ,0 0 - 1 2 0 ,0 0 down (amplititede of the current spike ), increased by the tensile stress applied that expose a new not passivated surface. - 1 4 0 ,0 0 84 85 86 87 88 89 90 91 92 93 T im e ( s ) T im e r e c o r d o f c u r r e n t d e n s it y a f t e r 3 h f r o m c h lo r id e a d d it io n o n A is i 3 0 4 L in t e n s ile s t r e s s Curre nt de nsity (uA/cm 2) 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 0 100 200 3 0 0 T i m e (s) 4 0 0 500 600 C u r r e n t d e n si ty fo r I n c o n e l l 6 0 0 i n C l - M e d i a 5 Inconel 600 alloy u A/cm 2 0 -5 -10 -15 Time record of current density for Inconel 600 in a 3,5% NaCl solution ,pH=3, at room temperature and relative magnification of transient spike -20 0 200 400 600 800 1000 T im e ( s ) Magnification of 3 current spikes Background Noise SpikeCharge (µC/cm2) Heght of Spike µA/cm2 4,9 15 µA/cm2 3 6 5 4,6 1,4 14 mm/y 4,00 Backgroud Noise 2,00 0,00 -2,00 7,5 x 10-2 uA/cm2 Immersion Time (h) 1,8 x 10-2 -4,00 -6,00 -8,00 -10,00 Charge: 4,87µ C/cm2 -12,00 -14,00 -16,00 215 6 5 0,5 15 217 219 0,63 x 10-2 221 223 225 Time (s) 227 229 231 233 T im e r e c o r d o f c u r r e n t d e n s i t y a f t e r 5 h f r o m c h lo r i d e a d d i t t i o n ( in c o n e ll 6 0 0 ) 2 5 ,0 0 2 0 ,0 0 1 5 ,0 0 1 0 ,0 0 fr o m c h l o r i d e uA/cm 2 T i m e r e c o r d o f c u r r e n t d e n si ty a fte r 6 h a d d i ti o n (i n c o n e l 6 0 0 ) 4 0 ,0 0 - 1 0 ,0 0 0 - 1 5 ,0 0 -2 - 2 0 ,0 0 -4 0 200 400 -6 600 800 1000 T im e ( s ) -8 -10 -12 -14 M a g n if ic a t io n o f a s p ik e o f p r e v i o u s s p e c t r a 4 ,0 0 -16 2 ,0 0 -18 200 400 T im e ( s ) 0 ,0 0 600 800 1000 M a g n i fi c a ti o n o f o n e sp i k e i n th e p r e v i o u s sp e c t r a Photograf taken by optical microscope 2 ,0 0 0 ,0 0 - 2 ,0 0 uA/cm 2 0 Cu r r e nt d e n s ity (u A/cm 2) Cu r r e nt d e n s ity (u A/cm 2) 5 ,0 0 - 5 ,0 0 2 - 4 ,0 0 - 6 ,0 0 - 8 ,0 0 Charge: 4,6 µC/cm2 - 1 0 ,0 0 - 1 2 ,0 0 - 2 ,0 0 - 1 4 ,0 0 - 4 ,0 0 - 6 ,0 0 - 1 6 ,0 0 - 8 ,0 0 T im e ( s ) 630 632 634 636 638 640 - 1 0 ,0 0 - 1 2 ,0 0 E.Charge: 5,0 µC/cm2 - 1 4 ,0 0 - 1 6 ,0 0 176 177 177 178 178 179 179 180 180 T im e ( s ) 7 Noise spectra transformation from the time domain to the frequency domain (FFT to obtain the PSD) The aim of this transformation is: To filter the frequencies not associated to the electrochemical reactions (amplification noises, instrumentation interferences, power current). To determine the slope of the (PSD) spectra as an useful parameter to distinguish between uniform and localized corrosion. Potential and current PSD Localized corrosion Calculated slope = -11db(A)/decade Calculated slope = -22 db(V)/decade PSD (V) for localized corrosion PSD (I) for localized corrosion Slope values for different corrosion modes 8 Potential and current PSD General corrosion Calculated slope = -6 db(V)/decade Calculated slope = -4 db(V)/decade PSD (V) for uniform corrosion PSD (I) for uniform corrosion Slope values for different corrosion modes Theoreticalcalculation calculationof ofmetal metalmass massloss lossduring duringaacurrent current Theoretical spike spike MetalDissolution Dissolutionduring duringaaCurrent CurrentSpike Spike Determinationofofhypothetic hypotheticPit Pitvolume volume Metal Determination Theory: IF R1 = radius maior of Pit in µm IF R2 = radius minus of Pit in µm If h = depth of the pit hole in µm If ? Fe= 7,3 µg3/µm3 We obtain : Æ Vpit = 1/3 πh(R12+R22+R1+R2) Example 1: depth h = 0,5 mm = 500 µm → R1= 4 µm → R2= 1 µm Vpit≈ 11,5 x 10+3 µm3 µg Fe = 84,1 x 10+3 µg Fe = 84,1 mgFe IF Hi,spk = Height of spike i in µA Hi,spk If ? tspk = duration time of a single spike i R1 if Meq = equivalent weight of Fe : Meq= 28 g/mole ? tspk If F = 96500 C (eletric charge of 1mole of electrons) If f spike : frequency of spike event : n° n°spike/sec h What’ What’s the amount of metal during a dissolution spike …mFe ? mFe = (H i,spk · ? tspk · Meq ) / F R2 Example 2: depth h = 0,05 mm = 50 µm → R1= 4 µm → R2= 1 µm Vpit≈ 11,5 x 10+3 µm3 µg Fe = 8,41 x 10+3 µg Fe = 8,41 mgFe Example 1: Hi,spk = 10 µA; ? tspk = 0,6 s mFe = 1,74· 1,74· 10-9 g Fe Example 2: Hi,spk = 100 µA; ∆tspk = 0,6s mFe = 1,74· 1,74· 10-8 g Fe metal dissolution during a day ? m Fe ,Day. ? mFe = 2,51 · 10-6 g Fe mFe = 2,51· 2,51· 10-5 g Fe Mass of Iron dissolved in general corrosion: m general If Icorr : Background Current Noise : 2 µA/cm2 Mgeneral: 5 · 10-5 gFe/day cm2 0,1µ 0,1µm/day cm2 9 Practical examples For: a mean height spike : Hi,spk =15, 30, 60 or 100 µA/cm2 a mean duration time of the spike ? tspk = 3 seconds a mean number of and spike in a day equal to 1440 or 4320 spikes we assume a hypotetic pit , with this characteristics: Dept = 25 µm ,Vpit ≈ 5,76 x 10+3 µm3 , 4,2 · 10-3 g Fe We obtain the pit formation for 1440 spike /day in this time: And the pit formation for 4320 spike /day in this time: Mean Height Spike Relative Mass of Iron dissolved Time to pit (µA/cm2) (g) (Days) 15 1,88 x 10-5 223 30 3,76 x 10-5 112 60 7,52 x 10-5 56 100 1,26 x 10-4 33,4 Mean Height Spike Relative Mass of Iron dissolved Time to pit (µA/cm2) (g) (Days) 15 5,64 x 10-5 74,3 30 11,28 x 10-5 37,3 60 22,56 x 10-5 18,6 100 3,78 x 10-4 11,1 CONCLUSIONS • Electrochemical Noise analysis can be successful applied to investigate corrosion processes and to estimate corrosion rate •Testing in the presence of SRB activity has shown that the corrosion onset and propagation growth is strictly connected to the bacteria metabolism. EN can be conducted under both static and dynamic conditions as well as under tensile loading • The PSD slope can be a useful parameter to distinguish among different corrosion modes 10 Appendix 5 New Technology for Prediction and Assessment of Corrosion in Refinery Operations R.D. Kane (Honeywell) Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 New Technology for Prediction and Assessment of Corrosion in Refinery Operations Russell D. Kane InterCorr International, Inc.* *Recently acquired by Honeywell Honeywell 1 Organization • Topics of Discussion – Ammonium Bisulfide Corrosion • SourWater JIP Phase I and II • Predict®-SourWater Software; release 2.0 – Amine Unit Corrosion • Amine JIP • Predict®-Amine – New JIP Activities starting in 2006 • Sulfuric Acid Alkylation • High Temperature Crude Oil Corrosivity - II 2 Honeywell 1 SourWater JIP Phase I & II • Title: “Prediction & Assessment of Ammonium Bisulfide Corrosion Under Refinery Sour Water Service Conditions” Phase I and II • Jointly developed by InterCorr and Shell Global Solutions • Phase I – H2S-dominated sour water systems (REAC) – Two year effort completed in 2003 • Extensive engineering database – parametric study of NH4HS concentration, H2S partial pressure, temperature, inhibitors, flow (wall shear stress). • 17 sponsors / approx. $1 million US • Predict®-SW Software – an integrated software tool for corrosion prediction and flow modeling for use in materials selection, risk assessment, inspection planning and enhanced unit operation. • Predict-SW 2.0 Software – is now available to both sponsors and non-sponsors; single-user and multi-user corporate licenses. Honeywell 3 Predict®-SW 2.0 • Use of design or actual unit conditions to assess of corrosion severity. Includes H2S partial pressure effects not found in current methods (e.g. Kp). Provides multiphase flow modeling to link unit conditions with JIP data. Queries iso-corrosion and parametric relationships over a broad range of system conditions. Output provides predicted corrosion rates for specific alloys based on • • • – – – • environmental conditions flow regime, and wall shear stress. Release 2.0 includes new features: – – – – 4 Output InputScreen Screen New parametric data from JIP provides Expanded understanding of major and minor process variables Updated Rules / Sensitivity Function View Data Units compatible with outputs from process models Benchmarking, reporting & online Help Honeywell 2 SourWater JIP – Phase II Phase II – NH3-dominated sour water systems • • Phase II currently in progress. Extensive engineering database – parametric study of NH4HS concentration, H2S & NH3 partial pressures, temperature, cyanides, flow (wall shear stress). Involved 11 companies and approx. $700,000 in funding. New Information: Conclusively shows a reversion to higher corrosion rates at high ammonia partial pressures. Predict-SW software will be updated with this new information/rules. Program sponsors have two year confidentiality period. JIP will run through mid-2006. • • • • • Sour Water Participants (I & II) – – – – – – – – – – – – – – – – – – – ChevronTexaco Energy Research & Technology Co. Flint Hills Resources, L.P Shell Global Solutions (US) Inc. ConocoPhillips, Inc. Petrobras - CENPES ExxonMobil Research & Engineering Sunoco Fluor Daniel Inc. UOP Saudi Aramco Syncrude Canada Ltd. Phillips Petroleum Co. Valero TOTAL BP Kuwait National Petroleum Co. Idemitsu Kosan Co., Ltd Lyondell-Citgo Refining LP Marathon-Ashland Petroleum Honeywell 5 Amine JIP Minimizing Amine Unit Corrosion • Data development combining chemical and flow simulation (similar to Sour Water program) • Program initiated with assistance of Flint Hill Resources. • The program involves five tasks: – – – – – • Input Screen Output Screen Task 1 – Baseline Data for Sour MEA, DGA, DEA Systems Task 2 – Temperature Task 3 – CO2/H2S Ratio Task 4 – Heat Stable Salts Task 5 – Development of a Software Corrosion Prediction Tool (Predict-Amine) Recently, tests included to evaluate MDEA. Program to be complete by mid-2006. Single user software license and 2 yr confidentiality period. New Lean Amine JIP being formulated. • • • 6 Honeywell 3 2006 JIP Activities • The previous JIP’s indicated that much work is needed to quantify the effects of process chemistry and flow conditions on corrosion of commonly used alloys. • This approach has proven successful in studying: – Nap acid, sour water and amine corrosion. • Based on end-user input, a similar parametric approach is being applied to: – Sulfuric acid alkylation unit corrosion – Current Nap Acid issues related to present limits for carbon steel, 5Cr, 9Cr, 12Cr and 316/317 • Programs are scheduled to begin in 2006: – Sulfuric acid alkylation: Q1 2006 – Nap acid: Q3 2006 Honeywell 7 Sulfuric Acid Alkylation JIP - 1 Prediction of Corrosion in Sulfuric Acid Alkylation Units • A highly profitability refining operation. • There is pressure on to maximize productivity (thru-put & availability) of alkylate processing units. • Program was based on a gaps analysis conducted in early 2005: – Corrosion rates for steel at low temperatures – Influence of ASO – Role of contaminants – Limits for 316 and Alloy 20 at high temperatures – Influence of welding – Influence of flow & regime 8 Limited base data in API 581 for reagent grade H2SO4 corrosion from 1950’s Honeywell 4 Sulfuric Acid Alkylation JIP - 2 • JIP Technical Program: • Task 1 – Chemical & Flow Modeling • Task 2 – Sensitivity studies on spent acid concentration, ASO and oxygenates • Task 3 – Parametric Study – Acid concentration – Temperature – Wall shear stress • Task 4 – Corrosion modeling Limited data developed more recently and development of Predict®indicates an effect of welding, temperature SA software. and velocity, but does not take into account • Sponsors will have a 2 year wall shear stress. confidentiality period – Includes single user version of software and use of data Honeywell 9 Minimizing Refinery Crude Corrosivity II • • • • • • • • Phase I was a pioneering JIP – Included support from over 20 companies – the most comprehensive experimental study. It identified critical parameters needed to better characterize the corrosivity of crude oil systems. Mechanisms of Nap Acid corrosion. Quantification of both chemical and flow-related mechanical factors. Limits for impingement attack of 5Cr, 9Cr & 12Cr. Influence of Nap Acid ring structures and sulfur speciation on corrosivity. Crude Corrosivity JIP-II starts in mid-2006 Sponsors will have a 2 year confidentiality period – Includes single user version of software and use of data 10 • New program focuses on: – – – – – Major limitations of currently utilized risk matrix in API 581 Combined effects of TAN and sulfur Liquid filled lines in turbulent flow for carbons steel, 5Cr, 9Cr and higher alloys Needs for quick screening test for corrosivity assessment Corrosivity software model (Predict®-Crude) to work with in-house proprietary assessment tools. Honeywell 5 Summary • New Technology for Prediction and Assessment of Corrosion in Refinery Operations: – Ammonium Bisulfide Corrosion • SourWater JIP Phase I and II • Predict®-SourWater Software; release 2.0 – Amine Unit Corrosion • Amine JIP • Predict®-Amine – New JIP Activities starting in 2006 • Sulfuric Acid Alkylation • High Temperature Crude Oil Corrosivity – II For more information contact R.D. Kane at: [email protected] 11 Honeywell 6 Appendix 6 Nickel alloys in hydroprocessing units J. Hucinska (Gdansk University) Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Nickel alloys in hydroprocessing units JOANNA HUCIŃSKA Gdańsk University of Technology, Gdańsk, Poland EUROCORR 2005, EFC WP15 September 6, 2005 • Institutos Superior Tecnico • Lisbon, Portugal Lay-out • Corrosion-erosion of reactor effluent air coolers (REACs) and piping • Corrosion-erosion of Alloy 825 • Questions 1 Corrosion-erosion of reactor effluent air coolers (REACs) and piping ¾ Problem in hydrocracking and high severity hydrotreating units ¾ Reasons of damage: presence of aqueous amonium bisulphide (NH4HS) and multiphase flow conditions ¾ Materials of construction: carbon steel, 321 steel, Alloy 800, Alloy 825 Corrosion-erosion of Alloy 825 in Used Oil Hydrotreatment Plant Injection point (water) Injection point (hydrocarbons) HP Separator Area of corrosionerosion Separator outlet (~300ºC): HC, H2O, H2, H2S, NH3 Alloy 825 piping Recycle gas washing column Column inlet (~100ºC) 2 IS Macroscopic characteristics of corrosionerosion after 5 months of service Nominal: ϕ 219,1x12,7 mm, Alloy 825 gr. UNS N08825, ASTM/ASME B/SB705 SEM micrograph of a cavity on the IS (free of corrosion products) bottom edge 3 Microscopic characteristics of corrosion-erosion Corrosion products Alloy 50 µm Fe Cr Ti Ni S Corrosion products on the IS, cross-section. SEM, EDS Reasons of Alloy 825 brittle fracture ¾ (NH4HS) + cavitation/droplet impingement ¾ Hydrogen? ¾ ? 4 Appendix 7 Metal dusting in plafforming CCR furnaces J. Hucinska (Gdansk University) Minutes of EFC WP15 Corrosion in the Refinery Industry 6 September 2005 Metal dusting in Platforming CCR furnaces JOANNA HUCIŃSKA Gdańsk University of Technology, Gdańsk, Poland EUROCORR 2005, EFC WP15 September 6, 2005 • Institutos Superior Tecnico • Lisbon, Portugal Lay-out • Characteristics of furnaces, tubes, service conditions • Non-destructive testing • Destructive testing • Questions 1 Unit: Platforming CCR (continuous catalytic reforming) E1 R4 R1 F1 F4 F2 R3 R2 F3 Characteristics of tubes and service conditions Characteristics Description Material of tubes Steel 9Cr-1Mo, gr P9 ASTM SA-335 Nominal dimensions 114,3 x 6,0 mm Environment Metal temperature Heavy naphtha after desulphurisation and hydrogen gas: 440-520°C (F1), 400520°C (F2), 450-520°C (F3), 470-520°C (F4), S~0.2 ppm (naphtha), S<0.5 ppm (hydrogen), ppH2~0.65-0.8 MPa 635ºC (design), ~600 ºC (service) Time of service 10 years 2 Non-destructive testing ¾ Visual – no scale on the outside surface (OS) of the tubes ¾ Wall thickness – no losses ¾ Ultrasonic wave attenuation measurements – decrease in attenuation Destructive testing • Visual – thin, loose deposits of carbon on the inside surface (IS) of the tubes • Metallographic: optical microscope (OM), transmission electron microscope (TEM) • Electron probe microanalyser (EPMA) • Tensile tests, Charpy-V impact tests 3 a) b) IS 150 µm zawartość C, % masy Cross-section of the tube wall, microstructure beneath the IS: a) fire side, b) refractory side. OM C 1,4 % 1,2 1 0,8 0,6 0,4 0,2 0 0 1 2 3 4 5 6 Distance from the IS, mm odległość od powierzchni, mm Cross-section of the tube wall, carbon profile. EPMA 4 Tensile tests Material Before service After service ASTM SA-335 Yield Stress MPa 337-400 269-281 205 min Tensile strength MPa 556-588 541-558 415 min Elongation % 32 20 27 Charpy-V impact tests: fracture energy KV Temperature, ºC 5 Charpy impact tests: % of ductile fracture % Temperature, ºC FATT 50=93ºC FATT – fracture appearance transition temperature Reasons of brittleness? 6 Literature data 5000 h pra ca ła ma nia , J 200 KV J 100 czas wyżarzania Time 550ºC 0 godz. 1000 godz. 5000 1000 godz. h 10000 godz. 0h 0 -100 10000 h 0 100 200 300 temperatura, C o Temperature, C Reason of brittleness: Laves phase Mo2Fe at grain boundaries (J.A. Hudson, S.G. Druce, G. Gage, M. Wall: Theoreticaland Applied Fracture Mechanics 1988, 10, p. 123) Examinations Mid-wall, carbon extraction replica. TEM 7 Chemical composition of precipitates, wt. % No Si P S Cr Mn Fe Mo 1 14.05 0.77 0.49 7.78 2.21 33.08 41.61 2 57.41 0.75 - 7.35 - 17.32 17.17 3 6.20 - - 56.39 1.00 28.26 8.15 4 20.93 - - 16.59 - 56.01 6.47 5 3.80 0.29 0.37 56.93 - 28.38 10.23 6 23.38 - - 29.72 - 27.73 19.17 7 16.15 - - 43.07 - 30.59 10.19 Questions ¾ Metal temperature 600ºC: too high for 9Cr-1Mo steel? ¾ Sulphur compounds added to the feed in platforming CCR unit are harmfull or advantageous ? 8