Corrosion and Scale at Extreme Temperature and Pressure

Transcription

1 Corrosion and Scale at Extreme Temperature and Pressure Paula Guraieb Tomson Technologies 1 Best of RPSEA 10 Years of Research - Ultra-Deepwater and Onshore Technology Conference August 30-31, 2016 The San Luis Resort, Spa & Conference Center, Galveston, TX rpsea.org

2 Presentation Outline o Project Overview and Timeline o Project Motivation and Objectives o Phase I Accomplishments o Phase II Accomplishments o Phase III Discussion 2 tomson.com

3 Motivation and Objectives o Motivation A lack of data and models for corrosion and scale at extreme temperature and pressure in ultra-deepwater reservoirs leads to uncertainty in predictions and operations. o Objectives Extend scientific understanding of corrosion and scale to xhpht conditions Establish xhpht lab test capabilities (250 C; 24,000 psig) Establish xhpht test methods Scale and inhibitor testing Corrosion and inhibitor testing Core flood testing at reservoir HPHT conditions Reduce operational and maintenance cost Mitigate environmental risk; improve safety Increase production security in ultra deepwater Create models rooted in experimental data 3 Source: LAMP 2015

4 Phase & Task Overview 4 o Phase I (Year 1): Tasks 1-4: Project Mgmt Plan; Tech. Status Assessment; Tech. Transfer; Reporting Task 5: Literature search on corrosion and scale at xhpht Task 6: Develop methodology to study scale and corrosion at xhpht and analyze with surface scanning instruments such as Vertical Scanning Interferometry (VSI) Task 7: Couple Task 6 results into viable models and experiments to validate Preliminary assessment of EOS and Pitzer equation Task 8: Detail report and recommendation for Phase II research o Phase II (Year 2 and 3): Task 9 - Collection of supporting data and models Task 10 - A preliminary design of imaging equipment Task 11 - Equation of State Development Task 12 - Peer Review Workshop Task 13 - Final Technical Report o Phase III (Post RPSEA funding) Continuation of xhpht corrosion and scale research for deepwater flow assurance Applied solutions to HPHT scale and corrosion

5 5 Timeline

6 Knowledge Gap 0 5 Pressure (psia x 1,000) Temperature ( F) TDS (mg/l x 1,000) and complex brine 400 Well known Unknown Conventional O&G production Current HT/HP production Deep water GOM Future xhpht 6 Water depth > = 1,500 m (~ 5,000 ft)

7 Phase I Accomplishments o Develop methodology to test corrosion and scale at xhpht o Successfully designed, built, and tested xhpht flow-through apparatus for corrosion and scale 24,000 psig 250 C 300,000 mg/l TDS o Fully custom HC-276 autoclave reactor designed and used o Bruker vertical scanning interferometer (VSI) Rapid/detailed surface analysis for uniform and localized corrosion 7

8 Phase I Accomplishments o Successful initial mineral solubility o Corrosion coupon (SS316, CS1018, CRA s) testing at xhpht o Electrochemistry equipment customized and applied at xhpht o Surface analyses techniques developed o Equation of state model development Before I-825, 250 C, 3 M NaCl solution, 60 psig CO2 Duration of experiment: 3 week Reactor Head Reference Electrode Counter Electrode After Working Electrode 8 Electrochemistry probes used in autoclave

9 Phase I Development ICP Corr. Inhib. Assay 24,000 psig pump VSI Lined tubing 9 xhpht flow-through HPHT column Programmable Oven HP Autoclave

10 Phase II Tasks o Task 9 - Collection of supporting data and models Subtask 9.1 Validate species activity coefficients at various HPHT and TDS conditions Subtask 9.2 Eliminate of ph measurement in HPHT solution theory Subtask 9.3 Nucleation kinetics and inhibition of scale formation Subtask 9.4 Investigate the thermal limit of scale inhibitors Subtask 9.5 Scale and corrosion inhibitor treatment methodology o Task 10 - A preliminary design of imaging equipment o Task 11 - Equation of State Model Development o Task 12 - Peer Review Workshop o Task 13 - Final Technical Report 10

11 Phase II Executive Summary 11 o Strictly anoxic condition (<< 1 ppb O 2 ) has been established Developed and designed apparatus to remove dissolved O 2 (DO) The tested DO concentration is far less than 1 ppb Ankerite (CaMg 0.27 Fe 0.73 (CO 3 ) 2 ) instead of magnetite (Fe 3 O 4 ) formed at 200 C under strictly anoxic condition in real brine o Solubility of iron sulfide (Troilite, FeS) was studied at xhpht Hard to study Limited studies o Nucleation kinetics studies of various scales and their inhibition Carboxyl ethyl inulin shows better inhibition efficiency toward ferrous carbonate at 100 C Sulphonated polycarboxylic acid (SPCA) shows good inhibition efficiency toward iron oxides at 250 C Formation of Fe-SPCA complex o Studies of thermal limit of scale inhibitors toward BaSO 4, CaCO 3 and SrSO 4 Polyvinyl sulphonate (PVS), Maleic acid copolymer (MAC) and SPCA show nearly 100% inhibition of all scales at 180 C Their inhibition efficiency toward BaSO 4 and SrSO 4 decreased dramatically at 250 C Prevent majority of CaCO 3 formation at 250 C o Inhibitor core flooding apparatus has been designed, customized and validated for inhibitor squeeze simulation

12 Phase II Tools Developed and Used o Dynamic tube blocking nucleation time determination o Electrochemistry (LPR, CP, EIS) o Packed column solubility tests o Increased autoclave testing capability (rotating cage, multiple setups) o Tubular corrosion coupon analysis o Core flooding apparatus HC-276 Autoclave w/ Electrochem Probes 12

13 Height (μm) Height (μm) Height (μm) VSI Surface Capabilities Flat Cylindrical Tubular VSI is powerful tool for surface characterization of both flat and curved coupons. Various shaped coupons used in autoclave, glass-cell, and flow-through have been analyzed using VSI. 13

14 Localized Corrosion is the Concern for CRAs at xht o VSI was developed as a powerful tool to detect localized pitting rapidly Alloy I C, 60 psig P CO mm/yr Uniform CR = mm/yr BCS PUBLICATION: Corrosion Science: Vol. 87, Oct 2014, p

15 Corrosion Sci. Paper: VSI for Uniform Corrosion Avg. CR units CR by VSI mm/y CR by WL mm/y R: um um Pre-test Ref Paper published with Bruker Corrosion Science: Vol. 87, Oct 2014, p Post-test R: um um Experimental Conditions: Ref C, 3 M NaCl solution 60 psi g CO 2 charged at 25 C ph 5 adjusted 3 weeks 15

16 Phase II Highlighted Accomplishments o Designed system to produce strictly anoxic (<< 1 ppb O 2 ) brine at xhpht Fundamentally different results in both scale and corrosion studies Reservoirs naturally anoxic o Mineral scale solubility at xhpht in flow through apparatus Extend prediction models and understanding o Thermal limit of inhibitors Stability of inhibitors after long term temperature exposure << 1 ppb dissolved O 2 ~92 ppb dissolved O 2 Synthesized Siderite powder anoxic vs. 92 ppb O 2 16

17 Phase II Highlighted Accomplishments o o o Effect of scale formation on corrosion at xhpht Kinetics Protective film/corrosion product formation Realistic field brine importance at xhpht Downhole conditions Production tubing Pitting evaluation of (CRAs) at xhpht Showed PREN as ineffective materials selection guide at temperature and pressure New Concept Defined: Repassivation Potential 17 Corrosion and scale inhibitor thermal stability at xhpht and realistic brine conditions Synergistic effects and importance of anoxic conditions Vertical Scanning Interferometry development Uniform and localized corrosion measurements Software development with Bruker

18 Introduction - FeS Iron sulfide o No gas phase of H 2 S present in the experiment o Performed in fume hood with H 2 S monitors o Present in several crystalline forms with different solubility o Phase composition can change with time and history of thermal treatment 18 H.A. Nasr-El-Din and A.Y. Al-Humaidan, Iron sulfide scale: formation, removal and prevention, SPE 68315, 2001

19 Solubility Studies using Flow-Through Apparatus o Lack of mineral solubility data to accurately predict scale formation at xhpht (up to 250 C and 24,000 psig) o Solubility of calcite (CaCO 3 ), siderite (FeCO 3 ) and magnetite (Fe 3 O 4 ) has been investigated o Highly customized with all wetted parts made of PTFE coated Hastelloy C-276 to resist corrosion at these conditions o Modified to allow for strictly anoxic sample collection Cooling Stage Anoxic brine storage Heating setup Column Anoxic sampling Back Pressure Regulator 19 Pump Pump (Chelating agent)

20 Intensity Characterization of Packed Troilite Before Experiments Experimental data Troilite PDF Fe0.99C0.01 PDF Theta XRD spectrum of troilite (FeS) before experiment o Black line shows the experimental data o Red circles show the standard troilite structure (PDF# ) SEM image of troilite (FeS) with sharp edges and smooth surface before experiment 20

21 Experimental Details Reaction: FeS (s) + H + Fe 2+ + HS Solubility product (K sp ) defined as: K sp,fes = m Fe 2+γ Fe 2+m HS γ HS Τa H + pk sp = log 10 (K sp,fes ) = log 10 (m Fe 2+γ Fe 2+m HS γ HS /a H +) Note: secondary dissociation constant K 2 for H 2 S is not accurately defined 21 o 1 M or 3M NaCl, 5 mm sodium citrate and 5 mm citric acid was used as feed solution under strictly anoxic conditions (<< 1 ppb O 2 ) o Retention time of 181 min (0.02 ml/min) in the packed column was chosen o Sample was analyzed using inductively coupled plasma (ICP) for total iron concentration

22 pksp pksp Troilite Solubility at 100 C 1 and 3 M NaCl 100C-1M NaCl 100C-3M NaCl pksp (this study) pksp predicted Linear (pksp (this study)) y = -3E-05x R² = pksp (this study) pksp predicted Linear (pksp (this study)) y = -3E-05x R² = Max. ΔSI= Max. ΔSI= y = -3E-05x R² = y = -1E-05x R² = ,000 10,000 15,000 20,000 25,000 30, ,000 10,000 15,000 20,000 25,000 30,000 Pressure (psig) Pressure (psig) 22

23 pksp pksp Troilite Solubility at 175 C 1 and 3 M NaCl 175C-1M NaCl 175C-3M NaCl 5.00 pksp (this study) pksp predicted Linear (pksp (this study)) 5.00 pksp (this study) pksp predicted Linear (pksp (this study)) y = -3E-05x R² = y = -3E-05x R² = Max. ΔSI= Max. ΔSI= y = -4E-05x R² = y = -5E-05x R² = ,000 10,000 15,000 20,000 25,000 30, ,000 10,000 15,000 20,000 25,000 30,000 Pressure (psig) Pressure (psig) 23

24 pksp pksp Troilite Solubility at 250 C 1 and 3 M NaCl 250C-1M NaCl 250C-3M NaCl 6 pksp (this study) pksp predicted Linear (pksp (this study)) 6 pksp (this study) pksp predicted Linear (pksp (this study)) 5.5 y = -3E-05x R² = y = -3E-05x R² = Max. ΔSI= Max. ΔSI= y = -6E-05x R² = y = -6E-05x R² = ,000 10,000 15,000 20,000 25,000 30,000 Pressure (psig) 2 0 5,000 10,000 15,000 20,000 25,000 30,000 Pressure (psig)

25 Intensity Characterization of Packed Solids After Experiments Experimental data Troilite (FeS) PDF Pyrrhotite (Fe11S12) PDF NaCl PDF Troilite (75.1%) 600 o o o Theta XRD of packed solids after 250 C experiment Both troilite (red dots) and pyrrhotite (blue squares) phases are shown NaCl (yellow diamonds) are also present Weight percentage in solid after experiment ~75.1% Troilite ~24.9% Pyrrhotite Pyrrhotite (24.9%) 25

26 Characterization of Packed Solids After Experiments 26

27 Summary of Iron Sulfide Solubility Study o First experimental study of FeS solubility under xhpht up to 250 C and 24,000 psig in 1 M and 3 M NaCl for model development o Safe method for studying sulfide species o Strictly anoxic condition (<< 1 ppb O 2 ) has been used to perform solubility experiments Feed solution preparation Sample collection o Reliable flow through apparatus has been used for solubility studies under xhpht and can be extended for other scale research 27

28 Intensity Potential vs. saturated Ag/AgCl / V Experimental Database Autoclave o G3, Ni718, I-825, L80, SS2507, G3, HC276, CS1018, CS 1010, 13 Cr o Weight loss method: 5 temps, 10 alloys, 3 concentrations = 300 coupons corroded and analyzed o LPR: 5 temps, 10 alloys, 3 concentrations = 300 coupons corroded and analyzed o Cyclic polarization 6 alloys, 2 temps, 2 concentrations, 2 polarization settings o Electrochemical impedance spectroscopy (EIS) o Imaged all coupons SEM XRD VSI I 825_250 C_3M NaCl Current density / A/m Exp CaCO3 60 Fe3O4 Ankerite 50 FeCO Theta

29 Intensity Experimental Database Flow-through corrosion SEM of Synthesized Ankerite Experimental Siderite Ankerite Calcite o Simultaneous temperature and pressure conditions (up to 250 C; 24,000 psig) HC-276 C1010 SS316L o Complex brine composition ICP for ions of concern (e.g. Fe, Ca, Mg, Sr) o Ankerite studied Ca(Fe,Mg,Mn)(CO 3 ) 2 Strictly anoxic (<< 1 ppb O 2 ) o Surface imaging techniques SEM VSI Θ

30 Experimental Database Packed column o In house synthesis of particles o Solubility at 150 C and 5,000 psig to 24,000 psig Calcite, Barite, Siderite, Magnetite, FeS Solubility at 250 C and 5,000 psig to 24,000 psig o Characterization of all solids XRD, SEM o ICP analysis of all samples collected Ions of concern for corrosion and scale Cooling Stage Heating setup Column Back Pressure Regulator Sampling Pump Pump (Chelating agent) 30

31 Experimental Database 31 o Tube blocking setup: scale nucleation and induction time Scale nucleation at xhpht (180 C data and 250 C) Barite, calcite, celestite, anhydrite, hemihydrate Titanium setup for zero iron background Siderite, Fe x O y o Ion concentration with time analysis ICP data for all samples (sampled 10 times over 2 hour test duration) Inhibitor return curve o Nucleation time o Various field based inhibitor concentrations o Varying temperature (100 C to 250 C) and pressure conditions o Direct injection inhibitor performance Sulphonated polycarboxylic acid (SPCA) Polyvinyl sulphonate (PVS) Carboxymethyl Inulin (CMI) Maleic acid copolymer (MAC) Polyacrylic acid (PAA) Polyacrylamide (PAM) BHPMP Sodium citrate

32 Publications o Journal Corrosion Science o OTC VSI application in corrosion Vol. 87, Oct Mineral scaling kinetics and inhibition 2014, pp: (2015 #25126) Pitting evaluation of CRAs at xhpht Corrosion of CRAs at xhpht in flowthrough (2014 #25193) (submitted) o NACE o Journal of Chemical Engineering Localized corrosion of CRAs at xhpht in (Rice) Examining the Consistency of autoclave (2015 #5620) Water Content Data in Alkanes Using the Solubility of FeCO 3 at xhpht (2015 Perturbed-Chain Form of the Statistical #5623) Associating Fluid Theory Equation of Uniform corrosion of CRAs at xhpht in State autoclave ( 2014 # 3978) o Journal of Chemical Physics Solubility of CaCO 3 at xhpht ( 2014 (Rice) Isolating the non-polar #4360) contributions to the intermolecular o SPE potential for water-alkane interactions FeCO 3 precipitation kinetics (SPE 2015) o Several other pending publications 32

33 Phase III 33 o Why Upcoming production from xhpht deepwater Continued industry need for xhpht applied research No startup time for continued research and development Demonstrated expertise in xhpht scale and corrosion research o When Currently seeking partners for continued research o Who Government funding Production companies Service companies o Outcomes & Benefits Accurate xhpht predictive modelling based on experimental data Inhibitor screening, development, and testing Materials selection database (CRAs, pitting tendencies) Applicable research in xhpht areas of interest

34 Cumulative Costs Cumulative Costs Cumulative Costs Budget o Total project cost is now met Full written report to follow at the end of August. o Cost Share provided at above required 20% level Project Costs Invoiced Technology Transfer Costs Project Month Planned Actual Invoiced Cost Share Project Month Planned Actual Planned Actual Project Month

35 Acknowledgements o James Pappas, President RPSEA o Bill Fincham, NETL / DOE o Roy Long, NETL / DOE o Working project group members: Anadarko Apache Aramco Baker Hughes BP Chevron Clariant ConocoPhillips Dow ExxonMobil GE Halliburton OneSubsea Nalco Champion Oxy Petrobras Schlumberger Siemens Shell Statoil Total 35

36 Teams Tomson Technologies o Mason B. Tomson, Prof., Ph.D., P.E. o Ross C. Tomson, J.D., M.E.S. o Paula Guraieb, M.S. o Chao Yan, Ph.D. o Nasser Ghorbani, Ph.D. o Shane Graham, B.S. Rice University o Walter G. Chapman, Prof., Ph.D. o Kenneth R. Cox, ProfPrac, Ph.D., P.E. o Essmaiil Djamali, Ph.D. o Dilip N. Asthagiri, Ph.D. o Artee Bansal, Ph.D. candidate o Wael Ahmed, Ph.D. candidate o Mason B. Tomson, Prof., Ph.D., P.E. o Ross C. Tomson, J.D. M.E.S. 36

37 Contacts Principal Investigator: Mason Tomson Tomson Technologies Presenters: Paula Guraieb Tomson Technologies Project Manager: Bill Fincham NETL Technical Coordinator: James Pappas RPSEA