See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/278685234 IBP 1143 2 Presentation Data · June 2015 CITATIONS READS 0 18 6 authors , including: Alex Thornton Clariant International Ltd. 7 PUBLICATIONS 6 CITATIONS SEE PROFILE All content following this page was uploaded by Alex Thornton on 19 June 2015. The user has requested enhancement of the downloaded file.
IBP 1143_12 FURTHER DEVELOPMENTS AND FIELD DEPLOYMENT OF PHOSPHORUS FUNCTIONALISED POLYMERIC SCALE INHIBITORS M.J., Todd, J.J., Wylde, C.J., Strachan and G. Moir (Clariant Oil Services - UK) Alex R Thornton (Clariant Oil Services-Scandinavia AS) J.Goulding (J. Goulding Consultancy)
Agenda 1. Quick Review of Previous work (IBP3530_10) 2. Additional Laboratory Test work 3. Field Application of ‘P’ -Functionalised Polymers
1. Previous Published Work IBP3530_10 (Todd et.al 2010) “Development of novel phosphorus functionalized polymeric scale inhibitors ” 2 x Generic Scale Inhibitor types : Phosphonates Polymers Hybrid Phosphonated Polymer Environmental and Inhibitor Performances are key drivers
1. Previous Published Work Why Add P-Functionality ? Phosphonates • Good effective scale inhibitors, long track record • Useful for majority of common oilfield scales • But … poor environmental profile (<20% Biodegradation ) • And … generally poorer ‘nucleation inhibition’ than polymers Phosphinocarboxylic Acid (PPCA) ...So why introduce them ? • Create a hybrid which captures the best performance characteristics of both parents • Need to introduce / optimise significant quantities of P-functionality • Giving Improved scale inhibitor efficiency • Also, Improved ‘Adsorption/Desorption’ characteristics • Also Improve facility for low concentration detectability ?
1. Previous Published Work How to ? Polymer, no P Functionality End Terminate In backbone (P-Tagged) P - Functionalised
1. Previous Published Work Result • Hybrids showing best performance characteristics of parents • Improved Static Jar Test performance • Equivalent dynamic tube blocking test performance Water mix (a) Water mix (b) 100 100 5 ppm 10 ppm 5 ppm 10 ppm 90 90 15 ppm 15 ppm 80 80 70 70 % Ba efficiency 60 % Ba efficiency 60 50 50 40 40 30 30 20 20 10 10 0 0 DETPMP P-S Co S Co DETPMP P-S Co S Co
Agenda 1. Quick Review of Previous work (IBP3530_10) 2. Additional Laboratory Test work 3. Field Application of ‘P’ -Functionalised Polymers
2. Further Laboratory Tests Scale Inhibitors Scale Inhibitor pH Description Product A 3 Novel Phosphorus functionalised Sulphonated Co-polymer Product B 4.5 Standard Sulphonated Co-polymer Product C 3 Phosphorus end-capped Polymaleic Acrylic Co-polymer Product D 5 Phosphorus functionalised Polymaleic Acrylic Co-polymer
2. Further Laboratory Tests Product A Inhibitor Efficiency Coreflood Product ‘A’ Coreflood : Forties 50:50, 95 o C, Clashach Outcrop Core 100 100 100.00 90.00 90 90 2 Hours 24 Hours 80.00 80 80 70.00 60.00 Ba 2+ Efficiency (%) Inhibitor Concentration (mg/L) 70 70 50.00 40.00 60 60 30.00 % Ba Efficiency 20.00 50 50 10.00 0.00 40 40 10 mg/L 25 mg/L 50 mg/L 75 mg/L Concentration 30 30 20 20 10 10 0 0 21 28 49 67 87 108 128 148 169 189 209 230 250 278 318 359 398 439 479 520 561 601 642 682 723 764 804 845 918 1,070 1,223 1,233 1,237 1,248 1,269 1,289 Cummulative P.V. Ba Efficiency 2 Hours Ba Efficiency 24 Hours Inhibitor Concentration Hyamine Inhibitor Concentration ICP-OES
2. Further Laboratory Tests Residual Detection & Impact • ICP [P] gave much higher residual scale inhibitor (RSI) concentrations • Good Correlation between Hyamine derived [INH] and actual Jar test performance • Post-Flood Jar Test at 2 and 24 hours match reference Jar Test results • Suspect core material interacted with polymer mix and preferentially retarded the high molecular weight/ high P Functionalised active constituents, flushing out medium and low M.Wt • Via ICP we see low M.Wt fragments returning preferentially (high Total P) which generates a false HIGHER scale inhibitor concentrations • G. M. Graham & K. S. Sorbie Paper No. 50 1994 • M. R. Rabaioli & T. P. Lockhart SPE 28998 1995
2. Further Laboratory Tests Product D Inhibitor Efficiency Coreflood Product ‘D’ Coreflood : Forties 50:50, 95 o C, Clashach Outcrop Core 100 100 100.00 90.00 90 90 2 Hours 24 Hours 80.00 70.00 80 80 Ba 2+ Efficiency (%) 60.00 50.00 70 70 40.00 Inhibitor Concentration (mg/L) 30.00 60 60 % Ba Efficiency 20.00 50 10.00 50 0.00 5 mg/L 10 mg/L 25 mg/L 50 mg/L 75 mg/L 100 mg/L Concentration 40 40 30 30 20 20 10 10 0 0 21.7 53.3 86.2 119.1 152.0 184.9 217.8 277.4 340.5 406.3 472.1 552.4 618.2 Cummulative P.V. Ba Efficiency 2 Hours Ba Efficiency 24 Hours Inhibitor Concentration Hyamine Inhibitor Concentration ICP-OES
2. Further Laboratory Tests Residual Detection & Impact • Good agreement between RSI via the two analytical techniques • Post-Flood Jar Test at 2 and 24 hours do not match reference Jar Test results • Suspect different core material interaction with Product D polymer mix • Effective scale inhibitor component more strongly retarded by matrix interaction with phosphorus functionalities • Explains significant difference in 2 and 24 hour Jar Test performance • Much higher gross scale inhibitor material return over first 200 PV • G. M. Graham & K. S. Sorbie Paper No. 50 1994 • M. R. Rabaioli & T. P. Lockhart SPE 28998 1995
2. Further Laboratory Tests Residual Detection & Impact • Good Correlation between Hyamine derived [INH] and actual Jar test performance • ICP [P] gave higher residual scale inhibitor (RSI) concentrations IMPORTANCE • RSI used as scaling health monitor for squeeze treatment performance/ trigger • All Polymer exhibit a range of molecular weights • Formation rock can chromatographically resolve mixtures by size and charge Recommendation Use specific polymer analysis for assessing RSI of functionalised scale inhibitors
Agenda 1. Quick Review of Previous work (IBP3530_10) 2. Additional Laboratory Test work 3. Field Application of ‘P’ -Functionalised Polymers
3. Field Application of Product ‘A’ in Well E23 Chalk Field Coreflood Sequence 100000 100000 130 C : Chalk Outcrop : Representative Field E Produced Water 10000 10000 Product A MIC 6 ppm Applied Inhibitor Concentration (ppm) Applied Inhibitor Concentration (ppm) Product B MIC 12 ppm 1000 1000 Product C MIC 10 ppm Product A MIC 6 ppm 100 100 Product B MIC 12 ppm Product C MIC 10 ppm 10 10 1 1 0 0 100 100 200 200 300 300 400 400 500 500 600 600 700 700 800 800 900 900 1000 1000 Cumulative P.V. Cumulative P.V.
Mature Field Naturally Fractured Low Magnesia Chalk 2 Primary Payzones ‘E’ and ‘T’ High Matrix Porosity, Low Matrix Permeability ‘E’ Formation ‘T’ Formation
High Matrix Porosity, Low Matrix Permeability Ionic Composition/mgl -1 32 % 1 1 – 10 mD mD Ion Average ‘E’ Average ‘T’ North Sea Species Formation water Formation Water water Na + 21937 50200 10890 TECTO TONIC NIC STYOL OLITE ITE - Tectonic fractures K + 197 500 460 Ca 2+ 3390 20200 428 - Stylolite type fractures Mg 2+ 374 1790 1368 Ba 2+ 253 920 0 Tectonic fractures are Sr 2+ 600 1690 7 Most important for the Fe 2+ 6 2 0 permeability Cl - 39902 120123 19760 SO 4 17 8 2700 2- HCO 3 - 421 125 140 K eff = K matrix + K frac Down wnho hole e Tempe mperature rature = 129 129 o C Seawater Waterflood since 1987 1 1 - 200 0 mD Now w 134 Producer Wells, majority are wet
Field Squeeze History Field ld Squeeze eeze Hist story ory by 01. June 2010 Squeezes ezes Squeezes m 3 Prod Water m 3 PW 120 10 000 000 Squeeze Treatments 9 000 000 Produced Water [m 3 ] 100 8 000 000 7 000 000 80 6 000 000 Water 5 000 000 60 Injection 4 000 000 Commences 40 3 000 000 2 000 000 20 1 000 000 0 0 Year
Field Squeezes Deployed from stimulation boat Bullheaded High Rate (40-60 BPM) Frac ball diversion Scale Squeeze / Acid Frac Scale Squeeze 99% performed using Pro roduct uct B C H C H C H C H 2 2 m n x S O H C O H 3 2
…….. North Sea Weather SISQ Planning – Other Important Considerations Boat Availability Has to return to port for loading Now using Denmark /UK to enhance turn-around Weather Stim vessel cannot deploy safely above 30 knots and 3.5m Platform Access Simultaneous Well intervention operations, drilling.
500um BaSO 4 ‘Blizzard’ 500um ESEM from of Well E-22 Water Sample
3. Field Application of Product ‘A’ in Well E23 Delta Barium Assessment 10 Trend of barium loss (scaling) 5 Delta [Ba 2+ ] 0 Time 5 10 Delta [Ba 2+ ] = [Ba 2+ ] THEORETICAL - [Ba 2+ ] ACTUAL [Ba 2+ ] THEORETICAL Evaluated via chloride ion factorisation and [Ba 2+ ]FW
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