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IBP 1143 2 Presentation

Data · June 2015

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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

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

• 1. Previous Published Work

Environmental and Inhibitor Performances are key drivers

• 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

...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 ?

Phosphonates

Phosphinocarboxylic Acid (PPCA)

• 1. Previous Published Work

Why Add P-Functionality ?

• 1. Previous Published Work

How to ?

End Terminate

(P-Tagged)

In backbone Polymer, no P Functionality P - Functionalised

• Hybrids showing best performance characteristics of parents
• Improved Static Jar Test performance
• Equivalent dynamic tube blocking test performance

10 20 30 40 50 60 70 80 90 100

DETPMP P-S Co S Co

% Ba efficiency 5 ppm 10 ppm 15 ppm 10 20 30 40 50 60 70 80 90 100

DETPMP P-S Co S Co

% Ba efficiency 5 ppm 10 ppm 15 ppm

Water mix (a) Water mix (b)

• 1. Previous Published Work

Result

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

10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100 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 % Ba Efficiency Inhibitor Concentration (mg/L) Cummulative P.V.

Ba Efficiency 2 Hours Ba Efficiency 24 Hours Inhibitor Concentration Hyamine Inhibitor Concentration ICP-OES

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00 10 mg/L 25 mg/L 50 mg/L 75 mg/L Ba2+ Efficiency (%) Concentration 2 Hours 24 Hours

Product ‘A’ Coreflood : Forties 50:50, 95 oC, Clashach Outcrop Core

• G. M. Graham & K. S. Sorbie Paper No. 50 1994
• M. R. Rabaioli & T. P. Lockhart SPE 28998 1995
• 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

• 2. Further Laboratory Tests

Residual Detection & Impact

10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100 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 % Ba Efficiency Inhibitor Concentration (mg/L) Cummulative P.V.

Ba Efficiency 2 Hours Ba Efficiency 24 Hours Inhibitor Concentration Hyamine Inhibitor Concentration ICP-OES

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00 5 mg/L 10 mg/L 25 mg/L 50 mg/L 75 mg/L 100 mg/L Ba2+ Efficiency (%) Concentration 2 Hours 24 Hours

Product ‘D’ Coreflood : Forties 50:50, 95 oC, Clashach Outcrop Core

• 2. Further Laboratory Tests

Product D Inhibitor Efficiency Coreflood

• G. M. Graham & K. S. Sorbie Paper No. 50 1994
• M. R. Rabaioli & T. P. Lockhart SPE 28998 1995
• 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
• 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
• 2. Further Laboratory Tests

Residual Detection & Impact

Use specific polymer analysis for assessing RSI of functionalised scale inhibitors Recommendation

Agenda

• 1. Quick Review of Previous work (IBP3530_10)
• 2. Additional Laboratory Test work
• 3. Field Application of ‘P’-Functionalised Polymers

1 10 100 1000 10000 100000 100 200 300 400 500 600 700 800 900 1000 Applied Inhibitor Concentration (ppm) Cumulative P.V. Product A MIC 6 ppm Product B MIC 12 ppm Product C MIC 10 ppm 1 10 100 1000 10000 100000 100 200 300 400 500 600 700 800 900 1000 Applied Inhibitor Concentration (ppm) Cumulative P.V. Product A MIC 6 ppm Product B MIC 12 ppm Product C MIC 10 ppm

• 3. Field Application of Product ‘A’ in Well E23

Chalk Field Coreflood Sequence

130 C : Chalk Outcrop : Representative Field E Produced Water

• Mature Field
• Naturally Fractured Low Magnesia Chalk
• 2 Primary Payzones ‘E’ and ‘T’
• High Matrix Porosity, Low Matrix Permeability

‘T’ Formation ‘E’ Formation

High Matrix Porosity, Low Matrix Permeability

• Tectonic fractures
• Stylolite type fractures

Tectonic fractures are Most important for the permeability

Keff = Kmatrix+ Kfrac

1 1 – 10 mD mD 32 % 1 1 - 200 0 mD

TECTO TONIC NIC STYOL OLITE ITE

Ion Species Ionic Composition/mgl-1

Average ‘E’ Formation water Average ‘T’ Formation Water North Sea water

Na+ 21937 50200 10890 K+ 197 500 460 Ca2+ 3390 20200 428 Mg2+ 374 1790 1368 Ba2+ 253 920 Sr2+ 600 1690 7 Fe2+ 6 2 Cl- 39902 120123 19760 SO4

2-

17 8 2700 HCO3

• 421

125 140

Down wnho hole e Tempe mperature rature = 129 129oC Seawater Waterflood since 1987 Now w 134 Producer Wells, majority are wet

Field ld Squeeze eeze Hist story

• ry

m3 Prod Water Squeezes ezes Field Squeeze History

by 01. June 2010

m3 PW Squeezes 20 40 60 80 100 120 Year 1 000 000 2 000 000 3 000 000 4 000 000 5 000 000 6 000 000 7 000 000 8 000 000 9 000 000 10 000 000

Squeeze Treatments Produced Water [m3]

Water Injection Commences

• 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

Field Squeezes

C H

2

m C H

2

C H n C H C O

2

H S O

3

H x

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.

SISQ Planning – Other Important Considerations

…….. North Sea Weather

500um ESEM from of Well E-22 Water Sample

500um

BaSO4 ‘Blizzard’

• 3. Field Application of Product ‘A’ in Well E23

Delta Barium Assessment

Delta [Ba2+] Time 5 10 5 10 Trend of barium loss (scaling) Delta [Ba2+] = [Ba2+]THEORETICAL - [Ba2+]ACTUAL [Ba2+]THEORETICAL Evaluated via chloride ion factorisation and [Ba2+]FW

Product A 1st & 2nd FIELD TRIALS IN WELL E-23

1.0 10.0 100.0 1000.0 10000.0 100000.0 50 100 150 200 250 300 350 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420

[RSI] mg/L [Ba] mg/L Days

Barium SQZ POLYMER MIC PHOSPHORUS

Product B Product A Product A

1.0 10.0 100.0 1000.0 10000.0 100000.0 50 100 150 200 250 300 350 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420

[RSI] mg/L [Ba] mg/L Days

Product B Product A Product A

• 50
• 45
• 40
• 35
• 30
• 25
• 20
• 15
• 10
• 5

5 10 15 20 25 30 35 40 45 50 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420

[Ba] mg/L Days

Product B Product A Product A

Product A 1st FIELD TRIAL IN WELL X-01

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 0.1 1.0 10.0 100.0 1000.0 10000.0 100000.0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

[Ba] mg/L [RSI] mg/L Days since Squeeze

Polymer Phosphorous Barium

1 10 100 1000 10000 100000 100000 200000 300000 400000 500000 600000 700000 800000

[RSI] mg/L Produced Water (BBLS)

Product A Product D Product C MIC

Product A 1st FIELD TRIAL IN WELL SF-16

Conclusions

• All polymers will inherently have a molecular weight variation, or poly-

dispersity.

• There will also be a compositional variation throughout this mixture
• The extent of these two phenomena depends on the synthesis used
• For these reasons care is required when using ‘analytical tags’
• Incorporation of phosphorus functionality will improve the scale

inhibition performance

• Incorporation of phosphorus functionality will improve retention of

the polymer in the near well-bore area

• This translates to an increase in squeeze lifetime compared to

existing polymeric inhibitors

Conclusions

• Several highly successful field trials have been conducted with the new

phosphorus functionalised product

• No formation damage or start up problems were encountered
• Given confidence in Chalk Field 1 (E-23 shown) to continue and push

treatment to squeeze life potential

• It was clear from the second field trial that Product A has the potential to

exceed the treatments previously deployed by Product B

• Product A exceeded squeeze lifetime expectations in Carbonate Field 2 (X01)

by 120 days protecting 160,000 m3 of produced water (additional 64,000 m3)

• The same extension in squeeze life was observed in X02 (Carbonate Field 2)

protecting 230,000 m3 of produced water (additional 90,000 m3)

• Initial scale inhibitor residuals indicate Product A will give an extension in

squeeze life in Sandstone field 1 (SF-16)

Acknowledgements

The authors would like to thank :

IBP Technical Committee

Selecting the Paper for Presentation at RIO OIL & GAS 2012

Clariant Oil Services

for granting permission to publish this paper.

And last, but not least, those hearty souls working tirelessly in the technical support and product application and development laboratories without whom this paper would not have been possible -

Angela Gibb, Marion Duncan and Jamie Kerr (Clariant Oil Services UK) Issam Aarag, Matsi Henriksboe (Clariant Oil Services Scandinavia AS)