IBP1143_12 FURTHER DEVELOPMENTS AND FIELD DEPLOYMENT OF PHOSPHORUS FUNCTIONALISED POLYMERIC SCALE INHIBITORS 1 Malcolm J. Todd , Alex R.

Thornton2, Jonathan J. Wylde3, Catherine J. Strachan4, Gordon Moir5 & John Goulding6
Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Abstract
As the oil and gas industry strives to replace ageing, environmentally undesirable scale inhibitors there is an ever increasing use of polymeric inhibitors. The incorporation of phosphorous functionality into a polymer backbone has been shown to improve inhibition efficiency, enhance adsorption characteristics and allow the polymer concentration to be analyzed by elemental phosphorus. It is known that some phosphorus tagged polymers can be problematic to analyze in oil field brines as they typically have a low phosphorus content which is difficult to determine from the background. The development of novel phosphorus functionalized polymeric scale inhibitors was previously described (IBP3530_10). This paper follows the development of the inhibitor class. Utilizing extensive laboratory testing the interactive nature of the scale inhibitors and reservoir lithology was studied. These novel phosphorus functionalized inhibitors were compared to a number of other available scale inhibitors. The incorporation of phosphorus functionality into polymeric inhibitors can be expensive utilizing traditional methods as the phosphorus containing monomers are the financially limiting factor. These are typically vinyl phosphonic acid (VPA), or vinyl diphosphonic acid (VDPA). The novel phosphorus functionalized monomers utilized herein are simpler to manufacture allowing higher phosphorus content within the polymer backbone. The addition of phosphorus into a polymer backbone has previously been known to exacerbate analysis issues in some commercially available scale inhibitors. This is due to incomplete polymerization reactions leaving free and/or inorganic phosphorus containing moieties which can interfere with the analysis, or low levels of phosphorus within end-capped polymers can make it difficult to determine the active concentration accurately within field brines which contain many impurities. Polymeric inhibitors are known to contain a range of molecular weights with varying monomer distribution, it was important to gauge this effect in reservoir analogues. A reservoir rock will act as a large chromatography column, separating out the scale inhibitor according to molecular weight and phosphorus content. That is the larger molecular weights will adhere more strongly than lower molecular weight fractions, whereas polymer chains containing larger phosphorus functionality will adhere to the rock significantly stronger than those without. Thus it is important to understand if there were components containing phosphorus but did not contribute to the inhibition of scale. In order to study these effects the phosphorus functionalized polymers were tested on very clean sandstone core plugs in a core

______________________________ 1 Ph.D., Team Leader - Clariant Oil Services 2 Ph.D., Product Specilaist - Clariant Oil Services 3 Ph.D., UK Business Manager - Clariant Oil Services 4 MSc., Flow Assurance Team Manager - Clariant Oil Services 5 BSc., Global Application Development Manager - Clariant Oil Services 6 Ph.D., Consultant - John Goulding Consultancy

Rio Oil & Gas Expo and Conference 2012 flood rig. Their adsorption/retention characteristics were studied. The scale inhibitor effluent was analyzed by numerous methods and confirmed by inhibition efficiency measurements. Following successful development, one of the phosphorus functionalized polymeric inhibitors was subject to sequential field-trial in a harsh BaSO4 scaling, highly naturally fractured North Sea carbonate reservoir. As this was the first deployment of this novel technology the scale inhibitor returns and water chemistry were monitored using a number of methods to assess the efficiency of the inhibitor at mitigating the BaSO4 risk. A number of previous technologies utilizing phosphorus tagging have resulted in false readings due to anomalous phosphorus signals. The results presented in this paper show a step change with the scale inhibitor analysis by both elemental phosphorus (ICP-OES) and polymer methods (cartridge/Hyamine) showing excellent correlation. Indirect analysis of the scale inhibitor performance by elemental Ba2+ measurement confirmed the results, as there was no drop in Ba 2+ concentration indicating no significant scaling before the re-squeeze operation was conducted. The phosphorus functionalised inhibitor provided superior performance compared to the incumbent product. This indicated that the use of total phosphorus for concentration identification was accurate in this case. Following the successful deployment in a carbonate reservoir the novel inhibitor class was also deployed in a number of North Sea sandstone reservoirs and one field wide case study is reported with details on the innovative management and implementation strategy has been given. Focus has been given to the application of these products and a detailed analysis of field proven benefits given. This paper concludes with a detailed comparison of these phosphorous functionalized scale inhibitors with the incumbent products they have replaced in the case histories described. The benefits application of these novel and innovative products have given to the operator are described along with a technical synopsis of incremental performance benefits.

1. Introduction
Inorganic scale deposition in oil and gas production facilities is a severe problem which if left untreated can seriously impede production. Removal of such deposits is time consuming and expensive, so prevention of such deposits is preferable. Common inorganic scales such as CaCO3, BaSO4, CaSO4 and SrSO4 are prevented by the addition of sub-stochiometric quantities (typically 1 to 10 mg/L) of scale inhibitors. Scale inhibitors are polyelectrolytes which have the capability to chelate metal ions and inhibit nucleation of scales, or are drawn into the growing crystal structure and as such distort the crystal growth preventing adherence and deposition. Traditional scale inhibitors are either phosphonates which adhere well to the reservoir mineralogy, are easily detectable and are efficient at inhibiting most inorganic scale deposits as crystal growth modifiers. The poor biodegradability of phosphonate chemistry has lowered their environmental profile and forced the industry to become more heavily reliant on polymers in environmentally sensitive areas such as the North Sea. Polymeric inhibitors tend to show efficient nucleation inhibition, however they are generally poor at adsorbing to reservoir rock matrixes and as a result can give unacceptably short squeeze lifetimes. Until recently the detection of polymeric inhibitors has been more difficult than that of phosphonates, however recent literature published by Graham (2010), Marshall (2011) and Hoeth (2012)have shown that modern analytical techniques are able to accurately detect most polymeric species, although the techniques can be more timeconsuming and costly. It has long been the aim of industry to combine the inhibition efficiency, adsorption capacity and detectability of phosphonate chemistry with the more environmentally acceptable polymeric chemistry as discussed by Bourne (2010), Fleming (2001) and Todd (2010). There are several reasons why phosphorus functionality is attractive for inclusion in polymeric scale inhibitors: 1. 2. 3. 4. More acceptable environmental profile than phosphonates Improved inhibition efficiency of polymeric inhibitors resulting in a lower minimum inhibitor concentration (MIC) Improved adsorption capacity resulting in an increase in squeeze lifetime Improved detectability resulting in faster and convenient laboratory methods

Graham (2010), Marshall (2011) and Hoeth (2012) noted discrepancies between total phosphorus measured by ICPOES and direct polymer methods. That is, erroneous phosphorus signals indicate that the scale inhibitor is above 2

Rio Oil & Gas Expo and Conference 2012 minimum inhibitor concentration (MIC) when in reality the true scale inhibitor concentration is lower and subsequently scale deposition could ensue. This observation is not true for all phosphorus tagged or phosphorus incorporated polymers as it depends on the synthesis method. The real question should be; does it matter if the erroneous phosphorus is present if it isnt relied on for scale inhibitor analysis? Phosphorus can still be used for effective analysis even for mixtures of scale inhibitors, common to subsea or deep water assets provided that appropriate sample clean up stages are included. This paper looks at several successful field trials of the next generation of phosphorus functionalised polymeric scale inhibitors first introduced in by this group, Todd (2010).

2. Field Trials
Following the improved performance provided by Product A in laboratory tests it was proposed for several field trials. Carbonate Field The first field application was based on the performance exhibited in Figure 1. The field in question is part of a highly fractured North Sea carbonate formation; three separate wells were treated with Product A. The well discussed in this paper is E-23. In order to measure the inhibition efficiency irrespective of that derived from scale inhibitor assay, the Ba2+ concentration was measured and compared to the theoretical Ba2+ concentration. Thus giving a measure of actual scale inhibition efficiency regardless of the scale inhibitor concentration measured. This was done by calculating the actual sea water breakthrough from the Cl- concentration measured and multiplying it by the Ba2+ concentration of the formation water and subtracting the measured concentration, as shown below in Equations 2 and 3 respectively.

; . (2) ; (3)
Thus a positive [Ba2+] indicates a BaSO4 scaling event. This technique accounts for background changes in Ba2+ concentration caused by changes in SWBT. In this case study Product A is the new phosphorous functionalised polymeric scale inhibitor and Product B is the incumbent sulphonated co-polymer. Product A has the same backbone structure as Product B but with the incorporation of the novel phosphorous functionalised monomers. The E-23 oil well has had significant water-cut from day 1 and at time of publication produced 3500 bwpd with a high barium sulphate scaling potential. The well has historically experienced scaling episodes downhole and is now kept incheck via scale inhibitor squeeze treatments every 120 to 140 days. Squeezes are ultra-high rate frac-ball diverted bullheaded treatments performed using Product B (PVS-Co scale inhibitor). Following extensive laboratory testing, the novel phosphorus functionalised PVS-Co scale inhibitor, Product A, was selected for field trial on E-23. Figure 1 presents the results obtained for three consecutive squeeze treatments on E-23, the first using incumbent squeeze inhibitor Product B, and the second and third using Product A. Scale inhibitor returns data comparisons are presented, with product A residuals analysed using both total phosphorus by ICP-OES and SPEHyamine polymer analysis. Scale inhibitor performance is assessed via the dissolved barium ion concentration in E-23 produced waters, see Figure 1, with a focus on the delta barium value (theoretical actual), see Figure 2. The MIC of each of the scale inhibitors is also indicated, see Figure 1. The associated MICs of both products were determined for E23 by dynamic scaling loop experiments as 8 and 3 mg/L for Products B and A respectively. The results of the first two field trials are shown in Figure 1. Time on the x-axis is presented in days since the last Product B squeeze. The Product B reference squeeze performed well and provided satisfactory scale control for 150 days, and 439,801 accumulated barrels of produced water protected before planned re-squeeze. Scaling monitors including the delta barium ion response confirmed that scale control was maintained across the full time period, see Figures 1 and 2.

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350

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Figure 1 Field returns of incumbent inhibitor Product B and the subsequent 2 field trials with Product A on Well E-23.

The first Product A squeeze design was a duplicate of that used in the reference Product B squeeze. Product A was squeezed successfully and the well returned to production without incident or upset. After 115 days and 515,260 accumulated barrels of produced water later E-23 was shut-in for planned re-squeeze. All monitors used to assess scaling health in the well indicated that the squeeze performed according to expectations. The delta barium ion plot confirmed that scale control was maintained across the full time period, see Figures 1 and 2. Residual scale inhibitor concentration was also used to assess the squeeze performance, and Product A showed that it was easily detectable by total Phosphorus and SPE-Hyamine in this formation providing two separate and compatible residual scale inhibitor residuals assessments for increased confidence. The second Product A squeeze was again a duplicate of the reference Product B squeeze on E-23, and was allowed to run for 165 days (shown as 265 to 430 days in Figure 1) before re-squeeze. Even at 165 days and 910,142 barrels produced water production, the squeeze appeared to still have significant reserve to go on. The potential of this product is clear as it remains above MIC, measured by either method and there is no associated drop in barium concentration. This second squeeze showed significant potential again for squeeze lifetime extension over the incumbent Product B. Interestingly, the residuals profiles for both Product A squeezes suggests that at time of shut-in, the residual profile had only just reached the plateau phase of the conventional residuals return profile, which provides additional confidence that indeed the squeezes could have gone on for some time further.

[RSI] mg/L

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[Ba] mg/L

5 0 -5 -10 -15 -20 -25 -30 -35 -40 -45 -50 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420

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Figure 2 Changes in barium concentration from the theoretical level predicted on Well E-23.

The initial performance testing for this field was done by core flood (Todd 2012). However the unexpected result was the total phosphorus signal by ICP-OES from the field samples matched the polymer signal. In the lab tests there was a persistently high total phosphorus signal which if measured alone would have masked the inhibitor dropping below MIC. If the assumption is made that the core sample used in the previous study (Todd 2012) is representative then what would be the cause for these different phenomena and the significance? It has been suggested by another research group, Hoeth (2012), that the addition of a large volume of main treatment during core floods (10 pore volumes) is unrepresentative of the treatment in the field. In the field a much lower volume, e.g. 0.2 of a pore volume approximately is applied and in the core flood experiments the over treatment could induce competitive adsorption between the main polymer responsible for scale inhibition and the phosphorus containing impurities. Although it is not clear if there is competitive adsorption in this case with Product A, there does appear to be an effect from reservoir clean up. As the inhibitor is pushed through the rock matrix it is foreseeable that at these relatively high temperatures (130oC) and the abundance of Ca2+ available to the treatment pill that any phosphorus containing moiety not attached to the polymer could be preferentially precipitated, thus cleaning the Product A treatment pill as it propagates through the near well bore formation. Further work would be needed to validate any such theory. Sandstone Field 1 Sandstone Field 1 is a UK North Sea operated field producing from a clean sandstone reservoir. Sandstone Field 1 is a mature asset which has been producing oil off the coast of Scotland since the early 1980s. A moderate sulphate and carbonate scaling tendency has been experienced throughout the field lifetime. Two wells had been field trialed using Product A in Sandstone Field 1; both wells were previously treated with Product D (phosphorus functionalised co-polymer), however due to environmental legislation this had to be substituted. The first attempt to replace Product D was done by squeezing Product C (phosphorous end-capped polymer). The wells treated have been designated SF-16 and SF-24. Both wells were treated without incident and no loss in productivity has been reported. Limited sampling opportunities are available with either well and as such not much data is available. The return profile for SF-16 is shown below in Figure 3 and is analogous to that observed in SF-24 (not shown).

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Figure 3 Residual scale inhibitor measured during production of SF-16

Field MIC for all products has been identified as 5 mg/L. Product D performed well before it had to be substituted. Product C do not perform as well historically compared to Product D. The performance of Product A to date is exceeding expectations and it is expected to continue to give improved results over the incumbents. It is hoped the continuing success of Product A will be reported in the future.

3. Conclusions
This paper discusses the development of the novel phosphorus functionalised polymeric scale inhibitors and focuses on the controlled and successful deployment of Product A. The improved efficiency data had previously been discussed at length by this group, Todd (2011). However the improved adsorption capacity had only been touched on briefly as questions with in the industry still existed regarding the validity of using total phosphorus as an analytical technique for measuring residual scale inhibitor concentration. Product A was successfully field trialed on two carbonate formations (one discussed) and one sandstone formation. No problems were encountered during treatment and all wells were brought back on-line without incident. In all instances Product A showed an improvement over the incumbent (PVS-Co polymer-Product B) on Carbonate Fields 1 and 2 and (phosphorus functionalised co-polymer Product D) on Sandstone Field 1. In some specific fields it would appear that total phosphorus can be used to measure residual scale inhibitor concentrations of Product A. However it is not this is possible in all cases, i.e. in lower temperature fields and it is hypothesized that clean sandstones would not have the necessary calcium source to aid in the insolubility of the nonpolymer bound phosphorus. It is clear that the polymer methods used throughout this study are suitable to give accurate scale inhibitor concentrations of Product A in produced water which are indicative of the species responsible for scale inhibition. The purpose of incorporating phosphorus functionality into a polymeric backbone was previously thought to have several advantages: 6

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1. 2. 3. 4.

More acceptable environmental profile than phosphonates Improved inhibition efficiency of polymeric inhibitors resulting in a lower (MIC) Improved adsorption capacity resulting in an increase in squeeze lifetime Improved detectability resulting in faster and convenient laboratory methods

Through environmental testing Product A has been shown to be classed as gold no-substitution warning for use in the U.K. North Sea. There is a marked improvement in inhibition efficiency of Product A, not only over the phosphonates and base-polymers it is replacing but the previous generation of Phosphorus end-capped and functionalised polymers. The improved adsorption capacity can be seen from both laboratory and field cases which is due to the increased capacity imparted by the Phosphorus functionality. This in turn relates to a lower MIC, and greater squeeze lifetimes. This relates to lower costs associated with deferred oil production and well intervention. Improved detectability was considered at the inception of polymeric inhibitors and it generally implies use of total phosphorus by ICP-OES which appears to be attractive if it works in the lab. However there is still no guarantee that if used on its own it will give a clear indication of the concentration of moieties responsible for scale inhibition. None-theless phosphorus incorporated into a polymer backbone could be used for analysis of a single inhibitor in a multicomponent stream, assuming: 1. 2. All the components are known Solid phase extraction is used to remove any unwanted impurities from either the field, or the supplied inhibitor.

It should be noted that these anomalies are not thought to manifest themselves during continual injection application as there is no substrate for chromatographic separation. The ability to analyse Product A in field returns by ICP-OES was not pivotal to its success as the increased performance outweighed the lack accurate detection.

Rio Oil & Gas Expo and Conference 2012 Acknowledgements The authors would like to thank Clariant Oil Services Ltd for granting permission to publish this paper. Thanks to Angela Gibb for her work on the core floods and Marion Duncan for her time spent on analysis. References
H.M. Bourne, G. Williams & C. T. Hughes Increasing Squeeze Life on Miller with New Inhibitor Chemistry SPE 60198 paper presented at the SPE International Symposium on Oilfield Scale, Aberdeen, UK, 26-27 January 2000 N. Fleming, H.M. Bourne, C. J. Strachan & A. S. Buckley Development of an Ecofriendly Scale Inhibitor for Harsh Scaling Environments SPE 65040 paper presented at the SPE International Symposium on Oilfield Chemistry, Houston, TX, U.S.A., 13-16 February 2001 G. M. Graham, I. Munro,N. Harvison, K.Marshall & M. Kyle Improved Scale Inhibitor Assay for Sulphonated Polymers in Oilfield Brines SPE 131100 paper presented at the SPE International Symposium on Oilfield Scale, Aberdeen, UK, 26-27 May 2010 L. W. Hoeth, E. Sorhaug, G. M. Graham, R. Stalker, S. L. Kidd & R. Wright Effect of Coreflood Test Methodology on Appropriate Simulation of Field Treatments Paper 14 presented at the Tekna 23rd International Oil Field Chemistry Symposium 19-21 March 2012 K. Marshall, M. Kyle & G. M. Graham Analysis of Sulphonated Polymers in Oilfield Brines SPE 141575 paper presented at the SPE International Symposium on Oilfield Chemistry, Woodlands, TX, U.S.A., 11-13 February 2011 M. R. Rabaioli & T. P. Lockhart Solubility and Phase Behaviour of Polyacrylate Scale Inhibitors and Their Implications for Precipitation Squeeze Treatment SPE 28998 paper presented at the SPE International Symposium on Oilfield Chemistry, San Antonio, TX, U.S.A., 14-17 February 1995 Scaled Solutions Ltd JIP, Interim report 1, Section 4 Study 0863 Core to Field Tests September 2011 M. J. Todd, C. J. Strachan, G. Moir & J. Goulding Development of the next Generation of Phosphorus Tagged Polymeric Scale Inhibitors SPE 130733 paper presented at the SPE International Symposium on Oilfield Scale, Aberdeen, UK, 2627 May 2010 M. J. Todd, A. R Thornton, J. Wylde, C.J. Strachan, G. Moir Clariant & J. R. Goulding, Phosphorus Functionalised Polymeric Scale Inhibitors, Further Developments and Field Deployment SPE 154135 paper presented at the SPE International Symposium on Oilfield Scale, Aberdeen, UK, 30-31 May 2012