SPE 87441 Development of an Enzyme Activated, Low Temperature, Scale Inhibitor Precipitation Squeeze System

J.A McRae (SPE), S. M. Heath (SPE), C. Strachan (SPE), L. Matthews (SPE), Clariant Oil Services, R. Harris (SPE), Cleansorb Ltd

Copyright 2004, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 6th International Symposium on Oilfield Scale held in Aberdeen, UK, 26-27 May 2004. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

This paper will also highlight how the use of the enzyme precipitation process can increase squeeze lifetimes when compared to traditional adsorption squeeze treatments at low temperatures. Introduction Scale is usually defined as the precipitation of solid minerals from production fluids, a reaction that can occur anywhere from the reservoir to topside production facilities during production. The type and severity of scale formation is directly dependent on ionic and gas compositions of formation waters and injection waters, pressure, temperature and other environmental conditions. Each producing well can therefore potentially have its own unique scaling regime. If left untreated, continuous buildup of scale can severely limit production potential, in some cases to the point where the system would have to be shut down temporarily to allow physical or chemical removal of the solid scale. In the majority of cases, especially in offshore conditions, this would not prove to be an economically feasible proposition, hence the need to prevent scale by the introduction of scale inhibitors into the production process. The most widely used method of combating the formation of scale downhole is to inject these scale inhibitor chemicals into the near-wellbore region, known as squeezing, which prevents or slows the nucleation and growth of the scale crystals over time. In a typical aqueous treatment, a large volume of scale inhibitor, known as a slug is injected into the reservoir and retained in the formation by one of two main mechanisms: 1) Adsorption by ionic charge to the rock surface (hydrogen bonding or calcium bridging) 2) Precipitation of the inhibitor into rock pore spaces. When production is resumed the scale inhibitor is released into the produced fluids to prevent/retard the formation of scale. The selection of type of squeeze treatment employed is dependant on a number of different different variables including the water chemisitry and scaling regime, the physical characteristics of the target well (completion type, temperature, pressure, porosity, lithology and production rates etc.) and the treatment lifetime required.

Abstract Since the early 1990s scale inhibitor precipitation technology has been routinely used throughout the North Sea to provide improved placement and extended treatment lifetimes when compared to conventional aqueous-based scale inhibitor squeeze treatments. Controlled precipitation technology is based upon the deployment of a specially formulated scale inhibitor package containing an organic additive that breaks down thermally and acts as a pH modifier resulting in in-situ scale inhibitor precipitation. However, the reliance on thermal degradation of the organic additive to cause precipitation means that this technology is limited to use in wells at temperatures > 85C. This paper describes the development of a low temperature, scale inhibitor precipitation delivery system. The new system is based upon the use of novel enzyme technology to break down the pH modifier using a non-thermal mechanism, thus allowing product deployment at low temperatures previously unavailable to the thermal degradation systems. Laboratory studies have so far indicated that the enzyme is effective at inducing scale inhibitor precipitation at both 40C and 80C. A description of the laboratory development and evaluation of the new enzyme precipitation technology including enzyme assay, full analysis of the precipitation mechanism and core flood studies to evaluate formation damage potential and retention and release characteristics will be presented.

www.petroman.ir

SPE 87441

In this paper, it is the precipitation method of adsorption that is mainly considered. Precipitation squeeze treatments have been routinely deployed in the North Sea as a method of extending squeeze lifetimes compared to conventional adsorption only squeezes1. In addition, the scale inibitor precipitation process can be used to increase the treatmnet lifetimes for products that otherwise do not exhibit favourable adsorption characteristics and would normally give poor squeeze lifetimes. Conventional precipitation squeezes involve formulation of a product to include divalent cations and depends on the in-situ formation of a sparingly soluble inhibitor salt at swept out locations from the near wellbore1. Acid-based scale inhibitors are generally unlikely to precipitate in the presence of divalent cations at low pH due to their high level of protonation. It is therefore important to control the pH of the product such that partial, or in some cases, full de-protonation of the molecule takes place in the presence of the cations, making the precipitation reaction thermodynamically favourable. Conventionally, this has been achieved by the inclusion of a thermally sensitive additive to the formulation that will break down at temperature causing increase in pH, increased de-protonation and therefore forcing the cation-inhibitor precipitate formation. Urea is an organic species that will undergo thermal hydrolysis at temperatures over 85C according the following reaction mechanism:
NH2CONH2 + (1+x) H2O NH4COO- NH2

BACKGROUND Enzymes are large amino-acid polymers produced by all living organisms to act as catalysts for specific biological processes. Most of the reactions they catalyse are essential to life and would only otherwise be possible under more severe conditions. Their use as catalysts means that only small amounts are used and they are not consumed in the reaction and are regenerated. Normally, enzymes are highly soluble in water and their biological nature often means they pose no threat to the environment. For these reasons, enzymes are often used in the place of more hazardous chemical steps in large-scale industrial processes. In general terms, enzymes can either be used to produce required products or degrade unwanted intermediates. Current uses of enzymes in oilfield systems include treatment of biopolymers, gel breaking/crosslinking and controlled acid production2. The biological nature of these enzymes means that they are rated as PLONOR additives and will not adversely affect the environmental category of the product. The enzyme used in this study will catalyse the degradation of urea and resultant production of ammonia and carbon dioxide. Its normal function is the hydrolysis of urea in plants or microorganisms as the final step in nitrogen mineralization. As described earlier, the formation of ammonia gives an overall increase in solution pH, reducing the solubility of a cationinhibitor complex species in scale inhibitor formulations. The mechanics of the reaction involving the enzyme compared to the thermal process are different but the products are the same and the reaction will generally take place at a much higher reaction rate. The proposed mechanisms for the enzyme reaction3 are presented in Figure 1. Reducing or increasing the amount of enzyme present will alter the reaction rate accordingly. In this paper we will present a study using enzymes as a lowtemperature replacement for thermal degradation of urea, in scale inhibitor formulations designed for precipitation squeeze treatments. LABORATORY EVALUATION The scale inhibitors used in the study were a sulphonated copolymer and a maleic acid based terpolymer, both suitable for low temperature inhibition of sulphate scales. The testing involved: 1) Evaluation of phase separation behaviour with inclusion of enzyme at temperatures not suitable for thermal degradation. Comparisons were made to behaviour under thermal degradation conditions. 2) Coreflood tests to evaluate the potential for formation damage and inhibitor release profiles of the enzyme precipitation system. Comparisons were made to adsorption only conditions in the absence of the enzyme.

2NH3 + CO2 + (x)H2O

The formation of ammonia causes the required increase in solution pH and subsequent incompatibility between the cations and inhibitor in solution. This reaction will only take place at these elevated temperatures and not at ambient conditions. This allows confidence that the inhibitor solution will remain stable under ambient conditions and precipitate will not form until the inhibitor solution reaches sufficient temperature in the wellbore after pumping and a shut-in period. The dependence on thermal degradation for pH control means that these products are limited to use in fields with reservoir temperatures of >85C. Below this temperature, the urea will either not degrade at all, and hence no precipitation will take place, or any hydrolysis will be so slow as to make the required shut-in period economically unfeasible. In order for this to become possible, there must exist a mechanism of causing the breakdown of urea at these lower temperatures and with acceptable phase separation and economical shut-in times. In this study a novel enzyme system to cause hydrolysis of the urea in the precipitation inhibitor formulation has been evaluated. This will eliminate the need for minimum BHT to ensure thermal degradation whilst offering the same end result of pH increase and formation of a sparingly soluble divalent cation inhibitor precipitate.

www.petroman.ir

SPE 87441

3)

Dynamic scaling loop tests to evaluate effect of enzyme addition on scale inhibitor performance. iii) iv)

hours at 120ml/hr to ensure complete brine saturation of the core material. Measure absolute permeability to brine at 20C. Deermine pore volume by injecting Lithium tracer in synthetic formation water. Heat system to test temperature, permeability to brine at this temperature. measure

As discussed earlier, these temperatures were chosen as they represent conditions under which thermally based inhibitor precipitation would not normally be considered. The thermal hydrolysis of urea below 85C is extremely slow and would not represent economic viablity as shut-in times to allow precipitation would be extended to >24 hours5. Static Phase Separation Tests

v)

vi) Static phase separation tests were conducted on formulations of the inhibitors with varying enzyme concentrations and solution pH. The formulations containing enzyme were heated to temperature in jars and the reactions followed by monitoring the changes in physical appearance and cation to inhibitor ratios over a 24-hour period. Samples of supernatent fluid were collected at various time intevals over the 24 hour test period and analysed for Ca, Mg and inhibitor content. Blank samples, i.e. containing no enzyme, were added at this temperature to ensure that any thermal effect that did take place would not be ignored. A sub-sample from the stable formulations before exposing them to elevated temperature was used as a control. Identical formulations of all without the enzyme present were also tested at 95C to evaluate the differences in behaviour under conditions at which urea is known to thermally degrade4,5. Core Flood Tests The coreflood tests detailed in this paper were carried out on Clashach core, a local outcrop sandstone believed to be generically representative of many North Sea sandstone formations. Synthetic laboratory formation water and seawater were used throughout this study, see Table 1. Corefloods were performed to evaluate the potential for formation damage and the scale inhibtor release profiles of the ezyme precipitation systems. Precipitation corefloods were performed with the sulphonated copolymer (scale inhibtor 1) and polymaleic acid (scale inhibitor 2) formulations at 80C and 40C respectively. Standard adsorption corefloods wer performed for comparitive purposes. The adsoprtion and precipitation corefloods were performed with the same amount of active chemical in order to enable a suitable comparison of the scale inhibtor return profiles. A summarry of the coreflood procedures is detailed below: Procedure i) Measure core plug and assemble within (Viton) rubber sleeve in Hassler core-holder at 1000psi confining pressure. Flood the core with synthetic formation brine (formation water A) at room temperature for at least 3

Flood core with crude at 120mls/hr for at least 3 hours to ensure residual brine saturation. Measure oil permeability to residual brine in the core Flood core with brine at 120mls/hr for at least 3 hours to ensure residual oil saturation. Measure brine permeability to residual oil. Inject approx. 6 pore volumes of formalated scale inhibitor into the core and shut in for 12 hours. Flood core with crude and measure post-treatment permeability values. Flow synthetic formation water through the core for ~800 pore volumes and collect effluent samples for ion and scale inhibitor analysis. Measure final permeability to formation water Flood with crude crude permeability and measure final

vii)

(viii)

ix)

x)

xi) xii)

xiii)

Clean core with alternative floods of methanol and toluene. Flood core with synthetic formation water and measure final absolute permeability to brine.

xiv)

Dynamic Scale Loop Tests Comparative barium sulphate scale tube performance tests have been conducted with the scale inhibitor in the presence and absence of investigate the effects of enzyme addition inhibition performance. blocking polymaleic enzyme to on scale

The experimental conditions are summarised as follows: System Pressure: System Temperature: Coil dimensions: Brine mixture: Pass criterion: Flow rates: 250 psi (17 mbar) 40C ID = 0.8 mm, L = 1000 mm 50:50 SW:FW (Field B brine) < 1psi increase in DP over 4 hour. 6 ml /min combined flow rate (50:50 mix, 3ml/min per brine).

. ii)

www.petroman.ir

SPE 87441

For the purposes of the test, 3 brines were prepared; an anion and cation brine, to separate the scaling ions, and an inhibitor dosed brine. The anions and cations were pumped together into the coil at a 1:1 ratio to give a noticeable pressure rise indicating that tube blocking due to scaling was occurring, The inhibitor was introduced and its concentration decreased stepwise until the pressure rise was observed to occur again, indicating the inhibitor was ineffective at that concentration. This technique is standard to the industry and is discussed in more detail in previous literature.6

in Figure 2. The data indicates that the rate of loss from solution of both species is high for the initial 2-3 hours after enzyme addition and levels off after this time. This indicates that the precipitation reaction is concluded after 2-3 hours and this also correlates with scale inhibitor 1 phase separation times. Dynamic scaling looptests Dynamic tube blocking tests were performed with a 50:50 mix of formation water B and seawater to assess the effect on scale inhibition of adding enzyme to scale inhibitor 2. The tests involved pumping anions and cations together into a heated coil and measuring differential pressure increases as mineral precipitate was formed. Identical formulations were tested, with the only difference being the addition of enzyme to one solution before injection to the coil. The Calcium concentration in each formulation was replaced with weight equivalent of Sodium Chloride for the purposes of this test to ensure that no precipitation of scale inhibitor would take place. This would affect the final result as the test cannot differentiate in situ between the formation of scale and inhibitor precipitate in the coil. The plot from the tube blocking test comparing the performance of scale Inhibtor 2 with and without the addition of enzyme is presented in Figure 3. In both tests the differential pressure remains constant as the inhibitor concentrations are decreased by 5ppm increments stepwise from 40ppm. When the inhibitor concentration reached 25ppm, for both formulations, the differential pressure was observed to increase indicating the formation of scale in the coil. This result gives a Minimum Inhibitory Concentration (MIC) of 30ppm for both formulations. The addition of enzyme therefore had no recognisable effect on the efficiency of the formulation to inhibit scale. Core Flood tests Coreflood tests were performed to identify the retention and release characteristics of both enzyme formulations of scale inhibitors 1 and 2 in Clasach core material. The subsequent return profiles were compared with equivalent aqueous adsorption mechanisms. This technique is useful in predicting likely chemical retention and treatment lifetime in the field, by replicating pressure, temperature and brine compositions as closely as possible.7 Analysis of the effluent brine during flowback allows direct comparison between the adsorption and precipitation mechanisms of retention. Scale Inhibitor 1 The inhibitor return profile for the adsorption only treatment with scale inhibtor 1 at 80C with formation water A is presented in Figure 4. The profile is of typical distribution, featuring an initial sharp decline in concentration, representing the removal of components of the inhibitor not adsorbed to the core. This is

RESULTS AND DISCUSSION Static phase separation tests Static phase separation tests were performed to provide an assessment of the effect of addition of enzyme to standard precipitation inhibitor formulations. The temperatures used (40 &80C) would normally be too low for products requiring thermal degradation of urea, providing solution pH increase. Identical formulations without the urea were also tested at 95C to display behaviour under thermally favourable conditions. All formulations were tested at 20% in synthetic seawater, the typical concentration in field applications. The enzyme was added to formulations of the scale inhibitor containing CaCl2 and urea. The phase separation times for different formulations of both inhibitors, adjusted to have different initial pH at 95C, are presented in Table 1. No enzyme was added to these products as the temperature should be high enough to ensure thermal degradation of the urea. All inhibitor formulations exhibited a large rise in pH from approx. 4 to 8 over 24 hours and phase separation was observed from 1-3 hours, see Table 1. This indicates that under these conditions, the urea was thermally hydrolysed, resulting in the precipitation observed. The phase separation times at 80C for the various formulations with scale inhibtor 1, with varying amounts of enzyme solution added, are presented in Table 3. The enzyme additions are expressed as normalised values and are linear increases in concentration. The Blank samples i.e. no enzyme addition, failed to phase separate within 24 hours at 80C, however, all samples with the enzyme added produced a precipitate, Table 3. It was clear that the amount of enzyme added has an effect effect on final solution pH. In the samples with no added enzyme, the phase separation was >24 hours and the pH did not rise above 5 in any of the formulations. This indicated that the urea did not undergo thermal hydrolysis under these conditions. The addition of enzyme to the formulations had a clear effect, in some cases causing almost instant phase separation, observed both visually and with increases in solution pH. The results of the losses of inhibitor and calcium from solution over time for formulation S1 with added enzyme are presented

www.petroman.ir

SPE 87441

followed by an extended period of slowly declining residual inhibitor concentration as the adsorbed chemical is released into the mobile aqueous phase passing through the core. After approximately 750 pore volumes of formation water were passed through the core, the residual inhibitor concentration had quickly dropped to 2-3ppm, see Figure 4. The inhibitor return profile for scale inhibitor 1 formulated with added enzyme to aid precipitation is shown in Figure 5. After approximately 750 pore volumes the residual inhibitor concentration was much higher ~25-30ppm, see Figure 5. This indicates that the inhibitor precipitation previously observed in the static tests has taken place in the core at 80C and has provided a more favourable inhibitor release profile when compared to the adsorption only squeeze, see Figure 6. The coreflood data indicated that the enzyme precipitation system with scale inhibitor 1 offers the potential to signifacantly extend treatment lifetimes. Scale Inhibitor 2 The inhibitor return profiles for scale inhibtor 2 at 40C in formation water B with and without the inclusion of enzyme to aid precipitation are presented in Figure 7. In the adsorption only treatment the inhibitor concentration dropped below the previously calculated MIC of 30ppm after approximately 250 pore volumes, see Figure 7. The formulation containing enzyme although releasing less inhibtor initially maintained an inhibitor release of ~46ppm, after 300 pore volumes had been eluted, see Figure 7. Again, it is clear that the addition of enzyme to the inhibitor formulation caused precipitation in the core and subsequent increase in inhibitor retention.

Coreflood testing indicated that the inclusion of enzymes into the maleic and sulphonated inhibitor precipitation formulations increased the retention of the scale inhibitor products in the core through induced inhibitor precipitation reactions at low temperature. This resulted in more favourable scale return profiles than with a conventional adsorption only squeeze and indicates the potential for substantial increases in treatment lifetime in wells with BHT 85C. Coreflood testing indicated that the enzyme precipitation system couldd provide a method for extending treatment lifetimes of sulphonated scale inhibitors that normally display very poor retention properties and would not be used for squeeze treatments.

REFERENCES 1 Bourne, H.M., Collins, I.R., Cowie, L.G., Nicol, M., Strachan, C.: The Role of additives on inhibitor precipitation solubility and its importance in extending squeeze lifetimes, Proceedings of Solving Oilfield Scaling 3rd International Conference, Aberdeen, UK 22-23rd January 1997 Harris, R.E., McKay, I.D., New applications for enzymes in oil and gas production, SPE 50621, Proceedings of the SPE European petroleum conference, The Hague, The Netherlands, 20-22 October 1998 CIURLI, S. et al (1999) Structural properties of nickel ions in urease: novel insights into the catalytic and inhibition mechanisms. Coordination Chemistry Reviews 190-192 (1999) 331-355 Cleansorb Ltd (2001) Private publication enzymes for scale inhibitor deposition. on

CONCLUSIONS In this paper, the use of enzymes has been evaluated to assess suitability for use in precipitation inhibitor formulations at temperatures not previously possible using thermally dependent products. Addition of enzyme solution to sulphonated copolymer and polymaleic scale inhibitors catalysed the breakdown of urea and formation of inhibitor precipitates in static phase separation tests at 40C and 80C respectively. 6 Identical formulations formed no precipitate at 80C without the addition of enzyme. Additional tests at 95C in the absence of enzyme inidcated that a precipitate could form under normal thernal breakdown conditions and this confirmed that the enzyme was the initiator of the scale inhibitor precipitation reaction at 80C. 7 Dynamic scaling loop testing proved that the addition of enzyme to polymaleic inhibitor precipitation formulations had no effect on their scale inhibition properties. 4

WILLIAMS GDM (1997) Development of enhanced precipitation scale inhibitors. MSc thesis. Robert Gordon University, Faculty of Science and Technology, School of Mechanical and Offshore Engineering. Graham, G. M. and Collins, I. R.: "Laboratory Procedures and their Control on Scale Inhibitor Ranking in Static and Dynamic Performance tests," SPE 74679, Proceedings of; SPE 4th International Symposium on Oilfield Scale, Aberdeen, UK, 30-31 January 2002. King, G.E. and Warden, S.L.: Introductory work in scale inhibitor squeeze performance: Core tests and results SPE 18485, Proceedings of SPE International Symposium on Oilfield Chemistry, Houston TX, 8-10 Feb. 1989.

www.petroman.ir

SPE 87441

Table 1 Synthetic water compositions

Table 3

Effect on pH of enzyme addition for Scale Inhibtor 1 Formulation / pH after 24 hours

Ion Na+ K+ Ca2+ Mg2+ Ba2+ Sr2+ ClSO42-

Formation Water A Mg/l 19,510 545 265 1020 145 285 33,190 1370

Formation Water B Mg/l 36,100 46 4000 636 230 225 70,500 100

Seawater Mg/l 10,890 460 1368 428 7 0 19,760 2960

Normalised enzyme conc. 0 0.25 0.5 1 2 4 10 12 S1 4.61 7.91 8.05 8.12 8.20 8.19 8.09 8.12

S2 4.45 7.87 8.23 8.02 8.28 8.42 8.27 8.31

S3 4.53 8.01 8.23 8.14 8.41 8.32 8.16 8.29

S4 4.71 7.98 8.36 8.24 8.12 8.09 8.42 8.41

S5 4.98 7.50 8.62 8.57 8.49 8.71 8.68 8.54

Table 2

Phase separation times for Scale Inhibtor 1 and 2 at 95C

Table 4

Phase separation times for Scale Inhibitor 1on addition of enzyme solution at 80C Formulation / phase separation time/hours

Formulation

S1 S2 S3 S4 S5 M1 M2

Initial pH in 20% SW 4.16 4.30 4.69 4.71 4.84 3.92 4.02

24 hour pH in 20% SW 8.18 8.32 8.50 8.49 8.53 7.98 8.10

Phase Separation Time 2.5 hours 2.5 hours 1.5 hours 1.5 hours 45 mins 2 hours 2 hours

Norm. enzyme conc. 0 0.25 0.5 1 2 4 10 12

S1 >24 8 2 1.25 1 <0.75 0 0

S2 >24 3 1 <0.75 <0.75 <0.75 0 0

S3 >24 2 1 <0.75 <0.75 <0.75 0 0

S4 >24 1.5 1 <0.75 <0.75 <0.75 0 0

S5 >24 1.5 1 <0.75 <0.75 <0.75 0 0

www.petroman.ir

SPE 87441

Figure 1: Proposed enzyme reaction mechanisms

Figure 3: Dynamic scaling loop plot evaluating effect of enzyme addition to Scale Inhibitor 2

Figure 2: Inhibitor precipitate formation analysis for Scale Inhibtor 1 over time by ICP-AES Figure 4 Coreflood return profile for Scale Inhibtor 1 without added enzyme

www.petroman.ir

SPE 87441

Figure 5

Coreflood return profile for scale inhibitor 1 precipitation formulation including enzyme

Figure 7

Comparison of inhibitor return profiles for scale inhibitor 2 for the standard adsorption treatment and the enzyme precipitation system

Figure 6

Comparison of inhibitor return profiles for scale inhibitor 1 for the standard adsorption treatment and the enzyme precipitation system

www.petroman.ir