SPE 24847

A New Solvent for Oilfield Scales

J.M. Paul* and E.R. Fieler, Mobil R&D Corp.
*SPE Member

Societyof P e t -

Engineers

Copyright 1992, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 67th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers held in Washington. DC. October 4-7, 1992. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the authorfs). 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 publicationreview by Editorial Committees of the Society of PatroleumEngineers. Permissionto copy is restricted to an abstract of net more than 300 words. Itlustrationsmay not be copied. The abstract should contain cwnspicuous acknowbdgmnt of where and by whom the paper is presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836 U S A . Telex, 730989 SPEDAL.

Abstract
Mobil has developed a new solvent to dissolve oilfield scales, including sulfates of barium, strontium and calcium, as well as calcium carbonate. Naturally occurring radioactive material (NORM), which is usually co-precipitated with barium and strontium sulfates, is removed by this solvent. Performance features of the solvent and case histories of field tests are reviewed. Materials compatibility with the solvent and disposal options are also briefly discussed.

isotopes (uranium and thorium decay products) are usually present in barium/strontium sulfate scale mixture~.~.'*~ Activities of these naturally occurring radioactive materials (NORM) can sometimes be high enough to present a potential health problem to workers. Ordinarily though, the problems are confined to appropriate disposal. This quandary has renewed interest in developing new solvents, particularly solvents with high specific activity for barium and strontium sulfate scales.

Laboratory Processes Introduction

Considerable production losses are associated with scaling in many oil and gas producing areas of the world.'^^?^*^ Scale inhibitors can often be used to control precipitation of calcium carbonate and calcium sulfate. If scale inhibition fails or is not applied, these scales can be removed using acid washes or combination treatments of chemical converters and hydrochloric acid. Due to the low solubility of barium , ~ sulfate, 2.4 mg/l in water at ~ O O C formation of this scale in wells, production tubing and surface equipment is an unwelcome event. Once formed, these scales are nearly impossible to remove from tubing, valves and surface equipment except by mechanical means. Co-precipitates of radioactive

A limited number of solvents are listed in the literature for use on barium and strontium sulfates?%10 However, the patent literature is well stocked with different schemes for removing barium sulfate scale.llJ2.13 Most of the literature concentrates on the use of some type of chelating agent, most often the amino polycarboxylic acids: for example, ethylenediaminetetraacetic acid (EDTA) and similar reagents.14 Other compounds suggested for dissolving barium sulfate include crown ethers, cryptands and other exotic and expensive m a t e r i a l ~ . l ~ * ~ ~
Although these chelating agents have been applied for removing oilfield scales, our experience with them was not wholly successful. The rate of dissolution, especially for producing wells, was far too slow to be

References and illustrations at end of paper.

845

A NEW SOLVENT FOR OILFIELD SCALES

SPE 24847

economical. Even with the assistance of mutual solvents or surfactant flushes, EDTAtype materials had difficulty in attacking oiland asphaltene-containing scale. Our first attempts at designing a solvent system were based on combining synergists with known chelating agents. Synergist activity stems from an idea that barium and strontium sulfates are converted to other compounds that are easier to dissolve. Potential synergists were identified by studying an unusual, but well known solid/solid conversion reaction.17 In this reaction, solid barium sulfate is converted to solid barium carbonate in a concentrated carbonate solution. Many sulfates will undergo this conversion reaction. The resulting carbonate is, of course, readily dissolved in dilute acid solution.

To date, 12 patents have issued that cover several solvent formulations and numerous practical applications. Applications include surface equipment cleaning, methods of downhole cleaning, localized agitation and solvent regeneration. Laboratory Data Dissolution experiments were performed at 25 and 100C. Experiments at the lower temperatures were performed in jacketed beakers with magnetic stirring. Temperature was maintained with circulated water from a constant temperature bath. High temperature experiments were carried out in roundbottomed flasks at 100C (reflux). In addition to a reflux condenser, a sample port was available in either a two- or three-necked flask. Stirring was accomplished by a magnetic stirring bar and chilled water was circulated through the condenser to provide reflux. Distilled water was used to make up all solutions. Initially, EDTA was used as the chelating agent. Later, and for most experiments, diethylenetriaminepentaacetic acid (DTPA) was used as the primary chelating agent. Reagent grade chemicals, or better, were used in all experiments. Dissolution tests were run for 7 hrs, with samples taken at 5, 10, 30, 60, 120, 240 and 420 min. A typical solvent composition is 0.5 M chelating agent, 0.1 to 0.5 M synergist and sufficient solid potassium hydroxide to raise tne pH to 12. Between 60 and 200 g/l of powdered, reagent grade barium sulfate was added to the solvent. Field Case Histories Mobil has conducted numerous solvent field tests over the past three years. The types of field tests include equipment cleaning, downhole tubinglequipment cleaning and several cases of injection and producing well stimulations. Producing well stimulations included near-wellbore formation squeezes and scale removal from perforations and gravel packs. A summary of results for a few of these tests are tabulated below.

Similar reactions employing other inorganic and organic anions as synergists can be written. Barium and almost any alkaline earth sulfate will undergo a solid/solid transformation in the presence of high concentrations of synergists (e.g., carbonate). The free energy of reaction of the barium sulfate to barium carbonate transformation, AGr, is approximately zero or somewhat favorable but indicates an equilibrium reaction. Experimentally, barium sulfate is approximately 70% converted to barium carbonate at equilibrium. From literature values of free energy (AGr) of various barium compounds, we were able to compile a group of synergists that display a favorable free energy of reaction.18~19~2OJl From these calculations, fluoride and oxalate anions emerged as strong candidates for synergists. Over the period of ,development other anions were found that performed well as synergists, but free energy data were not available in the literature. Whatever the mechanism of dissolution might be, we were able to find high performance synergists by the free energy prediction.

SPE 24847

JAMES M. PAUL and ELEANOR R. FIELER

surface Test: Stacked Production Tribing, East Texas, August, 1989.

Objective: To demonstrate the effectiveness of solvent at descaling and decontaminating production tubing in a field environment; field tubing cleaned by circulating heated solvent through pulled tubing (- 150F). Results: Using heated solvent, scale and naturally occurring radioactive material (NORM) were removed from four sections of tubing. All scale was removed within 1.5 to 2 hrs, completely decontaminating the tubing. The spent solvent was injected into a field disposal well without a problem.

Results: Restored production to a shut-in well by squeezing solvent into an open-hole completion in a carbonate formation. No emulsions were noted in returns. Initial swab production tests indicated an oil rate of approximately 320 bbl/D. The well had been shut-in for 13 months before treatment. Spent solvent was disposed of at a commercial injection site,

Deep Well Cleaning: Offshore Louisiana, December, 1990.

Objective: To demonstrate the effectiveness and efficiency of removing solid bridges of barium sulfate scale from two wells in an offshore field. These tests required the application of solvent in deep, hot, shut-in wells in an offshore environment. Results: Solvent removed scale above and around stuck tools in two wells. After fishing to remove a stuck tool, the tubing was open to flow and production was restored in one of the wells treated. In the second, a fishing tool was solidly lodged and could not be removed. If plugging and abandonment (PfA) are required, workovers will not be necessary; substantial savings potential ($2-3 MM). The spent fluid was injected in a commercial onshore oilfield disposal well.

Downhole Tests: North Central Texas, February, 1990.

Objective: To demonstrate, in three wells, that various treating methods are viable in removing downhole accumulations of sulfate scales and NORM. Results: Solvent circulated through coiled tubing was highly effective in removing scale and NORM from tubulars. Solvent was circulated down the annulus and up the tubing with a rod pump. Downhole tubing and rods were either completely cleaned of scale and NORM or reduced to low levels of activity by circulating solvent. The soaking method can be applied to stimulation work when the other methods are not available. Soaking opened a part of the perforations resulting in an increase of fluid production. Spent solvent was flowed back and injected with produced water in field disposal wells.

Deep Well Cleaning: Offshore Texas, January, 1991.

Objective: To demonstrate the effectiveness and efficiency of removing solid bridges of barium sulfate scale from a single gas well in an offshore field. This test required the application of solvent in a deep, hot, shut-in well in an offshore environment. Results; Solvent removed scale above and around a stuck plug in a gas well. After successfully fishing to remove a stuck plug, the tubing was open to flow. Gas production of -2.2 MMscflD was restored in the treated well.

Producing Well Stimulation: Central Alberta, December, 1990.

Obiective: To demonstrate that scale damage (bariumlstrontium sulfate) in the wellbore and near-wellbore formation can be removed by a simple squeeze application of solvent. Solventloil mixtures, at downhole temperature, were evaluated for emulsion tendencies. Emulsions were not observed in these tests.
847

A NEW SOLVENT FOR OILFIELD SCALES

SPE '24847

Note: Solvent was diluted 25-50% with sea water. This diluted solvent was not as effective as a concentrated dissolver, but it softened the scale so that wireline tools easily passed through the toothpaste-like soliak. The plug was latched and retrieved.
Producing Well Stimulation: Offshore UK (North Sea), April, 1991.
Objective: To remove barium and strontium sulfate scales from downhole tubing, perforations and near-wellbore formation and stimulate oil production. Solvent stimulation precedes a scale inhibitor squeeze. Results: Oil production following solvent squeeze increased 39% over pre-treatment rates. Oil production just prior to solvent stimulation was 1,300 bbl/D, compared to 1,800 bbYD following the treatment. Spent fluids were processed with the produced water.

pumping solvent; pressure decreased from 250 psi to zero at end of injection cycle. Fluid returns indicated substantial barium and strontium had been dissolved. Oil production increased approximately loo%, while total fluids increased by 63%. Spent solvent was injected with the produced water.

Injection Well Conversion/Stimulation: West Texas, February, 1992.

Obiective; To convert a former injector to a producer after reperforating and dissolving scale. Logs were run before and after solvent treatment to identify wellbore damage, permeability and porosity of formation. The well had been shut-in for approximately 20 years and was temporarily abandoned because of damage due to injecting incompatible waters and solids. Results; Following solvent stimulation, formation porosity increased according to log. Following solvent treatment, acid stimulation was completed on the well. A log following acid treatment showed no increase in porosity or permeability. Fluid level increased from 5,000 to 1,500 ft and initial oil production was 65 bbl/D and gas rate was 300 MscfID. It was concluded that solvent stimulation is a costeffective workover operation.

Injection Well Stimulation: Alberta, July, 1991.

Central

Obiective; To demonstrate that scale damage (barium & strontium sulfate) in a e l 0 md sandstone formation can be removed by a simple squeeze application of solvent. Results: Injectivity of a shut-in well was increased by at least a factor of two by squeeze injectinglsoaking solvent (overnight) into perforations in a tight sandstone formation. Spent solvent was left in the injection well.

Production Well Conversion and Stimulation: West Texas, March, 1992.

Objective; To convert a former producing well to an injection well following installation of a liner and re-perforation. The well had been temporarily abandoned for approximately 20 years. Solvent stimulation was completed after perforating the liner. Result% After solvent stimulation, before hooking up injection lines, the well began to flow oil with a flowing pressure of 1,400 psi. The well will be converted back to a producer following a petition to the Texas Railroad Commission for conversion. Other producers in the area typically flow oil at a rate as high as 100 bbl/D, at 1,400 psi flowing pressure.

Producing Well Stimulation: Central Louisiana, December, 1991.

Objective: To remove barium and strontium sulfate scales from downhole gravel pack and perforations and increase oil production. Reservoir fluids were displaced with 2% potassium chloride (KC1) solution to prevent contamination and dilution of solvent. Results: Positive results were noted while

SPE 24847

JAMES M. PAUL and ELEANOR R. FIELER

Results of early testing gave indications of several key elements that were used to develop the first successful barium/strontium solvent. One such element necessary for efficient chelating agent and synergist combinations is that the solvent must be neutralized with potassium or cesium hydroxide. Early in the work sodium salts of EDTA and DTPA were used, as received from suppliers, in 40 wt% active solutions. Synergists could not be dissolved in these high pH solutions that were neutralized with sodium hydroxide. In addition to the subtleties mentioned above, another characteristic of the mixture is the effect of halide ions on activity. All halide anions except fluoride were detrimental to the performance of the scale solvents. The amount of solvent activity reduction was greater as the size of the halide anion increased. Thus, fluoride had the most positive effect on rate and overall performance of the solvent and iodide had a strong inhibitive effect on barium sulfate dissolution. While fluoride enhanced the activity of EDTA-based solvents, DTPA-based solvents were not enhanced by fluoride; in fact they were inhibited. However, oxalate anion was found to be a good synergist when used with both EDTA and DTPA. Some of the described properties and performance effects are shown in Figures 1 through 5. These are optimum results under controlled laboratory conditions. Figure 1 compares the activities of EDTA and DTPMsynergist solvents. Note the fast initial rate of DTPAhynergist, as well as the overall greater capacity. The fast rate of dissolution is important in field applications where downtime is critical. The fast rate of dissolution has apparently been realized in several field tests. Minimal test times have produced large quantities of dissolved scale. In addition to the fast rate of reaction, the heated solvent also quickly removes oil and asphaltic material from the scale.

Figure 2 illustrates the capacity improvement as a result of temperature enhancement between 25 and 100C. The high rate is expected for most chemical reactions, including the dissolution of scale. Obviously the higher downhole temperatures are an advantage to using this solvent. In Figure 3, synergistic effects of oxalate and salicylate with DTPA are compared to chelating agent alone. Many synergists have been identified, but these are the most cost effective and readily available products. EDTA and EDTA plus synergist combinations are compared in Figure 4. Although oxalate anion is a superior synergist for DTPA, it is only mildly enhancing for EDTA-type solvents. Figure 5 contrasts solvent formulations using oxalate and fluoride synergists with DTPA at 25C. Performance of solvents formulated with DTPA and fluoride ion are affected similarly to the combinations of other halides with this chelating agent. Compatibility of various materials used in the oil field were evaluated in the presence of the solvent. Among the materials tested were: cements (Type A, C, G, and H), elastomers, plastics and various metals. Summaries of test results are given in Tables 1-3. Table 1 lists the effects of the scale solvent on the compressive strength of various API Class cements. Control samples (duplicate) were aged at 25C in tap water (72 hrs). Samples Al, A2, C1, C2, etc. were refluxed at 100C in distilled water (72 hrs). Samples A3, A4, C3, C4, etc. were refluxed in solvent at 100C (72 hrs). In all of the samples, weight loss of the cement was less than 8 percent. Table 2 lists solvent compatibility with elastomers that are commonly used in the oilfield. Results of two types of tests are given; Durometer (ASTM Type A) penetration tests and thickness measurements (micrometer), Controls were aged in distilled

A NEW SOLVENT FOR OILFIELD SCALES

water at 25C (7 hrs). Samples ("ON-Rings) were aged in refluxing solvent at 100C (7 hrs). In general, little detrimental effect is observed from contacting the "OM-ring material with the solvent. Table 3 summarizes compatibility of miscellaneous materials in the solvent. The metal and plastic samples were aged in solvent for four days at 200F. Corrosion rates were calculated (mpy) from measured weight loss of the metal coupons. The resulting corrosion rate for mild steel is very low and nearly nil for the other metals. Aluminum is not compatible with high pH solutions. In the field, aluminum fittings are known to perforate after 1 to 2 hours when in contact with the solvent. Therefore, this solvent should be avoided if aluminum is used in the oilfield. Little solvent effect is noted for the plastic materials. Conclusions New solvent shows increased rate and scale dissolution capacity (BaS04, SrS04 and NORM) when compared to EDTA. Temperature enhances solvent dissolution rate and capacity as expected for most reactions. Solvent does not cause secondary field problems such as emulsions, sludges or precipitates. Solvent is only mildly corrosive to steel, non-corrosive to alloys and is virtually nonreactive with plastics and elastomers. In field tests and normal production operations, solvent containing dissolved scale and NORM could be disposed of by injection in salt water disposal wells or by processing through the production system and re-injecting. Field case histories show that solvent is versatile for many oilfield scale problems. Applications include cleaning downhole tubing, decontaminating field equipment, and stimulating both injection and producing wells.

SPE'24847

EDTA = ethylenediaminetetraacetic acid DTPA = diethylenetriaminepentaacetic acid mg/l = milligrams per liter ppm = parts per million g/l = grams per liter M = molar (moles/liter) = solid (s) (aq) = aqueous wt% = weight percent = pounds per square inch psi AGr = free energy of reaction bbl/D = barrels per day scf/D = standard cubic feet per day = millidarcys md mpy = mils per year Acknowledgments The authors wish to thank Mobil Research & Development Corp. for permission to publish this paper. Thanks also to Baker Performance Chemicals (Solvent Licensee) for their support and helpful suggestions. Special thanks to Mobil affiliate personnel whose cooperation was critical for field test successes. References Anderson, R.: "Dealing with Radioactive Scale in Offshore Oil Production", Ocean Industry (Nov. 1990) 33-39. Mitchell, R.W, Grist, D.M. and Boyle, M.J.: "Chemical Treatments Associated with North Sea Projects", JPT (May 1980) 904- 12. Hawes, C.: "Barium Sulfate Scale in Oilfield Production", Ofshore (Oct. 1985) 79. Carmen, M., Bezerra, M., Khalil, C. N. and Ferreira, F.: "Barium and Strontium Sulfate Scale Formation Due to

SPE 24847

JAMES M. PAUL and ELEANOR R. FIELER

Association of Corrosion Engineers, Paper No. 26, Nashville, TN. 15. de Jong, F., van Zon, A., Reinhoudt, D.N., Torny, G.J. and Tomassen, H.P.M.: Recl. Trav. Chirn. Pays-Bas 102, (1983) 164173. 16. de Jong, F., van Zon, A., Reinhoudt, D.N., Torny, G.J. and van Zon, A.: "Chemistry of Crown Ethers XXXIII. A Crown Ether for Barium Sulfate-Dissolution Problems", 2nd Royal Soc. Chem. Industrial Chemistry in Oil Indust., International Symposium (Manchester, England), (1985) 241-68. 17. Patton, C.C.: Applied Water Technology , Campbell Petroleum Series, Norman, OK, (1986) 95. 18. Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H, Halow, I., Bailey, S.M., Churney, K.L. and Nuttall, K.L.: "The NBS Tables of Chemical Thermodynamic Properties", J. Phy. Chem. Ref. Data 11, Supplement No. 2 (1982). 19. Wall, F.T.: Chemical Thermodynamics, W. H. Freeman & Co., San Francisco, 1958. 20. Garrels, R.M. and Christ, C.L.: Solutions, Minerals and Equilibria, Harper & Row, New York, 1965. 21. Lewis, G.N. and Randall, M.: Thermodynamics, McGraw-Hill Book Co., New York, 1961.

Incompatible Water in the Namorado Field, Carnpos Basin, Brazil", SPE Latin Amer. Petl. Eng. Conf., Rio de Janeiro, Brazil, Soc. of Petl. Eng., SPE 21109 (1990). 5. Cowan, J.C. and Weintritt, D.J.: WaterFormed Scale Deposits, Gulf Publishing Company, Houston, TX (1976) 163. 6. Grice, K. J.: "Naturally Occurring Radioactive Materials (NORM) in the Oil and Gas Industry: A New Management Challenge", paper SPE 23384 presented at the 1991 First International Conference on Health, Safety and Environment, The Hague, Netherlands. 7. Smith, A.L.: "Radioactive Scale Formation", presented at the 1985 Second International Chemicals in the Oil Industry Symposium, Royal Society of Chemistry, Manchester, England, March 25-27. 8. Smith, A.L.: "Radioactive Scale Formation", JPT (Jun. 1987) 697-706. 9. Carrell, K.D.: "The Occurrence, Prevention and Treatment of Sulfate Scale in Shell Expro", SPE paper 16538 presented at Offshore Europe 87, Aberdeen, Scotland, September, 1987. 10. Mazzolini, E.I., Bertero, L. and Truefitt, C.S.: "Scale Prediction and Laboratory Evaluation of BaS04 Scale Inhibitors for Sea Water Flood in a High-Barium Environment", SPEPE (May i992) 18692. 11. Quattrini, F.J.: U.S. Patent 3,660,287, May 2, 1972.

SI Metric Conversion Factors

12. De Jong, R., et al.: U.S. Patent 4,190,462, February 26, 1980. 13. D'Muhala, T.F.: U.S. Patent 4,708,805, November 24,1987. 14. Olson, J.B. and Nolan, P.K.: "The Chemical Dissolution of Barium Sulfate (Barite)", Corrosionl92: National md x 9.869233 E - 04 psi x 5.894757 E - 00 "F (OF - 32)11.8 bbVD x 1.589873 E - 01 scflD x 2.863640 E - 02 mpy x 2.54* E - 02
- k2 r

= "C
= m31d

= m3ld
= mm/a

* Conversion factor is exact

Table 1-Solvent Compatibility with Oilfield Cements (Compressive Strength) Cement Type API Class A Control (duplicates) Compressive Strength, psig Strength, Average 5,500 Strength Loss, %

API Class C Control (duplicates) Cl

3,912 2.825

API Class G Control (duplicates) GI G2

4,912 3,913 5.300 4.606

6

API Class H I Control (duplicates) HI

I
5,312 4.175

Note: control samples were aged at 25OC in tap water (72 hrs). Samples Al, A2, C1, C2, etc. were refluxed at 100C in distilled water (72 hrs). Samples A3, A4, C3, C4, etc. were refluxed in solvent at 100C (72 hrs). In all cement samples, weight loss was 8 percent or less.

Table 2-Solvent Compatibility with Oilfield Elastomers

Note: controls were aged in distilled water at 25OC 17 hrs). s ' S a m ~ l e ("0"-Rings) were aged in r&uxing solvent at 100C (7 his).

Table 3-Miscellaneous Materials Compatibility in Solvent Sample Material Mild Steel Stainless Steel Hastelloy C-276 Viton Teflon PVC HDPE Compatibility, mpy, and/or Comments 3.6 mpy 0.0 mpy 0.22 mpy No changes in color/elasticity No changes in color/elasticity Color change No changes in color/elasticity

Note: material samples were aged in solvent, at 200F, for 96 hrs.

*I.
I

/*
,
50

Chelant/Synergist
o DTPA/Oxalate

o
0

,
100

,
150

m
200

,
250

,
300

,
350

l
450

~
0

400

50

100

150

200

250

300

350

400

450

Time, Minutes Figure 1. Rate of Barium Sulfate Dissolution

0.5 M Chelant, 0.5 M Synergist, pH=12,25'C

Time, Minutes Figure 2. Rate of Barium Sulfate Dissolution

0.5 M DTPA, 0.5 M Oxalic Acid, pH=12

I-:
* /V
V
.
-0
0

Chelant/Synergist

o DTPA/None

0 0

,
50

. ,

,
150

100

200

250

,
300

'

'

350

400

450

Time, Minutes Figure 3. Rate of Barium Sulfate Dissolution

0.5 M DTPA, 0.5 M Synergist, pH=12, 100C

Time, Minutes Figure 4. Rate of Barium Sulfate Dissolution

0.5 M Chelant, 0.5 M Synergist, pH=12,25"C

50

100

150

200

250

300

350

400

450

Time, Minutes Figure 5. Rate of Barium Sulfate Dissolution

0.5 M DTPA, 0.5 M Synergist, pH=12,25OC