EDTA Removes Formation Damage at Prudhoe Bay C.M. Shaughnessy, SPB, Exxon Production Research Co, WE. Kline, SPE, Exon Production Research Co Summary Formation damage has been observed in some wells of the Prudhoe Bay field. Laboratory and field testing con firmed that the primary cause of damage was the buildup of calcium carbonate scale either in the perforation tun- nels or in the formation sandstone near the wellbore. Conventional acid treatments could dissolve this scale, but scale reprecipitation from the spent acid caused rapid productivity decline. A scale-removal treatment with NazH2 cthylenediaminetetraacetic acid (EDTA) bas been developed that can effectively dissolve scale and chelate’ the dissolved metal ions. Chelation of the dissolved scale prevents scale reprecipitation. OF the 25 Prudhoe Bay wells acidized with EDTA through June 1982, 19 responded with significant productivity in- creases. In 17 of these wells, productivity has been sus- tained after treatment. Introduction ‘Soon after startup of the Prudhoe Bay field, a fraction of | the completed wells exhibited productivity-dectine rates significantly greater than the 10 to 20% /year anticipated by geologic and reservoir studies. A history of the well damage problem at Prudhoe Bay and the response by the working-interest owners has been described previously by Braunston.! ‘Although the reason for these high declines was not known initially, it was recognized that a successful response would require a coordinated program of engineering, field, and laboratory activity. A Well Damage Study Group was formed with representatives from the three major owners—Sohio, ARCO, and ‘Copyngnt 1988 Socety of Parloum Enghoors of AME OCTOBER 1983 Exxon. A review of drilling, completion, and well test data revealed two groups of high-decline wells. In one small group of wells, the onset of high decline rates could be traced directly to formation invasion by calcium-chloride brine. This brine was used as a comple tion/workover fluid at Prudhoe Bay because of its dens ty and freezing-point characteristics. In the second, larger group, there had been no formation invasion by calcium chloride. For these wells, the damage occurred solely from the production of reservoir fluids. Even though the wells produced only trace amounts of water, the most likely source of damage was some type of scale. Diagnostic field treatments supported the hypothesis that damage was caused by near-wellbore scale. As described in detail by Braunston,! the well productivity lost to damage could be recovered by reperforating the original imerval. This result showed the formation «damage to be in the perforation tunnels or very close to the wellbore. Carbonate-scale damage was indicated when productivity increases were obtained either by matrix acidizing with HCl or by simply spotting HCI in the wellbore across the perforations. Unfortunately, the initial productivity increase from any of these techniques was very shor-fived. The response of one well 10 repeated hydrochloric acid treatment is shown in Fig. 1 Ahigh decline rate was observed immediately following each treatment with HCL Laboratory studies to address this high-decline prob- lem proceeded in close cooperation withthe engineering and field activities. Experimental work confirmed that calcium carbonate scale is the primary cause of damage at Prudhoe Bay. Nondamaging workover fluids were for- mulated by employing mixtures of sodium bromide and sodium chloride as a substitute for calcium chloride: 83‘TABLE 1—COMPOSITION OF PRUDHOE BAY BRINE Surtace Sample 326 303 4a ‘o.002 HCO,";mmos, 90 pH 83 Fev mma However, the major unresolved problem was the short- lived nature of damage-removal treatments. This paper focuses on the development and testing of a new acid that removes CaCO scale damage and provides a sus- tained increase in well productivity. Damage Mechanisms ‘Scale deposition from brine can occur whenever there is ‘a change in equilibrium that reduces the amount of mineral that ean be held in solution, Changes in pressure and temperature can lead to precipitation, as can com- position changes resulting from fluid mixing. Describing the mechanisms of scale precipitation involves docu: ‘menting (1) the original brine equilibrium in the reser voir and (2) the effect of departures from reservoir equilibrium. Reservoir Equilibrium Conditions ‘The producing reservoir at Prudhoe Bay is a sandstone formation. The major carbonate constituent of the sand- stone is iron carbonate (FeCO 3), but a minor amount of | ‘ealcium carbonate (CaCO 3) is also present. Typical con- ditions of temperature and pressure are 200°F (93°C) and 4,200 psi (29 MPa). Reservoir gas contains about 12% COp, giving an equilibrium CO. partial pressure ‘of approximately 500 psi (3.4 MPa). Describing the conditions of scale formation requires accurate information on the composition of the reservoir brine. The composition of Prudhoe Bay brine was deter- ‘mined with samples obtained from three sources: surface samples, surface samples re-equilibrated to reservoir conditions, and bottomhole samples. Brine compositions ‘measured on samples obtained from all three sources are presented in Table 1 for atypical well. Because of changes in temperature and pressure, dissolved species in reservoir brine can be precipitated ‘when brought to surface conditions. Nevertheless, sur- face samples were sufficient for the determination of the sodium and chloride concentrations. Surface samples ‘were also used to determine which of the seale-forming ions is present in excess. The data in Table | show that Prudhoe Bay brine contains a large stoichiometric excess of bicarbonate ion (HCO). Thirty mmol/L (0 mmot/dm*) HCO, ~ remains even after the caleium and iron are reduced by precipitation to nearly zero. The high pH of 8.3 reflects the presence of this excess bicarbonate in the surface sample. A composition representative of reservoir brine was prepared by re-equilibrating a surface sample to reservoir conditions. The previously analyzed surface brine sam- ple was placed into a stirred pressure vessel along with Surface Sample Wireline ReEaulvated to Baltomhole Reservoir Conditions Sample 86 — 301 m2 50 50 03 oz a “ 47 = some crushed Prudhoe Bay reservoir sandstone. After the sample was equilibrated for several days at 200°F (93°C) and the reservoir COp pressure, it was withdrawn and analyzed, ‘The composition of the re-equilibrated brine is given in the second column of Table 1. When compared with the surface sample, the re-equilibrated brine contains significantly more’ calcium and bicarbonate. The dissolved-iron concentration is only slightly higher, even though FeCOs is the major carbonate mineral in the reservoir. An unusual feature of this brine is the high bicarbonate ion concentration of 42 mmol/L (2 mmol/ém3). This concentration is considerably greater than the HCO; ~ content of most oilfield brines,? which typically have less than 10 mmol/L (10 mmol/dm3). The reservoir-brine pH was determined experimentally to be 4.7 with a high-pressure pH electrode of a design given by Disteche. ‘Wireline bottomhole samples were taken to verify the caleium and iron concentrations obtained by re- equilibration. Cation precipitation from the bottomhole samples was prevented by preloading. the sampling chamber with tetrasodium EDTA, a chelating agent. The chelating agent stabilized the calcium and iron in solu- tion and prevented the formation of CaCO and FeCO, ‘The stabilized concentrations are given in the third col- umn of Table 1. These concentrations are in reasonable agreement with the equilibrium concentrations in the second column, Precipitation of CaCO scale from the brine was con- firmed when actual samples of downhole scale were ob- tained by wireline chipping. Chemical analysis showed that the scale consisted almost entirely of calcium car- bonate, even in wells that had never been exposed 10 calcium chloride. The combination of brine and scale analyses established CaCO as the primary mineral precipitated from Prudhoe Bay brine Calcium Carbonate Equilibrium ‘The equilibrium relationship governing caleium car bonate seale is given by Ca** +2HCOS BCACOy) +COr4+H20. (1) Dissolved calcium (Ca**) and bicarbonate (HCO) ate in equilibrium with solid calcium carbonate (CaCO) fand_ gaseous CO>. The concentration of dissolved CaCO3 depends on the CO partial pressure, temperature, and brine composition. The solubility of pure CaCO} was determined experimentally at 200° (93°C) for the brine composition in Table 1. TheBp Lis 2s eo ce[mazmix mara voi 8 a a ney WH] z wits 2 158 z : § 108 zt 08 2 snut : NUE 1977 ~—«197R~~«979~—~S*« SO High decline rates follow hydrochloric acid treatments (alter Braunston'). resulting CaCO} solubility curve is plotted in Fig. 2 for a range of COz pressures. In the region above the solubility curve, the solution is supersaturated, and ex cess calcium will tend to precipitate as CaCO}. Below the solubility there is no tendency for precipitation, A more general representation of calcium carbonate ‘equilibrium is given by Fig. 3. This plot of experimental ‘equilibrium data shows the amount of calcium that ean be held in solution at various bicarbonate ion concentra- tions. The curve at $00-psi (3.4 MPa) CO, pressure tum represents equilibrium conditions in the reservoir. On this curve is the point that corresponds to the reservoir brine composition in Table 1. Under flowing conditions, Grawdown reduces the bottomhole CO> partial pressure to 400 psi (2.9 MPa). The 400-psi equilibrium curve is also plotted in Fig. 3. As in Fig. 2, the equilibrium curves in Fig, 3 define regions of supersaturation. Any brine composition that lies in the region above an equilibrium curve is super: saturated at that pressure. Any composition below an equilibrium curve will not deposit scale at that CO» pressure, Natural Sealing Mechanism ‘The dashed arrow in Fig. 3 indicates the shift in ‘equilibrium that occurs when the reservoir brine is sub- jected to a pressure drop from 500 to 400 psi (3.4 t0 2.8 MP1). The original saturated composition lies above the 400-psi@G.4-MPa) equilibrium curve, meaning that precipitation is favored, In acconlance with Eq. 1, the arrow follows a diagonal path whereby two bicarbonate ions are precipitated for every calcium ion. The total amount of calcium precipitated is given by the indicated horizontal distance. During production, a reduction in CO) panial pressure is an unavoidable consequence of drawdown, Brine saturated at reservoir CO> partial pressure enters the drawdown region near the wellbore and deposits ‘CaCO scale. By this natural mechanism, scale buildup ‘can result solely from the production of formation brine: The natural mechanism of scale deposition was con- firmed experimentally with the apparatus shown in Fig, OCTOBER 1983, °> 100 200 300 400-500 CO, PARTIAL PRESSURE, PSI Fig. 2—Dissolved calcium depends on CO, partial pressure. DISSOLVED CALCIUM, MMOLE/¢ 200" (xe RESERVOIR “NpuceD” DISSOLVED BICARBONATE, MMOLE/ DISSOLVED CALCIUM, MMOLE/® Fig. 3—Scaledamage mechanisms. PreaEA PROP) Fig. 4—Laboratory apparatus for simulating seale depostion. asFig. 5—Scale buildup in a perforation. 4. The system consists of a 30-in. (76-em) core drilled ith a perforation 0.25 in. (0.64 em) in diameter and mounted in a high-pressure cell. The equipment is designed to allow upstream injection of CaCO4/CO> saturated brine at the low WOR'S characteristic of Prudhoe Bay wells. A constant pressure drop is main- tained by recirculating oil, and permeability damage is detected by measuring changes in the oil flow rate. Also, a seties of pressure taps along the length of the core records changes in the pressure-drop profile Experiments conducted with this apparatus showed that scale buildup occurred most rapidly within the per- foration tunnel. This observation was consistent with the near-wellbore damage observed at Prudhoe Bay. The {degree of perforation blocking can be visualized from the photographs in Fig. 5. These results confirmed that damaging accumulations of CaCO, scale can be eposited naturally from reservoir brine, even at low water cuts. Induced Scaling Mechani Ina conventional acid treatment, HCI spends on ealeium carbonate and iron carbonate to produce a concentrated solution of ealcium chloride and iron chloride. Fig. 3 il- lustrates how CaCO} precipitation can be induced by this spent HCI. Adjacent to the equilibrium curves is @ mixing line representing the various possible calcium and bicarbonate concentrations that can result when spent 15% HCI mixes with Prudhoe Bay formation brine, It can be seen that only a small amount of spent acid need mix with the reservoir brine to form a super- saturated mixture. Fig. 3 shows that a calcium concen- tration of only 6 mmol/L ean result in precipitation This scale deposition induced by spent HC] was also verified experimentally. Precipitation of calcium car- bonate was observed visually when spent HCI and for- imation brine were mixed in a windowed pressure cell under reservoir conditions of temperature and COs pressure. In addition, measurements of calcium solubili ly were obtained over a wider range of conditions than shown in Figs. 2 and 3. All the data confirmed that con- lacting even small amounts of spent acid with the forma- tion brine would lead to reprecipitation of the dissolved calcium. Seale reprecipitation was concluded 10 be the principal cause of the high decline rates that follow HCI treatments at Prudhoe Bay. 1785 invonev-] 106 Kort Fig. 6—Chetaton of metal ions depends on pH Chelation of Dissolved Scale ‘The rapid productivity decline that followed HCI seale- removal treatments provided a strong incentive to develop a new procedure that would both increase and sustain productivity. Elimination of scale reprecipitation was considered the key to sustaining increased produc- tivity. Although several methods of preventing. scale reprecipitation were investigated, the technique that shiowed the most promise was the use of a chelating ‘agent to hold the dissolved scale in solution. Chelation Chemistry In aqueous solution, a metal ion (M') has a specific number of surrounding coordination sites through which it can enter into chemical reactions. Certain organic molecules, called chelating agents (Y ~*), contain suffi- cient bonding sites withthe corect spacing 1 occupy all the metal-ion coordination sites. The resulting retal/chelate compound (MY ~2) contains the stoi metric ratio of one metal atom to one chelating agent molecule. M*tay-temy”? Q In the metal/chelate compound, bonding between the ‘metal jon and chelating agent reduces the reactivity of the metal ion toward other species. ‘The tendency of dissolved Ca * to react with HCO to form CaCOs, scale can be reduced by chelating the dissolved Ca** with an appropriate organic compound. Polyaminocarboxylic acids are chelating agents with strong bonding affinity for Ca**. These polyfunctional weak acids undergo stepwise loss of protons to reach their fully ionized state HyY=H* +HY-, @ HyYORHTHIRY ee ® HY eH? +HY3, cones 6 and HY SSH +y—4 0 JOURNAL OF PETROLEUM TECHNOLOGYTABLE 2—COMPARISON OF CHELATING AGENTS. ol Ethylonedamine tetraacelie acid (pra) 160 Diethylenetiamine entaacetie acid Caleium Conditional Stability Constants, Kyy (Fat 6) Ferrous Iron pi-5 p= 3h Ger) beso) e104) 190 5 50 (orpay 2 13 400,600 Nonycroxyethylethylene ‘laminotracetic acd (Hera) 6 13 100 800 Nitnlotiacete acid (NTA) 5 05 1 1 Because the metal ion can undergo a chelation reaction only with the fully ionized chelating agent (Y~*), the ‘metal and hydrogen ions must compete for the available yt Since most metal hydroxides are insoluble, another competition exists at high pH between the soluble ‘metal/chelate compound and the insoluble hydroxide: My -?+20H~ #M(OH)) +Y~ o ‘The final distribution of dissolved species depends on the individual equilibrium constants associated with the actions shown in Eqs. 2 through 7. These chemical ‘equilibria can be combined algebraically to yield a single equilibrium expression for the distribution of species. The effective (or conditional) stability constant Kegr is defined as: IMy 2] Keay ®) IM") 1Y je where [MY ~?} i the concentration of chelated metal, [M**] is the concentration of unchelated metal. and [¥ tee] is the concentration of total free chelating agent regardless of its state of ionization. The value of Kei is proportional to the ratio of the chelated-to-unchelated metal ion (MY —?)/{M**}) and is a ditect indicator of the bonding affinity between the metal and chelating agent. For weakly acidic chelating agents, Ka is strongly dependent on pH. Typical pH dependence is illustrated in Fig. 6. At very low pH, the chelating agent exists in the acid form and does not bond effectively with the ‘metal ions. Over the midrange of pH, the chelating agent is more fully ionized and maximum Ky, is reached, Although chelating-agent jonization is increased at high pH, metal hydroxides begin to precipitate, thus lowering the ratio of the chelated-to-unchelated metal species. This brief introduction into chelation chemistry pro- vides the background to explain the identification and testing of chelating agents. A more thorough treatment of chelation chemistry may be found in standard reference texts. Screening of Chelating Agents To increase and then sustain well productivity effective ly, it was necessary that a chelating agent meet three im- portant criteria: (1) have a strong affinity for Ca ** and OCTOBER 1983 Fe**, (2) maintain this affinity at Prudhoe Bay reser- voir conditions, and (3) be sufficiently acidic to dissolve scale. ‘A review of the chelation literature suggested that polyaminocarboxylie acids would display the high affini- ty forchelating Ca** and Fe** ions. A comparison of commercially available compounds was undertaken with published stability-constant data. The results of this comparison are shown in Table 2 for pH values of 4 and 5, which bracket the measured reservoir pH of 4.7 ‘As is apparent from the data in Table 2, chelating agent affinity for calcium is generally much lower than the affinity for iron, Therefore, the ability to chelate calcium assumed overriding importance. Of the com pounds investigated, EDTA has the highest stability con- stant for calcium chelation, At the reservoir pH of 4.7, EDTA has a Ky for caleium of about 3% 10° and a Ky for iron of about 110°. For stoichiometric amounts of ‘metal jon and chelating agent, about 98% of the dis: solved calcium and more than 99% ofthe dissolved iron will be chelated at reservoir pH. Although no data were available at reservoir temperature, the results of the screening study at room temperature were sufficiently promising to warrant more rigorous testing of EDTA. Chelation by EDTA ‘The next step in determining the suitability of EDTA for sustaining well productivity was to measure the actual amount of calcium chelated at Prudhoe Bay reservoir conditions. The experimental apparatus and techniques were similar to those used to obtain the data in Fig. 3 ‘The equilibrium relationship between dissolved Ca** and HCO; was measured at 200°F (93°C) and the reservoir CO> pressure. A similar relationship. was measured for solutions containing 239 mmol/L. of EDTA. As can be seen from the plot ofthese data in Fig 7, the difference between the two equilibrium. lines represents the amount of calcium chelated by EDTA For typical Prudhoe Bay, reservoir brine that contains 42: mmol/L. 42 mmolidm:) dissolved bicarbonate ion, the maximum amount of calcium that can be held in solution ‘without causing CaCO; 10 precipitate is 6 mimol/L (6 mmol/dm'). A brine with the same 42 mmol/L (42 mmot/dm’) of HCO s, but which also con tains 239 mmol/L (239 mmol/dm’) of EDTA can reach a dissolved calcium level of 230 mmol/L (230 rmmol/dm’) before precipitation begins. The additional veaN aa ao 30 DISSOLVED CALCIUM, MMOLE: Fig. 7—Cholaton of calcium by EDTA at reservoir conditions. Cn) DISSOLVED BICARBONATE, MMOLE/¢ 6 OF SPECIES o 2 eee Oe ~o Distribution of ionic species in EDTA solutions os os od g tees 5 os 4 zo 75°F : e) E a2 4 5 NasieoTA 2 os oo 25 a2 a3 ag HyEDTA Fig. Solubility of Na, H.EDTA. 798 224 mmol/L (224 mmot/dm?) of calcium is prevented from precipitating by the 239 mmol/L (239 mmol/dm?) of EDTA, ‘These experimental data confirm the effectiveness of EDTA to chelate dissolved calcium at Prudhoe Bay reservoir conditions, thereby. preventing CaCO3 reprecipitation. The remaining laboratory investigations could therefore focus on developing an effective scale removal treatment containing EDTA, EDTA Dissolves Scale With the chelating ability of EDTA firmly established, a fieldworthy well-treatment method for scale removal could be developed. A successful scale-removal fluid ‘would have t balance the amount of scale dissolved with the chelating power of EDTA. Scale-Dissolution Chemistry Calcium carbonate scale is readily dissolved by acid 10 yield dissolved calcium, COz, and water (Eq, 9). The Chelation behavior of EDTA requires one molecule of fully ionized EDTA (EDTA) to chelate each dis- solved calcium ion (Eq. 10). Since the final objective oF the scale-removal treatment is to achieve borh dissolu: tion and chelation, the desired chemical reaction is the combination of Eqs. 9 and 10, Adding CaCO; +2H* #Ca** +O +H20, ° and Ca** +EDTA~teCakDTA~? 10) equals CaCO +2H* +EDTA~#=*CXEDTA~? + CO, +H20. an Properties of EDTA ‘As can be seen from its chemical structure, EDTA con- tains four ionizable hydrogen atoms. ° ° mocen, city. com [HJO-C-CHy CH2-C-O[H] é é Each of the four hydrogens can be ionized in the manner shown by Eqs. 3 through 6 to yield a mixture of species in equilibeium: HEDTA#H3EDTA ~ #H,EDTA~?#HEDTA~> PEDTA~* a2) JOURNAL OF PETROLEUM TECHNOLOGYcacOs - HCL é. e@COs - HCI 4 38 10 4 B30 Fecos-Nats EDTA 3 “ 10+ 0s ACID CONCENTRATION, MOLE/C Fig. 10—kinatcs of scale dissolution by NaH, EDTA. 10 15 20 ‘The exact distribution of these species is depenclent on the equilibrium constants for each dissociation reaction land on the solution pH. The distribution of EDTA species calculated with Titerature’ constants at room temperature is shown in Fig. 8. For the pH range of 4 to 5. the predominant species is H2EDTA ?. Consequent- ly, the scale-dissolution reaction can be writen in a slightly modified form: CaCOy +H EDTA? CaEDTA“? + CO) +10. a3) EDTA is commercially available in various degrees of neutralization. Both sodium and ammonium salts of par- tially neutralized EDTA are available. A scale-removal fluid composed of disodium dihydrogen EDTA (NagH2EDTA) dissolved in water has the desired prop- ‘erties for acidizing. |. The treating fluid undergoes lite change in com- position when exposed to reservoir conditions 2. Tho amount of metal ion generated during scale dissolution by the acid functionality balances. the chelating capacity of the EDTA. 3. EDTA can effectively chelate metal ions to prevent scale reprecipitation by bicarbonate ion Dissolving Power of Na;H,EDTA The reaction products of scale dissolution by NazH> EDTA, namely CaEDTA ? and FeEDTA , are both highly Soluble. The primary limitation tothe dissolving power is the solubility of the NaoHzEDTA itself The Solubility of pure NaH>EDTA-2H,0 in water at 75°F {4°C) was measured as 0.298 moles per 1,000 g water {39.0 ThmbI (111 kg/m’) water}. For comparison, this solution has the same seale-dissolving power as 2.1% HCL “Measurements were also made to determine the effects, ‘of minor changes inthe hydrogen/EDTA ratio caused by normal manufacturing product variations and by possible contamination during field mixing operations. Solubility data were measured at 75 and 150°F (24° and 66°C) and are ploted in Fig. 9. As is evident Irom this figure, the Solubility of EDTA decreases very rapidly when the hydrogen/EDTA ratio. increases above 2.00, For OcroRER 1983 Ey 40 EDTA ‘TREATMENT {ECOMPLETION 6 0 lL RATE, 107 BBLID ° 1978 Fig, 11—Production history of wel reated wth NaH, EDTA. 19781980 1982 hhydrogen/EDTA ratios between 2.00 and 1.80, the solubility remains nearly constant To ensure maximum solubility and hence maximum, dissolving power, the hydrogen/EDTA ratio was specitied to be in the range 1,95 to 2.00. Measurements made on industral-grade Nay H3 EDTA have consistent- ly exhibited hydrogen/EDTA ratios of 1.96 to 1.99. Fur- thermore, close attention to detail during field mixing ‘operations has prevented contamination by acidic substances, Kinetics of Scale Dissolution by Na;H,EDTA Information on the rate at which an Na>H2EDTA solu- tion can dissolve scale is important for optimal job design. Laboratory tests on cores containing calcium car bonate demonstrated that most of the NayH>EDTA reacted after flowing through 6 in. (15 cm) of rock Since scale buildup had been shown to occur either in the perforation tunnels or very ncar the wellbore, effective removal of scale appeared likely. However, some qun- titative dissolution-rate data were desirable. ‘As described previously, the predominant carbonate mineral in the reservoir Sandstone is FeCO.. while the ‘damaging scale is composed largely of CaCOs, The rate fat which Na3H3EDTA dissolves these two carbonate minerals was measured with a rotating-disk apparatus. * Solutions containing 0.239 M NaH; EDTA were tested at 200°F (93°C) and 500-psi (3.4-MPa) CO» partial pressure. Disk rotation was extrapolated back t0 zero rotation speed to simulate the low-velocity conditions in pore space. A similar series of rotating-disk ex- periments were made for comparison purposes with HCL. ‘The results of this investigation are presented in Fig. 10. For HCI reactions, which are known to be very rapid and hence mass-transfer-controlled, CaCO and FeCO 5 showed similar dissolution rates. The rate at which NajH2EDTA. dissolves CaCO3 was. only” slightly slower than the rate for HCl. These data confirm that NagH2EDTA will rapidly dissolve CaCOy scale near the wellbore: It was further determined that NajH2EDTA dissolves FeCO} on the onier of 100 times more slowly than CaCOy. This result implies that NagH»EDTA will spend first on the damaging CaCO 5 scale and second on 189‘TABLE 3—VOLUMES OF SUCCESSFUL EOTA TREATMENTS. “Treatment Volume (ait (Im) 4010 100 05010128 10010 200 1.24 10228 20010 900 2.48 to 3.72 30010 360 3.72 104.48 the FeCO3 in the reservoir. This selectivity for scale dissolution can largely offset the limited total dissolving power of NasH3 EDTA, Field Implementation Laboratory tests demonstrated that EDTA could dissolve CaCO scale and prevent its reprecipitation, Field testing was implemented to evaluate the effectiveness of EDTA acidizing on actual damaged wells. Job Design Prior to field testing it was necessary to establish the im portant design parameters: EDTA concentration, treat- ‘ment volume, and additive compatibility. Chemical ‘manufacturers supply disodium dihydrogen EDTA as a solid, which must be dissolved in water to prepare the actual acidizing fluid. Laboratory mixing studies established an optimal field concentration of 0.239 M [82 bm Nay Hy EDTA:2H O/bbI (91 kg/m?) of water). AAs this concentration was near the solubility limit of 39 Ibm/bbt (111 kg/m?) at 75°F (24°C), it was not feasible to obtain premixed concentrated solutions for dilution at the well, Instead, solid NayH3EDTA was dissolved on site with frequent checking to ensure complete dissolution AAC the field treatment concentration of 0.239 M, each 100 bbl (16 m*) of NaH EDTA solution can dissolve and chelate 880 Ibm (400 kg) of CaCO scale. To ensure an excess, of dissolving power, carly treatments employed 500 bbl (80 m') of treating fluid. For the typical Prudhoe Bay perforated interval of 100 ft (30m), 4 500-bbI (80-m') treatment corresponds to about 200 gal/ft (2.48 m3/m). Once the success of these large lreatments had been established, smaller treating volumes of 250 bbl (40 m') and 100 bbl (16 m3) were employed, Finally, the compatibility of EDTA with treatment ad. ditives was evaluated carefully. Additives consisted of a corrosion inhibitor, a water-wetting surfactant, an an- tisludge agent, and an oil-soluble resin-diverting agent Laboratory tests determined that no undesirable interac- tions occurred between the additives and the NayH» EDTA. All the additives were demonstrated to be fully effective, and the Na7H>EDTA mainiained its full dissolving and chelating capacity Field Results Considerable field experience has been gained with EDTA since the first well was treated at Prudhoe Bay in 1979. Although itis not the intent of this paper to review field results, an illustrative example and a general state- iment of results are presented to document the successful application of EDTA acidizing technology 1790 ‘The production history of a well acidized with EDTA, is shown in Fig. 11. During a workover of this well, several hundred barrels of CaCl» brine invaded the for” mation. Although the oil-production capacity in Jan. 1978 was more than 21,000 B/D (3300 m°/d), produc tivity declined steadily over a 2-year period to less than 2,000 B/D (320 md) by the end of 1979. In Feb. 1980, this well was treated with $00 bbl (79.5 m*) EDTA acidizing fluid (32 Ibm NazH;EDTA/bbL (91 kg/m?) of water]. The EDTA was injected through the production tubulars and displaced with a cubing volume of diesel. After treatment, oil productivity in- creased to more than 19,000 B/D (3000 m3/d), in dlicating that the scale damage was removed. More im- portant, well productivity was sustained following the treatment, Between 1979 and June 1982, EDTA acidizing was used to treat 25 Prudhoe Bay wells believed to be dain- aged by CaCO, scale. In 19 of these wells, production rates Were restored nearly to the levels observed before the onset of decline. Analysis of the wells where produc- tivity was not restored showed the problem to be incor rect candidate selection; these wells were not damaged by caleium carbonate seale. In 17 of the 19 wells that did respond to EDTA, the post-treatment productivity in- ‘crease was sustained. Table 3 shows the EDTA volumes employed in those successful treatments Current Studies As described in this paper, the primary incentive for developing an EDTA acidizing fluid was to eliminate the very rapid productivity decline that followed conven- tional HCI acidizing. However, it was anticipated that other techniques, such as the application of scale- inhibition chemicals, would be needed to address the ‘ongoing “‘natural’” scale deposition from produced brine. Although not originally anticipated, field results with EDTA have shown that even wells prone to natural sealing have remained free of high decline rates for long periods of time. This result implies the existence of some longterm seale-inhibition mechanism. Studies are being conducted currently to quantify this inhibition effect under downhole conditions. An independent field pro- gram is also under way to test other chemicals designed specifically for scale inhibition. Conclusions ‘The laboratory and field data gathered during the course of this investigation warrant the following conclusions. 1. Formation-damage problems experienced in some wells at Prudhoe Bay can be attributed to the buildup of the perforations or near the 2A scale-removal treatment consisting of NajH EDTA dissolved in water can dissolve scale ef- fectively and chelate the dissolved metal ions to prevent seale reprecipitation. 3. Field treatment results have shown that well pro ductivity is sustained after treatment with EDTA. Of the 25 Prudhoe Bay wells acidized with EDTA through June 1982, 19 responded with significant productivity in creases. In 17 of these wells productivity has been sustained, JOURNAL OF PETROLEUM TECHNOLOGYAcknowledgments We thank all past and present members of the Prudhoe Bay Unit Well Damage Study Group. Participating organizations are Sohio Alaska Petroleum Co,, ARCO “Alaska Inc., Exxon Company, U.S.A.: Westem Div... and ARCO Plano Research Laboratory, the Standard Oil Co, Warrensville Laboratory, and Exxon Production Research Co, We also thank the Prudhoe Bay Uni Exxon Company, U.S.A., and Exxon Production Research Co. for permission to publish this paper References 1. Brunson, 3. “Investigation of Well Damage Case Histon. paper SPE 10040 present at the 1982 Intemational Ptoleum Exhibion and Tectnical Symposium, Bejing, China, March im 2. Ostoll,A.G.: lureducrion 10 Olfed Water Techuology, Nall ‘Ass, of Comason Engineers, Houston (197) 3, 3, Distche, Av "pH Mearorements with Gia Blecie Wisanding 1500 kglom™ Hydrate Pressure.” Rev Sei Ins (1959) 30, 474-78 OcToRER 1983 4. Buller, LIN lone Eguilibcium-—A. Mathematical Approach ‘Adiison Wesley Publishing ‘Co. Ine., Reading, MA" (1968) Sar-93, 5, Day, RA Jr and Underwood, AL: Quanurve Anais, se ‘ond evan, Pretce all In. Faglewonsd Clif, NJ (967) 177-93 {ess 10 Chelation, Dow Chemical Co. Miland, ML (1978), Krapten, J: Aas of Metl Ligand Eauiiria in gues Solution, Jolin Wiley & Sons Ine, New Yooh City (1978) 779 . Lit) M, and Sera, G' “Chemical Reactions on @ Routing sk," Chem, Eg. Sei (1968) 19, 861-88 SI Metric Conversion Factors eR OR-32/1.8 L x 1.0" psi X 6.894757 E+00 sqin. x 64516" E400 Cason atric. wr +00 retina ty Pee tree nt anche etiaptreeesmernceertemes 1791