Paper No.

41

THE PREDICTION OF SCALE AND COZCORROSION IN OIL FIELD SYSTEMS

J. E. Oddo Champion Technologies, Inc. P.O. Box 450499 Houston, TX 77245-0499 M. B. Tomson Rice University Department of Environmental Science and Engineering -MS519 P.O. BOX 1892 Houston, TX 77251-1892

ABSTRACT This paper describes methods to predict common mineral scales and corrosion in gas and oil fields. The calculations result from the unification of the scale prediction methods of Oddo and Tomson and the C02 corrosion prediction methods of de Waard and Lotz (Corrosion 93, Paper No. 69). Background development of the calculations is discussed in the paper. The scale prediction algorithms accurately calculate many of the parameters needed for the corrosion estimations that were proposed in the original paper by de Waard and Lotz. By including the calculated values, more accurate corrosion estimates are obtained. The scale prediction calculations have also been updated and revised to more accurately predict mineral scale deposition. This paper includes field examples of scaling and corrosive production systems to illustrate the use of the methods. The prediction model uses produced water chemistry and production volume data, as well as, flowing wellhead temperature and pressure and bottornhole temperatures and pressures to estimate temperatures and shut-in and flowing pressures in a well to calculate the needed parameters. The model will accept a dovmhole pump and can be used with wells containing rod and electrical submersible pumps. The calculations are quite accurate and result in a scale/comosion model that can be used to develop field treatment strategies and/or assist in material selection. As is true with the de Waard and Lotz methods, the corrosion calculations predict a worst case corrosion scenario. INTRODUCTION Scale and corrosion in gas and oil wells and facilities continue to be serious and costly problems. Accurate prediction algorithms to determine the severity and location of scale deposition and corrosion allows for an early treatment program development and designing special materials into the production system to minimize the impact of the predicted problem. Production costs can then be significantly reduced. It is essential to recognize the relationships that exist between scale and corrosion for effective corrosion prediction and treatment. In a severely corrosive fluid environment, scales can form a protective coating over exposed surfaces, reducing or completely eliminating corrosion. This is the concept that resulted in the Langelier Saturation Indexl which was put forth as a method to protect water delivery pipelines. An accurate and effective corrosion prediction algorithm must include produced water chemistry data and accurate scale prediction algorithms as well. The scale prediction methods used in this paper are revised equations based on the methods of Oddo and Tomson.24 Oddo and Tomson derived equations from the chemical properties of the needed components of mineral scales to determine the degree of saturation of the scale in the produced water at the temperatures, pressures and ionic strengths (a function of the
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@1999by NACE International.Requestsforpermissionto publishthismanuscriptin anyform,inpartorinwholemustbe made inwritingto NACE

International,Conferences Division, P.O. Box 218340, Houston,Texas 77218-8340. The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association.Printedin the U.S.A.

TDS) of interest. The volubility constant of a two component salt with equal charges on the cation and anion can be defined as follows:
K,p = {CaionxAnion}

(1)

where the &p is equal to the volubility constant and the {} denote activities and not concentration. The ratio of the ion activity product to the volubility constant is a measure of the under or oversaturation of the salt with respect to a specific solution. As other authors have done, Langelierl for example, the degree of saturation of a scale is given by the Saturation Index or the logl O of the ratio of the ion activity product of the scale components to the volubility product of that particular scale. OddoTomson defined a conditional volubility product that varied with temperature, pressure and ionic strength to eliminate the need for activity coefllcients in the calculations. The Oddo-Tomson Saturation Index is defined as follows: (CationXAnion) KC [

SI = log,~

(2)

where S1 is the Saturation Index, the () denote concentration and not activity and the & is the conditional equilibrium constant and is a function of temperature, pressure, and ionic strength. The corrosion prediction equations used in this paper are those of de Waard and Lotz. 5 In their paper they present, as an introduction, a mechanism for carbon dioxide corrosion and include in the paper the data horn which their equations were derived. This background information will not be repeated here. Where deviations from the original derivations are made to develop the model presented here, it will be so noted in the text. SCALE PREDICTION Derivations of the scale prediction equations and the background theory have been presented elsewhere3 and will not be presented again in this paper. However, the fictional form of the equations used to calculate the needed volubility and stability constants has been changed from five or six terms to eight terms. Generally, the equations are of the form: + PI + g*115 + h*T*15 -loglO(Kc ) = a + b*T + C*T2+ d*P + e*15 (3)

where Kc is the conditional constant, T is Temperature (F), P is pressure (psi) and I is the ionic strength of the produced water (molar). The parameters for the eight terms and their associated calculated constants used in this paper are defined and shown in Table 1. The revised recommended equations for the calculation of the Calcite Saturation Index (SIC)are shown in Table 2. Table 3 shows an example of a Saturation Index calculation for gypsum. The calculation parameters are the same as defined above. The other Saturation Index calculations for the sulfate scales are done in the same manner except a different conditional volubility equation and the relevant metal cation are used. CORROSION PREDICTION De Waard and Lotz5 derived the following equation as a general prediction equation for the corrosion of carbon steel:
Vcor= ~

1 1

(4)

+ Vreac, c vma,y~

is the phase where VCO, is the corrosion rate in mrnlyr., Vma.. is the mass transfer rate through the boundary layer and Vrgacf boundary reaction rate. The equations necessary to calculate the parameters in Equation 4 areas follows: c= Re2+2.62x10b log,o(Vrcac, )=[ 5.8-= +0.67 loglo (f J(B) CO,)] x FPH, and (5)
(6)

273 + t

(7) where Re is the Reynolds Number, t is temperature Celsius, fg is the figacity coefficient, P(B)C02 is the partial pressure of COZ in bars, FP~ is the pH correction factor (see de Waard and Lotz and below), D is the diffhsion coefhcient, v is the kinematic viscosity (m2/see), U is the liquid flow rate (mls), d is the hydraulic diameter (m), and [H2C03 ] is the total aqueous carbon dioxide and carbonic acid concentration (M). Further, the unknowns in the above equations can be calculated using the following equations and by following the discussion in the text: log10FP~ = 0.3 l(PHSa, PH..( ) pH~a, = 5.4 0.66 loglO&gP(B)coz ), (for pHac, , see text) ,og10 = 1.3272(20 - t)- 0.001053(t - 20)2 (t+ lo5)pf V= 1X 10bvpf(0.0625)pW (8) (9)

6, (t= Celsius temperature),

(lo)

(11)

(12)

~ ~ T(K)

~lo.,~

v
[H2d=

, (T(K)= Kelvin temperature),

(13)

fgPco2 l(WOKM )

(14)

(NOTE: The parameters to calculate: -log10 K~ are in Table 1, and fg are in Table 2) In the above equations T(K) is the temperature Kelvin, pH,at is the pH where FeC03 or Fe304 is at saturation in the solution, pHac, is the actual pH of the solution, v is the dynamic viscosity (cp), pf is the density of the fluids and pW is the density of the produced water. These and other parameters will be discussed below. The results of Equation 4 were subsequently modified in the de Waard and Lotz paper to account for other effects on the overall corrosion rate. These effects will be briefly described in the section below on Correction Factors so that the reader can understand how the scale and corrosion prediction algorithms have been combined. Deviations in This Paper from de Waard and Lotz Derivation The parameter c in Equation 4 was defined by de Waard and Lotz to be a constant where c = 2.62x 10b. However, it was found that corrosion predictions in wells with relatively low flow rates were significantly underestimated with c equal to a constant. In this paper the c parameter is made a fimction of the Reynolds Number (Equation 5) and is correlated with the corrosion equations by setting c equal to the de Waard value of 2.62x 106 at a Reynolds Number of 0.0. The c value increases with the square of the Reynolds number (Equation 5). With c defined in this manner, the corrosion equations gave reasonable results for wells with low flow rates, and the c V~a$~ term (Equation 4) becomes negligible at higher flow rates as required and noted by de Waard and Lotz. The kinematic viscosity was calculated from Equation 7. This equation differs slightly fkom the equation used by de Waard and Lotz. The dynamic viscosity needed for the Reynolds Number calculation was obtained from the kinematic viscosity (Equation 8).6 The dynamic viscosity was corrected for the ionic strength of the water using data from Bradley, page 24-17.7 A new kinematic viscosity was then calculated ffom the corrected dynamic viscosity (Equation 8) for use in the corrosion equation. Oil viscosity was also included in the Reynolds Number calculations for the model shown in the Field Examples section of this paper. The oil viscosity was estimated by the method of Beggs and Robinson.8 The value of1710 in the temperature term of Equation 6 was calculated to be 1543 in the general corrosion equation by de Waard and Lotz. However, this value seemed to overestimate the corrosion rate in well systems with high Reynolds

Numbers. In the model presented here, the previously derived value of 1710 (see de Waard and Lotz) was used in the corrosion equation. It may very well be that the value of 1543 is more correct, but more corrosion rate data is needed to test this aspect of the model. The parameter [H2C03 ] (Equation 7) can be calculated using equations available in the de Waard and Lotz paper. However, all of the parameters necessary to make this calculation, the fugacity coefficient, the partial pressure of C02, and the Henrys Law Constant are available in the scale prediction calculations. The scale prediction calculations for these variables were used because they are fimctions of temperature, pressure and, ionic strength. The value obtained in the de Waard and Lotz paper is a fimction of temperature only. In the original derivation, pHact (Equation 8) was intended to be measured or calculated using methods that are not described in de Waard and Lotz paper. In the model developed by Oddo and Tomson23,the pH at any point in the system can be calculated using the scale prediction algorithms. The calculated pH is used in this paper as pHacf. This is not a small issue based on the practical ditllculties involved with obtaining meaningful pH values in a pressured flowing system, especially, downhole. CORRECTION FACTORS TO THE GENERAL CORROSION EQUATION The correction factors described below are multiplied times the results of the General Corrosion Equation (Equation 4) and decrease the amount of corrosion predicted. Neither the corrections for glycol or inhibition are included in this discussion, or in the derived model. Effects of Scale Deposition Protective films formed by the deposition of mineral scales have long been known to reduce or eliminate corrosion in pipes. FeC03 (or Fe304 ) fihn deposition is accounted for in the de Waard and Lotz paper with the following equation: 2400 T(K) 0.6 loglo (f #(13)co, ) 6.7 (15)

loglo

F.ca/e

where F is a general correction factor with value of 0.0< F$Cale <1.0 and &P(B)co2

is the figacity of carbon dioxide in

bars. The I%gacitycoefficient Jg, the mole ffaction ofC02 (Table 2) and the total pressure at any point (calculated flowing pressure) are calculated when obtaining the Saturation Index for calcite scale and are used in Equation 15 to obtain a value for
fcale.

In addition to FeC03 (or Fe304 ) deposition, calcite scale deposits will also reduce or eliminate corrosion. Another scale correction factor is introduced in this paper to account for the effects of calcium carbonate scale on the overall corrosion rate. The same approach taken in the above discussion was applied. A correction factor Fcalc,leis defined with values of 0.0 ~ Fcalcll.s 1.0. FCalCl,e is defined numerically as:
Fcalc,,e = 0.0 if SIC> 0.4; Fcalc,[e = 1.0 if SIC< -0.4, and -0.4< SIC 0.4 then

Fca/cm

(.)
o g

SIC + 0.4

(16)

is set equal to 0.0 because this is the value knOWIIfrom field experience when when the SZC value is 0.4 or greater, Fcafc,,e calcite scale will deposit in a non-turbulent production system. Local turbulence caused by a choke, a constriction in the pipe, an elbow, a drop, etc. will increase the scaling tendency locally. If calcite scale deposition is taking place, the corrosion rate should be 0.0. Fcalcileis set equal to 1.0 when SICis equal to or less than -0.4 and is a linear fiction from 0.0 to 1O dependent on SIC . More information is needed regarding the transition zone between definite scaling with no corrosion, and corrosion with no influence by the saturation of scaling materials. It is obvious that any other bulk massive scale should also inhibit corrosion, e.g. barite. However, more information regarding the controlling S1 values for definite scale deposition of these other scales is needed. Correction terms for other scales could be included in the model. FOIIis introduced as a factor to correct the corrosion rate in low water cut oil wells, the water is assumed to be entrained in the oil phase and not available to react with the tubing. De Waard and Lotz set this term equal to zero when the water cut is less than 30V0and the liquid velocity is greater than 1 mk.ec, and to 1.0 when these conditions are not met. In this paper the factor is increased linearly to from 0.0 to 1.0 ffom water cuts of 15?/. to 30% (Equation 17).

If the water cut is < 15XO and the velocity of the liquids is >1 m/see., then FOi[ = 0.0, if 15A<watercut<300A,Foil = watercut / 30 ,and if none of these conditions are met, FO,I =1.0 FIELD APPLICATIONS OF THE MODEL To apply the model in the field, some additional information is required. Temperatures and pressures in the well system need to be estimated for inclusion in the calculations at intervals in the well. In the model shown, the temperature is calculated using a linear assumption of temperature gradient in the wellbore. This can introduce serious errors in some systems involving massive carbonates, for example. However, in most cases this assumption should not affect the overall scale and corrosion predictions dramatically. The bottomhole shut-in pressure is calculated horn the input pressure gradient. This number is required to calculate bottomhole Yo COZ in the gas phase if the Yo C02 at the surface is unknown. Even if the ?40 C02 is known at the surface, it is wise to run the model without inputting a
0/0

(17)

C02. The water chemistry (Total Alkalinity) should be adjusted to calculate a

0/0 C02 at the surface that is consistent with the measured value. This procedure will tend to reduce errors in the alkalinity measurements, especially if the alkalinity of the weak organic acids is not measured and is unknown. Unfortunately, the contribution of the weak organic acids to the total alkalinity is not commonly measured. However for accurate calcite scale and corrosion prediction. a value for the weak ormnic acid alkalinity is recndred or the total alkalinity must be altered by the procedure above if the AC02 is known with confidence for that particular well. A good estimate of the weak organic acid alkalinity can be easily obtained in the field or in the laboratory while measuring total alkalinity. The fraction of the total alkalinity due to bicarbonate can then be calculated as a function of temperature and pressure for each point of interest in the system. The value required by calcite scale prediction algorithms is the true bicarbonate alkalinity. (See 0ddo-Tomson3 for a complete discussion.) For these reasons, poor results will be obtained from the model by forcing a 0/0 COZ measured value on a water chemistry that does not include a measurement of the contribution to the total alkalinity of weak acids other than bicarbonate. In this case, it is better to alter the total alkalinity until a calculated which is consistent with the measured value. If no measured
0/0 0/0

C02 is obtained

C02 value is available, it is imperative to obtain a value for

the alkalinity due to other weak acids. It is also unwise to use field average values for the YO COZin a particular well; poor results will generally be obtained. Flowing pressures in the well were calculated using the weight of the produced gas and liquid column and the wellhead pressure. The flowing tubing pressure is calculated from the wellhead, down the hole and, also from the bottomhole conditions up the wellbore to the wellhead pressure. When convergence is obtained to less than 1.0 psi at intervals in the wellbore, the pressure is accepted as an accurate estimate of the flowing pressure. The weights of the produced fluid columns are corrected at intervals in the wellbore for the temperature and pressure effects on the density of water9, the solution gas and oil density and gas expansion. Pressure drop in the wellbore due to flow is calculated using a combination of Equations 18 and 19.

yg(qg%L
(P1)2 -(P2Y 25.2 (d,y 1

(18)

0.00001 15J,(q~~ y~L

PI P2=

(19)

(di~

where p, is the inlet pressure, p2 is the outlet pressure, ~~ is the specific gravity of the gas at standard conditions, J, is the appropriate friction factor, L is the length of pipe in feet, T is temperature in degrees Rankine, qg is the gas flow rate in MMCFD, d, is the pipe ID in inches, qL is the liquid flow rate in barrels per day and YLis the specific gravity of the liquid relative to water. The friction factors for the gas phase and the liquid phase were held constant at 0.015 and 0.04, respectively, but could be calculated. The model calculates a bubble point pressure using the solution gas calculations, if a bubble point will be encountered in the well. The bubble point pressures calculated in the model were consistent with the bubble point pressures estimated from me the Lmater Comelation 11calculated flow~g pres5ure5 are used for scale and corrosion calculations, since those preSSUreS operative during flow.

Required input into the model is shown in Table 4. The input data for the example wells shown in the remainder of this paper are shown in Table 5. A sample input and output page is shown in Table 6. The scale and corrosion predictions are also shown graphically in the model as in Figure 1. Well and Facilities Examule 1. The first example depicted in Table 6 and Figure 1 is a well with an electrical submersible pump (ESP) set near the level of the perforations. The model predicts that the fluids are corrosive below the level of the pump and into the ESP. As is common in an ESP, the temperature of the fluids is increased fkom one end of the pump to the other. At the output side of the pump, the system is scaling relative to calcite due to the 50 F increase in temperature in spite of the pressure increase. As the temperature decreases in the upper parts of the well, the system becomes corrosive again and serious corrosion is predicted in upper parts of the well. The most serious corrosion being at about 1600 feet. Scale is again predicted in the flowlines after the choke and in the heater treater (Table 6). Note that the fluid level in this well is a negative number indicating that the well will flow at the surface without a pump. In the field, the pump in Examplel failed atler less than three months in the hole. When the tubing and pump were pulled from the hole, serious corrosion was found at the input side of the pump and in the tubing tirther up the hole, being most severe in the region of about 1500 feet. The pump failed due to calcite scale deposition in the pump, most severe in the mid and upper sections of the pump. Scale in the surface facilities also occurred as the model predicted. The iron concentration in the produced water was 35 mg/1 and consistent with the corrosion occurring in the well when compared to the sandstone calculated iron concentration (Sandstone Calc. Iron, Table 6) of 3 mg/1. The sandstone calculated iron concentration is derived for sandstone reservoirs fi-om the comparative solubilities of iron and calcium carbonate, the calcium concentration, and the overall water chemistry. The calculation does not work well in carbonate reservoirs because they can be deficient in iron relative to calcium due to the depositional environment. Exanwle 2. Although the model is capable of temperature and pressure input to depict surface facilities, in the interest of space, only the graphical well profiles will be shown for the last three examples. The input parameters, however, are shown in Table 5. Figure 2 is a graphical depiction of the scale and corrosion profile of the second example. The well is produced with a rod pump set 4000 feet above the perforations. The well produces 50 MCFD, 25 BOPD and 200 BWPD from a depth of 8,500 feet. The well fluids are corrosive throughout the entire well with the worst corrosion taking place in the area of the pump. However, the model assumes the same tubing size to the perforations. In this well there is no tubing set below the pump, and the actual corrosion rate in the 6 inch casing below the pump is much less than that shown in Figure 1. A separate calculation can be run with 6 inch tubing size to show the corrosion rate below the pump. In addition, when entering the ID of the production tubing in calculations, the diameter of the rod must be subtracted fi-omthe ID. The well depicted by Figure 2 must be treated with corrosion inhibitor evety two weeks, or failures will occur within one to two months atler a workover. As the model shows, the most serious corrosion is in the region of the pump and is less at shallower depths. No scale has been detected in this well which is consistent with the model predictions. The barite saturation index increases to 0.49 at the wellhead, but this is not sufllcient to precipitate barite scale. Laboratory experiments done at Rice University suggest that the saturation index necessary to precipitate barite scale is much higher than the 0.4 S1 used for calcite and in the region of 0.9.12 Figure 2A shows the same well profile as figure 2, but all of the alkalinity was attributed to bicarbonate, ignoring the alkalinity due to other weak acids. In addition, the calculated XO C02 in the gas phase was ignored and the measured value of 3.4% was input. Note the dramatic increase in scaling tendency and the decrease in the corrosion rate. The fact that the scaling tendency is so high in a liquid well downhole at the perforations should be a clue that there is a problem with the input data. The total alkalinity was 1586 mg/1, while the (ignored) alkalinity due to other weak acids was 1013 mg/1. Even if the weak organic acid alkalinity had not been known, a reasonable estimate for the scale/corrosion tendencies in the well could be obtained by entering values for the weak acid alkalinity until the 0/0 C02 calculated was consistent with the measured value. Figure 2B shows the same well profile as Figs. 2 and 2A, also ignoring the alkalinity due to weak acids other than bicarbonate. However, in this example no Yo C02 was input into the model. The model calculates a VO C02 in the gas phase of 20.5V0. The result is a predicted corrosion rate over 2.5 times as high as would be calculated with the other weak acids included in the calculations. This example illustrates the importance of correcting the total alkalinity for the contributions of other weak acids for accurate scale and corrosion predictions. Examule 3. Figure 3 shows a rod pump well fi-om west Texas that produces from a carbonate formation. The field has been water flooded with water having a high sulfate concentration. Production of 130 MCFD, 54 BOPD and 110 BWPD is from 6,500 feet with the pump set at 3132 feet. The well produces two types of mineral scale. Gypsum scale is deposited shallow in the formation, in the perforations and deep in the wellbore. The well is corrosive from the pump to about 1500 feet and must be treated with corrosion inhibitor. Calcium carbonate scale is deposited in this well from the wellhead down to about 1000 feet. In addition to the corrosion treatment, the well is squeezed periodically to inhibit scale deposition.

The model correctly predicts the scale and corrosion profiles in the well. The model predicts anhydrite scale as the thermodynamically predicted calcium sulfate phase, but it is known that gypsum ofien forms kinetically when anhydrite is predicted thermodynamically. 13The calcium sulfate S1 threshold for scale deposition can also be shown to be lower than that for calcite scale in laboratory work done at Rice University. 14The numerical value appears to be about 0.2, but more work needs to be done to determine this value accurately. However, this value appears to correctly predict the calcium sulfate scale deposition in this well. Examule 4. Figure 4 depicts a gas well offshore Louisiana. The well produces 4 MMCFD and 300 BWPD tlom a depth of 15,000 feet. As is common in deep gas wells, the wellbore scales with calcium carbonate at the level of the perforations and in the production tubing deep in the wellbore. The scale problem in this well was so bad that the tubing was bridged completely with calcite scale near the perforations. The well was treated with coiled tubing to apply acid to the scale and acid was flushed into the formation to bring the well back into production. The well becomes corrosive in the upper 10,000 feet with the most severe corrosion taking place in the upper 4,500 feet of the well. Again, the model correctly predicts the scale/corrosion profile. No barite scale has been found in this well, but barite scale was recovered downstream due to a water incompatibility problem. The iron concentration in the produced water was 204 mg/1.The high iron concentration is consistent with the corrosion occurring in the well, especially when compared to the calculated sandstone iron concentration of 7.2 mg/1. Many gas wells scale deep in the well due to the relatively light fluid column. The temperature is hot downhole, but the pressure in the wellbore can be significantly reduced relative to the reservoir due to the light fluid column. The pressure decrease at constant temperature is conducive to calcite scale formation. Exanmle 5. Figure 5 is the scale corrosion profile of a gas and oil well onshore Louisiana. The well produces 2.9 MMCFD, 1,100 BOPD and 300 BWPD from a depth of 15,522 feet. The flowing tubing pressure is 2,000 psi at the wellhead. The scale corrosion profile is similar to Example 4 above, but the scaling tendency is less at the perforations due to the increased pressure caused by the heavier fluid column in this example. The well has a positive scaling tendency for its entire length which decreases the corrosion that might be expected. However, due to the high flowing tubing pressure, the well is corrosive with the most severe corrosion taking place at the wellhead. This well experienced abnormal pressure declines in its production history. The declines in this well were attributed to scale in the area of the perforations. This was due to the pressure decrease noted in this region atler the scale and corrosion model was applied. An acid job brought the well back to full production. A scale squeeze should be performed on this well to eliminate scale deposition in the future. AVAILABILITY OF THE MODEL The above calculations can be programmed in a spreadsheet to generate a comprehensive scale and corrosion model. Since flowing pressures are required for accurate calculations, an algorithm to calculate flowing pressures must be developed in-house, or a commercial program obtained that can be combined with the prediction equations. The resulting calculations are accurate and useful in determining why failures have occurred, predicting tkture failures, determining chemical use rates, and in materials selection. The model is available at no charge Ilom the authors. In addition, the ScaleSoft@model is available from Rice Universi~ that can perform S1 calculations on other scales. The ScaleSoft model will also generates a Pitzer calculation for the relative saturation of these scales and others. ACKNOWLEDGEMENTS The authors wish to express their thanks to Champion Technologies, Inc. for their support in the publishing of this paper. REFERENCES 1. W. G. Langelier, J. AWWA 28 (1936) p. 1500. 2. J. E. Oddo and M. B. Tomson, J. Pet. Tech. 34 (1982) p. 1583-1590. 3. J. E. Oddo and M. B. Tomson, SPE Prod. and Fat. Joum. Feb. (1994) p. 47-54. 4. S. L. He, A. T. Kan, M. B. Tomson and J. E. Oddo, A New Interactive Sotlware for Scale Prediction, Control and Management, SPE Annual Tech. Conf. and Exh., Paper No. 38801, (San Antonio, TX: SPE, 1997). 5. C. de. Waard and U. Lotz, Prediction of COZCorrosion of Carbon Steel, Corrosion 93, Paper No. 69, NACE, Houston, TX, 1993). 6. J. F. Swindells, Handbook of Chemistry and Physics, (R. C. Weast, Cleveland, OH: The Chemical Rubber Co., 1970), p. F-36. 7. H. B. Bradley, Petroleum Engineering Handbook, (Richardson, TX: SPE, 1989). 8. H. D. Beggs and J. R. Robinson, J. of Petri. Tech. Sept., (1975) p. 1140-1141. 9. G. S. Ken, J. of Chem and Eng. Data 12 (1967): 67-68.

10. 11. 12. 13, 14.

M, Vasquez and H. D. Beggs, J. Pet. Tech. June, ( 1980): p. 968-970. J. A. Lasater, Trans., AIME 213 (1958): pp. 379-381. M. B. Tomson, Personal Communication, (1997). J. C. Cowan and D. J. Weintritt, Water Formed Scale Deposits (Houston, TX: Gulf Publishing Co., 1976), 586 p. M. B. Tomson et al., Development and Transfer of Technology Regarding Scale and NORM Scale Control, Gas Research Institute, Project No. 5095-250-3352, August (1996).

TABLE 1. PARAMETERS NEEDED FOR THE CALCULATION OF THE CONDITIONAL CONSTANTS.

Calcium Carbonate Scale Prediction Constants Conditional Constant a b c

K~ K, Kz Kw K,C K Note: K==

2.238 6.331 10.511 7.981

4.730

6.348E-3 -8.278E-4 -4.123 E-3 4.820E-3

-3.288E-4

-9.972E-6 9.297E-6

1.234E-5 -2.118E-5

6.580E-2 -0.491 -1.255 -2.725 -0.595 0.170

-3.300E-2 0.379 0.867 1.183 0.557 -0.211

4.790E-2 -6.506E-2 -0.174 -0.1207 -7.665 E-2 5.949E-2

1.596E-4 -1.458E-3 -1.588E-3 -2.904E-4 -1.470E-3 1.716E-4

7. 142E-6 -2.564E-5 11.183E-6 -6.973 E-5

5.852E-6 -1.429E-5

3.839

5.849E-3

-8.682E-6

9.900E-7

K&

and is used to calculate the true bicarbonate alkalinity, see Oddo and Tomson.3

Sulfate Scale Prediction Constants Conditional Constant a b K,, 2.301 3.599 4.053 2.884

1.740E-3
-0.266E-3

4.553 E-6
9.029E-6

-7.801E-6
-5.586E-5

-3.969
-0.847

2.280
5.240E-2

-0.459
8.520E-2

-6.037E-4
-2.090E-3

K sPg
KSP~

-1.792E-3
9.327E-3

11.400E-6
O.188E-6

-7.070E-5 -3.400E-5 -5.3 15E-5

-4. 197E-5

-1.734 -1.994 -4.003

-2.082

0.562 1.267 2.787

0.944

-2. 170E-2 -0.190 -0.619

-8.650E-2

-6.436E-4 -3.195E-3 - 1.850E-3

-1.873 E-3

K spa KSP~ KSPCI

10.147
6.090

-4.946E-3
2.237E-3

11.650E-6
5.739E-6

where: K~ is the Henrys Law Constant as defined in the previous papers referenced in the text, K1 is the first dissociation constant of carbonic acid, Kz is the second dissociation constant of carbonic acid, K,w is the conditional volubility product for calcite (calcium carbonate), K.C is the dissociation constant for acetic acid, K,, is the stability constant for the magnesium sulfate solution complex, and K,Pg, KSph, K,w, K~Pb and K~wl are the conditional volubility products for gypsum (calcium sulfate dehydrate), hemihydrate (calcium sulfate hemihydrate), anhydrite (calcium sulfate), barite (barium sulfate) and celestite (strontium sulfate), respectively. The equations are of the form: + iW + g*115 + h*T*15. -loglO( Kc ) = a + b*T + C*T2+ d*P + e*15

TABLE 2. THE RECOMMENDED EQUATIONS FOR THE CALCULATION OF THE SATURATION INDICES FOR CALCITE SCALE.
Calcite Scale Saturation Gas Phase Present Index Calculations

HCOpH = log10 Pygfg

''c='0g10Pa2%i)2l+6039+'4463x
H
+ 8.569+ 5.520x 103T 2.830 x 10-6T2 1.330x 10-5P 0.42515+ 0.3461 1.716x 10-2115 1.298x 10-3T105
yg =

where: f~ = exp~7.66x10-3 +8.0 xIOq TO5 2.1 1XIO-5T~05 +(5.77 x 10q +3.72 x10-5T05 -5.7 x10-7 T)P+(4.4x10G -2.96 x10-7T05 +5.1 x10-9 T)P15jand Yt Pf&5.O x BWPD + 10.0 x BOPD)X 10-5 (T+ 460)x MMCFD

1.0+ [

1
6T2 7.419x1O 5P1.9611 05 +O.695I1.136X1O 211.5 _ 1.604x 104T1005

Gas Phase Absent

(Ca2 )( HCO~)2 SIC = loglo

I

C02 c aq

+3.801 +8.115x1O 3 T+9.028x10

HCO~ + 6.331 8.278 x 10-4T + 7.142 x 10-GT2 2.564 x 10-5P 0.49115+ 0.3791 6.506 x 10-2115 1.458 x 10-3T105 pH = IogIo c:: where:

[1

for wells past the bubble point and ntCoz is the total number of moles of carbon dioxide produced per day and V~~and VOare the volumes of water c: * and oil produced per day in liters or: Coz = log,o PC02 2.212- 6.51x 10-3T + 1.019 x 10-5T2 1.290x 10-5P 7.70 x 10-215- 5.90x 10-2I for fluids past the gas removal point (e.g. the separator). 1%0 call
Measured H with gas phase present or absent

SIC = loglo I Ca2+)(HCO~)]+ pH 2.53 + 8.943 x 10-3T + 1.886 x 10-6T2 4.855 x 10-5P 1.47015 + 0.3161 + 5.370 x 10-2115 + 1.297 x 10-3T105

where T is temperature (F), P is pressure (psi), I is Ionic Strength (molar), Yg is the mole or volume fkaction of carbon dioxide in the gas phase at a specified temperature and pressure, y, is the mole or volume fraction of carbon dioxide in the gas phase at room temperature and pressure and fg is the figacity of cabon dioxide gas at a specified temperature and pressure.

TABLE 3. SAMPLE SULFATE SCALE CALCULATION.

Gwsum Scale Saturation Index Calculation

The values for the constants for the eight terms are shown in Table 1.
Calculate: Calculate:

log10K,t = 2.301+ 1.740x 10-3T + 4.553 x 10-6T2 7.801 x lo-bp -3.96915 + 2.2801 0.4591]5 6.037 x 10-4T105 K,t = 10IOg K

Calculate:

z =
CM

Ca2+mg/1 + Mg2+mg/1 + Sr2+mg/1 + Ba2+mg/1 137330 24304 87620 40080

Calculate:

Cso, =

SO~-mg/l
96000

~
Calculate free sulfate:

0;- =

,-l+Kst(xcM-cso,

)]+{(l+Kst(xcM-cso4 2K,t

)}+4Kstcso4}0"5

Calculate the free metals: [g2+]=CM,/cMg/(l+ KS,[sO~-)

k~2+l=CSr/(I+K.~ bO:-Dl~~2+l=c~a/(l+~ ka2+l=c.a/(l+~~k~~-D

Calculate the required Saturation

Index, in this example, gypsum:

g=lOgOIF)Or

1. =@loka2+l@

+3.599 0.266x10-3 T+9.029x10AT2

5.586x10-5P

0.847Z05 +5.24 x10-21 +8.52 x10-215 2.09x10-3T105

TABLE 4 INPUT INTO THE SCALE/CORROSION PREDICTION MODEL ID Well Casing (inches) (Req. if Annular Flow) Wellhead Temperature (F) Annular Flow? YiN Wellhead Pressure (psi) Pump Depth (feet) (if applicable) Separator Temperature (F) Pump Fluid Output Temperature (F) (if pumping) Separator Pressure (psi) Gas Production (MMCFD Shut-in Fluid Level (feet) (if pumping) Oil Production (BOPD) Water Hardness (mg/1as CaC03 ) (Optional) Water Production (BWPD) Calcium (mg/1) API Oil Gravity Barium (mg/1) Gas Gravity Relative to Air Strontium (m#l) (Optional) Ambient Temperature (F) Iron (m#l) Temperature Gradient (F/100) Weak Organic Acids (mg/1 as HCO~ ) (see text) Total Alkalinity (mg/1as HCO~ ) Top of the Perforated Interval of Interest (feet) Pressure Gradient (Shut-in psi/foot) Sulfate (mg/1) Measured Yo COZ in the Gas (Not Recommended) Chloride (mg/1) OD Well Tubing (inches) (Req. if Annular Flow) Magnesium (mg/1) (Optional if Hardness Known) ID Well Tubing (inches) Standard Field, Well and Operator Identification

TABLE 5. INPUT VARIABLES OF THE SCALE/CORROSION MODEL FOR THE EXAMPLES SHOWN IN THE PAPER.
Example Number
Variable 1 2 3
A

Wellhead Temperature, F Wellhead Pressure, F MMCFD BOPD BWPD API Oil Gravity Gas Gravity Ambient Temperature, F Temp. Gradient, F per 100 feet Mid Point of Perforations, feet Pressure Gradient, psi per foot Measured Yo COZ, gas phase ID Well Tubing, inches Pump Depth, feet Pump Output Fluid Temp., F Shut-in Fluid Level, feet Hardness, mg/1 Calcium, mgll Barium, mgll Strontium, mg/1 Iron, mg/1 Magnesium, mg/1 Weak Organic Acids, mg/1 Total Alkalinity, mg/1 Sulfate, mgll Chloride, mg/1

158 420 0.262 171 237 40 0.78 70 2.6 5500 0.30 NA 2.3 5400 263
-200

85
30 0.050 25 200

31 0.73
70

1.6 8500
0.40

1850 270 1 38 35 270 200 476 260 12360

NA 2.1 4500 149 -1oo 1430 348 44 NA 225 31 1013 1586 12 25100

75 20 0.13 54 110 22 0.80 70 0.80 6500 0.40 NA 1.7 3132 98 350 19600 6440 0.1 NA 2.0 853 73 1530 3100 60300

120 500
-4.0 0.1

2;0
2000 2.9

59 42 0.68 70 1.9 15000 0.47 NA 2.6 NA NA NA NA 650 126 NA 204 36 0 174 8 21770

1100 300 38 0.78 70 1.34 15522 0.47 NA 2.8 NA NA NA 27060 10204 575 NA 178 248 41 102 10 102900

Operator:

TABLE 6 EXAMPLE INPUT/OUTPUT TO THE SCALE/CORROSION PREDICTION MODEL Well Name: Example 1 Field:
Input Variables Concentrations in mgll Concentrations in mg/1 Sodium 270 Mg usedin Calculations Lo TDS 38 Specific Gravity 35.0 Ionic Strength (M) 2001Sandstone Calc. Iron 476 Water Cut % 260.0 011 Density (gmlcm) 123601Moies Gas/Dav L Moles OWDay
1850

Output Variables I 7469 Hydraulic Diameter (in) 270 Liquid Veloeity (ft/see) IdVelocity (m/see) 21141 Llqui( 1.015 Intake Pump Pressure (psi) 0.38 Outtake e Pump Pressure (psi) 3.OIIntakePump Temperature (F) 58.1 IIePoi33L if any (psi) 0.8251 Bubbl . 313861 lPerforation Temp. . (F) I 1228092 Calculal ~tedBHSIP (psi) .. 2062%OlCalculated BHFP (psi) I lBaSO. Bottomhole Shut-in S1
I

Wellhead Temperature (F) Wellhead Pressure (psi) Separator Temperature (F) Separator Pressure (psi) Ambient Temperature (F) Temp Gradient FI1OO feet Mid Point of the Perfs. Press. Gradient (psi/ft.) Production Tubing ID (in) Production Tubing OD (in) Casing ID (in) Annular Fiow? YIN Pump Depth (ft), if any ..~.. Fluid Temp. - Pump Disch#~-

1
I

158 Hardness as tacos (Not ~.imd) 420 Calcium as Calcium 100 Barium 15 Strontium 70 Iron !. Acid Alkalinity as HCOJ 2.60 Weak Org. 5500 Total Alkalinity as HCOJ 0.30 Sulfate ~2.30 Chloride Mess. % COZ@ 75 F and 14.7 psi lions of Mill----- CnhiCFt. ___ .. . .. of . (k ___ ner ~.. Dav -... Barrels Oil Produced per Day 1 5400 Barrels of Water Produced per Day Ml] .API --. . . oil . .. Crnvitw -.-.
..J

I
I I I I I I I I 1
1

1.15 0.9255 0.2821 I I 10001 I 13901 4 2121 NA I I 2131 I 1650 I I 1020 -0.071 288.2
0.86

I I~~ay I

I 1

-2001Gas Gravity Shut-in Fluid Level (ft) 1 1 Input not Recommended (See Read Me) I Calc Static I Calc. Calc. Calculation Point Pressure Flow Press. Description I Temn. (IO I Denth Mt) Bottomhole 213 5500 1650 io20

I 1711 237 40 Calc. % C02 @ SC 0.78 Calc. %0 C02 @ Perfs. S1 I CaC03 0.18 I S1 Barite -0.04

Gas Phase Present?

Corrosion mmlyr 1.73

1.52 HCOJ Flowing Bottomhole (m#l) 1.23 Bottomhole COZFugacity Coeff. Log of Molar Calcium S1 S1 SI S1 HemiI Gypsum I Hydrate / Anhydnte I Ceiestite -1.70 -1.67 -1.23 -0.44

-2.1716 pH I Calc. 5.88

PumpIntake PumpOutput

212 263
247 242 232 221 211 x-u-l -.,. 190 179 169 158 158 158 140 180 100

5400 5400
4590 4320 3780 3240 2700
?160 ----

1629 1629
1454 1396 1288 1184 1083
QWi

1000 1390
1215 1157 1049 945 844 747 654 565 480 420

1.78 0.00
0.00 0.00 0.00 0.58 1.41 2.34 2.69 2.59 2.32 2.10

0.18 0.74
0.58 0.53 0.42 0.32 0.22 0.12 0.03 -0.06 -0.14 -0.23

-0.03 -0.12
-0.10 -0.09 -0.07 -0.05 -0.0)2 0.00 0.03 0.06 0.09 0.12

-1.70 -1.63
-1.65 -1.66 -1.67 -1.69 -1.70 -1.71 -1.72 -1.73 -1.73 -1.74

-1.67 -1.57
-1.60 -1.61 -1.63 -1.65 -1.66 -1.68 -1.69 -1.70 -1.70 -1.71

-1.23 -0.92
-1.01 -1.04 -1.11 -1.17 -1.24 -130 -1.37 -1.44 -1.51 -1.58

-0.44 -031
-0.35 -0.36 -0.39 -0.41 -0.44 -0.47 -0.49 -0.51 -0.54 -0.56

5.88
5.92 5,92 5.93 5.93 5.93 5.94 5.95 5.96 5.98 6.00 6.02

I I

I I

---

I 1

Wellhead Flowline Choke In Treater Treater

1620 1080 540 0 0 0 0 0 0

893 804 719 659

NIA NIA
NIA NIA N/A

400 50
15 15 15 N

1.96 0.00
0.00 0.00 0.00

-0.21 0.65
0.92 1.48 0.35

0.12 0.14
0.20 0.08 0.34

-1.74 -1.72
-1.73 -1.69 -1.74

-1.71 -1.69
-1.70 -1.66 -1.71

-1.58 -1.57
-1.69 -1.41 -1.97

-0.S6 -0.55
-0.59 -0.49 -0.68

6.04 6.89
7.34 7.49 7.18

3.00 2.50 2.00

1.50 1.00

0.50 0.00 -0.50

-1.00 -1.50

-2.00 t
o

1000

2000

3000
Depth (feet)

4000

5000

6000

FIGURE 1- Example of the graphical output of the Scale/Corrosion Prediction Model, and the well used as Example 1. Note the temperature increase in the pump causes an increase in calcite scaling tendency and a decrease in corrosion rate and in barite scaling tendency. 5.00

4,00

3.00

2.00

1.00 A
0.00

t .00 J
o

1000

2000

3000

4000
Depth (feet)

5000

6000

7000

8000

9000

FIGURE 2- The Scale/Corrosion profile of the well used for Example 2. The model calculates a percent carbon dioxide in the gas phase of 3.3876 vs. a measured value of 3.4%.

1.00 ,
0.901 0.80 ,8 0.70 ,, 0,60 ut 0.50 8 0,40 ,D 0.30 ,, 0.20 aD 0.10 t, 0.004 I 0.10

J
o

1000

2000

3000

4000

5000

6000

7000

8000

9000

Depth (feet)

FIGURE 2A. - The Scale/Corrosion profile of the well used for Example 2 ignoring the alkalinity due to weak acids and attributing all of the alkalinity to bicarbonate. Although, the model calculates a percent carbon dioxide in the gas phase of 20.5%. the actual measured value of carbon dioxide of 3.4%was inuut into the model. This results in a much decreased corrosion rate and a substantial increase in the calcite scaling tendency. Note the high scaling tendency at downhole conditions in an oil and water well which is a strong indication that there is a problem with the input data.
12.00 k

10.00 a,

8.00. v

6.00 I.

4.00 ..

2.00. ,

0.00 t

2.00 J
o 1000 2000 3000 4000 5000 6000 7000 8000 9000

Depth (feet)

FIGURE 2B - The Scale/Corrosion profile of the well used for Example 2 ignoring the alkalinity do to weak acids and attributing all of the alkalinity to bicarbonate. The model calculates a percent carbon dioxide in the gas phase of 20.50/. resulting in the very high corrosion rates illustrated.

~
Scale Saturation Index or Corrosion (mm/yr)

c)

Scale Saturation
Index or Corrosion (mmlyr) 0 UI 0 0 o in 0 0 0 o m o 0 0 o

5MAo A o 0 0 0 0 0 0 0 0 0 0 0

A.@. 0 0

mm 0 0

3.50 ~

3.00

2.50

2.00

1,50

1.00

0.50

0.00

0.50 J

J
2000 4000 6000 8000 10000 12000 14000 16000

Depth (feet)

Figure 5. The Scale/Corrosion profile of the well used for Example 5.