Journal of Petroleum Science and Engineering 28 2000. 3353 www.elsevier.

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Analysis of acid returns improves efficiency of acid stimulation: a case history

K.C. Taylor a, ) , H.A. Nasr-El-Din a,1, Ragheb B. Dajani b,2
a

Laboratories R & D Center, P.O. Box 62, Saudi Aramco, Dhahran 31311, Saudi Arabia b BJ Serice Arabia Ltd., P.O. Box 14037, Dammam 31424, Saudi Arabia Received 24 June 1999; accepted 26 June 2000

Abstract Techniques are demonstrated to evaluate acid stimulation treatments based on chemical analysis of the return fluids. The techniques can provide information about the source of formation damage, the amount and type of scale in the casing, the efficiency of the acid treatment, and the amount of iron control chemicals required for similar treatments. As an example, these methods were used for the acid stimulation treatment of a typical seawater injection well Well A. in a large carbonate reservoir in Saudi Arabia. Over a 2-day period, more than 50 field samples were collected. More than 700 chemical analyses were eventually made on these samples. Analysis of the casing pickle fluids showed that 235 kg of iron from corrosion products, as well as a significant amount of acid-insoluble iron carbide, Fe 3 C, was produced. Measurement of iron II. and iron III. concentrations showed that the iron corrosion products in the casing contained mostly iron oxides such as rust or mill scale. The pickle treatment prevented the injection of this material into the formation around the wellbore. Otherwise, the main acid treatment would have flushed all of this material into the reservoir and reduced injectivity. Analysis of the matrix acid flowback samples showed that iron control chemical concentrations in the acid could be reduced with significant cost savings. The extent of acid dilution and the amount of unreacted acid were also determined. The results showed that 125 kg of calcium sulfate was dissolved from the near-wellbore region during flowback. Acid stimulation of Well A increased the injectivity index II. of the well from 0.12 to 0.21 m3rdayrkPa 5 to 9 bblrdayrpsi., an increase of 75%. The acid stimulation was successful and the evaluation methods provided useful information to improve the success of future treatments. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: injection well; stimulation; formation damage; iron control chemicals; pickling acid

1. Introduction
Corresponding author. Fax: q 966-3-876-2811. E-mail addresses: taylorkc@mail.aramco.com.sa K.C. Taylor., nasrelha@mail.aramco.com.sa H.A. Nasr-El-Din., mdajani@bjservices.co.ae R.B. Dajani.. 1 Fax: q 966-3-876-2811. 2 Fax: q 966-3-858-8128.
)

The seawater injection system for a large carbonate field in Saudi Arabia has more than 400 km of pipeline and can supply 0.67 million m3rday 4.2 million barrels per day. of treated seawater. In this

0920-4105r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 0 - 4 1 0 5 0 0 . 0 0 0 6 6 - 8

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353 Table 2 Analysis of injected seawater and low sulfate water used in Well A Component Injected seawater mgrl. 16,870 700 2,040 4,150 30,040 160 53,960 - 0.01 7.5 1.0418 Water used in Well A mgrl. 210 137 48 270 371 210 1,257 1 8 1.0011

system, corrosion must be maintained at a reasonable level, and water quality must be high enough to prevent excessive losses of injectivity Brown et al., 1979; Bayona, 1993.. Extensive sections of the pipeline are internally coated to reduce corrosion. Water quality standards have been established and are shown in Table 1. Corrosion control in water injection systems was reviewed by Patton 1993.. Chen and Ahmed 1998. recently gave a review of the coating effectiveness and water quality. Even with these measures, injectivity of some wells in the reservoir has gradually decreased and acidizing treatments only partially restore injectivity Bayona, 1993; Chen and Ahmed, 1998.. As the cumulative water injection increases, the acidizing effectiveness decreases. To address these trends, a detailed investigation of an acidizing treatment of a typical injection well in the field was initiated. Most water injection wells in this carbonate reservoir are vertical with openhole completions over an interval of 60 to 120 m 200 to 400 ft.. Static bottom hole temperatures are 498C to 658C 1208F to 1508F.. Static bottom hole pressure is approximately 27.5 MPa 4000 psig. at 2271 m 7450 ft.. Treated seawater Table 2. is injected to maintain the reservoir pressure. To restore injectivity, damaged wells are stimulated using 15 wt.% HCl. Various acid diversion techniques have been used. Ginest et al. 1993. evaluated three different acid placement techniques in the carbonate reservoir. These included conventional bullhead treatments, coiled tubing with nitrogen foam diversion, and coiled tubing without divert-

Sodium Calcium Magnesium Sulfate Chloride Bicarbonate Total dissolved solids Iron pH Density, grcm3 at 15.58C 608F.

Table 1 Water quality requirements for seawater injection Bayona, 1993. Component Total suspended solids Particle number and size Specifications - 0.2 mgrl Maximum of 200 particles greater than 2 m m per 0.5 ml of water - 10 ppb a - 14 mgrl 7.07.5

Dissolved oxygen Sulfide pH b

a b

This is in agreement with Patton 1993.. pH is adjusted to prevent the precipitation of calcium carbonate.

ing agents. The goal of the work was to improve the efficiency of stimulation of the long openhole sections in the formation as a result of drilling mud damage. They concluded that coiled tubing treatments with nitrogen foam diversion were more effective than conventional bullhead jobs; however, surface washout does not currently allow the use of coiled tubing in some of the wells in this reservoir. The gradual injectivity decline observed in these wells may be a result of near-wellbore plugging or deep damage by particulates over an extended period of time. Possible sources of this damage include the precipitation of iron III. hydroxide from previous acidizing treatments Crowe, 1985., the formation of calcium sulfate scale from the seawater that is injected Allaga et al., 1992. or the formation of iron sulfide and biomass as a result of microbial corrosion reactions Lee et al., 1995.. Allaga et al. 1992. showed that calcium sulfate precipitation inside a sandpack resulted in a gradual permeability decline. Iron sulfide has been identified as a corrosion product in seawater injection systems Chen and Ahmed, 1998; Little et al., 2000.. The plugging of the formation over time with both acid soluble and acid-insoluble particulates would be consistent with the type of injectivity loss observed by Bayona 1993.. Water injection wells can contain large amounts of iron scale from pipe corrosion. This corrosion occurs from oxygen in the injection water or from microbial action. If acid is bullheaded into a water

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injection well, iron scale will rapidly react with the acid. Total iron concentrations up to 100,000 mgrl have been reported in acid returns from other water injection wells Gougler et al., 1985.. Corrosion in the casing can be present in several forms. If small amounts of oxygen are present in the injected water, then iron oxides will form. In air, this rust or mill scale contains three layers of iron oxide Coburn, 1984.. The outer layer is primarily ferric oxide, Fe 2 O 3 . The layer closest to the steel is ferrous oxide, FeO. The intermediate layer can be represented as Fe 3 O4 or FeO P Fe 2 O 3 . In the latter, the ratio of iron III. to iron II. is two to one. If 15 wt.% HCl reacts with sufficient Fe 3 O4 to give a solution containing 45,000 mgrl total iron, then the reacted acid will contain 30,000 mgrl iron III. and 15,000 mgrl iron II.. Acid reaction with rust reduces the acid concentration in this example from 15 to 7 wt.%. This dissolved iron can lead to plugging in the critical near-wellbore region. Two reactions can occur with iron III. that can lead to precipitation of iron compounds. If hydrogen sulfide is present, then iron III. will react to form elemental sulfur Crowe, 1985; Taylor and Nasr-ElDin, 1999.. In the absence of hydrogen sulfide, iron III. hydroxide will precipitate as the pH increases above 1 Taylor et al., 1999a, Taylor and Nasr-ElDin, 1999.. Iron II. will not precipitate as a hydroxide until the pH increases to a value of about 7 Crowe, 1985.. Iron control chemicals are not able to maintain iron III. concentrations above 10,000 mgrl in spent acidizing fluids. For instance, to keep 10,000 mgrl iron III. in solution at 528C 1258F. requires 22 l of acetic acid and 12 kg of citric acid per 1000 m3 of 15% HCl Dill and Smolarchuk, 1988.. It is not recommended to exceed this level of acetic acid and citric acid, since precipitation of calcium citrate may occur. Calciumriron complexes with citric acid formed at high citric acid concentrations in partially spent acids Taylor et al., 1999a.. Several chemical studies of acid flowback samples have been reported. Gdanski and Peavy 1986., Almond et al. 1990., Shuchart 1995. and Nasr-ElDin et al. 1996. examined acid return samples in sandstone reservoirs. Nasr-El-Din et al. 1999., Dahlan and Nasr-El-Din 2000. and Mohamed et al. 1999. examined acid returns in carbonate reservoirs.

No comprehensive chemical studies of acid flowback samples from water injection wells have been published, to the best of our knowledge. The objectives of this study are to: 1. demonstrate techniques to evaluate acid stimulation treatments based on chemical analysis of the return fluids, 2. use these techniques in Well A to identify the source of formation damage, the amount and type of scale in the casing, and the efficiency of the acid treatment, 3. evaluate the amount and type of iron control chemicals that were used, and 4. make recommendations to improve future similar treatments. 1.1. Well description Well A is a seawater injection well in a large carbonate reservoir in Eastern Saudi Arabia. The injectivity of this well has been decreasing since injection began in 1993. The injectivity index decreased from 0.53 m3rdayrkPa 22 bblrdayrpsi. Nov.r93. to a value of 0.12 m3rdayrkPa 5 bblr dayrpsi. before the treatment. The damage to this well is significant and has been occurring over a number of years. The well has an openhole completion in the interval from 2215 to 2324 m 7268 to 7626 ft.. The well was acidized using 3.8 cm 1.5 in.. coiled tubing in 1992 to improve well injectivity. At that time, 15 m3 95 barrels. of 15 wt.% HCl containing a surfactant 0.2 vol.%., a corrosion inhibitor 0.4 vol.%. and a friction reducer 0.2 vol.%. were injected into the formation. No iron control chemicals were used and the well was not flowed back after the treatment. Instead, the reacted acid was displaced into the formation using seawater. A caliper log indicated a washout approximately 0.6 m 25 in.. in the zone from 2215 to 2217 m 6751 to 6757 ft.. A spinner test indicated that most of the injected water was going into a narrow zone that extended from 2228 to 2256 m 6791 to 6876 ft.. The well has a 17.8 cm 7 in.. liner from the openhole section to 742 m 2262 ft.. All of the casing in the well is J-55 low carbon steel. The wellbore volume is nearly 61 m3 383 barrels. and the static bottom hole temperature is 588C 1378F.. A typical geochemical analysis of the seawater injected into Well A is given in Table 2.

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1.2. Description of the treatment Mixing and water tanks were inspected, and samples were taken of all chemicals on site before the treatment began. The treatment chemicals collected at Well A were: Breakerriron control Erythorbic acid, reduces iron III. to iron II. Citric acid, prevents precipitation of iron III. by forming a soluble complex in spent acid Cross-linking agent Surfactant, to improve the contact between the live and spent acids with reservoir rock Polymer, to increase the viscosity of the in situ gelled acid Mixed samples of the pickle acid containing all additives A mixed sample of the 10 wt.% in situ gelled acid containing all additives A mixed sample of the 15 wt.% acid containing all additives Low salinity water for mixing of acids, pre-flush and post-flush The corrosion inhibitor was already present in the acid when it arrived on site. On the first day of the treatment, the well was flowed back using reservoir pressure to flush out the wellbore. Samples were collected and the flowrate was determined by measuring the time required to fill a container of known volume 0.16 m3 .. The rate was found to be 22.3 m3rh 140 bblrh..

On the second day, the casing was pickled before the matrix acid stimulation treatment. Compositions of the fluids that were used in the treatment are given in Table 3. Treatment stages, volumes, pumping rates and surface pressures are listed in Table 4. The pickle treatment was performed to remove rust and scale from the casing. This part of the treatment was designed so that penetration of the acid into the formation would be minimal. The acid 8 m3 . was displaced down the casing with 50 m3 315 barrels. of a low salinity low sulfate water until the acid was close to the openhole section. The well was then flowed back to flush the spent acid from the casing. Chemical analysis of the low sulfate water used in the treatment is given in Table 2. To enhance acid placement efficiency, matrix stimulation of the well was carried out in 15 stages Table 4.. The first stage used low sulfate water as a spacer between the reservoir water and the acid. This reduces mixing of the spent acid with seawater. Seawater contains high concentrations of sulfate, while spent acid contains high levels of calcium. Mixing of the two fluids leads to precipitation of calcium sulfate that can damage the formation in the critical near-wellbore area. The low sulfate water pre-flush was followed by alternating slugs of 10 wt.% in situ gelled HCl and regular 15 wt.% HCl. The in situ gelled acid uses a polymer and a cross-linking agent to form a high viscosity acid over a narrow pH range. The purpose of the in situ gelled acid was to provide acid diversion and increase the flow of acid into the lower permeability zones. Approximately 0.96 m3rm 77

Table 3 Acid formulation for Well A Fluid 15 wt.% HCl acid for pickling. Pre-flush 15 wt.% HCl In situ gelled 10 wt.% HCl Overflush
a b

Chemical additives 0.3 vol.% corrosion inhibitor 0.2 vol.% surfactant in low sulfate water a 0.3 vol.% corrosion inhibitor, 1.1 vol.% acetic acid b , 0.56 wt.% citric acid b , 0.2 vol.% surfactant 0.3 vol.% corrosion inhibitor, 2.0 vol.% gelling agent, 0.045 wt.% breakerriron control, 0.2 vol.% buffer, 0.45 wt.% cross-linker Low sulfate water a

Composition of low sulfate water is given in Table 2. This amount of acetic acid and citric acid can keep approximately 5000 mgrl of iron III. in solution in spent acid at reservoir temperature.

K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353 Table 4 Treatment stages, volumes, rates and surface pressures for Well A Stage of treatment Fluid Volume m3 . 8.0 50 60 2.2 1.9 2.7 2.2 4.5 4.0 5.1 4.5 5.7 5.1 4.5 5.7 10.6 77 37 23 Pumping rate m3rmin. 1.1 2.4 3.2 1.3 1.3 1.4 1.6 1.7 1.9 1.9 1.9 2.1 1.9 2.1 1.9 2.1 1.33.3 Surface pressure MPa. 7.6 12.8 4.1 15.2 14.5 14.5 14.5 14.8 15.2 15.2 15.2 15.2 15.2 15.5 15.5 15.5 16.5

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Well pickle 15 wt.% HCl Pickle post-flush Low sulfate water Pre-flush Low sulfate water 1 15 wt.% HCl 2 10 wt.% gelled acid 3 15 wt.% HCl 4 10 wt.% gelled acid 5 15 wt.% HCl 6 10 wt.% gelled acid 7 15 wt.% HCl 8 10 wt.% gelled acid 9 15 wt.% HCl 10 10 wt.% gelled acid 11 15 wt.% HCl 12 10 wt.% gelled acid 13 15 wt.% HCl 14 Overflush Total 15 wt.% acid m3 . Total in situ gelled 10 wt.% acid m3 .

galrfoot. of acid was injected into the openhole section. The treatment was followed by injection of approximately 77 m3 483 barrels. of low sulfate water. The well was shut in for 70 min for reaction of the acid with the formation before it was flowed back. Over a 2-day period, more than 50 field samples were collected. More than 700 chemical analyses were eventually made on these samples.

pH meter was used at the well site and was calibrated with buffers pH 4 and pH 7. before sample measurement. 2.2. Laboratory measurements Calcium, magnesium, iron, sodium, aluminum and zirconium concentrations were measured by inductively coupled argon plasma emission spectroscopy ICP.. Acid content of flowback samples was measured by titration of a known acid volume with 0.1 N sodium hydroxide solution to an endpoint of pH 4.2 using an autotitrator. Chloride ion was measured with an autotitrator using 0.1 N silver nitrate solution. Sulfate ion was measured by turbidity with 0.1 N barium chloride solution. Density measurements were made with a digital density meter at 15.58C. The pH was measured with an AgrAgCl single junction pH electrode. Total dissolved solids were determined by addition of the concentration of the chemical species measured. Analysis of filtered suspended solids was done using X-ray diffraction XRD. and by the energy dispersive X-ray spectrometer attachment of a scanning electron microscope SEM..

2. Experimental studies 2.1. Field measurements Total dissolved iron and ferrous iron were measured at the wellsite using the procedure of Taylor et al. 1999b.. Ferrous iron was measured in the field because iron II. is rapidly oxidized to iron III. in the presence of air. Acid content of the injected acids was measured by titration of a known acid volume with 1 N sodium hydroxide solution to a phenolphthalein endpoint pH 9.. Accurate volumes were measured using calibrated autopipettes. Density was measured with a portable densitometer. A portable

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

3. Results and discussion 3.1. Chemicals used during the treatment Water of low salinity and sulfate content Table 2. was used in the treatment for the pre-flush, for mixing the acids and for the post-flush. The chemical composition of the injected fluids is shown in Table 5. Two different samples of the pickling acid were taken after it was mixed to demonstrate the reproducibility of the measurement methods. The acid concentration was very close to the target value of 15 wt.%, and the measurement made at the well site was in good agreement with the value measured in the lab. The 10 wt.% in situ gelled acid contained 180 mgrl aluminum and 325 mgrl zirconium from the cross-linking additive. The sulfate concentration, at 924 mgrl, was much higher than the value of 270 mgrl found in the mixing water. This additional sulfate is either from the acid additives or from an interference in the method. All four of the injected acid samples had low iron concentrations with values from 44 to 84 mgrl. This shows that some iron contamination occurred during transport and mixing of hydrochloric acid. 3.2. Well flowback (before acid treatment) This stage of the treatment was included to flush out any suspended material in the wellbore. Flow rate was measured at the beginning and at the end of the flowback, and was 22.3 " 1.5 m3rh 140 " 10

barrelsrh.. This measurement was extremely useful in later calculations of the casing pickle fluid returns. If the flowrate of the well is known, then material balance calculations can be conducted using the concentrations of produced chemical species. Based on the well flowrate, 2.75 h should be required to flush out the wellbore volume of 383 bbls. Fig. 1 shows the concentrations of sulfate, magnesium, calcium and bicarbonate in the produced fluids. The sulfate concentration shows a large increase after 1.4 h of production. The concentration of sulfate in injected seawater is approximately 4150 mgrl and is shown in the figure. An increase in calcium concentration also occurs 1.5 h after flowback. The value increases from approximately 650 mgrl the value expected in seawater. to approximately 1500 mgrl. In addition, an increase in density of the flowback fluids Fig. 2. and the TDS occurs at the same time as the increase in the calcium and the sulfate concentrations. No change is observed in the magnesium or bicarbonate concentrations. At the same time as the density increase, the pH measured at the wellsite. gradually decreases Fig. 2.. If the observed increases in sulfate concentration was due only to calcium sulfate, then the calcium concentration would increase by approximately 875 mgrl. This value is very close to the increase of 850 mgrl that was observed. Therefore, it is likely that the increase in the calcium and sulfate concentrations is due to the dissolution of calcium sulfate. The concentration of calcium sulfate increased at 1.5 h after flowback started, corresponding to 33.4 m3 210 barrels. of brine production. This is lower than the

Table 5 Chemical analysis of acid injection fluids Variable Aluminum mgrl. Calcium mgrl. Magnesium mgrl. Sodium mgrl. Chloride mgrl. Sulfate mgrl. Zirconium mgrl. Total iron mgrl. Density at 15.58C grcm3 . Wtrwt.% HCl at wellsite Wtrwt.% HCl at lab Pickle acid a1 - 10 116 30 146 148,544 535 - 10 44 1.0722 14.21 14.21 Pickle acid a2 - 10 110 30 146 148,125 481 - 10 44 1.0723 14.75 14.20 10 wt.% in situ gelled acid 180 214 39 418 85,599 924 325 59 1.0561 9.67 9.67 15 wt.% acid - 10 112 30 145 138,928 438 - 10 84 1.0716 13.50 13.50

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Fig. 1. Flowback analysis before acid treatment.: sulfate, calcium, magnesium and bicarbonate.

volume of the wellbore 60.9 m3 383 barrels.., indicating that the calcium sulfate may be present as a scale on the lower part of the casing. Calcium sulfate may form a scale due to the temperature increase that occurs when the seawater flows down

the wellbore to the formation. The solubility of calcium sulfate in seawater gradually decreases as the temperature is increased Silcock, 1979.. In desalination plants, untreated seawater will usually produce a calcium sulfate scale when heated above 778C

Fig. 2. Flowback analysis before acid treatment.: pH and density.

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

1708F. Cowan and Weintritt, 1976.. The reservoir temperature is 938C 2008F., but the bottomhole temperature at well A is now only 588C 1378F. due to long-term water injection. If water is produced from the well, then the seawater in the formation flowing back to the wellbore will be cooled. If it flows through an area of precipitated calcium sulfate or anhydrite, then it will dissolve some of it. It is then possible for the seawater flowing out of the formation to contain more calcium and sulfate than the concentration seen in the injected seawater. The amount of calcium sulfate dissolved by the flowback fluid was calculated as 125 kg. The calculation used a flow rate of 22.3 m3rh 140 bblrh. and an injection water sulfate concentration of 4150 mgrl. Chloride and sodium concentrations in the flowback samples did not change significantly during the flowback, and were very close to those expected in seawater Table 2.. During the last hour of the well flowback stage, the average chloride and sodium concentrations were 30,873 and 16,972 mgrl, respectively. The weight ratio of chloride to sodium in the injected brine is 1.82 to 1, based on these values. Total iron and ferrous iron concentrations in the produced fluids were measured and were less than 10 mgrl. No suspended solids were present in the

flowback samples. In general, the samples were clear. Sulfate-reducing bacteria SRB. are known to be present in the seawater injection system Bayona, 1993.. The samples collected from 3 h until the end of the flowback were initially clear and had a slight odor of hydrogen sulfide. The iron concentration in these samples was 2 mgrl or less. Within 2 days, they had become cloudy with a light yellow color. It is likely that this material was elemental sulfur formed by the oxidation of hydrogen sulfide by oxygen, see for example Little et al. 2000.. 3.3. Casing pickle fluid returns The pickling acid contained only a corrosion inhibitor as an additive, and the acid concentration was nearly 15 wt.%. The chemical composition of the pickling acid is shown in Table 5. Fig. 3 shows the acid concentration and the total iron concentration in the flowback samples. The maximum acid concentration in the samples was 9.7 wt.%, while the maximum total iron concentration was 23,600 mgrl. The dissolution of rust from the casing can account for most of the decrease noted in the acid concentration, as will be described in the next paragraph. This means that the acid was not

Fig. 3. Flowback analysis pickle treatment.: hydrochloric acid and total iron.

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significantly diluted during the pickle treatment. Some dispersion is observed in Fig. 3 as the acid concentration profile is slightly broadened. The flow was turbulent as the acid was pumped into the casing and during the flowback. The composition of the dissolved iron that flowed back following the pickle treatment is shown in Fig. 3. The total iron content was measured by two different methods. ICP spectroscopy was used in the lab analyses. Total iron and iron II. concentrations were also measured by the field method of Taylor et al. 1999b. after the samples were brought back to the lab. The results obtained by the field method are in excellent agreement with the ICP method. Maximum concentration of iron II. was 10,000 mgrl. Measurements in the field with and without sample filtration gave results that agreed within 5%. The measured maximum iron concentrations give a ratio of iron II. to iron III. of 0.67 to 1, compared to a theoretical ratio of 0.5 to 1 in Fe 3 O4 FeO P Fe 2 O 3 .. The ratio of iron II. to iron III. produced during the entire flowback of the pickle fluids was 0.9 to 1. This was calculated using the iron concentrations in the produced fluids and the flowback rate of the well. The source of this iron could be gradual surface corrosion before the pickle treatment, or from rust that was already present in the casing. In addition to millscale or rust, a source of iron II. may be present, most likely as FeS. The latter is usually present as a byproduct in systems contaminated with SRB Nasr-El-Din et al., 1996; Little et al., 2000.. Several research groups have reported the measurement of ratios of iron II. to iron III. during various acidizing operations. In field samples, Smith et al. 1969. observed that the ratio of iron II. to iron III. in spent acidizing fluids varied from 5:1 to 10:1. In contrast, Well A showed an average ratio of iron II. to iron III. of 0.9 to 1. The relative amount of iron III. in this well was much higher than previously reported results. More details on iron II. to iron III. ratios are given by Loewen et al. 1990. and Taylor et al. 1999b.. From Fig. 3, the mass of iron dissolved from corrosion products during the pickle treatment can be calculated, since the flow rate of the well during flowback is known. A total of 235 kg of iron was produced in the pickle flowback samples. Less than 0.5 kg of iron was present in the injected pickle acid.

Scale deposits on the casing were dissolved by the acid, since direct reaction of steel and hydrochloric acid produces only iron II. Kaesche, 1985.. If iron sulfide was the dissolved corrosion product, then only iron II. would be produced. The high amount of iron III. present clearly indicates that an oxygencontaining corrosion product was present as the major scale component. This corrosion product could have been present as mill scale when the casing was originally put in place. If oxygen was present in the injection water, rust could also have formed over long periods of time. The returning acid samples were black in color and contained suspended solids. These solids were isolated by filtration 0.45 m m., dried, weighed, and analyzed. Fig. 4 shows the concentration of solids by filtration together with the acid concentration in the produced fluids. The filtered material was a fine black powder and was collected from samples with acid concentrations up to nearly 10 wt.%. XRD analyses of selected samples are shown in Table 6. It is important to emphasize that the XRD results show crystalline material only. Based on these tests, many of the samples contained iron carbide as a major component. However, the sample at 2.2 h into the flowback contained major amounts of akaganeite -FeOOH... This mineral should be acid soluble. It may have occurred in the sample by oxidation of an iron compound after the sample was isolated. At 2.9 h into the flowback, acid is no longer produced and the solids contain mostly silica, gypsum, and clays. The approximate compositions of the suspended solids are shown in Table 7. These results were made by energy dispersive X-ray spectrometry. This method gives an approximate elemental composition for atomic weights greater than 16 oxygen.. The method does not distinguish between crystalline and amorphous materials. In all cases, iron was the major component. Sulfur was a significant component in some cases, meaning that iron sulfide could be a component of the suspended solids. Iron carbide Fe 3 C. is known as cementite or cohenite and is a component of carbon steel Dugstad et al., 2000.. Cron et al. 1971. studied the reaction of various acids and bases with low carbon steels. The mode of acid attack was found to be a function of the applied potential, pH of the environment, and the anion present. Either the ferrite or the

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

Fig. 4. Flowback analysis pickle treatment.: suspended solids and HCl concentration.

carbide phases could be reactive or non-reactive, depending on the electrochemical conditions. In Well A, it is likely that the iron in the steel casing was corroded and the acid dissolved the corrosion products, but left small particles of iron carbide behind.
Table 6 XRD analysis of solids from pickle flowback

The results shown in Fig. 4 also support this hypothesis. If the solids were 100% Fe 3 C, then it can be calculated that 1500 mgrl of the solids would contain nearly 100 mgrl of carbon. If a flowback sample contains 25,000 mgrl total iron, then the

Major: ) 20 wt.%. Minor: 1 to 20 wt.%. Trace: 0 to 1 wt.%. Shaded area shows samples that contained HCl when collected.

K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353 Table 7 Energy dispersive X-ray spectrometry of solids from pickle flowback concentration, wt.%.

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Shaded area shows samples that contained HCl when collected.

percentage of carbon in the iron is 0.4 wt.%. This is remarkably close to the amount of carbon expected in low carbon steel, typically 0.4 to 0.5 wt.%. In the conditions of the casing pickle treatment, it appears that the iron carbide was not soluble in the acid. It may have been coated with a non-soluble material or with biomass. The chloride concentration in the flowback samples reached a maximum of 132,000 mgrl, com-

pared to a value of 148,000 mgrl in the injected pickle acid sample Table 5.. This result shows that dispersion led to a small amount of dilution of the injected pickle acid. The final chloride concentration in the pickle flowback samples is the value expected for seawater. Values of sulfate, calcium and magnesium in the flowback samples are shown in Fig. 5. The low values of calcium during the acid flowback 2.0 to

Fig. 5. Flowback analysis pickle treatment.: sulfate, calcium, and magnesium.

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

2.4 h. show that the acid slug did not contact the formation. The sulfate concentration 2.0 to 2.4 h. in the pickle acid increases from 590 to 880 mgrl, higher than the injected value of 510 mgrl. The solubility of calcium sulfate gypsum. increases in aqueous solutions at low pH or high ionic strength Carlberg and Matthews, 1973.. This indicates that some sulfate scale is being removed from the casing. Assuming an initial concentration of 510 mgrl sulfate, and using the well flow rate of 22.3 m3rh 140 bblrh., it was calculated that 3.7 kg of gypsum CaSO4 P 2H 2 0. was dissolved from the casing. After 2.6 h, the calcium and magnesium levels approached the values of the formation water that were seen in Fig. 1. These results show that the flowback time was sufficient to completely lift the pickle acid from the wellbore. In Fig. 6, aluminum concentration and pH are shown for the flowback fluids. The concentration of zirconium was also measured and found to be less than the detection limit of the ICP instrument 1 mgrl.. These measurements were made because both aluminum and zirconium are present in the cross-linker used in the acid diverting stage. It was necessary to establish a baseline for aluminum and zirconium concentrations to evaluate results from the matrix

acid treatment. The presence of aluminum in the pickle flowback samples probably results from acid interactions with clay minerals Simon and Anderson, 1990.. The source of these clays is the upstream sand filters. The clays are deposited on the casing and leached aluminum ion on contact with the acid. 3.4. Matrix acidization fluid returns Well A was flowed back for 5 h after the matrix acidization treatment. The pH values of the produced fluids are shown in Fig. 7. Values measured at the wellsite and in the lab were in good agreement. The high pH values measured at the start of the flowback are due to sodium carbonate used at the very end of the treatment to flush out the surface lines. This high pH fluid did not reach the formation. From Fig. 7, a minimum pH value was reached at 2.7 h after the start of the flowback. The pH was above a value of five for two consecutive samples after 5 h. The flowback was terminated at this stage, as planned. The hydrochloric acid concentration of the matrix acid flowback samples is shown in Fig. 7. A maximum concentration of 1.7 wt.% HCl was reached at 2.88 h after the start of the flowback. The acid concentration gradually tapered off to zero after 5 h.

Fig. 6. Flowback analysis pickle treatment.: aluminum and pH.

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Fig. 7. Flowback analysis matrix treatment.: acid concentration and pH.

If the flow rate is estimated to be 22.3 m3rh 140 barrelsrh., the area under the curve can be integrated to show that 1.9 m3 12 barrels. of 15 wt.% HCl did not react with the formation and was flowed

back from the well. It is likely that this unreacted acid was in a cavity or washout and was not in direct contact with the formation. The unreacted acid is only 1% of the total volume of acid that was in-

Fig. 8. Flowback analysis matrix treatment.: total iron.

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

jected. Increasing the soaking time from 70 min is not likely to have a large effect on the amount of unreacted acid. Iron concentrations in the flowback samples were measured, Fig. 8. Iron II. was measured at the wellsite and is compared to total iron measured by ICP in the lab. The maximum iron concentration of 170 mgrl occurred at 2.5 h and was almost entirely in the iron II. form. The values of iron II. measured in the field are higher than some of the total iron measurements made in the lab due to experimental errors sample oxidation.. Using the well flowrate and the data in Fig. 8, a total of 6 kg of iron was produced in this stage. No solids were produced with the samples containing iron. These iron concentrations are relatively low, and since iron II. is the predominant species, very little iron control chemicals are required. For future treatments in similar water injection wells, when a pickle treatment is used, citric acid can be used as the iron control chemical at a concentration of 0.22 wt.%. This quantity of citric acid is sufficient for iron III. concentrations up to 500 mgrl at temperatures up to 658C 1508F. Taylor et al., 1999a.. The density of the produced fluids was measured as a function of flowback time. At 2.5 h, the density rapidly increases then stabilizes near 1.041 grcm3,

indicating that the spent acid begins to flow back at that point. However, the density then increased to a maximum of 1.065 grcm3 at 5 h, in contrast to the density of the seawater 1.044 grcm3 .. At 5 h, the pH value increased to more than 5 Fig. 7.. It is clear that the flowback time was not sufficient, and that the pH value is not effective for determining the length of the flowback time. Measurement of the density of the produced fluids should be used to determine the optimum flowback time. Chloride and sodium concentrations in the flowback samples are shown in Fig. 9. The mass average injected chloride concentration was 118,300 mgrl, based on both the concentrations and relative volumes of the 10 wt.% in situ gelled acid and the 15 wt.% regular acid. The acid that initially flowed back was diluted with both the low sulfate water chloride concentration of 370 mgrl. and seawater chloride concentration of 30,000 mgrl.. This dilution factor can be calculated, because the sodium concentration should result only from the injected seawater. The weight ratio of chloride to sodium in the seawater was reported as 1.82 to 1, as mentioned previously in the section on the initial well flowback before acid treatment.. Fig. 10 shows the results of the calculations that can be made using the total chloride concentration,

Fig. 9. Flowback analysis matrix treatment.: chloride and sodium.

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Fig. 10. Flowback analysis matrix treatment.: measured and calculated chloride values.

the sodium concentration, and the measured acid concentration. The chloride from the live acid decreases from approximately 17,000 to 1800 mgrl. This is calculated from the measured hydrochloric acid concentration. At the same time, the chloride contributed from the seawater increased from 9000 to 26,000 mgrl. The remaining chloride was contributed from the acid that reacted with the formation, which decreases slightly from 6700 to 5600 mgrl. By using the well flowback rate and the concentration values of chloride that reacted with the formation, it can be calculated that less than 7% of the injected acid was produced. The same technique could be used on calcium and magnesium to calculate the amount of dolomite that reacted with the acid Dahlan and Nasr-El-Din, 2000.. For Well A, however, insufficient spent acid was produced for these calculations. This occurred because pH was used to determine the amount of time the well should flow back after the treatment. The flowback time should be increased and the optimum time determined using a portable density meter. The acid flowing back from the well was significantly diluted Fig. 11.. At 2.70 h when acid first flowed back from the well, it had been diluted to 20% of the injected concentration a dilution factor

of five. by mixing with injected seawater and the overflush. By 4.1 h, the produced acid was at 6%, a dilution factor of 17. When the fluids flowed back, they were a mixture of spent and live acids. Fig. 11 also shows how much of the acid produced from the formation did not react with it. Initially, 70% of the acid was unreacted and that amount decreased to 25% by 4.1 h. At 4.1 h, the acid was extremely diluted by a factor of 17. and 25% of this acid had not reacted with the formation. This agrees with well logs that show a large washout zone or cavity is present in the well below the casing shoe. This washout zone, at the top of the openhole section, occurs in a zone that contains anhydrite. The large volume of this washout can act as a mixing container for acid and spent acid flowing back from the formation. If unreacted acid remains in the washout zone at the end of injection, then it will gradually mix with spent acid flowing up the casing as the well is flowed back. As the spent acid flowed back from the well, it was produced with seawater, the post-flush and the pre-flush. The proportion of low sulfate water decreased and the proportion of seawater increased with time Fig. 11.. At 2.7 h after flowback, when the acid and spent acid production began, seawater

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

Fig. 11. Matrix flowback composition.

already made up 30% of the total produced fluids. By 4.1 h, nearly 90% of the total fluids produced was seawater. Finally, Fig. 11 shows the percentage of chloride from spent acid in the flowback samples. These values decrease from 25% to approximately 15%, and show that a relatively constant amount of spent

acid was produced, although the amount of unreacted acid was decreasing rapidly. This may mean that the spent acid was produced from a different zone or zones than the live acid. Fig. 12 shows the concentrations of sulfate, magnesium and calcium in the fluid returns. The calcium concentration is close to the expected value from the

Fig. 12. Flowback analysis matrix treatment.: sulfate, magnesium and calcium.

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amount of spent acid calculated in Fig. 11, for the period 2.7 to 4 h. After that, the calcium concentration increases, indicating that a larger amount of spent acid is being produced. However, a calcium concentration of approximately 80,000 mgrl results when 15 wt.% HCl completely reacts with limestone. This shows that the spent acid flowing back from the well was highly diluted. Magnesium concentration is near 2200 mgrl, as compared to a value of 2000 mgrl in the seawater. Some magnesium is probably present in the formation in the form of dolomite. A large amount of sulfate is seen in the flowback samples. The peak values of 5000 to 6000 mgrl are similar to those observed in the flowback samples before acid treatment. shown in Fig. 1. Sulfate values fluctuate at 4 h and later, because precipitation of gypsum CaSO4 P 2H 2 O. occurred due to the high calcium levels in these samples. Gypsum was identified by XRD analysis as the major component Table 6.. These results show that calcium sulfate has a limited solubility in the flowback samples. Once the solubility limit is exceeded, precipitation of gypsum occurs. The solubility of gypsum in seawater with a 3 wt.% chloride content. at 258C is 0.458 wt.% Silcock, 1979.. This corresponds to a calcium con-

centration of 1060 mgrl and a sulfate concentration of 2540 mgrl. The concentrations of calcium and sulfate in the spent acid in Fig. 12 are both significantly higher than these values. The calcium concentration is approximately 7000 mgrl and the sulfate concentration is approximately 4000 mgrl. Either the samples are not at equilibrium with respect to gypsum, or additives in the acid stimulation fluids increase the solubility of gypsum in seawater. It is known that partially hydrolyzed polyacrylamides and polyacrylic acids are used as calcium scale inhibitors Przybylinski, 1989.. The 10 wt.% in situ gelled acid contained an acrylamide copolymer and may inhibit gypsum precipitation. Zirconium and aluminum concentrations in the flowback samples are shown in Fig. 13. The concentrations of these metals were measured because they are present in the in situ gelled acid that was injected into the reservoir. Both zirconium and aluminum were produced during the flowback time 2.7 to 4 h. After 4 h, aluminum was present in the samples but zirconium concentrations were below the detection limit of 1 mgrl. From 2.7 to 4 h, a significant amount of unspent acid flowed back from the well Fig. 11., accounting for the produced zirconium. After 4 h, the produced fluids contained only seawa-

Fig. 13. Flowback analysis matrix treatment.: zirconium and aluminum.

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ter and spent acid. These results indicate that zirconium may precipitate or adsorb in the formation. Work is underway to determine the rate of propagation of zirconium and aluminum in the formation. 3.5. Treatment ealuation Before the acid stimulation treatment, the injectivity index II. of the well was 0.12 m3rdayrkPa 5 bblrdayrpsi.. This value increased to 0.21 m3r dayrkPa 9 bblrdayrpsi. after the treatment, an increase of 75%. Flowmeter results could not be obtained because of the large washout present directly below the casing shoe. However, it is likely that a significant percentage of the flow into the formation is into the region identified in the 1993 injection profile 2228 to 2256 m 7310 to 7400 ft... The injectivity of the well may have declined as a result of particulates carried into the well by the 5.6 million m3 35 million barrels. of seawater that have been injected to June, 1999. These particulates contain significant amounts of acid-insoluble material. This includes the iron carbide identified during the pickle treatment and in previous sampling at the seawater treatment plant. Other acid insoluble particulates include fine sand particles and clay minerals. 3.6. The importance of pickling the casing Return samples from the pickle treatment contained up to 15,000 mgrl of iron III. and up to 1500 mgrl of suspended solids. The maximum practical amount of iron III. that can be complexed is 10,000 mgrl Taylor et al., 1999a.. This requires 12 kgrm3 of citric acid and 22 lrm3 of acetic acid Dill and Smolarchuk, 1988.. At higher concentrations of citric acid, precipitation of calcium citrate may occur. When the casing is pickled, a citric acid concentration of 2.4 kgrm3 in the main acid treatment is sufficient to prevent precipitation of iron III. hydroxide in the near-wellbore region. The pickle treatment also prevents the injection of acid-insoluble casing scale into the formation. The cost of the pickle treatment itself was very small compared to the chemical cost of the treatment. For a 37.9 m3 10,000 gal. matrix acid stimulation, using a pickle treatment and reducing the amount of citric acid and

acetic acid reduced the treatment cost by more than 15%. 3.7. Acid diersion In the treatment design, alternate stages of regular 15% HCl acid and 10% in situ gelled HCl were bullheaded. The objective of this staged process was to provide effective acid diversion during the stimulation treatment. In situ gelled acid can be used to stimulate carbonate reservoirs that have significant permeability contrast. Basically, these acids consist of an acid-soluble polymer, a pH buffer, a cross-linker and a breaker. The polymer in this system forms a gel within a narrow pH range. As a result of gel formation, the viscosity of the acid increases in situ and acid diversion can be achieved. Ultimately, the gelled acid will form wormholes evenly distributed over the entire target zone. This gel will improve acid placement and control acid fluid loss Yeager and Shuchart, 1997; McGee et al., 1997.. When hydrochloric acid is injected into the formation, it has a pH of nearly zero. The pH of the acid increases as the acid reacts with the carbonate rock. At a pH value of approximately 2 to 4, the polymer reacts with the cross-linker and forms a very viscous gel. This reaction is reversible, but is dominant at this pH range. The viscosity of the acid can reach 1000 cP Yeager and Shuchart, 1997. and is able to divert unreacted acid further into the well bore. As the acid continues its reaction, the pH will rise further. At pH values greater than 4 to 5, the viscosity of the gel decreases as the polymer and cross-linker dissociate. A breaker is used in some types of gelled acid to ensure a complete reversal of the cross-linking process Yeager and Shuchart, 1997.. The reduced viscosity of the spent acid is designed to improve its removal from the formation. In the treatment design, maximum pumping rate was to be achieved while holding pressure constant below wellhead maximum pressure 17.2 MPa 2500 psi.. and formation fracture pressure. The significant parameters to be evaluated are pumping rate and volume of the injected fluids. During the pre-flush stage, the pressure steadily climbed to 15.9 MPa 2300 psi. Fig. 14.. During this time, the average injection rate of 3.3 m3rmin 20.7 bpm. was maintained Fig. 15.. Upon switch-

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51

Fig. 14. Surface pressure and bottom hole pressure as a function of time.

ing to the acid, the rate was reduced to 1.4 m3rmin 8.8 bpm. to facilitate switching between the low volume stages. The rate was then increased to 2.0 m3rmin 12.8 bpm, but was limited by the surface pressure.

As the first stage of acid reached the formation, the injection rate increased to maintain a constant surface pressure. The rate increases from 2.0 to 3.3 m3rmin 12.8 to 21 bpm. while the treating pressure remained constant. This indicates that as the acid

Fig. 15. Injection rate and cumulative injection as a function of time.

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K.C. Taylor et al. r Journal of Petroleum Science and Engineering 28 (2000) 3353

reached the formation, injectivity increased. As injection of the acid continued, the injection rate decreased until the post-flush reached the formation. This shows that diversion was occurring during acid injection. After 83 min, the injection rate increased as the post-flush was injected into the formation. 4. Summary Techniques were demonstrated to evaluate acid stimulation treatments based on chemical analysis of the return fluids. These techniques were used in Well A to identify the source of formation damage, the amount and type of scale on the casing, and the efficiency of the acid treatment. 1. During flowback of the well before the pickle treatment., 125 kg of calcium sulfate dissolved from the near-wellbore area. 2. The pickle treatment was highly effective, dissolving an estimated 235 kg of iron from tubular corrosion products. 3. The pickle fluid returns contained black suspended solids that were mostly iron carbide, Fe 3 C. 4. For the pickle treatment, the acid volume 0.29 galrft, 0.36 lrm. and the flowback time 4 h. were sufficient. 5. The iron control chemical concentration can be reduced for similar low temperature water injection wells that are pickled before acid stimulation. Citric acid at 0.22 wt.% 20 lbr1000 gal of 15 wt.% HCl. is sufficient to keep 500 mgrl iron III. in solution. 6. When it flowed back from the well, the injected acid was diluted between 5 and 17 times based on calculations using the chloride concentration as a tracer. 7. The pH value of the flowback fluid is not an adequate criterion to determine the flowback time. The density of the aqueous phase should be used instead.

work. The Chemistry Unit and Advanced Instruments Unit of Saudi Aramco provided valuable assistance with this work. The authors thank M. AlRamadhan, Dr. H.R. Rosser and G. Polkowski for useful discussions.

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Acknowledgements The authors thank the Saudi Arabian Oil Company Saudi Aramco. for permission to publish this

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