SPE 23817 SPE ‘Sooty of Petratoum Engnoers A New Technique for the Evaluation of Acid Additive Packages LR. Houchin, W.E. Foxenburg, M.J. U and Jun Zhao, OSCA Inc. oprah 190, Socity ot Percaum Engine, ‘ys paar was ste er ronan 3 a SPE Program Carnie foi [rfonwion ef he Soka of Polar Engen er, membranes ‘Palen Engen ‘Ts paper was prepare or poston a th SPE hn. Symptom Formation Daape Cone halt n Latoya, Laur, Febuary 26-27, 182 review of efomatn cots i an ebavct subite bythe au), Covars thepaer ‘Dyess hav no eon rudy te Sacer of Eesur Engsrs a ar aij saeco te are The matric presrad Gane not noceeu oect fresno Se mong a mo psicaton ron by Estoril Comins oe Scey "Somosen 9 copy treeiind war anorectal net rire tan wae, Myoelae yet cn Tabs el oan Srepean conan ‘anor end by eho th pape rae. WaUbraran, SPE, PO. Bak 895898, hare, TX THESE USA. Tn, 750089 SPEDAL ABSTRACT ‘The expanded use of sandstone matrix acidizing techniques may have been the most significant trend of ‘the turbulent 1980's. Gulf Coast operators have found that remedial acid treatments cost a fraction of that required for a comparable offshore completion. Improved design and application techniques now provide economic success rates greater than 80% with ‘most’ treatments paying out in less than 30 days. However, one area that continues to frustrate designers of acid treatments is the unpredictability of crude oil reservoirs. Current testing procedures are inadequate, failing to accurately replicate the interaction between the treating fluid and acid sensitive crudes. Reliance on these procedures can produce catastrophic facility upsets, downhole emulsion blocks, reduced damage removal efficiency or result in a marginal treatment response. ‘A new simplified laboratory testing procedure was developed which more accurately simulates treatment effects under reservoir conditions. This laboratory test demonstrates the need for less reliance on surfactant non-emulsifiers and an expanded use of mutual solvents, Field data confirms more accurate prediction ‘of acid compatibility. In addition, acid treatments ‘eFerences ard Tlustrations at end of paper. designed utilizing this laboratory procedure showed greater initial production response and maintained the incremental increase for a much longer time. Design guidelines are presented which address concerns. of ‘mutual solvent/corrosion inhibitor incompatibility, high temperature applications and treating requirements. volume INTRODUCTION Remedial sandstone matrix acidization of crude oil reservoirs has become the primary tool of experienced engineers to maximize profits at minimal cost. Gidley! found that the stimulation response from acid treatments of gas or water injection wells was somewhat predictable. However, the high degree of variability of crudes made the acidization of crude oil unpredictable, requiring pre-stimulation laboratory testing and evaluation of the unique, site specific nature of individual oil wells. This study focused on developing laboratory test procedures and design criteria to more accurately predict acid ‘treatment response in crude oil reservoirs. reservoirs extensive ‘The problems associated with acid induced emulsion formation upon stimulation of oil wells was addressed by Mobil Oil in the mid 1950's. Suboptimized results with operational complications such as emulsion blocks ‘and facility upsets were occurring far too often. Mobil[A NBW TECHNIQUE FOR SWE EVALLATION OF ACID ADOTTIVE PACKAGES see 2381) required its engineering staff to take samples of the treating fluids being delivered to location and mix them with a fresh crude sample from the well. If @ 90% acid breakout was not achieved in 10 minutes, the truck was sent back to the yard. The service companies got the ‘message. The Mobil test became the first standard for pre-stimulation testing. Most of the acid additives used to pass this test were cationic surfactant. This class of surfactants were found to oil wet sandstone reservoirs? Anionic surfactants, though compatible with the wettability characteristics of sandstone reservoirs, were usually incompatible with the cationic acid corrosion inhibitors. To avoid blending difficulties and operational. failures associated with surfactantiformation incompatibility, there was a shift toward the use of nonionic surfactants for emulsion prevention. As a general rule, these nonionic surfactants were a little slower acting, often requiring ‘more than the 10 minutes breakout required by the current test non-emulsifiers. In the late 1970's, API Bulletin, RP-42 attempted to standardize pre-stimulation testing procedures. This procedure recommended only the _ hydrochloric hydrofluoric (HCLHE) mud acid be tested for sandstone This updated version of the Mobil Oi! Company test did not set specific standards for acid break out times. Nor was the HCl preflush evaluated for its emulsion potential. As a result, this procedure never received widespread industry acceptance. reservoirs. The industry test requirements have evolved to testing all acid stages with a 50:50 mix of live acid (plus additives) to crude, requiring a 90% acid breakout in 15 minutes at approximately 150°F (66°C), or bottom hole temperature. The major deficiency of this current practice is that it assumes the live acid with all of ite associated additives represents the fluid that intermixes with erude in the formation. This study has found that these critical additives, through chemical mass transfer effects, are initially adsorbed onto the formation matrix, leaving the acid front untreated, Furthermore, critical crude sensitivity to acid containing. dissolved iron and other acid reaction products must be evaluated to ensure acid/crude compatibility. ‘A new test procedure for pre-stimulation evaluation of acid compatibility is provided. Laboratory and field data indicates this simple laboratory test procedure has been effective in preventing those operational problems such as emulsion blocks and catastrophic facility upsets. In addition, the resultant acid treatment not only produced at a higher initial rate, but maintained the ineremental increase for a much longer time. While the acid additives were selected in order to pass this new test procedure, it became obvious during the course of this study that numerous unanticipated benefits had been derived. This paper includes these design factors ‘and field evaluation data utilized by the authors which produced better, longer lasting results DEVELOPMENT OF TESTING PROCEDURES Several authors have reported severe surface emulsions when acid returns are flowed back to central facilities” Dunlap etal. suggested that both facility upsets and downhole emulsions occur as a consequence of inadequate pre-job compatiblity testing.’ Other authors have demonstrated that _— surfactant non-emulsifiers, used to prevent these emulsification tendencies, may preferentially adsorb onto mineral surtaces®? This adsorption results in the surfactants being unavailable in the acid fluid front where formation damaging emulsions can form. The challenge ‘was to develop a test procedure that more accurately replicated reservoir conditions. ‘The first step was to determine the effect of nonionic surfactant adsorbtion. Hall? had evaluated the adsorbtion effect of anionic and cationic surfactants in fan acid solution after being flowed through a sand pack. However, he did not look at the nonionic surfactants that are currently in use. A 6 foot long (183m) by 2 inch diameter (50.8 mm) core test apparatus was constructed according to specifications established by King! This apparatus contained Berea cores assembled in series, wrapped with a triple thickness fiberglass mat and sealed with resin, Fluid taps were located every 6 inches (1524 mm) for sampling purposes. Three widely used nonionic surfactant non-emulsifiers were added to a 15% HCL acid solution and flowed through the test apparatus. Fluid samples were taken from each sample port and ‘with an acid sensitive crude. The acid front wasSPE 23817 L.R, HOON, Wt _ FOMNEERG, MJ. USIE, & J. ZNO calculated at rate versus time. A 100 cc sample was collected from each sample port as the acid front passed. The sample was split and duplicate emulsion tests were run, The results were averaged and are reported in Tables 1 and 2 There was no variation sreater than standard 25% experimental error. All nonionic non-emulsifiers failed to effectively function after only 6 inches (152.4 mm) of acid penetration into the core (See Table D. Acid solutions containing 10% ethylene glycol monobutyl ether (EGMBE) in addit to the surfactant showed slightly better non-emulsion performance even at 24 inches (6096 mm) of penetration. Tables 1 and 2 show only that data in which the additive system provided functional rnon-emulsion properties, therefore, no data is reported beyond a penetration of 24 inches (608.6 mm). Obviously, a 6 foot (L83 m) core test apparatus is not practical for routine testing purposes. However, the sand pack approach used by Hall? could be easily adapted to simulate these adsorption effects on acid compatiblity. A sand pack composition and step-wise procedure was developed as shown in Appendix A. An attempt was made to duplicate the effects observed in the long core apparatus. Figure 1 shows a comparison of the acid breakout of a typical Gulf Coast crude using. both the current testing procedure and the new sand pack test. The current procedure showed a >90% acid breakout in 15 minutes, but only a trace when the acid solution was flowed through the sand pack. ‘The first step in validating the new Sand Pack Method (SPM) was to add it to our existing test regimen. Test results indicate that, as observed in the long core test, the surfactant non-emulsification function was almost always lost due to adsorption. When surfactant loading was increased to compensate for adsorption in the SPM test, an over-treat condition was created in the standard live acid test. The only acid treatment that consistently passed both tests was the addition of mutual solvents or alcohols with low levels of surfactants. Figures 2 and 3 demonstrate the difference between the likely effect of an acid/surfactant front and one containing acid/surfactant/mutual solvent. Figure 2 shows the advance of an untreated acid front (HCI preflush) due to adsorption of the surfactant. Eventhough some desorption will occur later stages, the untreated front has displaced much of the cil that was located in the near wellbore region. If instantaneous emulsification does not occur, it becomes progressively less likely that there will be sufficient energy applied to cause emulsification as the front penetrates due to a reducing velocity with the radial expansion. Therefore, a greater emphasis was placed on the additive package in the acid preflush, particularly since the field being considered in the field trial had @ history of facility upsets and difficulty unloading after acid stimulation, IELD RESULTS ‘The most common acid system utilized in the Gulf Coast is shown in Table 31%! his system evolved because of three primary features which include: low acid strength/concentration, lower volumes and a brine/mutual solvent post flush. The logic behind this system is that while it may be sub-optimized, it is less likely to induce damage from incompatible mineral acid reactions, weakening of the matrix binder by over stimulation or The brine/mutual solvent postflush would not interfere with the acid corrosion inhibitor and would remove excess inhibitor from the formation face, thereby. leaving the formation water wet. The initial field trial involved 1 acid jobs from one single structure in the offshore eastern Gulf of Mexico. The first two treatments used the current standard acid design and resulted in platform shut down due to facility upsets during the acid flow back. Tables 4 and 5 show the alternative acid systems that were subsequently applied. System A (Table 4) had EGMBE ‘added to the acid preflush and the brine postflush. Our concern was the untreated acid front causing an ‘emulsion and the benefits of EGMBE in the postflush were still valid. System B (Table $) provided EGMBE in all aqueous stages. This system was first attempted because the SPM test indicated inadequate acid breakout in the mud acid (HCLHE) test. Acid volumes were reduced to accommodate pre-approved AFE limits on both treatment designs. There was no technical basis, {or this decision when it was originally made. ‘The performance of all three acid designs for the 11 wells in the field trial are shown in Table 6, All of the wells are geologically similar with near identical 457a [A NEW TECHNIQUE FOR THE EVALUATION OF ACID ADDITIVE PACKAGES ___SPE 23817 reservoir properties including interval length. Build up data was not available, therefore, 6 month cumulative production was provided. Both systems A and B were flowed back to the central facility without causing an upset. They also provided a 20% improvement over the production increase experienced with the initial two treatments. System A produced almost double the cumulative production, ‘when compared to results obtained through the current standard acid design, while the production from System B virtually tripled. The value of Acid Flow Back analysis has been previously documented in the literature!°4 Acid Flow Back analyses were conducted on each treatment. An average of 10 samples were collected during the acid return, Sample collection was initiated when pH began to drop and was continued until a consistent pH of 25 ‘was reached. Microscopic analysis of the crude showed fa presence of rigid film emulsion on the wells where the current standard acid design was used (Table 7). ‘The results of ICP (Inductively Coupled Plasma Emission Spectroscopy) ion analysis on acid returns are presented in Table 7. Although the focus of this paper does not include an indepth analysis of Acid Flow Back results, a general overview may help explain some field results. For example, the siliconaluminum (S:AD) ratios are almost identical on the three treatments, but the total ion concentrations of Si and Al increased in proportion to the increased usage of EGMBE. The higher the total ion concentration of Si plus Al, the higher the cumulative production increase. More importantly, all five wells treated with System B maintained at least some incremental increase for 6 months. No well treated with either of the other two systems maintained their incremental increase for this length of time. DISCUSSION ‘A search of the literature provides an interesting confirmation as to the outcome of this field trial. Just fas in this field trial, Gidley! had shown that the success rate of acid treatments more than doubled when EGMBE was added to the treatment solution. His study used a larger sample of wells treated, and yet, the results of average production increases were more dramatic. He found that adding EGMBE to the HCL acid preflush more than doubled his average production increase. This was exactly the same results as reported in this study. ‘The most important finding was that this study showed a three fold production increase and Gidley experienced five fold increases when EGMBE wwas added to the HCLHF mud acid. He concluded that fone of the most common mistakes made in the application of acid treatments was no mutual solvent in the mud acid treatment. There, are several plausible explanations for why EGMBE or other similar mutual solvents are so ‘effective when added to the mud acid stage. One likely explanation is that the most common inorganic component of formation damage is comprised of clays and silts that have become oil wet or are part of a complex organic/inorganic deposit 178 This damage can only be removed by a mud acid solution with sufficient solvent solubility to simultaneously remove oil barriers while dissolving clays and silts" White this may explain the higher production increase, it is difficult to explain the longevity of the treatment response. Perhaps, by more completely removing these complex deposits, it takes more time for the damage to re-occur. ‘The authors considered two other possible explanations. ‘Short term production responses appear to be associated with post-stimulation fines migration. The source of ‘these fines can be acid reaction products such as colloidal silica, or fines liberated by excessive acid volumes weakening the matrix binder. This field study showed higher recovery of potential acid reaction products (Table 7) when EGMBE was added to the acid solution. The EGMBE may be preventing the acid corrosion inhibitor from oil wetting particles such as hydrated silica and causing them to floceulate. The tendency of EGMBE to water wet particles and keep them dispersed, should allow them to flow out of the reservoir instead of plugging it. The efficiency of EGMBE and other associated mutual solvents to strip oil wet films from surfaces raises some interesting corrosion inhibitor performance questions Which are addressed in the next section.SPE 23817 E.R, HOOCHIN, W.E. Mod. USIB, & 3. ZO Another factor likely to produce short term results is the release of fines due to excessive acid volumes weakening the matrix binder. It has long been established that, with sandstone matrix acidizing. once near wellbore damage is removed, the maximum treatment response has been reached 920 Additional live mud acid “penetration usually starts to produce fines and induce damage. The volumes of acid were reduced in this field trial in order to compensate for the added cost of the mutual solvent. These lower volumes may have been sufficient to remove most, if not all, of the near wellbore damage without excess live ‘mud acid producing fines, ‘OPERATIONAL CONSIDERATIONS Several investigators have raised questions about mutual solvent compatibility with acid corrosion inhibitors°7122 The authors feel that acid corrosion inhibitors are available that can be used with mutual solvents up to 200°F (93°C), see Table 8. The use of ‘mutual solvents in acid solutions will usually require a higher loading of corrosion inhibitor. Flocculated solids found in the presence of high corrosion inhibitor concentration and EGMBE have been reported.” However, these reports have involved a limited group of inhibitors at very high loadings of 2%. A good Practice is to require corrosion test data with the specific inhibitor and mutual solvent selected for the acid treatment. In addition, inhibitor loss due to filtration should be evaluated if acid solutions ‘containing corrosion inhibitors are to be filtered If a well with a bottom hole temperature above 200°F (G3°C) must be acid stimulated to. be economical consider some of the following design options: D Run a compatible brine (% NH,CD preflush containing mutual solvent instead of adding the ‘mutual solvent to the HCI preflush. 2) Substitute organic acids for mineral acids such as 10% acetic acid for 7.5% HCI or 102% aceticHF for 751.5% HCLHF. Organic acids are much Jess corrosive than mineral acids. 3) Minimize acid contact with tubulars a, ‘The mud acid stage spends so quickly at these temperatures that it can only remove very near wellbore damage. Reduce volumes by 78% and test results, Then, additional stages can be run if needed. b. Increase pump rates. This not only minimizes contact time, but will enhance diverters that perform marginally at higher temperatures. 4 Reduce concentration of mutual solvent. Emulsions are less stable at high temperatures ‘and require less chemicals to prevent. The use of organic acids and improved iron control can help prevent rigid film emulsions at elevated temperatures. One of the most important functions of mutual solvent is to prevent the oil wetting effect of acid corrosion inhibitors. If the ‘mutual solvent concentration is reduced, it is a ‘good practice to incorporate design techniques that also lowers the inhibitor loading, These guidelines should help when high temperature reservoirs are encountered. The best insurance when designing acid treatments is to assure they are completely tested. Testing procedures should accurately simulate reservoir conditions. Standardized test. procedures should not be used as the sole criteria for ‘acid/erude compatibility. Flexibility in test procedures are required to simulate the wide range of variables encountered in sandstone matrix acid treating of crude oil reservoirs. CONCLUSIONS 1D The current industry accepted acid compatibility testing procedures were found to inadequately simulate the downhole performance of acid additive packages. 2 A new test procedure has been provided that more accurately replicates the actual treatment performance in the field, Acid treatments developed by utilizing this procedure have been effective in preventing facility upsets, and more> » ° importantly, the treated wells have produced at hhigher initial rates and maintained these rates for a much longer time period. Laboratory tests and field results indicate that the current practice of relying exclusively on surfactanVnon-emulsifiers to achieve acid ‘compatibility usually provides unpredictable results which have typically produced suboptimized treatments and/or emulsion related upsets. ‘An expanded use of mutual solvents was required to meet acid compatiility objectives. The addition of mutual solvent to the aqueous preflush and the HCLHF mud acid stage is more important than the current practice of adding it only to the brine postflush. Extending the production increase beyond 6 months only cecurred from treatments in which mutual solvents were added to the HCLHF mud acid stage. Guidelines are provided to address concerns of mutual solvent/corrosion inhibitor incompatibility. ‘The organic component of formation damage and acid compatibility may be the most critical factors affecting treatment optimization. This study shows that preventing acid induced emulsions and sludges, ensuring adequate solvent solubility of aqueous acid systems, and incorporating maximum wettability features are paramount to successful matrix acidization of crude oil reservoirs. These features will allow for the removal of oil coated complex organicfinorganic deposits, the dispersibility and recoverability of acid reaction products and minimization of acid induced damage. Optimizing the acid additive package while lowering the total volume of treating fluids resulted in both a lower initial cost and the highest level of incremental increase in oil production. 6 [A NBW TRCINUIQUE FOR JHE EVALUATION OF ACID ADDITIVE PACKAGES spe 23817 ACKNOWLEDGEMENT The authors would like to thank the management of OSCA, INC. and GREAT LAKES CHEMICAL CORPORATION for permission to publish this paper. REEERENCES D Gidley, JL: “Acidizing Sandstone Formations: A Detailed Examination of Recent Experience,” paper SPE 14164 presented at the 1985 SPE Ann. ‘Tech. Conf., Las Vegas, Nevada, Sept. 22-25. 2) Product Data Bulletin Manual; Aquaness ‘Chemical Company; Houston, TX, 1989. 3) McLeod, H.O. "Stimulation"; SPE Short Course 4) “API. Recommended Practices For Laboratory Testing of Surface Active Agents for Well Stimulation,” API RP-42, Second Edition, January, 1977. 5) Houchin, LR, Dunlap, D.D., and Domike, KM. "The Occurence and Control of Acid - Induced Asphaltene Sludge” paper 19410 presented at the 1990 SPE Formation Damage Control Symposium, Lafayette, LA Feb. 22-23. ©) Coppel, CP: “Factors Causing Emulsions Upsets in Surface Facilities. Following Acid Stimulation”, J. Pet. Tech. (Sept. 1975) 1060-65. Dunlap, DD. and Houchin, LR: “Evaluation of ‘Acid System Design and Formation Damage Using Polarized Microscopy” paper 19425 resented at the 1990, SPE Formation Damage Control Symposium, Lafayette, LA Feb. 22-23 8 Sutton, GD. and Lasater, RM: “Aspects of Acid Additive Selection in Sandstone Acidizing,” peper SPE 4114 presented at the SPE-AIME 47th Annual Fall Meeting, San Antonio, TX Oct. $11, 1972. 9) Hall, BE: "The Role of Mutual Solvents in Sandstone Acidizing”, J. Pet. Tech. (Dec. 1975), 1439-42,spe 23817 LR. HOUCKIN, W.B. FOMENEERG, MAJ. USIE, & J. 280 10 w 2B w 15) 16 ™ 18) 1» King, GE. and Lee, RM: “Adsorption and Chlorination of Mutual Solvents Used in Acidizing” paper SPE 14432 presented at the 1985 SPE Annual Technical Conference, Las Vegas, Nevada, Sept. 2225. McLeod, H.0. "Matrix Acidizing", J. Pet, Tech. (December 1984), 2055-68. Brannon, D.H., Netters, C.K. and Grimmer, PJ. “Matrix Acidizing Design and Quality Control ‘Techniques Prove Successful in Main Pass Area Sandstone”, JPT (Aug. 1987), 931-942, ‘Almond, S.W., Brady, JL, and Underdown, DR: "Prudhoe Bay Field Study - Return Fluid Analysis", SPT (April 1990), 466-472. Fambrough, J.D, Brady, JL, and Almond, SW: "Return Fluid Analysis From the Sadlerochit Formation, Prudhoe Bay, Alaska: A Laboratory Study - Part II", SPE 22079 Gidley, IL: “Stimulation of Sandstone Formations with the Acidizing Mutual Solvent Method", JPT (May 197D, 551-558, Hoouchin, LR, and Hudson, LM: “The Prediction, Evaluation and Treatment of Formation Damage Caused by Organic Deposition”, SPE 14818, Proc. 7th Formation Damage Control Symp., Lafayette, (1986) 83.90, Efthim, EP. etal, “Evaluation and Treatment of Organic and Inorganic Damage in an Unconsolidated Asphaltic Crude Reservoir” SPE. 19412 presented at the SPE Formation Damage ‘Symp. in Lafayette, Feb. 22-23, 1990. Bilden, DM, etal, "Evaluation and Treatment of Organic and Inorganic Deposition in the Midway Sunset Field, Kern County, CA, SPE 20073 presented at the 60th CA Regional Meeting held in Ventura, CA, April 46, 1990, "New Method Proves Value of Nov. 19, 1979, Paccaloni, G. Stimulation Planning” G3, 155-160, » » 2 2) Paccaloni, G: “Field History Verifies Control, Evaluation” OGI, Nov. 26, 1979, 61-65. Woodroof, RA. Jr, Baker, IR, and Jenkins, RA Irs Inhibition of HydrochlorieHydrofluroic Acid/Mutual Solvent Mixtures at Elevated Temperatures", SPE 5645 presented at the 1975 SPE Annual Tech. Conf. ‘and Exhibition, Dallas, Sept. 28 - Oct. "Corrosion Davies, DR. Lievaart, L. and Nitters, G: "The Effects of Corrosion Inhibitors and Mutual Solvents on Matrix Acidizing Treatments", SPE 17153 presented at the 8th SPE Symp. on Formation Damage Control, 1988, Bakersfield, cA. Houchin, LR. Dunlap, D.D., and Hudson, LLM: “Field Mixing and Filtration of Acid Stimulation Fluids", OTC 244, presented at the 18th Annual OTC Conf. in Houston, TX, May 5-8, 1986, APPENDIX A ‘CRUDE OIL - ACID COMPATIBILITY DETERMINATION _ Overview Compatibility of the crude oil with the acid system is determined by first running standard non-emulsion tests? on the live acid (with and without additives) and then filtering the optimized acid “package” tnrough a sandiclay pack filter bed. The initial non-emulsion tests are designed to determine the optimum live acid package as well as the crude’s sensitivity to variables such as acid strength, acid type, and presence of soluble ferric (43) iron. The iron is added to the acid (2000 mp/D to check for sludge sensitivity or rigid film emulsion formation. This iron sensitivity testing is ‘especially relevant for asphaltic crudes and many times results of compatibility testing may dictate a preflush treatment prior to the introduction of the acid. Once the live acid system is formulated and optimized, it is filtered through a sand/clay pack and the nnon-emulsion tests (compatibility) are re-run. In this way, the surfactant adsorption is simulated and the as‘A NB TECHNIQUE FOR THE EVALUATION OF ACID ADDITIVE PACKAGES SPE 23817 downhole compatibility assured. If the previosly obtained 90% breakout and associated good wettability characteristics are not maintained, mutual solvent(s) are added to the system (and/or additional surfactant) until post-filtration compatibility is achieved. The mud acid stage is filtered through the same pack as the HCL *Standard_non-emulsion testing involves mixing 50:50 ratios of acid systemerude oil under low shear, placing mixture in 100 cc graduated cylinders and into a water bath at bottom hole temperture, or 150°R, whichever is ower. The percent acid breakout is monitored every $ minutes and observations made of the wettability characteristics, ‘A compatible mix is defined as having greater than 90% breakout within 15 minutes and displacing good wettability characterises, Outline Step: Determine acid type and strength to be tested based on mineralogy, suspected Step2: Determine compatibility of crude with chosen live acid prior to addition of additives. Step3: Determine compatibility of crude with live ‘acid plus corrosion inhibitor. Step 4 Determine compatibility of crude with live ‘acid plus corrosion inhibitor’ and additives (non-emulsifiers, anti-sludge surfactants, iron control agents, ec.) = Optimize additive package to provide 290% acid breakout within 15 minutes. Step S: Filter optimum live acid package (acid + additives) through sand/clay pack and determine compatibility with crude oil. Step 6: Add mutual solvent to acid "package". if necessary, and filter through sandiclay peck. Determine compatibility with crude oil, + Optimize treatment to provide 290% ‘acid breakout within 15 minutes SANDICLAY PACK FILTRATION PROCEDURE FOR ‘ACID NON-EMULSJON TESTING _ Equipment/Apparatus/Reagents *1-9.cm ID Plastic Buchner Filter Funnel *1-9¢m OD Whatman No. 4 Filter Paper *1- Sidearm Filter Flask * Standard Pack Material*: 10:10:80 w% ‘Wyoming bentonite clay:fine silica flour:100 mesh sand * Stock solution of 3% NH,CL * 100 oc graduated cylinders * Vacuum pump or aspirator set up * Waring Blender and jars * Rheostat a ~ If mineralogy indicates much higher percentages of clay, the pack formula may be adjusted accordingly. FILTER PACK PROCEDURE D_ Mix 100 cc of the acid system to be tested, 2 Prepare filter pack by mixing 200 g of the blended pack material with 250 cc of 3% NH,Cl solution to make a slurry. 3) Filter slurry in Buchner funnel using a Number 4 Whatman filter paper to form the sand pack. Collect +220 ce of brine effluent and discard. This volume assures the pack will not exaggerate dilution of the acid with excess NH,CI brine. 4 Filter the acid system. Collect the first 20 ce of effluent and discard. 5) Collect the remainder of the filtered acid and transfer 50 ce to the blender. Add 50 ce of oil sample and mix on low shear for 1 minute.PE 23617 E.R. HOUCHIN, W.E. FOXENEERG, MAJ. USIE, & J. ZHN0 © Place the mixture into @ hot water bath at the ; ‘SLMETRIC CONVERSION FACTORS wells bottom hole temperature or 150°F, whichever is lower. 7 Fox OF-3yI8 ="c : nox 1 Measure volume % acid dropout at $ minute 1 john ay intervals. ‘= | om 8) Evaluate at 15 minutes to determine if industry accepted standard of 90% by volume acid Gropout has been achieved. In addition, the overall fluid quality should be observed (oil quality, water quality, presence and rigidity of interfacial layer, wettability, and sludge sensitivity). TABLE 1 Agsorption effect of Non-ionic Surfactants Plowing through 6 Foot Long Core Apparatus Percent Acid Breakout (15 min./150°r (66°C) Non-ionie Sample 41 Sample 42 Sample 43 Surfactant initial (er in.) (2 fat) (38 ins) 154 Hel only trace = —_ Sure. #2 3a ae ea Sure. 42 52 1 Fy Sure. #3 32 n 32 maBLe 2 Adsorption Effect of Non-ionic surtactants/ mutual Solvent Flowing through 6 Poot Long core Apparatus Percent Acid Breakout (15 min./150°F (66°C) Non-tonie Sample 42 Sample #4 Sample #8 Surfactant/eGMse Initial (2 ins) (24 fn.) (iB fat) Sure. 41/58 xompe 100. 96 10 Sure. #17108 gorse = 100 38 6 Sure. 42/58 EGNBE 98 34 6 Surf. 42/108 eonBe 97 34 6a Sure. 43/58 EGNBE 35 31 Fe Sure. #37108 eoNBe 95 32 50 58 ecmne 30 30 36 10% EBMBE 32 at ieSPE 23817 fcurcent typiont Calf coast Acid reataent 8 Solyent Petia Gene), eee eons uo 4SPE 23917 TABLE 8 24 nour Corrosion mates, (1b/sq. ft.) at 185°r 3 inhibitor 0% EGHBE 5% EGNBE 2103 EoMBE ° 574 Net. NT. 2 -011 +021 +032 3 -008 -018 -030 a -008 -011 +010 1.6 Nt. -005 -009 7.5 + 1.58 HCL BF & nhibitor o% zompe 5% _EOMBE 103 BoMBE ° +235 NT Nt. 2 -066 01 1025 3 016 -015 +019 8 +009 +009 008 1.6 NT. -005 +006 NLT, = not tested Fra. 1—10)7 5% Hol pratuehcurent test mathod,() 7.5% HC! preftuhisand pack metho, ‘and (C) 7.5% Hcl EGMBE/eand pack methsre 23617 F.2d am he ed oho tt nebo on tt tron hwy on fa et os mre