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SPE 37015

A New Acid for True Stimulation of Sandstone Reservoirs


Gino Di Lullo SPE, Phil Rae SPE/BJ Services

Copyright 1996, Society of Petroleum Engineers, Inc.


ability of the formation rock is sometimes reduced by invasion
This paper was prepared for presentation at the 1996 SPE International 6th Asia Pacific Oil & of water base filtrates, either from drilling, completion, work-
Gas Conference held in Adelaide, Australia, 28-31 October 1996.
over or treating fluids. These fluids can damage the matrix by
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
swelling and dispersing clays or even by inducing the precipi-
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to tation of scales. Also, in high permeability formations under
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at high differential pressure some particles can invade the forma-
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Permission to copy is restricted to an abstract of not more than 300
tion and plug some pores.
words. Illustrations may not be copied. The abstract should contain conspicuous acknowledg- Hydrofluoric and hydrochloric acid mixtures (generally de-
ment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box
833836, Richardson, TX 75083-3836, U.S.A., fax 01-214-952-9435. scribed as mud acids) have been chosen to treat these forma-
tions since they dissolve clays from drilling mud and react
with most constituents of naturally occurring sandstone 1. The
dissolution of these materials will enlarge and interconnect
Abstract
pores, allowing the produced fluids to move easily. Kinetics
Hydrochloric:hydrofluoric acid mixtures have been exten-
of mud acid reaction with sandstone is heterogeneous, com-
sively used to treat sandstone reservoirs, however, their appli-
plex and difficult to predict. However, the overall reaction rate
cation has been restricted to restoring the natural permeability
depends mainly on the nature of the surface reaction within
of the formation. A combination of rapid spending with clays
the pore. Unlike quartzitic fines, clays are unstable and easily
and silicates, matrix unconsolidation in the near wellbore area
protonated thus very reactive and therefore dissolved at a
and subsequent precipitation of various reaction by-products
faster rate by HF acids. Nevertheless, when reacted with HF
has limited the usefulness of mud acid for matrix stimulation
acids under isolated condition, both clays and quartz have
treatments.
similar solubility. The solubility of these minerals with 3%
Several existing "retarded HF acids" mixtures have been
HF mixtures is close to 8 times lower than the amount of
tried with mixed results. The marginal reduction in reaction
limestone dissolved per gallon of 15% HCl. Thus to produce
rate of these acid systems could not overcome the huge con-
in sandstone reservoirs equivalent stimulation results to those
trast in surface area between clays and quartz, which dominate
obtained in limestone, the acid volume must be several times
HFs reaction rate. Also, various in-situ-generated acids
larger.
were developed and pumped, with questionable to poor results
During matrix stimulation treatments, the main factors that
due to premature or improper mixing of the solutions, both in
contribute to matrix dissolution by injected acids are the
the tubulars and in the formation.
availability of minerals and their surface area. Therefore pore
This paper discusses the chemistry and development of a
lining and flocculated clays, carbonates, scales and invading
new acid that can completely replace HCl in HCl:HF mix-
particles are more vulnerable to acid attack than any frame-
tures. Compared with available HF acid systems, the new HF
work minerals. Moreover, clays have much higher surface
acid has lower reaction rate and limited solubility with clays,
area than quartz, hence increasing their dissolution rate, leav-
but higher reaction rate and dissolving power with quartz. As
ing quartz minerals virtually untouched. Thus, as more acid is
a complement, various field treatments are discussed and a
injected, more clays and cementitious materials are dissolved
complete database with production data is presented.
especially in the big pores and the formation becomes pro-
gressively weaker until it eventually re-compacts to lower
porosity and permeability levels.
Introduction The by-products of sandstone dissolution 1 by HF acids are
The framework of sandstone formations is normally made up amorphous compounds and complex fluosilicates, fluoalumi-
of quartz, silicate grains, feldspars, chert and mica. These nates and fluoride salts which by nature have extremely low
minerals are bonded together by secondary minerals that pre- solubility. They reach saturation at very low concentrations
cipitated from connate water, occupying partially the original and produce precipitates with varied consistencies.
pore spaces, for instance, over growth quartz, carbonates and Consequently, to prevent permanent damage from occur-
pore lining clays. The porous fraction and hence the perme- ring, the dissolving power of HF acid is adjusted so that no
2 A NEW ACID FOR TRUE STIMULATION OF SANDSTONE RESERVOIRS SPE 37015

more than minor damage to the formation can occur. Actually formations. An ideal acid then to "truly stimulate sandstone
engineers have limited 2, 6, 7 HF acid volume and concentration formations", must dissolve quartz faster, limit solubility of
so much that today, jobs are designed just to overcome dam- clays and/or carbonates and reduce or delay formation of sec-
age (skin equal to zero) and true stimulation (negative skin) is ondary precipitates.
out of the question. As secondary precipitation and
unconsolidation effects on well productivity are difficult to New HF Acid Mixture
predict, they are not accounted for in the design phase. Thus, As used in the oil field, mud acid 1, 9 is a dilution of HF acid in
there is a big discrepancy between the theoretical and the HCl. Usually prepared by dissolving ammonium bi-fluoride in
actual PI obtained in the field from these acid jobs . HCl, a mixture of 1% HCl and 123 pounds of NH4HF2 will
generate 1% HF acid solution. Regular mud acid (12:3
Retarded or Slow reacting acids HCl:HF) is hence made from 15% HCl, where 3% HCl is
Slow reacting acids such as 3, 6 fluroboric, fluroaluminic and used to hydrolyze the fluoride salt. Excess HCl is added with
hexa-fluro-phosphoric were developed between the 70s and the sole purpose to increase the solubility of byproducts of the
the 80s to increase the depth of permeability alteration. Al- reaction with formation minerals. The 4:1 HCl:HF ratio is
though results were better, they were not substantial and not based on studying primary reaction of HF on alumino-
even commercially applicable on undamaged formations. silicates. Recent studies however 10, which investigated sec-
Most of these acid systems rely on the use of weak organic ondary reactions with fluoroaluminates recommended that this
acids and their secondary reactions to slowly generate HF. ratio need to be increased to at least 6:1 or to an optimum of
During sandstone acidizing treatments the reactions are mass 9:1, so that potential precipitation of fluoride salts is reduced.
transfer limited, i.e. : reaction rate is limited by the rate at A new HF acid mixture was developed 8, 9 using a phos-
which HF can reach the reactive surface. Thus, in a radial phonic acid complex to hydrolyze the fluoride salts instead of
flow pattern live acid penetration is marginally increased (Fig. HCl. This acid has 5 hydrogens available that will dissociate
6B) and unconsolidation and precipitation effects slightly re- at different stoichiometric conditions, hereafter referred as
tarded. Sequential treatments such as an HCl acid stage fol- "HV acid" (five hydrogens). Mixtures of HV acid and
lowed by a fluoride salt stage were tried to improve acid pene- NH4HF2 produce an ammonium phosphonate salt and hydro-
tration. They rely on adsorption of the hydronium to the clay gen fluoride, hereafter referred as "Sandstone Acid." Twenty
surface during the acid stage and generation of HF later while gallons of HV acid per 1000 gallons of water are required to
pumping the fluoride salt stage. Uneven distribution and react with approximately 123 pounds of NH4HF2 to produce a
placement of the fluids in the matrix and high clay dissolution 1% HF acid solution.
produced mixed results from these treatments. Self generating During preparation of Sandstone acid, an adequate supply of
mud acid eliminated these hurdles as it hydrolyzed in the for- fluoride anions is provided by the ionization of the dissolved
mation to yield hydrogen fluoride. Unfortunately under these fluoride salt, but the formation of a molecule of HF requires a
conditions, rock solubilization is limited to the acid in the pore combination of a hydronium ion and a fluoride anion. Since
space, which is insufficient to enlarge the pores enough to the concentration of hydronium is kept low by the pH of the
provide cost effective increases in well productivity. To coun- mixture, so is the concentration of active HF. Therefore, an
teract this limitation, self generating mud acid treatments were equilibrium is created by the buffering action of the weak acid
sometimes preceded with mud acid, creating again uncertain- and the weak acid salt. When the acid reacts with the forma-
ties as regards unconsolidation and precipitation problems. tion, the equilibrium of the system is upset and above process
The porosity improvement obtained (ratio between: original is activated again until equilibrium is re-established. Thereaf-
porosity + dissolved clays and solids, divided by the original ter, as long as the concentrations of the solutes are adequate,
porosity) is limited to the space occupied by clays and car- the rate of acidization reactions of the solvents is quite con-
bonates, which is a minor portion of the rock. Without de- stant. When sandstone acid is prepared, only the three strong-
stroying matrix integrity, post stimulation porosity ratios are est hydrogens hydrolyze to produce HF. The rest will not be
thereby limited to 1.4 and penetration depth of less than 6 utilized as they hydrolyze at pH higher than 4, which is not
inches. This new porosity ring can improve the PI by no more practical at downhole conditions. The strongest hydrogen be-
than 10 percent (Fig. 1) which in most of the cases is not haves as HCl and the weakest as Carbonic acid. This buffering
worth the risk and jobs are designed only to remove damage. effect will slow down the reaction rate with clays and carbon-
Because of these limitations, mud acids, retarded acids and in ates by several folds, equivalent to retarded acids. Also, the
situ generated acids are unable to produce outstanding stimu- reaction rate can be fine tuned by partially replacing HV acid
lation results on sandstone formations. It is clear from figure 1 with another acid. For example, muriatic will form HF at a
that there must be a balance between live acid penetration and faster rate than organic acids. Depending on sandstone acid
porosity ratio for a successful acid treatment. A porosity ratio formulation, its starting pH will range between 2.2 and 3.8.
between 1.6 and 2 and rx above 3 will produce healthy flow In addition, and more relevant to sandstone stimulation are
improvements. The only way to obtain higher and deeper po- the following synergistic effects : (1) When the reaction with
rosity ratios would be to enhance quartz dissolution around the formation starts, an aluminum-silicate-phosphonate plat-
the pores, as quartz occupies the major fraction of sandstone ing is formed over the clays by chemi-adsorption (Fig. 2).
SPE 37015 GINO DI LULLO/PHIL RAE 3

This coating has a thickness narrower than a micron, has low ever, can not overcome the fast reaction of HF with clays and
solubility in weak acids (HF acid, carbonic acid) and water, carbonates. Thus, most mathematical models used to predict
but is rapidly dissolved by HCl and to a lesser extent, by or- production increases 1, 2 consider instantaneous clay dissolu-
ganic acids. tion and neglect quartz dissolution. When sandstone acid is
From then on, this film will block further reactions with utilized, these models must be modified to account for only a
those clays, limiting their dissolution and, therefore, prevent- limited dissolution of clays and cementitious minerals and
ing disintegration of the matrix. Dynamic solubility tests on slightly higher quartz dissolution rates. The graphical output
clays indicate that their dissolution is somehow proportional of this model, Figures 6A & 6B, plots the PI ratio and acid
to the surface area - volume ratio of the clay. For example, on penetration versus Volume of Acid injected on virgin sand-
the lower end, smectite and illite dissolution are limited to stone formations treated with various HF acids. It assumes (1)
around 35 percent and on the higher end, kaolinite dissolution clays dissolution is instantaneous but limited between 35% to
is limited to near seventy percent. Because the coating over 95%; (2) the dissolution of quartz is time-dependent; (3) po-
the clays is acid soluble, small volumes of muriatic acid or rosity-permeability-PI (Fig. 1) relation proposed by Gatewood
formic acid may be used to fine tune clay dissolution and to et al 2 is valid and finally (4) that only 65% of the rock is con-
optimize the design. Figure 3 is a plot of smectites solubility tacted by the acid. This value was selected after evaluating
versus time for 3% mud acid, sandstone acid and sandstone acid returns on core flow tests and studying various porosity
acid with added HCl or acetic acid. The slope of the initial distribution on cores which maintained matrix integrity before
portion of these curves (first ten minutes) measures the reac- and after acid stimulation (Fig. 5). Notice that pores with di-
tion rate; the subsequent portions of the graph (flat portion) ameter smaller than 8 micron are hardly acidized, however,
measure to what extent each acid can dissolve and limit the above this size the curves shift to the right indicating pore
clay solubility. (2) HV acid, as most phosphonates, has out- enlargement. From this plot, one can conclude that pore en-
standing adsorption and water wetting properties that catalyze largement rather than pore interconnection is the main cause
HF reaction with quartz. Even though the reaction rate is for permeability improvement.
lower than mud acid, quartz solubility becomes higher as time
passes. As can be seen on Figure 4, quartz solubility with Core Flow Testing
sandstone acid is around fifty percent better than with mud Frequently, core flow tests are run across short cores (3
acid. Adsorption 3 however, is dependent on the pH of the inches) or series of cores (up to 3 feet) 3, 9 to help in designing
carrier fluid. Thus in the presence of HCl or acetic acid, the matrix acid jobs. Nonetheless, due to the difference in flow
solubility improvement is reduced to near 30 percent. (3) Last pattern their results must be carefully evaluated and should
but not least, like other anionic phosphonates, HV acid is a only be used in a qualitative manner. In these tests the pore
superior dispersant, has sub stoichiometric sequestering prop- volume increases linearly instead of radially, producing opti-
erties and is an excellent antiscalant, thereby defer- mistic porosity ratios and live acid penetration and overstated
ring/inhibiting formation of precipitates in the near wellbore matrix deconsolidation and secondary precipitation effects.
area. When testing with mud and retarded acids, long cores are re-
Titration of sandstone acid with a solution of sodium silicate quired to allow for a complete acid reaction so that permeabil-
(20 Be) to pH 3.8 (12000 PPM Si) showed no formation of ity responses are meaningful. Several tests 11 using four cores
precipitates. Moreover, the solution remained stable for over in series (having a combined length around 9.6 inches) were
12 hours at atmospheric conditions. When the same titration run to compare mud acid (benchmark) and sandstone acid at
test was performed with regular mud acid, the solution be- 1.5% HF concentration (10 pore volumes each). The Berea
came cloudy at 6000 PPM of Silicon and at 12000 PPM mal- sandstone cores used in this study were cut from the same
ladrite precipitated heavily, even though the pH was still slab, their mineralogy was 82% quartz, 11% feldspars and 7%
acidic (1.6). clays (4% illite, 3% kaolinite and traces of chlorite), having
With sandstone acid, as with self generating mud acids, 18% porosity and 64.2 mD Klinkenberg gas permeability.
when the injection is ceased there is still live acid available in This is a low clay/carbonate content core, thereby porosity
the pore spaces. Delaying flowback allows the remaining acid ratios obtained after acidification with HF acids will be
to continue reacting, but only with the quartz, as the clays are mainly limited by the amount of quartz and feldspars dis-
protected by the coating, improving the permeability even solved and the duration of the test. The results listed on table 1
further. show the inadequacy of mud acid to treat sandstone forma-
tions. It disintegrated half of the first core, stimulated the next
Theoretical Production Increase two and plugged the last one. Also, based on the compressive
Complete zone coverage is one of the most important factors strength of the cores (Table 2), we can see that the penetration
affecting the success or failure of matrix stimulation treat- was limited to no more than 6 inches. Weak sandstone acid +
ments. To avoid injection of acids only on the path of least 1% HCl produced a substantial permeability improvement
resistance, higher rates are recommended 4 to generate enough across the complete interval. Also, the compressive strength
differential pressure across the interval, thereby distributing data of all cores is equal to 66% 3% of an untreated core
the acid homogeneously. These matrix injection rates how- indicating even acid distribution. It is obvious from these data
4 A NEW ACID FOR TRUE STIMULATION OF SANDSTONE RESERVOIRS SPE 37015

that sandstone acid was still active on the last core and its per- and pumped in three stages using 20 barrels of 75% quality
formance was limited by its dissolving power (volume and/or foam pill (foamed overflush). Following the treatment, pro-
concentration). A new set of core flow tests was then per- duction increased to 11130 BFPD with 89% water cut. Net oil
formed comparing regular sandstone acid (RSA), regular production increased by 353 barrels per day (a 44% increase)
sandstone acid + 2% acetic acid (RSAA), regular sandstone and well PI was calculated to be 31.4 (75% more than after
acid + 1% HCl (RSAH) with commercially available retarded gravel pack). Two months later, the well was producing 10400
acid systems (3% fluroboric and 3% fluroaluminic). The re- BFPD with a 91% water cut and a calculated PI of 32.5. Actu-
sults are listed on Tables 1 & 2. The retarded acids performed ally, well production at the moment is limited by the capacity
well stimulating all four cores. However, upon analyzing the of the ESP.
permeability response and the compressive strength of the
cores after stimulation, it became obvious the uneven acid Low permeability well onshore Indonesia
distribution versus penetration depth. Also, the compressive This well was completed in 1988. Since then several zones
strength of the first core clearly indicates that acid volumes have been abandoned and new zones have been perforated. In
and their concentration could not be increased. An interesting January, 1996 the well was producing 348 BFPD with a 68%
fact is that the permeability improvement of 3% fluroboric water cut from 24 feet interval at 2200 feet (10 mDarcies, 28
acid is only slightly better than weak sandstone acid, which % porosity and 190F BHST). Formation mineralogy on this
may be attributed to its poor dissolving power with quartz. zone indicated low quartz content (60%) with 20% clays (8%
Like retarded acids, RSAA and RSA stimulated all four cores. illite-smectite, 9% chlorite and 3% kaolinite), 10% carbonate
RSAH however, proved too strong for the testing period, dis- content (calcite, dolomite, siderite) and 10% potassium-
solving quartz and feldspars in excess leading to a zero com- feldspars. Because of the complexity of this rock, acid jobs in
pressive strength on the first core (this will not happen at this layer are rarely performed, however, this well was only
higher injection rates and radial flow patterns). The perme- producing 110 BOPD (16% of wells initial production) and a
ability responses from the core flow test with sandstone acid sandstone acid job was recommended. The well was treated
show how easily it can be fine tuned for different mineralo- with 50 gpf of HCl preflush, 125 gpf of 3% sandstone acid
gies. Also, if compared with retarded acids, RSA produced and 40 gpf of 7.5% HCl afterflush. Preflush and afterflush
overall permeability response 3 times higher. Interesting as volumes were kept low to prevent matrix unconsolidation as
well (Fig. 5), is the fact that sandstone acid produces higher carbonates are part of the cementitious material in this forma-
porosity enlargement than retarded acids, probably due to tion. Until today (110 days after the acid job), the well has
higher quartz dissolution, but not as excessive as the com- been producing an average of 380 BFPD with a water cut of
bined dissolution of clays and quartz produced by mud acid . 50%, thereby increasing oil production by 71%.

Case Histories Large interval, geothermal well in Philippines


The following jobs were selected to show the ability of sand- This well is part of an onshore geothermal field in Philippines.
stone acid to stimulate sandstone formations. A database with In this field, the wells are completed with a slotted liner cov-
the first 18 jobs performed in Asia is enclosed on Table 3. ering around 2500 ft of low permeability and porosity vol-
Also, sandstone acid treatments were performed in other areas canic sandstone, microfractures are encountered throughout
around the world, as of today, all jobs have produced positive the complete interval and are believed to be the main path for
stimulation results. steam production. Most wells are acidized just after comple-
tion to remove drilling debris, drilling mud and silica scales.
High permeability well offshore Indonesia Also, after some production time, wells are re-acidized for
This offshore well was completed with a gravel pack in a 47 silica scale removal purposes. Scaling up is severe because of
feet net interval at 4700 feet TVD (gross height of 60 feet steam flashing, high temperatures (460F), high dissolved
TVD, 30% porosity, 1 Darcy permeability and 180F BHST). silica in produced water (average 850 PPM) and high produc-
Initial production was 11060 BFPD with 70% water cut, the tion rates. Since 1984, these wells were acidized successfully
PI was calculated to be 18. After one year, the total production using a strong mud acid formulation (10:5 HCl:HF) mainly
decreased to 8497 BFPD with 83% water cut and a calculated because of the high silica content in the scales (70 to 90 per-
PI of 8.7. As in most artificial lift wells, the production drop cent). As these wells are situated in a populated area, several
was attributed to fines migration, change in wettability due to environmental problems such as transportation of concen-
organic build up in the near wellbore and increased water cut. trated HCl, acids fumes while mixing and flow back of toxic
Formation mineralogy indicated high quartz content (96%) treating fluids (containing high concentration of corrosion
with potentially migrating kaolinite (3%) and small amounts inhibitors) were a major concern, the operator was looking for
of carbonate, siderite and illite. A sandstone acid job was de- a more suitable way to stimulate this field. Sandstone acid was
signed to stimulate the well, the treatment consisted of 25 gpf recommended instead of mud acid based on its higher silica
of xylene preflush, 100 gpf of 7.5% HCl preflush, 200 gpf of dissolving power and anti-scaling properties. Also, its low
3% sandstone acid, 100 gpf 7.5% HCl afterflush and finally a HCl requirements minimize acid fumes while mixing the acid
3% ammonium chloride overflush. The treatment was foamed and reduce by one third the volume of corrosion inhibitor re-
SPE 37015 GINO DI LULLO/PHIL RAE 5

quired at BHIT. This well was drilled to 6003 ft and com- Conclusion
pleted with 2900 ft of slotted liner, net producing interval is 1. Mud acid is only adequate for damage removal. Acid
around 400 ft and had an intermittent initial production and volumes and acid concentration should be kept as low as pos-
steam KPH equal to zero. A sandstone acid treatment was sible to minimize matrix unconsolidation and secondary pre-
designed with 75 gpf of 10% HCl preflush, 75 gpf of 5% cipitates.
gelled sandstone acid plus 3% HCl and a fresh water over- 2. It is important to run multitap core flow tests to evaluate
flush at injection rates varying from 8 to 12 barrels per min- acid response. However, results are only qualitative and per-
ute. Pre and post injectivity test indicated a successful treat- meability response and treatment design cannot be extrapo-
ment (2.4 folds increase) and the well was then shut down to lated for field application.
connect it to the production line (power plant). After six 3. Retarded acids at least double live acid penetration when
months, when the well was finally tested, it produced steam at compared to mud acid (at the same concentration) on linear
130 KPH fully open (75 PSI wellhead pressure) and 108 KPH core flow tests. In spite of this, when this penetration is con-
steam, 35% choked (205 PSI wellhead pressure) which is verted into radial geometry the final effects on depth of poros-
equivalent to 5 MW. ity alteration and production are minimal.
3. Porosity distribution on untreated cores and acidified
Short interval, geothermal well in New Zealand cores demonstrate that pore enlargement is the contributing
This well was completed in 1984 at 4790 ft with a 6 5/8 factor for permeability improvement, rather than interconnect-
inches casing cemented in place. The well was perforated at ing new pores.
4757 feet, 43 feet above the basement (33 feet gross height, 4. A new acid system has been developed for sandstone
low permeability and porosity with several natural fractures acidizing. The acid system is unique in several aspects : (1) it
interconnecting the wellbore and a BHST of 446F). The for- is slow reacting; (2) has limited solubility with clays; (3)
mation mineralogy indicated 45% quartz, 22% clay, 28% feld- higher dissolving power with quartz and (4) it minimizes det-
spars and 5 % carbonates. Production from this well was low rimental effects such as secondary precipitates without resort-
since its completion (0.5 MW) and an acid job was rec- ing to the use of high HCl:HF ratios.
ommended. The well was treated with 125 gpf of 10% HCl 5. When compared with mud and retarded acid, sandstone
preflush, followed by 250 gpf of 3% gelled sandstone acid and acid is less corrosive and user friendly (initial pH around 3), it
an overflush of 125 gpf of 10% HCl to be pumped at 8 barrels also requires reduced amount of corrosion inhibitors.
per minute. Well response was slow because of cool down 6. Production engineers are reluctant to use high volumes
effect, however, after 2 weeks, the production increased to 3 of HF acid based on historical facts, however, based on this
MW which is a six fold increase. study, the authors believe that it is possible and safe to use
sandstone acid volume as high as 500 gpf and/or concentra-
tion up to 6% HF, if the acid treatment is properly designed.
Nomenclature 7. Even though it is too early to fully evaluate, core flow
BFPD = barrels of fluid per day and field results indicate that sandstone acid can indeed stimu-
BOPD = barrels of oil per day late sandstone formations. As of today, all acid jobs per-
BHIT = bottom hole injection temperature formed with this system have been successful in producing
BHST = bottom hole static temperature positive production increases.
ESP = electric submersible pump
GPF = gallons per foot
HCl = hydrochloric acid Acknowledgments
HF = hydrogen fluoride We wish to thank the management of BJ Services for permis-
HF Acid = hydrofluoric acid sion to publish this paper. Also, special thanks to Atikah bte
KPH = kilo pound per hour Ahmad, Joel Boles and Steve Metcalf who provided the labo-
mD = millidarcy ratory data and to Rick Stanley, Ewen Marnock and Edgar
MD = measured depth Francia for compiling data for case studies and finally to
MW = mega watts Catherine Siew and Soh Beng Teck for editing this paper.
NH4HF2 = ammonium bifluoride
PPM = parts per million
PI = productivity index References
TVD = true vertical depth 1. Williams, B.B., Gidley, J.L., Schechter, R.S. : "Acidizing Fun-
rw = wellbore radius damentals" Monograph Volume 6, chapters 3, 4, 8 and 9, SPE
rs = stimulation radius 1979.
rx = rs/rw 2. Gatewood, J.R., Hall, B.E., Roberts, L.D., Lasater, R.M. :
"Predicting Results of Sandstone Acidizing", JPT June 1970.
3. Gdanski R. : "ALCl3 retards HF acid for more effective stimu-
lations" Oil & Gas Journal , October 1985.
6 A NEW ACID FOR TRUE STIMULATION OF SANDSTONE RESERVOIRS SPE 37015

4. King, G.E., Warden, S.L. : "Introductory Work in Scale In- nical Conference and Exhibition, Washington, DC, 4-7 Octo-
hibitor Squeeze Performance: Core Test and Field Results" ber 1992.
paper SPE 18485 presented at the SPE International Sympo- 8. BJ Services Mixing Manual, August 3, 1995.
sium on Oilfield Chemistry in Houston, TX, 8-10, 1989. 9. Di Lullo, G., Sookprasong, A., Hibbeler, J. : "Sandstone Acid
5. Cheung, S.K., Van Arsdale, H., : "Matrix Acid Stimulation Technical Bulletin", September, 1995.
Studies Yield New Results with a Multitap Long-Core Per- 10. Gdanski, R.D., Shuchart, C.E. : "Newly Discovered Equilib-
meameter", JPT January 1992. rium Control HF Stoichiomtry" paper SPE 30456 presented at
6. Ayorinde, A., Granger, C., Thomas, R.L. : "The Application the 1995 SPE Annual Conference and Exhibition, Dallas,
of Fluoboric Acid in Sandstone Matrix Acidizing: A Case Texas, October 22-25, 1996.
Study" paper IPA 922323 presented at the 21st Annual Con- 11. Stim. Lab "Acid Comparison Testing", SL43H3, Houston,
vention, Jakarta, October 1992. June 1996.
7. Pacalloni, G. : "A New, Effective Matrix Stimulation Tech-
nique" paper SPE 24781 presented at the 67th Annual Tech-
Table 1 - Multitap Core Flow Test

ACID TYPE PERMEABILITY RATIO TREATMENT


CORE 1 CORE 2 CORE 3 CORE 4 OVERALL TIME
1.35 inches 2.5 inches 2.5 inches 3.25 inches 9.6 inches MINUTE
WEAK MUD ACID 0.04 * 6.63 2.90 0.85 ** 2.67 144
WEAK SANDSTONE ACID 2.55 1.54 1.85 1.74 1.83 146
REGULAR S. ACID 49.00 1.91 1.32 1.73 8.32 144
REGULAR S. ACID + ACETIC 5.00 1.62 1.51 1.50 1.90 132
REGULAR S. ACID + HCl 23.60 2.20 1.78 1.47 4.63 122
REGULAR FLUROBORIC 3.50 2.10 1.46 1.76 1.96 126
REGULAR FLUROALUMINIC 7.80 1.96 1.58 1.66 2.58 96

* - UNCONSOLIDATION
** - PRECIPITATION

Table 2 - Multitap Core Flow Test

ACID TYPE UNCONFINED COMPRESSIVE STRENGTH (PSI)


CORE 1 MIDDLE CORE 4 AVERAGE AVG. VIRGIN
SECTION CORE
WEAK MUD ACID unconsolidated 3922 5500 3140 5297
WEAK SANDSTONE ACID 3667 3361 3489 3505 5297
REGULAR S. ACID 637 4253 5526 3472 5297
REGULAR S. ACID + ACETIC 1681 3073 3641 2798 5297
REGULAR S. ACID + HCl nil 3056 4813 2623 5297
REGULAR FLUROBORIC 1732 2623 4635 2996 5297
REGULAR FLUROALUMINIC 1859 2623 3387 2623 5297
SPE 37015 GINO DI LULLO/PHIL RAE 7

Table 3 - Sandstone Acid Treatment Summary In South East Asia

FORMATION DATA SANDSTONE ACID WELL'S


COUNTRY WELL SANDSTONE TEMP VOLUME PRODUCTION HF OTHER
O
TYPE QUARTZ SILI- CARBO- F GAL/FT BBL BEFORE AFTER CONCEN- ACID
CATES* NATES TRATION
PHILIPPINES GEO 61 39 0 250 75 240 0 2 MW 5% HCl 3%
GEO 61 39 0 250 75 450 0 2 MW 5% HCl 3%
GEO 58 42 0 250 75 350 0 5 MW 5% HCl 3%
GEO 58 42 0 250 75 350 0 5 MW 5% HCl 3%
GEO 70 30 0 250 75 740 3 MW 7 MW 5% HCl 3%
GEO 70 30 0 250 75 740 3 MW 7 MW 5% HCl 3%
GEO 70 30 0 312 75 500 3.7 MW 5.2 MW 5% HCl 3%
GEO 70 30 0 312 75 500 3.7 MW 5.2 MW 5% HCl 3%
INDONESIA OIL 65 6 29 210 150 110 0 BOPD 37 BOPD 3% Acetic 2%
OIL 65 6 29 210 150 80 0 BOPD 5 BOPD 3% Acetic 2%
OIL 90 10 0 186 125 24 TRACES 60 BOPD 3% Acetic 2%
OIL 72 6 22 189 125 20 20 BOPD 122 BOPD 3% Acetic 2%
OIL 76 24 0 216 140 25 5 BOPD 400 BOPD 3% Acetic 2%
OIL 64 36 0 210 120 50 30 BOPD 38 BOPD 3% Acetic 2%
OIL 82 18 0 140 125 71 110 BOPD 190 BOPD 3% HCl 1%
OIL 51 48 1 250 150 143 240 BOPD 290 BOPD 3% Acetic 2%
OIL 96 4 TRACES 180 200 223 801 BOPD 1154 3% HCl 1%
BOPD
NEW GEO 45 50 5 220 250 195 0.5 MW 3 MW 3% HCl 1%
ZEALAND

* SILICATES = FELDSPARS + CLAYS

Figure 1
Sandstone Acidizing
1.80

1.70
rx = rs / rw
rx = 15.0

1.60 rx = 12.0

1.50 rx = 9.0
PI Ratio

1.40
rx = 6.0
1.30
rx = 3.0
1.20 rx = 1.5

1.10

1.00
1.00 1.20 1.40 1.60 1.80 2.00 2.20

Porosity Ratio
Figure 2
8 A NEW ACID FOR TRUE STIMULATION OF SANDSTONE RESERVOIRS SPE 37015

Left side SEM, untreated smectite; center SEM, smectite treated with regular mud acid; right side SEM, smectite treated with regular
sandstone acid. Notice the colloidal coating protecting the clay, and on the edax, the low silicon peak and the additional phosphorous
peak.

Figure 3
Dynamic Smectite Solubility
100

90 A

80

70
% Solubility

60 B
50
C
40

30 D A : R. Mud Acid
20
B : R. SA + 1.5% HCl
C : R. SA + 2% Acetic Acid
10 D : R. SandStone Acid (SA)

0
0 5 10 15 20 25 30

Time, minutes
SPE 37015 GINO DI LULLO/PHIL RAE 9

Figure 4
Dynamic Quartz Solubility
30

25
D
B
C
20
A
% Solubility

15

10
A : R. Mud Acid
B : R. SA + 1.5% HCl
5 C : R. SA + 2% Acetic Acid
D : R. SandStone Acid (SA)

0
0 10 20 30 40 50 60

Time, minutes

Figure 5
Pore Size Distribution Frequency
100
virgin core
acidized core (Mud Acid)
acidized core (Retarded Mud Acid)
Distribution Frequency (%)

acidized core (SandStone Acid)

10

1
1 10 100

Pore Size Diameter (microns)


10 A NEW ACID FOR TRUE STIMULATION OF SANDSTONE RESERVOIRS SPE 37015

Figure 6A
Theoretical PI vs Acid Volume
1.40

8.5"
A
1.30

B
PI Ratio

1.20
C

1.10 A : R. SandStone Acid


B : R. Retarded Acid
C : R. Mud Acid

1.00
0 100 200 300 400 500
Acid Volume (gal/ft)

Figure 6B
Theoretical Radial Acid Penetration vs Acid Volume
2.50

8.5"
A
2.00
Radial Acid Penetration, ft

B
1.50
C

1.00

A : R. SandStone Acid
0.50
B : R. Retarded Acid
C : R. Mud Acid

0.00
0 100 200 300 400 500
Acid Volume (gal/ft)

KH = 1250 mdft, S=0, Porosity = 12%, 80% Quartz, 19% Clays and 1% Carbonate. Temperature 180F, 3% HF.

Consider no matrix unconsolidation or secondary precipitation effect.