.
SPE 36907
Improved Success in Acid Stimulations
C.E. Shuchart, SPE, and R.D. Gdanski, SPE, Halliburton Energy Services
Copyright 1996, Society of Petroleum Engineers Inc
This paper was prepared Iof presentation at the 1996 European Pelroleum Conference
m M[lan, Italy, October 22-24
Thm paper was selected for presentation by an SPE Program Commmtee Iollowmg rewew of
miormatmn conlamed m an abstract submilted by the author(s) Contents of Ihe paper, as
presented, have not been rewewed by the Soc#efy ot Petroleum Engineers and are subject to
correction by the author(s) The malerml, as presenled, does nol necessarily reflect any
posmon of the Society of Pelroleum Engfneers, Its officers, or members Papers presented at
SPE meeltngs are sublect 10 pubhcahon re.few by Edttonal Committees of the Society of
P8tfoleum Engineers Permlssmn !0 copy is restricted to an abs!ract of not more than 300
words Illustrations may nof be copied The abstract should contain Conspicuous acknowledge
men! 01 where and by whom the paper IS presented Wrde Ltbrarlan, SPE, P.O Box 833836,
Richardson, TX 75083-3836, U S A, lax 01-214-952-9435
Abstract
Recent studies in sandstone acidizing have shown the impor-
tance of HCI in maintaining the volubility of the reaction
produc[s of HF acid. However, HCI can cause such damage as
corrosion, crude oil sludging, and instability of formation min-
erals. These problems can become severe at elevalcd tcmpcra-
turcs. HF fluids based on acetic acid and formic acid can
successfully ovcrcomc these problems. Despite tbe successful
application of the organic-based HF fluids, very Iittlc work has
been done to understand and optimize these systems. Fluid
reactivity s[udies, flow tests, and flowback analyses following
field treatments were undertaken as a means of studying acetic-
HF and formic-HF fluids. Severe, damaging precipitation of
aluminum fluorides during the HF reactions was discovered
with these fluid systems. This paper will discuss these results
and tbe development and application of a new organic-HF fluid
systcm that overcomes the precipitation problems and maintains
all the advantages of acetic-HF and formic-HF fluids. Labora-
tory flow tests, returns analyses, and case histories of tbe new
system will be also be presented.
Introduction
Over the years, the need for alternatives to HC1-based acidizing
fluids has been realized, Common problems associated with
HC1-based fluids include high reactivity, high corrosivity,
sludging tendencies when the fluids contact crude oils, and the
sensitivity of clay minerals and zeolites.’n These problems are
aggravated at higher temperatures. Organic acids, such as acetic
acid, formic acid, and combinations of the two have overcome
many of these problems.
References at the end of the paper.
!!i!! m
Societyof PetroleumEngineers
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with a New Organic-HF System
Ion Exchange and Clay Swelling. One problem with organic
held acids that has been overlooked until rcccntly is ion cxchangc.y
Organic acids are weak acids that have a very low degree of
ionization. Therefore, an organic acid by itself cannot ion-
exchangc or prevent clay swelling or fines migration. Pumping
plain organic acids into a forma[ion would be like treating it wi[h
fresh water. As a result, 570 NH4C1 must be added to all organic
acid fluids used in sands[one formations to overcome these
problems,
HC1 Sensitivity of Clays. It has long been known that a select
group of minerals will decompose in the presence of HC1 or any
strong acid.’” The most common minerals in this group arc
cbloritc and zeolites. Their instability in strong acid is dircc[ly
related to their structure. Alumina layers are attacked by the
strong acid, which causes their structures to collapse. This
collapse results in a residual silica gel mass that can bc scvcrcly
damaging. Therefore, the usc of organic acids in place of HCI in
acidizing formations containing these minerals is imperative.
Recent research has shown that all clays (with their Iaycrcd
structures) have a temperature above which they arc no Iongcr
stable in HCI. ” Fig. 1 (Page 7) plots the stabilities of clays in
HCI with respect to temperature. For example, a formation at
225 °Fcontaining 109ZO illite would be considered HC1-sensitive;
therefore, organic acid-based fluids should be used instead of
HC1-based fluids to prevent formation damage.
Aluminum Precipitation. Despite the successful application
of the organic-based HF fluids, researchers have done Iit[lc to
understand and optimize these systems. The chemistry of HCl-
HF fluid systems, however, has recently been studied in much
detail.’~ This paper is an extension of the earlier work, focusing
on organic-HFfluid systems. Fhrid reactivity studies, flow tests,
and flowback analyses following field treatments were per-
formed to study the currently used acetic-HF and formic-HF
fluids. A somewhat surprising observation from these tests was
the nearly complete precipitation of aluminum fluoride com-
plexes during the HF reactions. This paper will discuss these
results and the development and application of a new organic-
HF fluid system that overcomes [be precipitation problems and
maintains all the advantages of acetic-HF and formic-HF fluids.
Laboratory flow tests, returns analyses, and case histories of the
new system will be also be presented.
327
2 IMPROVEDSUCCESS IN ACID STIMULATIONS
Results and Discussion
Returns Analyses Method and Procedures. Experimental
andevaluation methods for returns analyses fororganic-HF fluids
areesscntially the same as those for HC1-HF fluids. The best way
to determine if the samples are valid acid flowback satnplcs is 10
follow the pH and Fe contents of the samples. The pH will
typically range from 2 to 4. Late return samples will typically
have a higher pH as the acid continues to react through the
tertiary reaction of HF acid with formation rnincrals. The
dissolution of iron from formation minerals is incvi[ablc and its
presence is a good indication of spent acid fluids.
The usc of inductively coupled plasma (ICP) analysis is
standard. The Al and Si conccn[rations give insight into the HF
reactions. Most returned fluid samples obtained after any HF
treatment typical lycontain 50t0250 mg/Lof Si. Tl~cl()lvsilicon
content is cxpcctcd since the silicon fluorides react completely
above about 100”F. The residual silicon in solution rcprcscnts
the volubility of’ silica gcl.t~ Integrating the use of ‘“F NMR
Spectroscopy greatly improves the analysis and provides [IN
actual distribution of fluoride on silicon and aluminum. This
type of analysis is essential in cvalwstirrg the secondary and
tertiary reactions of HF acid with formation minerals.
Solids analysis by X-ray diffraction and X-ray Iluorcsccncc
dctcrmincs tbc identity of any precipitates or other rcturnccf
solids. In rnostcfiscs, the solids ob(ained in returns arc identified
as fcrrmatiol] fines. Iron hydroxide will also prccipi[a[c from
most Ilowback samples; howc~,cr, it is almost alw:]ys asw~cia[cd
with exposure of [be samples 10 air, which caLIscs oxida~ion of
Fe:+ to Fe’+ and subscquen[ prccipi[ation. Secondary prccipita-
(ion of HF rcac[ion products typically occurs within the f(lrma-
tion and is not casity idcn[ificd as solids in the re[urned samples.
precipitation of fluosi]ica[es or flluminum iluoridcs mLIsl be
inferred from solu[ion analyses.
Chloride analyses dctcrminc [hc cxten[ of mixing with
formation hrlncs, complc[iwr fluids, or kill Iluids. This inlornla-
lion is only helpful when samples or analyses of lhc lluids arc
available. Ammonium (N H4+)analyses can also help dctcrminc
mixing ol prcllushcs and ovcrtlushcs. With organiu acid-based
fluids, NHdCl should also bc included for ion excbangc.
Arrothcr very useful tool for analyzing organ ic-HF !luids is
total organic carbon (TOC). Sirwc most o(her lluids in the
formation will contain little or no TOC dissolved in the aqueous
phase, TOC is an cxccllcnt too! for providing estimates of
mixing and dilution of the stimulation fluids wi[h formation
waters.
Acetic-HFTreatment and Returns Analysis. Optimization of
matrix acidizing treatment designs in Thailand has been an
ongoing process. Several years ago, acid designs in a particular
formation had been changed from HCI-HF to acetic-HFbecausc
of the presence of 5 to 2070 chlorite. The typical bottomhole
temperature was approximately 200”F (93°C) A flowback
analysis project after the acetic-HF treatments would determine
if the designed fluid system could be further optimized. Numer-
ous returns analyses after HCI-HF treatments had been con-
328
WITH A NEW ORGANIC-HF SYSTEM SPE 36907
ducted, but these analyses were the first documented returns
analyses conducted after acetic-HF treatments.
The treatment design consisted of 10% acetic acid preffush
followed by 7.5% acetic acid- 1.0% HF. The overflush fluid was
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NHiC1. The (reatmcnts were staged into two to three scqucnccs
separated by foamed NH,CI diversion stages. The WCII was
flowed back as soon as the displacement fluid was pumped, and
samples were obtained over the next 24 hours.
The pH of the returned fluids ranged from 3,9 to 4.4, wi(h
the pH increasing the longcr[hc fluid rcrnaincd in [hc forma[ion.
This pHbchavior isconsistcn[ with thcslow, continued rcac[ion
ofthc Iluids with :]lulllino-silic:itcs (the tcr(iary reaction of HF
acid) and (I1c po[en (ial mixing of the spent acid fluids with
slightly alkaline forrna(ion brirrcs.
The total organic carbon (TOC) and chloride contents
helped provide insigb[ into [he mixin: of the various trcatmcn[
stages. The acetic acid and acetic-HF sta:cs contained no
chlorides and very high TOC corwcn(rations, whi]c the NH,CI
stages crrntnincd rnodcra[c chloride ccmccntrations and Ii[(lc or
no TOC. Similar values of TOC and Cl were obtained for each
sample, which su:gcs[cd that [he mixing of all stimulation
stages and small amounts of formation brine was nearly uni-
form, This result is not unreasonable, since the trca[mcnts were
divcr[cd. and the IO[a[ volumes of’ [be twatmen[s were quite
small (2,700” (o 4,000 :al). Frt)ln the TOC and Cl- data, the
rclurncd samples from tbcsc lrcalmcn(s consisted of 25 to 50(%
spcn[ acetic-HF acid.
The irc~ncon(cnt of [bc samples ranged f’rom2000 [O5400”
nl& \\hich incrcascd [hc Ion$cr Ihc Huid resided in (I)c
f(mnation. Mos( of (1wiron appeared to be m Fe:+ in !hat i~did
not prccipita[c from solution until cxtcndcd exposure to air. The
silicon c[mtco[s were low’, as expected, approximately 150 10
200”nlu/L,
. However, the aluminum contents were a]so Very I(w
( 100 I()530 m@ L), which suggested almost complclc precipit:i-
tlon c)fa]uminum fluoride reaction products In the spcn[ acctic-
HF. Based on the fluid design and dilution, return samples
should have contained (([ /(’(/.s/?500” mg/L of Al basal on the
assumption of 2.5 F/Al and no te]tiary rcac( ion, Values CXCCCJ
ing 5000 mg/L were anticipated. l’JFNMR spcc[roscopy verified
that the samples contained no silicon fluorides and only small
amounts of aluminum lluoridcs, with F/Al ratios of 2,5 to 2.8.
The rc[urns anulyscs supported the concerns of aluminum
fluoride precipitation in organic-HF systems and the need for an
improved systcm,
Formic-HF Treatment and Returns Analysis. In Columbia,
a formic-HF acidizing lrca[ment was conducted (o remove
damage caused during drilling. Flowback analyses were con-
ducted to better understand the fluid system and optimize future
trealmcnts, Return samples revealed that the major problcm and
damage was caused by whole mud. HF fluids are only effective
in removing HF-solubledamage, such asdrillingmud filter cake
and solids, not whole mud. The formic-HF fluid did still react
with formation minerals and drilling mud solids, but overall, the
treatment was not effective. Analysis of the flowback samples
still provided much information about the formic-HF reactions.
SPE 36907 C.E. SHUCHART,
Results from the analyses were very similar to those from
the acetic-HF treatments previously described. The pH of the
samples was 3.0 to 4.2 with very high iron contents. These acid
return samples were definitely good. Once again, the only
silicon in solution was soluble silica gel, 60 to 150 mg/L. The
aluminum concentrations were higher than observed in acetic-
HF returned fluids, but this result might be expected because of
the higher acidity of formic acid vs. acetic acid. However, the
300 to 1400 mg/L of aluminum was still much Iowcr than
anticipated, Again, significant precipitation of aluminum fluo-
rides was suspected, The returns analysis of acetic-HF and
formic-HF treatments clearly showed [hat serious precipitation
problems were associated with [he currently available organic-
HF fluid systems.
Understanding the Aluminum Precipitation. The chemistry
of HCI-HF fluid systems has recently been studied in much
detail.’~” The usc of “F NMR Spectroscopy has been essential
for determining the actual chemical species in solution and (he
distribution of fluoride among those species. This current study
hits expanded the chemical knowledge to organic-HF fluid
systems,
A key piece of information is the equilibrium of HCI,
aluminum fluorides, and silicon fluorides during the primary
and sccondwy reactions of HF acid wi[h alumino-silicates. The
fluoride distribution strongly depends on the acid concentration
as shown in Fig. 2 (Page 7). For example, in 13,5% HC1-1 .57c
HF, a F/Al ratio of 1,3 is typically observed during these
reactions, whereas in 7.5% HC1-1.57r HF, the F/Al ratio is
approximately 1.6. The F/Al ratio approaches 3.0 as the pH of
(hc fluid increases. This is exactly where organic-HF fluids
come into (he picture and why acetic-HF and formic-HF fluids
precipitated aluminum fluorides. The dominant aluminum fluo-
ride species at this F/Al ratio is AIFJ, which has very poor
so]ubility and would be expcctcd to precipitate almost as soon
as it is formed,
IYF NMR Spectroscopy of laboratory-spent m-ganic-HF
fluids and the field-treatment acetic-HF and formic-HF return
samples described above, has verified this high F/Al ratio.
Consequently, only low levels of aluminum can bc maintained
in solution with the currently available fluids. Alternate sys-
tems, such as low HF concentrations ,5 buffer-regulated sys-
tems,h” and alternating stages of fluoride salts and acid’? only
address the HF reactivity. They do not address the HF reaction
products, or more specifically, the F/Al ratio and eventual
precipitation of AlF,.
The first attempt to overcome the problem of AIFj precipi-
tation was to decrease the F/Al ratio during the HF reactions by
adding HCI to the organic acid systems. At Icast 3% HCI was
required for this method to prevent aluminum precipitation
hascd on the laboratory spending tests. However, the advantages
of using an organic-HF system were compromised. Above
approximately 200”F, corrosion control became much more
difficult in the mixcdorganic acid-HF-HCl systems. In addition,
HC1-sensitive minerals decomposed significantly more in these
329
R.D. GDANSKI 3
combination fluids than they did when HCI was not present.
More important is the fact that consumption of at least a portion
of the HCI by decomposing minerals, ion exchange, or dissolu-
tion of carbonates is inevitable. The lower acidity would lead to
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higher pH values, higher F/Al ratios, and subsequent precipita-
tion of AIFJ. In these cases, the precipitation may occur a li[tle
farther from the wellbore, but could still impair ultimate produc-
tion. Even with a detailed description of the mineralogy, these
reactions would be very difficult to predict,
The second approach was to expand beyond the use of acetic
and formic acids and investigate the use of alternative acid
systems. The basis of the new sys[cm would be to prevent AIF1
precipitation while maintaining all the advantages ofacetic-HF
and formic-HF fluid systems. Ion exchange and compatibility
with multivalent ions, such as Fe, Ca, and Mg, would also be
required. The understanding of these requirements and the HF
reaction processes has led to [he development of two new
proprietary systems.
The key components of the ncw systems, which will be
referred to as new acid systems I (NAS-1) and H (NAS-H), are
ncw organic acids that can coordinate aluminum fluoride com-
plcxcs and buffer the spent HF fluids. The coordination of
aluminum fluoride complexes alters the aluminum-fluoride
equilibria, which minimizes the amount of AIFj in solution and
forces the HF reactions to lower F/Al ratios. The cffectivcncss
of these new systems will bc emphasized in the laboratory
results, flowback analyses, and [he production results discussed
in following paragraphs.
Acid Sensitivity Reactions. Several tests were conducted for
determining (he acid sensitivity ofvarious minerals, The miner-
als were exposed to the acids for I to 2 hours at 200”F. The
solutions were examined with ICPand the solids were examined
with X-ray diffraction to determine the amount of dissolution
and the percentage of residual mineral remaining after acid
exposure. Acids tested included HCI at various concentrations,
formic acid, acetic acid, and NAS-11 without HF. In Test 1, the
stilhite, a zeolite, was tested at 200°F for I hour, In Test 2, core
material from Japan was tested at 200°F for 2 hours. The acid-
scnsitive mineral in the core material was cocrensite, a chlorite-
smectite.
Table 1 (Page 7) shows results from the acid-sensitivity
tests. In both cases, 15% HCl totally destroyed the mineral of
interest. Lower HCI concentrations were less aggressive, but
significant decomposition still occurred. Even with 1.7% HCI,
the amount of HCI required to protonate ABF to make 1.5% HF,
227c of the corrensitc still decomposed within 2 hours. Both
stilbite and corrensite showed good stability in the organic acids
(formic, acetic), and NAS-11 without HF.
Laboratory Reactions of Organic-HF Fluids. To better
understand the results of the returns analyses from the acetic-HF
and formic-HF treatments, batch reactions with kaolinite at
75°F (24°C) and 200”F (93”C) were conducted as a means of
studying the reactivity and potential precipitation of these
fluids. To ensure adequate fresh clay for the fluids to react, 25
4 IMPROVED SUCCESS IN ACID STIMULATIONS
g of kaolinite was irdded to 100 mL of acid. Tests with lower
clay/acid ratios showed that the secondary and tertiary reactions
were inhibited by the filming effect of silica gel in these static
reactivity tests, and complete reactions could not be obtained.
Returns analyses of flowbacks from actual treatments have
shown that above approximately 100”F (38”C), the secondary
reaction goes to completion within the timeframe ofatreatmerm
Various fluids were tested, including HCI-HF, acetic-HF, for-
mic-HF, mixed systems, and NAS-I and NAS-11. Only a few of
the tests will be presented and discussed in this document. The
fluids and clay were mixed at room temperature and heated to
the required test temperature. Samples were removed at various
time intervals, filtered hot, and analyzed by ICP for Si and Al.
19FNMR spectroscopy was conducted on all samples to deter-
mine the fluoride distribution and calculate the percentage of
fluoride precipitated.
Low-temperature reactions were initially conducted with
fluids, and results are shown in Table 2 (Page 7). At 75°F
(24”C), the secondary reaction is very slow, and the silicon and
aluminum concentrations should be approximately the same
when reacting with a clay with a Si/Al ratio of 1.0, such as
kaolinite, Al,Si,O,( OH),.
Both formic-HF fluids (Test 1) and acetic-HF fluids (Test
2) showed precipitation of aluminum fluoride complexes and
volubility of silicon fluoride complexes. Precipitation was even
observed at 1 hour of reaction when little or no secondary
reaction had occurred. The precipitate was identified as AIFj.
For the acetic-HF fluids, most of the fluoride precipitated with
only 238 mg/L of Al in solution after 1 hour of reaction. At
longer times, the secondary reaction proceeded, and precipita-
tion continued to occur in both fluid systems. This behavior is
evident by the decreasing silicon concentrations and the rela-
tively constant or decreasing aluminum concentrations. Test 3
was conducted with [he NAS-11 fluid system. In this case,
aluminum fluoride precipitation was minimized. At longer
times, precipitation was reduced to zero because the system
could coordinate aluminum fluoride complexes as the HF
reactions proceeded. As the data show, the secondary reaction
is very slow at this temperature.
At 200°F (93”C), the secondary reaction will go to comple-
tion relatively quickly; therefore, the HF concentrations were
reduced to 1.09’o as a means of minimizing the aluminum
precipitation. Testing was conducted with fluids prepared with
ammonium bifluoride (ABF) as well as with ammonium fluo-
ride (AF). Results are shown in Table 3 (Page 7). Once again,
almost complete precipitation of aluminum fluorides occurred
as the acetic-HF fluids (Tests 5 and9) reacted with the kaolinite.
The secondary reaction went to completion (as noted by the low
silicon content), and the aluminum concentration should have
approached or exceeded 5000 to 10000 mg/L. However, the
aluminum concentration was less than 700 mgl. in Test 5 and
only 500mg/L in Test 9. In general, solutions prepared with AF
were somewhat more susceptible to precipitation as the con-
sumption of acid to protonate the fluoride salt gave a slightly
330
WITH A NEW ORGANIC-HF SYSTEM SPE 36907
higher pH system and subsequently a higher F/Al ratio in
solution. Forrnic-HF fluids (Tests 4 and 8) performed substan-
tially better, but 2170 to 29% fluoride precipitation was also
observed in these tests.
Both NAS-I and NAS-11 fluids completely prevented alu-
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minum fluoride precipitation. At 1.5 hours of reaction, the
aluminum concentrations exceeded 5000 mglf+ and when the
reactions were allowed [o proceed over 24 hours, aluminum
concentrations increased more than 10,000 mg/L, since these
improved fluids dissolved more ahrmino-silicates without any
aluminum fluoride precipitation.
Laboratory Flow Tests with Organic-HF Fluids. Several
flow tests determined the rate and severity of AIFj precipitation
from acetic-HF and formic-HF[reatments and [he precipitation’s
impact on fluid flow. Two comparative tests were conducted at
150°F witha 3-ftcolumn packed with amixtureof90% sand and
10% bentonite clay. The first system tested consisted of 10’-ZO
acetic acid followed by 10% acetic acid- 17’oHF. Both fluids
contained 5% NHqCl for ion exchange and the prevention of
freshwater shock. Upon flow of the HF stage into the column,
permeability increased for the first 4 in. of the core, but an
immediate permeability decline occurred between the 4- and 6-
in. pressure ports and between the 6 and 12-in. pressure ports.
Fig. 3a (Page 8) shows the permeability results, with the HF
fluid response being from 2.1 pore volumes (PV) to about 3.2
PV. The overall permeability of the column increased from
about 20 md to 25 md. Fluid analyses determined that the
effluent was fluoride-deficient. The F/Al ratio in solution was
above 2.5, and approximately 30% of the fluoride had precipi-
tated as AIF1. These results suggest that the AIFj precipitation
occurs very quickly and during the primary reaction of the HF
acid. As the secondary reaction proceeds, more AIFj precipi-
tates as the fluosilicic acid dissolves more of the aluminum
from the clay minerals.
The test procedure was then repeated with NAS-11 fluid.
Again, permeability increased in the first 4 in., but it also
increased for the 4- to 6-in. sections and later increased in the 6-
to 12-in. section. No damaging precipitation had occurred. The
effluent analysis showed high aluminum concentrations and a
F/Al ratio of about 2.2. So even in flow, the NAS-11 system
prevented aluminum fluoride complexes from precipitating.
The permeability results shown in Fig. 3b (Page 8) show the HF
fluid response being from 2.1 to approximately 3.2 PV. The
overall permeability of the column increased from about 20 to
35 md.
Three additional comparative tests were conducted at
250°F in 12-in. Berea cores. The fluids tested were 10?ZO acetic
acid -1 % HF, NAS-1, and NAS-H. The effluents were analyzed
for aluminum concentrations. Fig. 4 (Page 8) shows results for
the three tests. In these tests, a small amount of carbonate was
still present as the spent fluids exited the cores. Even so, the
NAS systems clearly held the aluminum in solution while the
acetic/HF fluid lost 50% of the aluminum to precipitation
within the core.
SPE 36907 C.E. SHUCHART,
New Treatment Designs, Returns Analyses, and Production
Results (Case Histories). Gur’fCoast NAS-11 Treatment and
Returns Analyses. In the Gulf of Mexico, a well was experienc-
ingcontinued decline in production. X-ray analysis of formation
core revealed trace to 570 analcime scattered throughout the
zone of interest. Analcime is from a group of minerals known as
zeolites, Zeolites have a cage-like structure that makes them
susceptible [oahighdegreeof ioncxchangc and HCI sensitivity.
Even at room temperature, HCl will decompose analcimc,
which leaves a silica gel mass that can greatly reduce permeabil-
ity If The forma[ion also contained significant illite and illite-
smectite, both of which will also decompose in HCI at the BHT
of 206°F (Fig 1, Page 7). Because of the presence of significant
zeolites and other HC1-sensitive minerals in these formations,
organic acids were recommended in place of HC1-based fluids.
In 1994, a 97c formic acid- 1.5% HF treatment was con-
ducted. Production increased three-fold, but within 3 months,
production had dropped to below prestimulation levels. In early
1996, another stimulation treatment was attemptccf. Since HCl-
based fluids could not be used, and the previous formic-HF
treatment was unsuccessful, a new HF system was ncccssary.
Based on the knowledge obtained through the study of organic
acid systems, a NAS-11 fluid system was proposed A tubing
wash was conducted with HCI to remove iron scales since
organic acids do not efficiently dissolve iron oxides. The fluid
was gas-lifted back to surface to prevent it from entering the
formation and causing damage. The formation preflush con-
sisted of 57o NH~Cl to satisfy the high ion exchange capacity of
the formation followed by IOYCacetic acid-5% NHiCl to remove
carbonates and continue ion exchange.
The stimulation fluid was NAS-11 followed by 5% NH,CI
overflush anddisplaccment. The NAS-11 fluid was chosen as the
main acid stage because it would prevent zeolite and clay
decomposition associated with HCI fluids and it would avoid
secondary precipitation associated with acetic-HF and formic-
HF fluids. NAS-11 also has ion-exchanging capabilities equal to
5% NH,CI.
Based on injection tests and initial tubing pressures before
the treatment, a rate of 1.25 bbl/min resulted in a tubing pressure
of 500 to 570 psi. The final tubing pressure after the entire
treatment had entered the formation had declined to 233 psi at
a higher pump rate of 1.75 bbl/min. The NAS-11 treatment
removed substantial skin damage.
After the treatment, flowback samples were collected and
analyzed to determine the reactivity of the NAS-11 fluid and its
capacity to prevent aluminum fluoride precipitation. The pH
values of most of the samples were in a narrow range of 3.35 to
3.86, which was slightly lower than the ranges observed in
samples re[urned after acetic-HF and formic-HF treatments.
The samples also contained 4000 to 8000 mg/L of Fe, so it was
easy to determine that this was an excellent set of acid returns.
The extent of dilution of the spent NAS-11 fluids was deter-
mined with a combination of the Cl- , NHJ+, and total organic
331
R.D, GDANSKI 5
carbon (TOC) analyses. The samples consisted of approxi-
mately equal amounts of spent NAS-11 and preflush fluids with
only minimal dilution with formation brine. Figs. 5 and6 (Page
8) show results of ionic analyses.
The key to understanding the system is the ICP analyses of
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the samples, in particular the Si and Al concentrations. ‘9FNMR
Spectroscopy also provided the fluoride distribution among the
Si and Al. Low silicon levels, 100 to 200 m#L, were observed
in all samples, but no silicon fluorides were observed. This result
signifies that the secondary reaction of HF went to completion,
as expected at this temperature, and the residual silicon content
was soluble silica gel. The aluminum concentrations were 1200
to 4400 mg/L, as predicted based on the HF reactions, treatment
design, and mixing. These values are similar to those observed
in return samples from 970 HCL 17CHFand 7.57o HC1-I .57c HF
treatments;’~ tbc values are much higher than those observed in
returns following acetic-HF and formic-HF [reatments, For an
undiluted NAS-11 fluid system, about 6500 to 10000 mg/L of Al
would be predicted. Based on the fluid design for this treatment,
at Icast 5070 dilution of the NAS-11 fluid (2,000 gal) would be
cxpcctcd from mixing with the designed preflush fluids (2,500
gal total). Additional dilution likely occurred with the overflush
and formation waters. As previously mentioned, [his dcgrcc of
dilution was also supported by the TOC, Cl-, and NHd+concen-
trations observed in the samples.
Table 4 (Page 7) compares
Al concentrations, pH, and
F/A 1 ratios of the various The F/Al ratio in the
treatments.
NAS-11 returns ranged from 18 to 2.2. The lower F/Al ratio
compared to acetic-HF and formic-HF fluids reveals a more
efficient use of HF in the NAS-11 fluids. In addi[ion, the F/Al
ratios decreased the longer the fluids were in the formation,
corresponding with a subsequent increase in pH. The tertiary
reaction of HF continues throughout the time the fluids are in
contact with the formation, which increases the aluminum
concentration, consumes acid, and increases the concerns of
precipitation of aluminum fluorides, This behavior emphasizes
the need to recover fluids as soon as possible from any HF
acidizing treatment. The NAS-11 system successfully pre-
vented the precipitation of aluminum fluoride complexes in all
acetic-HF and formic-HF returns previously analyzed. Be-
cause it acts as a buffer and can chelate aluminum fluoride
complexes, the NAS-11 system actually becomes more effec-
tive in preventing aluminum precipitation over time.
Production results following the NAS-11 treatment were
excellent. Flush production following the treatment peaked at an
eight-fold increase. Currently, 4 months later, the production
and pressures are stabilized showing a three-fold incrcasc in
production .Fig. 7 (Page 8) shows the overall production profile
for the well; the formic-HF and NAS-11 treatments are labeled.
NAS-I Treatments in Thaifiznd. As discussed earlier,
acetic-HF treatments in Thailand resulted in precipitation of
aluminum fluorides within the formation. Introduced in 1996,
6 IMPROVED SUCCESS IN ACID STIMULATIONS WITH A NEW ORGANIC-HF SYSTEM SPE 36907

NAS-I avoids these problems and improves stimulation results. 3, Norton, S.J. and Smith, CD.: “Sand Control Installation and

The particular well in question was completed in 1994 at an Mechanical Design,” paper OTC 7886 presented at the 1995
Annual Offshore Technology Conference, Houston, May 1-4.
initial production of 1,000 B/D. By 1995, production had
4. Van Domelen, M. S,, Ford, W. G. F., and Chiu, T. J.: “An Acid
declined to 300 B/D and slowly died because of the declining
Expert System for Matrix Acidizing Treatment Design,” paper
rate and the water in the wellbore. Before the acid treatment,

Downloaded from http://onepetro.org/SPEEURO/proceedings-pdf/96EUROPEC/All-96EUROPEC/SPE-36907-MS/1954143/spe-36907-ms.pdf/1 by Halliburton Energy Services Group user on 08 August 2021
SPE 24779 presented at the 1992 SPE Annual Technical Confer-
the well was tested under gas lift and produced 300 B/D. The ence and Exhibition, Washington, DC, Ocl. 4-7.
treatment design consisted of multiple treatments selectively 5. Wehunt, C. D., Van Arsdalc, H,, Warner, J, L,, and Ali, S, A,:
placed with coiled tubing. The treatment fluids consisted of “Laboratory Acidization of an Eolian Sandstone at 380”F,” paper
10% acetic acid-5% NHICl preflush and an NHqCl overflush SPE 25211 presented at the 1993 SPE [nterna[ional Symposium
with NAS-I as the main stimulation fluid. Treatments were on Oilfield Chemistry, New Orleans, Mar. 2-5.

diverted with two to three stages of foamed NH,CI. Atotal of 6, Abrams, A,, Lybarger, J. H,, Richardson, EA., and Neasham,
J, W.: “The Development and Application of a High-pH Acid
1,500 bbl of fluids was pumped over 1,500 ft of gross interval
Stimulation System fora Deep Mississippi Gas Well,” paper SPE
in four separate treatments.
7565 presented at the 1978 SPE Annual Technical Conference
Production results following the treatments were excellent.
and Exhibition, Houston, Oct. 1-3, 1978,
After 3 days of well cleanup, the well was flowing naturally at 7. Jacobs, I. C,: “Chemical Systems for the Control of Asphaltene
300 B/D. After gas lift was installed, the rate consistently Sludge During Oilwell Acidizing Treatments,” paper SPE 18475
improved over 45 days to reach 900 B/D. Water cut was presented at the 1989 SPE International Symposium on Oilfield
unchanged at 3570. Chemistry, Houston, Feb. 8-10.
8. Lamb, W.J. and Kunze, K.R.: “Method for Acidizing Siliceous

Conclusions Formations,” U.. SPatent No. 4,648,456, March 10, 1987,

9. Gdanski, RD.: “Fractional Pore Volume Acidizing Flow Experi-
●
Inasmuch as clays are concerned, organic acids act like
ments,” paper SPE 30100 presented at the 1995 SPE European
fresh water. Organic-based systems used in sandstone
Formation Damage Control Symposium, The Hague, May 15-16.
formations must be capable of ion-exchange and must
10. Simon, DE. and Van Domelen, MS.: “Stability of Clay Minerals
prevent clay swelling. in Acid,” paper SPE 20624 presented at the 1990 SPE Formation
●
Analyses of flowbacks following HF acidizing treatments Damage Control Symposium, Lafayette, Feb. 22-23,
can help determine the extent of HF reactions and the Il. G(fanski, R. D.: “Kinetics of the Tertiary Reaction of HF on
precipitation of reaction products. Alumino-Silicates,” paper SPE 31076 presented at the SPE
✎
As shown by batch reactivity tests, core flow tests, and Formation Damage Symposium, Lafayette, Feb. 14-15, 1996.

returns analyses from actual treatments, most of the alumi- 12. Shuchart, C,E. and Buster, D. C.: “Determination of the Chemis-

num dissolved by acetic-HF and formic-HF fluids precipi- try of HF Acidizing with the Use of lYFNMR Spectroscopy, ”
paper SPE 28975 presented at the 1995 SPE International Sym-
tates. The pH of the fluids determines [hat a high F/Al ratio
posium on Oilfield Chemistry, San An[onio, Feb. 14-17.
is maintained in solution with subsequent precipitation of Shuchart, C, E.: “HF Acidizing Returns Analyses Provide Unrler-
13.
AIF,, standing of HF Reactions,” paper SPE 30099 presented at the
✎
Flow testing shows that AIFj precipitation is quick and 1995 SPE European Formation Damage Control Symposium,
could cause significant near-wellbore damage. The Hague, May 15-16.
✎
New acid systems developed can overcome precipitation 14, Gdanski, R.D, and Shuchart, C, E,: “Newly Discovered Equilib-
problems while maintaining all the advantages of an rium Control HF Stoichiomctry,” YPT (Feb. 1996) 145-149.

organic-HF fluid system. These unique systems can alter 15. Hall, B. E.: “A New Technique for Generating In-Situ Hydrofluo-
ric Acid for Deep Clay Damage Removal, ” JPT (Sept. 1978)
[he aluminum fluoride equilibria, thereby minimizing the
1220.
amount of AIF1 in solution and preventing its precipitation.
16. Underdown, DR., Hickey, J.J., and Kalra, SK.: “Acidization of
✎
Field results from treatments with the new acid systems
Analcime-Cemented Saridstone, Gulf of Mexico,” paper SPE
have been very successful. In one case, a forrnic-HF 20624 presented at the 1990 SPE Annual Technical Conference
treatment failed to give sustained production increases and Exhibition, New Orleans, Sept. 23-26.
while the NAS-11 treatment in the same well resulted a
three-fold production increase that lasted for more than 4 S1 Metric Conversion Factors
months. ft x 3.048* E-01 =m
‘F (°F-32)/l .8 = ‘C
References
1. Van Domelen, MS. and Jennings, A.R.: “Alternate Acid Blends
for HTHP Applications,” paper SPE 30419 presented at Lhe 1995
Offshore Europe Conference, Aberdeen, Sept. 5-8.
2. Dill, R.W. and Keeney, B. R.: “Optimizing HC1-Formic Acid
Mixtures for High Temperature Stimulation,” paper SPE 7567
presented at the 1978 SPE Annual Technical Conference and
Exhibition, Houston, Oct. 1-3.

332
SPE 36907 C.E. SHUCHART, R.D. GDANSKI 7

Table l—Acid Stability in Various Acids at 200”F Table 4—Summary of Returns Analyses from Field
Treatments with Various Fluid Systems
Test 1 Tesl 2
Fluid Residual Residual Fluid PH Al (mg/L) F/Al ratio
Stilbite (“A) Correnaife (%) 90/0 HCI.1% IIF 2,6to 3.0 1000 to 5000 0.5 to 0,8

Downloaded from http://onepetro.org/SPEEURO/proceedings-pdf/96EUROPEC/All-96EUROPEC/SPE-36907-MS/1954143/spe-36907-ms.pdf/1 by Halliburton Energy Services Group user on 08 August 2021
15% HCI 1.4 0 7.5% HCI-1 .5% HF 2,8 to 3.2 1000 to 6200 1.2tol,6
8.10/. HCI 20 formic-HF 35 to 4.0 120to 1440 2 3to 2.6
5.o% HCI 28 . .. acetic-HF 3.9t04.4 i 60 to 560 2.5 to 2.8
3.30/. HCI ... 53 NAS-11 34 to 3.9 1200 to 4400 1.8 to 2.2
1.7% HCI ... 78
10°/0 formic .. 94
10°/0acetic 98 99
VAS-11,no HF 89 89

Slilbde

Table 2—Reactions of Organic-HF Acids Kaalin ite

with Kaolinite at 75° F f

FIuori de
Al Si 60
Test Fluid
‘ours (mg/L) (m@L) Prec;$tio”

1 t OOAform!c.1 .50/. HF 1 2230 2480 18

a
{w!th ABF) 5 2772 2514 11

18 2651 1728 31
Bentonfle
2 10O/.acetic.1 ,5% HF 1 238 2036 50
o 1 1
(with ABF) 5 491 2197 43
ioo Zoo 300 400
18 519 1772 53 lempc+rstoreF
3 NAS-11 1 26U6 2661 9
Fig. l—Acid instability rating for various alumino-silicates in HCL
(with ABF) 6 2609 2831 3
25 3611 2630 0
3.0

1 +
+
++

Tsble 3—Reactions
with Kaolinite
of Organic-HF
at 200” F
Acids
1I .*+
Fluoride .:20

1
A
Al SI p
Test Fluid
‘ours (mg/L) (mg/L) f’re=’$:st’”” #A
4 10% formic-1.0% HF 1.5 4278 240 21
ii
?
A

L
i 5
I(wlth ABF)
I1O% acetic-l.OO/~ HF
~ 3.0
I 1I .5
1 4685
677
I 195
277
I 23
79 I
l-l I
.W7 I 1 QA I FWr 1

I 1
i
u
I I
I 1
I i

Fig. 2—HCI dependence of efuminum fluoride distribution during

the secondary reaction.

333
a IMPROVED SUCCESS IN ACID STIMULATIONS WITH A NEW ORGANIC-HF SYSTEM SPE 36907

u
8000 40s00
—M *Fo
-61 -N
-K - m
60W zomo

Downloaded from http://onepetro.org/SPEEURO/proceedings-pdf/96EUROPEC/All-96EUROPEC/SPE-36907-MS/1954143/spe-36907-ms.pdf/1 by Halliburton Energy Services Group user on 08 August 2021
2om I omo

o 0
1 2 3 4 5 6 7 n 9 10

Sample Number
o 2 4 6
Pore Volumes
Fig. 5—ICP analysis of returns following NAS-11field treatment.
(a)

4 80000
~TOC ---Cl- eNN4+ +PM

3 Wooo

1 2WIO0

0 o
o 2 4 6
1 2 3 4 5 6 7 8 9 10

Pore Volumes Sample Number

(b) Fig. 6—Solution analysea of returna after NAS-11field treatment.

Fig. 3—Permeability reeponses from flow teste with 10% acetic

acid-1 % HF (top) and NAS-11(bottom).
-7

-6
-Ed

-5

-4

-3

-2

-1

fonnlc.NF
04 10
0 5 10 15 20 25

1 1 --&- NAS4 Months

+- NAS41
om Fig. 7—Normalized oil production for well acidized with formic HF
I 1
I I
I T
1 followed by NAS-11.
Zm m 600 8W
Volume of Effluent

Fig. 4--Aluminum concentrations of effluent from organic-HFflow

tests.

334