SPE 37281

Society of Petroleum Engineers

Chemical Study of Organic-HF Blends Leads to Improved Fluids
Chris E. Shuchart, SPE, Halliburton Energy Services
Copyright 1997, Society of Petroleum Engineers [nco
This paper was prepared for presentation at the 1997 SPE [nternationa[ Symposium on Oilfield
Chemistry held in Houston, Texas, February 1821.
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Abstract
Organic-HF blends have successfully stimulated sandstone for-
mations with corrosion concerns, HCI-sensitive mineralogy,
and/orcrude oil incompatibilities, three conditions in which the
use of typical HCI-based fluids can result in severe damage.
Despite the success of such blends, very little work has been
published on the reactivity of organic-HF fluids with alumino-
silicates. Recent work on the chemistry ofHF acidizing focused
on HCI-HF systems. [ This paper discusses the chemistry of
organic-HF systems as determined by laboratory reactivity
tests, 19F nuclear magnetic resonance (NMR) studies, and or-
ganic-HF flowback analyses.
Laboratory reactivity testing revealed severe precipitation
problems associated with the currently used acetic-HF and
formic-HF systems. Flowback analyses after organic-HF field
treatments fully supported the laboratory results. A 19F NMR
spectroscopic study of the fluoride distribution throughout the
primary, secondary, and tertiary reactions helped explain the
precipitation and when it might occur. From this work, new
organic-HF systems were developed that prevent precipitation
while maintaining all the advantages associated with the acetic-
HF and formic-HF fluids. The retarded nature of these systems
is discussed in this paper.
Introduction
Common problems associated with HCI-based fluids include
high reactivity,2 high corrosivity,3 sludging tendencies when
fluids contact crude oils,4 and the HCI sensitivity of clay,
minerals and zeolites,S These problems are aggravated at higher
temperatures. Organic acids, such as acetic acid, formic acid,
References at the end of the paper.
675
and combinations have overcome many of these problems. The
recent realization that organic acids act like fresh water has led
to the addition of 5% NH
4
CI to organic acids used in formations
containing clays and zeolites that are capable of ion exchange
and/or susceptible to swelling or fines migration."
Acetic-HF and formic- HF fluids were developed because of
the problems associated with HCI-based HF fluids, However,
very few studies have investigated the chemistry of these
systems, Recently, we discovered that HCI-HF fluids obey a
chemical equilibrium during the primary and secondary reac-
tions,7 As a result, the fluoride distribution, and in particular the
F/AI ratio, depends upon the acid (H+) concentration. For
example, a solution containing 13.5% HCI-1.5% HF reacted
with alumino-silicates will have a F/AI ratio of approximately
1,3 during the primary and secondary reactions. However, at the
low acid (H+) concentrations of organic acids (pH 1 through 4),
the FI Al ratio of organic-HF fluids during these reactions would
be 2,5 to 3.0. The dominant aluminum fluoride species in spent
organic-HF solutions would be AlF/ and AIF
3
, The acid depen-
dence on the F/Si ratio is only slight. In HCI-based fluids, the
F/Si ratio is considered to be constant at 5.0; the dominant
species is HSiF
s
' In organic-HF systems, the F/Si ratio is about
5.5, and the dominant species are HoSiFo and HSiF
s
,l Based on
the fluoride distribution, the prirri'ary reaction (Eq. 1) and
secondary reaction (Eq. 2) for organic-HF fluids can be written
in the general terms below.
HF + M - Al- Si H
2
SiF
6
+ HSiF
s
+ AIF;+ + AlF3 +M+ ................................................. (l)
H
2
SiFr, + HSiF
s
+ M - Al- Si + H+ Si0
2
Hp
+ A IF; + + AlF3 + M+ ................................................. (2)
As reported in a previous paper,s flowback analyses from
acetic-HF and formic-HF field treatments showed that alumi-
num fluoride precipitation had occurred, Laboratory spending
tests and flow tests showed that AIF3 precipitated from the
acetic-HF and formic-HF fluids quickly upon spending because
of the high F/AI ratio and the poor solubility of AlF
3
, Two new
2 CHEMICAL STUDY OF ORGANIC-HF BLENDS LEADS TO IMPROVED FLUIDS SPE 37281
acid systems were developed to prevent precIpItation. This
paper presents additional details concerning the chemistry of the
acetic-HF and formic-HF systems as well as the new acid
systems.
Results and Discussion
Acid-Returns Analyses. Analyses offlowbacks after acidizing
treatments highlighted the precipitation problems associated
with acetic-HF and formic-HF fluids. Flowbacks from several
7.5% acetic acid- I.5% HF acid treatments in Thailand showed
low silicon and aluminum concentrations, high F/AI ratios, and
pH values of approximately 4. BHSTs were approximately
200F. Silicon levels of 50 to 200 mg/L revealed that the
secondary reaction went to completion, as would be expected in
HCI-HF fluids. 19F NMR spectroscopy of the samples showed
that no silicon fluorides remained in solution. The low alumi-
num concentrations (160 to 560 mg/L), and subsequently low
fluoride levels indicated aluminum fluoride precipitation in the
formation during the treatments. After accounting for dilution
with non-HFfluid stages and formation brine, we calculated that
at least 75 to 95% of the fluoride had precipitated. The F/AI
ratios in the flow backs were 2.5 to 2.8.
Flowback analyses from 9% formic-3% HF treatments in
Colombia showed similar results. With 3% HF, much higher
aluminum concentrations would be expected without precipita-
tion. However, only 120 to 1440 mg/L of aluminum were
observed in solution. The F/AI ratios and pH values were only
slightly lower than those observed in the acetic-HF returns.
Again, over 75% of the fluoride had precipitated within the
matrix of the formation.
New Acid Systems-Laboratory Spending Tests. To prevent
the aluminum fluoride precipitation, we investigated the use of
alternative acid systems. The purpose of the new system would
be to prevent AIF3 precipitation while maintaining all the
advantages of acetic-HF and formic-HF fluid systems. Ion-
exchanging ability and compatibility with multivalent ions,
such as Fe, Ca, and Mg, would also be required. The understand-
ing of these requirements and the HF reaction processes led to
the development of new proprietary systems.
The key components of the new systems, which will be
referred to as "new acid systems" (NAS), are new organic acids
that can coordinate aluminum fluoride complexes and buffer the
spent HF fluids. The coordination of aluminum fluoride com-
plexes helps alter the aluminum-fluoride equilibria, which mini-
mizes the amount of AIF3 in solution and forces the HF reactions
to lower FI Al ratios.
Batch reactions with kaolinite at 200F were conducted as
a means of studying the precipitation of aluminum fluoride
complexes from acetic-HF and formic-HF fluids and develop-
ing new organic acid systems. Before tests were conducted,
25 g of kaolinite was added to 100 mL of acid to ensure adequate
fresh clay for the fluids to react. Various fluids were tested,
including HCI-HF, acetic-HF, formic-HF, and the two new acid
676
systems, NAS-I and NAS-II. The fluids and clay were mixed at
room temperature and heated to the required test temperature.
Samples were removed at various time intervals, were filtered
hot, and then analyzed by inductively coupled plasma (ICP) for
Si and AI. 19F NMR Spectroscopy was conducted on all samples
as a means of determining the fluoride distribution and calculat-
ing the percentage of precipitated fluoride.
Testing was conducted with fluids prepared with either
ammonium bifluoride (ABF) or ammonium fluoride (AF).
Table 1 shows representative results of fluids prepared with
ABF. Almost complete precipitation of aluminum fluorides
occurred in the reaction of kaolinite with acetic-HF fluids (Test
1). The secondary reaction had nearly gone to completion (as
noted by the low silicon content) and the aluminum concentra-
tion was expected to approach or exceed 5000 mg/L. However,
the aluminum concentration was only 677 mg/L after 1.5 hours,
giving 79% precipitation of the fluoride. Continued precipita-
tion and lower aluminum concentrations were noted at longer
reaction times. Solutions prepared with AF were somewhat
more susceptible to precipitation because the consumption of
acid to protonate the fluoride salt gave a slightly higher pH
system and subsequently resulted in a higher F/AI ratio in
solution. Formic-HF fluids (Test 2) performed substantially
better, but 2 I % of the fluoride precipitated. The formic-HF
returns analyses described previously, where 75% or more ofthe
fluorides precipitated, suggest that the laboratory results are
very conservative.
Both NAS-I and NAS-II fluids completely prevented alu-
minum fluoride precipitation. At I.5 to 2 hours of reaction, the
aluminum concentrations exceeded 5000 mg/L. When the reac-
tions were allowed to proceed over 24 hours, aluminum concen-
trations increased to over 10 000 mg/L, since these improved
fluids dissolved more alumino-silicates without any aluminum
fluoride precipitation.
New Acid Systems-Preventing Precipitation. The new acid
systems prevented aluminum fluoride precipitation throughout
the primary and secondary reactions. Several samples from the
laboratory spending tests were analyzed by 19F NMR spectros-
copy to help reveal the mechanisms behind the new acid
systems. 19F NMR spectroscopy has proven to be an excellent
tool to allow us to observe the distinct silicon fluoride and
aluminum fluoride species in solution during HF reactions. I
Fig. la shows the room-temperature NMR spectrum of a
NAS-II solution reacted with kaolinite at 200F for 1 hour. At
this point in the experiment, the primary reaction was complete
and the secondary reaction was 90% complete. The figure shows
only the aluminum fluoride region of the spectrum. The peaks
are very broad, which suggest multiple aluminum fluoride
species in equilibrium and fast exchange. Similar spectra were
observed with the formic-HF and acetic-HF fluids that were
reacted with clay. The anticipated aluminum fluoride species
were AIF/ and AIF
3
.
SPE 37281 C.E. SHUCHART 3
As a means of slowing down the exchange processes, low-
temperature NMR experiments were then conducted. LiCI was
added to the samples, which prevented the aqueous solutions
from freezing and the equilibria from changing. Fig. Ib shows
the low-temperature spectrum of an acetic-HFfluid reacted with
kaolinite at 200F. The fluid was prepared with 10% acetic acid
and ABF with HCI to give 1.5% HF. (The addition of the HCI
provided a lower FI AI ratio and limited the amount of AIF3
precipitation. About 20% of the fluoride still precipitated at this
point in the test). Four much sharper signals were observed. The
assignment of the signals was then made based on numerous
NMR experiments with various standards and controlled mix-
tures. The two sharp signals result from AIF/. In an octahedral
environment, the fluorides on aluminum could be opposite each
other (trans) or next to each other (cis) giving two possible
isomers for AIF/. The small, sharp signal between these two
peaks was identified as AlP+, and the broad signal to the left was
identified as AIF 3" The broadness of the AIF 3 signal suggested
multiple isomers. From this data, a FI AI ratio of 2.4 was
determined. This ratio is slightly lower than expected for this
fluid, which has a pH of2.7, but precipitation of AIF3 did occur,
which caused a lower F/AI ratio in solution.
Fig. Ie shows results from a similar experiment with the
same NAS-II fluid used in Fig. la. At low temperature, as many
as 20 signals were observed. Each signal represents a different
fluoride environment, which indicates as many as 15 aluminum
fluoride products. NAS-ll's chelating ability allows this many
species to form when isomerization and degrees of substitution
are taken into account. The chelation of the aluminum fluoride
species alters the aluminum-fluoride equilibria, which mini-
mizes the amount of AIF, in solution, thus preventing its
precipitation.
Live HF Studies. During this study, the 1
9
F NMR spectra of
"live" organic-HF fluids were obtained. The results were quite
surprising: the position of the signalfor the "live HF" changed
depending on the fluid. For example, in NAS-II and an acetic-
HF solution prepared with ABF, the signals appeared at -71 and
-68 ppm, respectively (Fig. 2). However, when a mixture of the
two acids was prepared with AF as the fluoride salt, the signal
was observed at -59 ppm. Control studies showed that actual HF
appears at -86.8 ppm, while free fluoride (from AF) appears at
-42.5 ppm.
The disparity between these results was quite surprising, but
it can be explained if we consider the pKa values of HF acid and
the organic acids. Most organic acids, including acetic acid,
formic acid, NAS-I, and NAS-II are not strong enough to fully
proton ate fluoride. The actual degree of protonation of a organic
acid and fluoride mixture can be determined based on its pKa
values. Results for several acid systems that use AF as the
fluoride salt are shown inFig. 3. Similar curves can be generated
for systems that use ABF.
677
These studies show that the 19F NMR chemical shift of a
organic-HF solution can be used for determining the amounts of
free fluoride and HF. This information correlates extremely well
with the calculations when pKa values are used. The chemical
shift is simply an averaging of the chemical shift of the two
species. For example, 10% acetic-l % HF prepared with ABF
showed an NMR signal at -68 ppm. This result corresponds to
58% HF and 42% F, which agrees well with pKa calculations.
These results reveal a distinct advantage for organic-HF
fluids. Since the HF reaction on sand is the square function of the
HF concentration,9 the reaction rate of organic-HF systems on
sand is greatly reduced compared to HCI-HF systems that have
the same fluoride concentration. As the HF reacts, more HF is
quickly generated from the free fluoride and organic acid. The
ultimate amount of HF reacting is the same as in HCI-HF
systems. Therefore, organic-HF fluids act as retarded HF sys-
tems that allow deeper clay-damage removal. In fact, when used
in a core flow test, NAS-II improved permeability throughout
the entire length of a 12-in. core.
s
This effect was not apparent
in acetic-HF and formic-HF systems, likely because of the
almost immediate precipitation of AIF
3
, which negated any of
the fluid's stimulation effects.
Conclusions
Significant precipitation of aluminum fluorides occurs with
acetic-HF and formic-HF fluids during a stimulation treat-
ment. Therefore, these fluids should be avoided.
NAS-I and NAS-II strongly chelate aluminum fluoride
complexes, thereby forming numerous species and prevent-
ing AIF3 precipitation.
The low acidity of most organic-HF fluids, including NAS-
I and NAS-II, results in only partial protonation of the
fluoride salts. As a result, these fluids act as retarded HF
systems.
References
I. Shuchart, C.E. and Buster, D.C.: "Determination of the Chemis-
try ofHF Acidizing with the Use of
19
F NMR Spectroscopy," SPE
28975 presented at the 1995 SPE International Symposium on
Oilfield Chemistry, San Antonio, Feb. 14-17.
2. Van Domelen, M.S. and Jennings, A.R.: "Alternate Acid Blends
for HTHP Applications," SPE 30419 presented at the 1995
Offshore Europe Conference, Aberdeen, Sept. 5-8.
3. Dill, R.W. and Keeney, B.R.: "Optimizing HCl-Formic Acid
Mixtures for High-Temperature Stimulation," SPE 7567 pre-
sented at the 1978 Annual SPE Technical Conference and Exhi-
bition, Houston, Oct. 1-3.
4. Norton, S.1. and Smith, C.D.: "Sand Control Installation and
Mechanical Design," OTC 7886 presented at the 1995 Annual
Offshore Technology Conference, Houston, May 1-4.
5. Van Domelen, M.S., Ford, W.G.F., and Chiu, T.1.: "An Acid
Expert System for Matrix Acidizing Treatment Design," SPE
24779 presented at the 1992 Annual SPE Technical Conference
and Exhibition, Washington, DC, Oct. 4-7.
4 CHEMICAL STUDY OF ORGANIC-HF BLENDS LEADS TO IMPROVED FLUIDS SPE 37281
6. Gdanski, R.D.: "Fractional PoreVolume Acidizing Flow Experi-
ments," SPE 30100 presented at the 1995 SPE European Forma-
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1997 Production Operations Symposium, Oklahoma City, Mar.
9-11.
Table 1-Reactions of Organic-HF Acids
with Kaolinite at 200F
Test Fluid
[AI] [8i] Fluoride
(mglL) (mg/L) ppt (%)
1 10% acetic-1.0% HF 677 277 79
2 10% formic-1.0% HF 4278 240 21
3 NAS-I! 5416 258 0
4 NAS-I" 7540 439 0
"Data at 2 hours; remainder of data at 1.5 hours.
(c) -3O'C
(b) acetlc-HF, -30'C
FI (a) NAS-II, RT
-70 -75 -80 -85 -90
o
Fig. 1-
19
F NMR spectra of "spent" organic-HF fluids
678
I
I
J
I I
-50 -60 70
o
I
-80
'-- NASI with HCI
NAS((
10%A cetic1% HF
ed with ABF prepar
NAsn +
I prepare
AceticHF
d with AF
-90
Fig. 2-'9F NMR spectra of "Jive" organic-HF fluids
100
u.
J: 75
...
0
c
0
;:
50 IV
C
0
-

0..
;;e
25
0
0.0 0.5 1.0 1.5 2.0 2.5
Organic Acid Conc (M)
Fig. 3-Degree of fluoride protonation in organic-HF fluids prepared
with ammonium fluoride (AF)