Guidelines Regarding the Use of Alcohols in

Acidic Stimulation Fluids

B. R. Keeney, Halliburton Services
J. G. Frost, Halliburton Services

Introduction
One of the problems associated with treating gas wells in the organic acid for the desired stimulation reaction is
sandstone formations is the slow recovery of the spent possible.
acid solution. This problem often results from high water
saturation in the critical matrix surrounding the wellbore. CH3 COOH + CH3 0H ~~ CH3 COOCH3 + H2 0
Water blocks can be caused by the capillary forces present acetic acid methanol methyl acetate
in porous rock and by the high mobility ratio of gas and .....................( 1)
water. 1 When a well is put on production following a However, in an alcoholic solution of hydrochloric acid,
workover or a stimulation treatment, the gas forces some a reaction takes place, that results in the formation of
of the water out of the rock and then may break through, organic chlorides. The following are two examples.
leaving a high water saturation around the wellbore. This
residual high water saturation reduces the effective per- CH3 0H + HCl ~. CH3 Cl

meability of the formation to gas flow.
The lower alcohols have been used for a number of
years in acidic stimulation fluids to aid in rapid recovery
of spent acid. The reasons for this use are well founded.
Alcohols aid ,in cleanup of spent acid by lowering the
surface tension and increasing the vapor pressure of the
solution. 2 In recent years, this technique has gained popu-
larity to the extent that it is used routinely in gas- well
stimulation treatments and, to some degree, in oilwell
acidizing.
This paper deals with an undesirable side reaction at-
tendant when alcohols are used in acid. Even under
moderate-temperature conditions, alcohols will react
readily with acid. 3 In the cases of organic acids (acetic or
formic acid, for example), these reactions will result in
ester formation, with the only resulting problem being
possibly a loss of available acid for the stimulation reac-
tion. Even this may be of small consequence since the
esterification reaction is reversible aq.d regeneration of
methanol hycfrochloric acid methyl chloride
+H2 0 (2)
CH3 CHOHCH3 + HCl ~
isopropanol hydrochloric acid
CH3 CHClCH3 + H20 .... (3)
isopropyl chloride
This reaction poses a genuine' problem in acidic gas·-
well stimulation. A reaction such as in Eq. 2 or Eq. 3 is
irreversible, and any HCllost to this reaction can not be
regenerated, as was possible with organic acids (Eq. 1).
Thus, this reaction competes with the acidic-stimulation
reaction for the HCI content. A second problem concerns
the reaction products themselves. Although the presence
of organic chlorides in natural gas might not present any
special problems, their presence in produced crudes or
distillates is considered a serious contamination. For these
reasons, this paper is limited to HCI-alcohol reactions.

Using alcohols in acidic stimulationfluids for fast cleanup ofspent acid can lead to the formation
ofhigh concentrations oforganic reaction products and an attendant loss ofavailable acid. The
problem can be minimized by limiting the alcohol concentration to a maximum of32 percent (by
volume) and by limiting treatment temperatures to 175°Ffor sandstone and 200°Ffor limestone
formations.

552 JOURNAL OF PETROLEUM TECHNOLOGY

Comparisons are presented of the amount o~ aGid con-
sumed at various temperatures by t4e reaction ofHCI with
three different alcohols: methanol, iso.propanol, and
ethanol. The effects of alcohol concentration, acid
strength, time, and temperature on the rea<;tion of
methanol with HCI are also studied. :Methanol was
selected because of its common use in field operations.
The solubility of methyl chloride in kerosene is also
investigated.
Test Procedure and Equipment
The HCI-alcohol, solutions were prepared using reagent-
grade chemicals and deionized water. The st~ength.ofthe
reagent-grade HCI was- 37.8 percen.t (23.3°Be). All the
test solutions initially contained the amount of HCI that
would be normally present in a HCI-H2 0 solution of
equival~nt strength. After mixing, the solutions were ti-
trated to determine the exact acid content.
The pressure or reaction vessel used for conducting the
.1-hour tests was a test cell presently under consideration
by the joint NACE-API Standards Committee for Corro-
sion Inhibitor Evaluation. The test cell was modified
slightly for investigating the effects of time on. the acid-
alcohol reactions. A second pressure vessel for holding
the test solution at rOOm temperature (72°P) was fitted to
the reaction cell. The reaction cell ,was filled with
kerosene apd was preheated to the desired rest tempera-
ture. The acid-alcohol solution was then displaced from
the pressure vessel (at 72°P) into the heated cell under 600
psi nitrogen pressure. ~ample injection was c6nsid~red
complete when an equivalent amount of kerosene had
been displaced through a backpressure regulator, set at
500 psi, on the preheated cell. The nitrogen pressure was
then lowered to 500 psi and the line was reconnected to the
cell so that samples could be periodically withdrawn
Fig. l-Effect of various alcohols on acid strength.
Fig. 2-Effect of various alcohols on acid strength.
MAY, 1975
t4rol1gh a discharge valve· while mairitaining a constant
pressure of 500 psi. The ,acid samples .were then retitrated
to determine the remaining acid content.
Determinations of the so~ub.ility of methyl chloride in
kerosene were conducted using a, Wickbold combustion
apparatus, an instru;ment. in which organIcally bound
chlorine is converted to titratable chloride ion. The tes~
solutions were prepared by .bubbling gaseous methyl
chloride through samples of kerosene for I-hour periods at
?2°P and atmospheri,c pressure. T~e chloride ion concen-
trations of the samples were then measured with the
Wickbold apparatus at various time intervals. The
methyl chloride content was calculated from the chloride
ion determinations.
Discussion of Data
The effects of various concentrations of methanol, iso-
propanol, and ethanol on acid-st~ength reduction 'Of HCI
at temperatures of 200° and 300 P, for a period of 1
0
hour, are shown in Pigs. '1 and 2. In all the tests, the initial
acid content of the alcohol-a<;id mixtures wa~ equivalent
to the amount of HCI present in a IS-percent HCI-H2 0
solution .
0
. At a temperature of 200 P, the reactivity order of the
three alcohols with HCI was methanol > isopropanol
> ethanol. It should be noted that these reactivities
are based on volume rather than on molar concen-
tratio~s .of. the alcohols. At the higher temperature. of
30bop, t~e residual acid concentrations w:ith ethanol and
isopropanol were almost identical, while significantly
lower acid conc;entrations were measured at this tempera-
ture with methanol.
The amount of acid conversion as a function of time (0
to 60 minutes) was measured for four different concentra-
tions of methanol (16, 32, 48, and 64 volume percent) in
IN MINUTES
Fig. 3-Effect of various concentrations of methanol on acid
strength as a function of time.
Fig. 4-Effect of various concentrations of methanol on acid
strength as a function of time.
553
 TABLE l~VOLATILITY OF METHYL CHLORIDE IN KEROSENE
Test Temperature: Room Te.mperature (72°F)
Pressure: Atmospheric
Time Methyl Chloride
(hours) (gm/liter)
Initial 30.1
1.0 26.3
3.0 24.8
6.0 23.7
48 22.7
72 21.2
Fig. 5,-Effect of various concentrations of methanol on acid
strength at increasing temperatures.
HCl at temperatures of 200 0 and 300oP. These data are
shown in Pigs. 3 and 4.,At a temperature of 200°f, no
measurable acid loss was recorded for concentrations .of
16 and 32 volume percent methandlduring a 45-minute
period. This is significant in that methanol, at concentra~
tions as high as.32 volume percent, possibly could be used
when treatip.g 3: limestone formation because of the rapid
spending action of the acid on the rock. At the higher
conc,entration of 48 volume perc~nt. methanol, a small
amount of acid loss (0.25 percent) was recorded after 45
minutes. Even though this amount of acid conversion Fig. 6-Reduction in acid strength with various concentrations of
HCI containing 64 percent (by volume) methanol.
appears to be small, it represents the formation of methyl
chloride in the acid solution at a concentration of 3 700
mg/liter. A significant amount of contamination of 'pro- valved when using alcoholic-HCl solutions for .stimula-
duced hydrocarbons could result from this ,concentration tion treatme~ts of .oil-bearing formations because of the
of methy~ chloride. Even higher acid· losses were recorded possibility of contaminating the hydrocarbon- production
with methanol at £1 concentration of 64 volume percent. fluids with organic chlorides.
Prom 'the reduction in acid strength , the rate at which Conclusions
methyl.chloride was, produced at 300oP, at all four con-
centration~ of methanol, indicates th~ undesirability
1. Alcohols will readily react with 'acid solutions to
of using this alcohol at elevated temperatures. form organic reaction products, with an accompanying
, Pig. 5 sh0'Ys the effects of increasing temperature on loss.of acid strength.
the reduction of acid strength for the four concentrations 2. When alcohols are used in Hel stimulation treat-
of methanol ..The'se data sh~w that there was no significant ments, organic chlorides may, be formed as reaction
loss of acid strength with methanol concentrations up to products.
32 volume percept until the temperature exceeded 175°P. 3. One of these reaction products, methyl chloride, has
This is relevant when ~onsidering sandstone acidizing in been shown to have a high degree of solubility in a
which mixeq acid solutions of HP-Hel are used routinely. hydrocarbon fluid.
In. these treatments, a large portion of the Hel may not 4. The acid-alcohol reaction in acidic stimulation
rapidly spend on ,the formation. As a result, this acid fluids can be minimized by limiting the alcohol concentra-
would b~ available to react with methanol. Th~s, if these tion to a maximum of 32 volume percent, arid by limiting
~ea~ment temperatures to 17sop for sandstone and 200 P
0
acid mixtures with alcohol are considered for a sandstone
treatment, the ~imits of 175°P and/or 32 volume percent for limestone formations. The guidelines may require
m~thanol should ~e used as guidelines to help in prevent- modification as additional information becomes
ing this acid-alcohol reaction. , available.
Fig. 6 shows red.uction in acid strength as a function of Acknowledgment
time for three different concentrations (5, 10, and 15
percent) of~Cl cqniaining 64 volume percent methanol at We wish to express our appreciation to Halliburton Ser-
2500 P. A significant,reduction in acid strength was mea- vices for permission to prepare this paper, and to our
sured with all three concentrations of Hel in less than 30 co-workers fot their help in collecting the data.
minutes.. This indicates that lower-strength HCt·HP- References
alcoholic ·acid solutions still may not eliminate' organic
1. McLeod, H. 0., McGinty,.J. E., and Smith, C. F.: "Alcoholic Acid
ch1~ride formation 1?ecause of the significant amount Qf
Speeds Clean-Up in Sandstones," Pet. Eng. (Feb. 1966) 38, No.2,
organic chlorides formed even with acid strengths as low 66-70., .
as 5 percent. 2. McLeod, H. 0., McGinty, J. E., and Smith, C. F.: "Deep Well
To determine if methyl chloride has sufficient solubility Stimulation With Alcoholic Acid," paper S.PE 1558 presented at the
ip. oil to be consi~ered a significant contaminant, its vol- SPE-AIME 41st Annual Fall Meeting, Dallas, Oct. 2-5,1966.
3. Bordwell, Frederick G.: Organic Chemistry, The Macmillan Book
atility in kerosene was determined at 72°P and. atmo- Co., Inc., New York (1964) 59-60. JPT
spheric, pressure' (see Table 1). It was found that JPethyl
chloride has a very high degree of so~ubility in kerosene Original manuscript received in Society of Petroleum Engineers office July 30, -1974.
~ven when allowing the solu:tion to stand for a period of72 Rev.ised·manuscript received Feb: 10, 1975. Paper (SPE 5158) was first presented atthe
SPE-AIME 49th Annual Fall Meeting, held in Houston, Oct. 6-9,1974. @Copyright 1975
hours. This information further points out problems in- American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc.

554 JOURNAL OF PETROLEUM TECHNOLOGY