.

,-

Ipii)t m

Societyof PetroleumEngineers
SPE 30419

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Alternate Acid Blends for HPHT Applications
Mary S. Van Domelen, SPE, Halliburton Energy Services, and Alfred R. Jennings, Jr., SPE,
Mobil E & P Technology Center

Copyright 1995, Society of Petroleum Engineers Inc.

The example application includes the use of an organic
This paper wes prepered for presentation st the Oifshore Europe Conference held in Aberdeen, acid blend to effectively stimulate the 350”F ( 175°C) Arun
Scotland, September 5-8, 1995.
limestone formation in Indonesia. A total of 17 large-scale acid
This paper was selected for presentation by an SPE Program Committae following review of
reformation contained in an abatract submitted by the author(s). Contents of the paper, as
fracs and a similar number of large matrix-acidizing treatments
preeentwd, have not been reviewad by tha Scciety of Petroleum Engineers and are subjeot to have been performed over the past 3 years. Rheology and
correction by the author(s). The material, as presamtad, does not naceasariiy rtitect any
position of the Society of Petroleum Engineers, ita officers, or members. Papers presented at corrosion data will be presented with the details of the treat-
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Permission to copy ia restricted to an abstract of not more then 300
ment procedures and production responses.
words. Illustration may not be copiad. The abstract should ceotain conspicuous acknowledge
ment of where and by whom the paper is presented. Write Librarian, SPE, P.O. Box 833336,
Richardson. TX 750s3-38S$, U. S. A., fax 01-214-952-9435. Introduction
Corrosion is defined as the deterioration of a substance (usually
a metal) caused by a reaction with its environment. The
molecules of acids ionize in a water solution to release the
Abstract
hydrogen ion from the acid’s constituent elements. The strength
Protecting completion and production equipment is of utmost
of an acid is proportional to the concentration of hydrogen ions
concern during acidizing. The higher the temperature, the more
present. The attack of acid on metal tubulars manifests itself
difficult it is to protect metal against corrosion, and the required
through the dissociated hydrogen ions of the acid solution,
inhibitor loadings increase with temperature, resulting in greater
which results in the oxidation and dissolution of iron at the
likelihood of formation damage. In addition, the protection
anodic sites on the metal surface with the attendant reduction
times are reduced dramatically, which can potentially limit
of hydrogen ions and generation of hydrogen at the cathodic
well stimulation treatments (for example, fluid volumes caused
sites.
by pump time limitations). These problems become increas-
Acid corrosion can be minimized by the use of corrosion
ingly severe in formations with bottomhole temperatures greater
inhibitors. The following factors will influence the perfor-
than 250”F ( 120”C).
mance of commonly available inhibitors:
Even if adequate corrosion protection can be achieved
during stimulation, post-treatment production of chlorides ●
temperature
associated with the injected HC1-based acids remains a prob-
●
acid strength
lem. There is increasing concern when the wellbore contains
●
contact time
high-alloy metals, such as stainless and duplex steels, which ●
inhibitor concentration
are susceptible to hydrogen embrittlement and chloride stress
9 concentration and compatibility of various acid additives
cracking. When combined with the possibility of erosion
corrosion caused by high production rates, acidizing high- Increases in any of these factors, except inhibitor concen-
-pressure, high-temperature (HPHT) wells poses risks. tration, will increase corrosion rates. Unfortunately, the rela-
A combination of organic acids (acetic and formic) can be tionships are not straightforward. For example, increasing the
used instead of hydrochloric acid (HCI) to minimize corrosion temperature by 50°F from 150”F to 200”F will cause a less
problems in high-temperature applications. The blends are proportional increase in corrosion compared to a similar incre-
designed so that the dissolving power is equivalent to HC1with mental temperature increase from 250°F to 300”F. A 5V0
significantly reduced corrosion rates and the absence of Cl- increase in HC1 concentration from 1070 to 1590 will not yield
ions. Some of the gelling agents developed for HC1yield higher the same effect on corrosion as would a similar 570 incremental
viscosities in organic acids on an equivalent polymer-loading increase from 15$%to 20!Z0HC1.
basis. The end result is an organically based, high-temperature Acid comosion is also strongly influenced by the chemical
acid system that uses existing technology and is technically and composition of the steel. Therefore, metal chemistry is an
economically more attractive than an HC1-based system. important factor when acid corrosion of steel is considered. API

References at the end of the paper. 523

2 ALTERNATE ACID BLENDS FOR HPHT APPLICATIONS SPE 30419

specifications are based on the physical properties of the metal, Inhibitor effectiveness is a function of the inhibitor’s
such as tensile strength, rather than chemical composition. As capability to form and maintain a film on the steel surface. For
a result, tubing within an API standard, such as J-55, may vary this reason, most corrosion inhibitors are only marginally ‘
significantly in chemical composition from one manufacturer soluble in acid solutions. Permeability reduction may occur
to the next. Even different lots of the same grade of tubing made because of plugging caused by high molecular weight or

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by one manufacturer may vary considerably. Carbon and low- limited-volubility components in the inhibitor blend.
-11 -..
2t11UY
. .-1-
SL&l>
---
dlG
---*:
pa
-..1-.-1
LIWCII
# -.-n..
1~ PIUIIV
- *-
w
.Jcw; mt; n”c
v CUM-.,=
;“
. . . ch~~.:~~! ~e~~ahiii!y ~]tera[!on is of Particular COnCernin sandstone
composition. acidizing since most corrosion inhibitors are cationic and are
strongly adsorbed. Mutual solvents can be used to minimize the
High-Alloy Steels and Associated Corrosion adsorption of corrosion inhibitors on the formation; however,
Problems the addition of mutual solvents will often decrease the corro-
l+”
5 i~llL--11- .,--1.
auuy mkbta ..,a*a “n+,
wU- UVLJ.WU cd fnr il .9A
nunO.. uac nrndllrt
... B-u inn lmtil
~. .-. -v..=.. . .... . ~!~n-inhibilor performance. 11-12
recently when tapping deep, hot, hostile reservoirs become Most corrosion inhibitors require internal surfactants to
common. Drilling through and producing from high-tempera- remain dispersed in the acid blend. Sometimes, the dispersant
ture formations that contain hydrogen sulfide (H2S), carbon package can increase the tendency for acid-oil emulsions to
dioxide (C02j, corrosive brine, or coniiiiiadcms has led to $.— :.. . . . . . 111
lU1 111 111 alGa3
;.. ...h;,.h
w 111*I1
ha
Lie
frm.mcat;, am
1“1 ,1, cst, ”..
(.
“rL”v
1A c.nntninc hiu~
““.....1 ..” ...~ .

increased use of high-alloy steel tubular goods. concentrations of paraffin or asphaltene.

Alloyed steels used in the petroleum industry are called Because the effects of corrosion inhibitors on the forma-
corrosion-resistant alloys (CRAS). The most commonly used tion vary widely, a minimal amount of inhibitor should be used
CRAS are the chromium alloys, such as 13Cr and duplex in a particular application. This approach can be accomplished
stainless steels, including AF-22 and SAF-2205. In extreme by a better understanding of the inhibitor performance and
environments, highly alloyed nickel austenitic stainless steels, control of treatment parameters. For example, in high-tempera-
such as inconel, incoloy, and hastelloy are used. ture applications, reducing the acid concentration slightly,
Popularity of CRAS has increased because of their durabil- minimizing contact time, or using cooiing preiiushes may
ity and favorable economic factors in the steel market. The allow lower inhibitor loadings to be used. Another alternative
initial expense in purchasing CRAS is often justified when the to HCI is the use of organic acids.
total costs of alternative strategies are considered, because
CRAS require less maintenance and have a longer anticipated Application of Organic Acids
service life. Mobile Bay and the surrounding areas in southern Since HCI is cost-effective and generally leaves no insoluble
Louisiana and Mississippi offer the greatest history in the safe, reaction products, it is the most commonly used acid in
cost-effective use of CRAS in hostile environments. 1-4Wells in stimulation operations. Corrosion concerns, however, may
this area produce from the Norphlet, Smackover, and Tuscaloosa limit the use of HCI in HPHT applications. Lower injection
formations that typically have high C02 and H2S contents and rates caused by surface pressure limitations can contribute to
are classic HPHT examples. longer tubing contact times for a specific acid volume. When
Although 13Cr and duplex CRAS resist chemical attack by lower injection rates are combined with high temperature, acid
the corrosive production environment, they are highly suscep- concentrations and pump times must often be limited. The
tible to corrosion from mineral acids (HC1 and HF) commonly reduction in total acid-dissolving power combined with shorter
used in stimulation operations. ‘-~A corrosion-inhibitor pack- contact times with the formation may result in less efficient
age that is Specificaiiy th%igiied fOr SiuGii~l~t~iiiiigy Shtiid k
..h......l.. +’n..
Sulllulatlull
t..a”t-amt.
uGaL1nlbln La.

selected to minimize damage to high-alloy steels during Acetic acid (CHJCOOH) and formic acid (HCOOH) are
acidizing.8 weakly ionized, slow-reacting, organic acids. The use of acetic
Even if adequate corrosion protection can be achieved with acid for well stimulation was first proposed nearly 35 years
CRAS during acidizing, post-treatment production of chlorides ago. 13The use of mixtures of organic acids and organic/mineral
associated with the injected HC1-based acids remains a prob- acids to stimulate high-temperature formations became popu-
lem because 13Cr and duplex CRAS are susceptible to hydro- lar in the 1970s.14-16Two factors make organic acid systems
gen embrittlement and chloride stress-cracking. more attractive: (1) significantly lower corrosion rates and (2)
extended reaction times.
Formation Damage Caused by Corrosion Inhibitors Acetic acid is available in concentrations up to 100%,
In cases in which acid corrosion can be adequately controlled while formic acid is available in 70 to 90% concentrations. For
with existing technologies, there is still concern about the field use, however, acetic solutions are normally diluted to 15%
effect of the corrosion inhibitors on the formation to be or less. At concentrations greater than 15%, one of the reaction
stimulated.9-10Formation darnage can be caused by several products, calcium acetate, can precipitate because of its limited
mechanisms when the formation is overtreated with corrosion volubility. Similarly, the concentration of formic acid is nor-
inhibitors.

524
SPE 30419 MARY S. VAN DOMELEN, ALFRED R. JENNINGS 3

really limited to 15% because of the limited volubility of maximum of 0.05 lb/ft2 weight loss to be acceptable. The
calcium formate. acetic/formic blend met this requirement without the addition
When the dissolving capacity of organic acids are com- of a corrosion-inhibitor intensifier. The organic system is less
pared to equal strengths of HC1, formic acid, and acetic acid, corrosive, and formation damage caused by the absence of the
the organic acids are less effective than HC1 on a weight- limited-volubility inhibitor intensifier is less likely.

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percentage basis. Formic acid has approximately 76% of the The choice in inhibitor intensifier is important. The tests
dissolving capacity of HCI while acetic acids have only 58%. with the HC1/acetic blends were conducted with two different
If various combinations of HC1,acetic acid, and formic acid are intensifiers, copper iodide and copper chloride. Sometimes
used, it is possible to achieve dissolving powers equivalent to proper selection of the inhibitor intensifier can reduce the
20% HC1. Table 1 compares the calcium carbonate (CaCOq) required corrosion-inhibitor loadings.
dissolving capacities of various acid blends.
Application of Gelled Acids
TABLE 1-DISSOLVING CAPACITIES
Gelling agents are often used in fracture acidizing to increase
OF VARIOUS ACID BLENDS the iive acid penetration distance and to heip controi fiuid ioss.
Gelling agents are also used during perforation washes and
Acid Type CeCOa Equivalent
wellbore cleanouts in both sandstone and limestone formations
end Concentration (lb/Mgel ecid)
to help transport fines out of the wellbore. The efficiency of
7.5% HCI 890 large matrix-acidizing treatments can be enhanced when
15% HCI 1,840 viscosified acids are used. 17-19
Natural polymers are unstable in strong acids, so synthetic
2070 HCI 2,512
gelling agents are required. Commonly used high-temperature,
10% Formic 910 acid-gelling agents are copolymers consisting of various ratios
10% Acetic 710 of polyacrylamide (PA), acrylamidomethylpropane sulfonic
15% Acetic 1,(265
acid (AMPS), and polydimethylaminoethylacrylate quatemized
with methyl chloride (DMAEA-Q). The relative ratios of these
7.5yo Formic- 14yo HCI 2,420
three monomers in the polymer will influence(1) the capability
10% Acetic - 14% HCI 2,380 of the polymer to crosslink, (2) the viscosity yield of the
9% Formic- 13% Acetic 1,830 polymer on a per-pound basis, and (3) the upper temperature
limit of the gelled-acid system. 20’2’Regardless of the synthetic
gelling agent selected, the viscosity of the gelled acid solution
Corrosion Rates with HCI and Organic Acids will decrease as temperature increases.
Table 2 shows the difficulties in designing a corrosion
inhibitor system. This table contains corrosion data for three
TABLE 2-COMPARATIVE CORROSION DATA N-8(I STEEL
different base acid systems. Comparisons of corrosion rates
4 HOURSat300”172% CORROSION INHIBITOR
with and without high concentrations of gelling agent are
Coneent. Waight Loss
presented. The tests were conducted for 4 hours at 300”F Aeld Type Additives
(lb/Mgal) (lb/w)
(150”C) on low-alloy, carbon steel (N-80). Details of the test
20% HCI CU212Intensifier 100 0.080
procedures are given in Appendix A. Six of the tests were
performed on static samples, while the seventh sample was 20?’0HCI CU21ZIntensifier 100 0.449
- ... ..-
dynamically stirred. tieumg Agent 14U
The first point to note is how the addition of gelling agent 20’%HCI CUJ2 Intensifier 100 0.233’
affected corrosion rates. The gelling agent used was a high- Gelling Agent 140
temperature, high molecular-weight polymer. Some additives
will influence corrosion rates. However, it is not normally ls~o HCI - CUJZIntensifier 100 0.020
recognized that high concentrations of gelling agents will have 11YOFormic
such a significant impact. The increased corrosion rates with 13% HCI - CuzlzIntensifier 100 0.175
gelled acid are believed to be caused by mobility effects since 110/-Efinni-
, , ,G, “,, ,,,” ~#!~~g ~&~! f ~~
there is a significant difference between static and stirred test 4m.-./, IA, -.. -, ,_.-_-,r--- . m,-. ,-. mr. .
results. Id-70n~l - UU2UIZ merrsrrmw I vu U.UL4

The advantages of an organic acid blend over mineral acids 11% Formic Gelling Agent 140
are readily apparent based on the corrosion weight losses in 13% Acetic Gelling Agent 140 o.o~~
Table 2. The 1390 HCI -1190 formic blend has an equivalent 9% Formic
dissolving power to 2090 HCL The 1390 acetic -990 formic ● stirred ratherthan static test.
blend is equivalent to 15% HCL The industry considers a
4 ALTERNATE ACID BLENDS FOR HPHT APPLICATIONS SPE 30419

Essentially no information regarding the use of synthetic

1
i! -W FOnniC.
13%Aatlc+mlbJNg81
Colllng ASsnt A i polymers in organic acids was found. The most useful refer-
: 120 ;> ----- ---. -:--4 .- .L- ---- -r -..-.l_-.:_ —–l-.—.-—.
,-- l-fin
-15% tlel + W lbMgd Qolling Ag.nt A CIICISSptX UUIIWI LU LIK usc UI synmeuc polymers m EuK and
h
I conformance-control applications. Since pH and brine compo-
~ 100J -15% w + B3Ihmgd QDlling AgOntB

a sition affect the viscosity of PA copolymers, it is logical to

9804 \
I
assume that acid gelling agents may function differently in

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organic acids that buffer at higher pH values than HC1.

Economic Comparison Between HCl and Oraanic _—...-

Acid Blends
The base acid cost for a formic/acetic acid is normally about

twice that of Hcl; however, inhibition costs are generaiiy iess.

Enhanced viscosity in organic acids is the second key to the
Time (rein) economic advantage of using organic acid blends instead of
HC1 in high-temperature applications. The reduction in corro-
sion-inhibitor loading combined with the reduced gelling agent
requirement (for a specific viscosity) results in a cost reduction
Ii’im.ra- -1 “-...-
onmt~imchi-h-iamn.m~nt,,-a .haalnmw Amt. #a. t.sm in
. .. th~
.... tnt~l
.. .. . m-id
..”. = hlemrl
“.” ... A w“.., “~ illIIct~att=c
. Tmhln .L,uouu. ”o a .I *?7f PE.-d bAfi -
,“ L
- =6-= ..0 u.~.. -.”...uw.w.u. u ,,.””.”~j Uct.(1 ,“, Lw” Ww’’=-u”.
commercially available acid-gelling agents that are compared The target viscosity was 40 cp (at 170 secl) with a corrosion
on an equivalent polymer-loading basis in 1590 HC1 at 270”F. protection time of 6 hours on 13Cr steel. Under these condi-
This data was generated using a Model 50 Farm Viscometer for tions, the total cost per Mgal of an organically based system
a North Sea project.22 Gelling Agent A is described in Ref. 21, was about 2590 less than an equivalent HC1-based system.
and Gelling Agent B is described in Ref. 23.23After 30 minutes This comparison was made based on typical US book
at 270°F with a loading of 93 lb/Mgal, both polymers yielded prices with no discounts considered. l%e absolute costs of the
less than 20 cp apparent viscosity at 170 see]. chemicals are not important since transportation and stocking
Figure 1 also contains rheology data for a 9% formic - 13% costs in other parts of the world may result in substantially
acetic acid blend gelled with Agent A. This information was different price schedules. The relative comparison, however,
generated with the same viscometer and identical test proce- will remain consistent regardless of location. As the tempera-
dures used for the 15% HC1, gelled-acid rheology. The gelled ture increases, the economic advantages of organic acid blends
organic acid data are the average of four runs. While the increase.
gelling-agent loading was reduced from 93 to 70 lb/Mgal, the
resultant viscosity essentially doubled. Case Study: Arun Limestone
A literature review did not present a clear explanation for The Arun Field, operated by Mobil Indonesia, is one of the
the enhanced viscosity in the organic acid blend. The most largest and most productive gas reservoirs in the world. The
probable explanation is a combination of two effects: field is located in the northern part of Sumatra (Figure 2).
(1) greater hydrolytic stability of the polymer backbone at Currently, 66 wells produce a total of 3.3 Bscf/D of gas and
higher temperatures in the organic acids and (2) less hydrolysis 120,000 bbl of condensate per day. The largest production trees
of the pendent side chains, providing greater steric hindrance ever installed in the world, 24 ft tall, weighing 22 tons, and
that helps minimize polymer syneresis. 9-in. production bores, are needed to handle these highly

TABLE 3-COST COMPARISON FOR HCI AND ORGANIC ACID SYSTEMS

6 HOURS AT 270”F;CORROSION LOSS <0.05 lWft2 on 13 Cfi Viscosity 40 cp st 170 see-’

Additive 15% HCI 9% Formic -13°41Acetie Cost Retio

Bsss Acid (per Mgsl) $1,000 $2,400 2.40
Corrosion Inhibitor 20 gal HACI at $50/gai 20 gal OACI at $35/gal 0.70
Inhibitor Intensifier 15 gal HACI at $65/gal none required 0.00
Gelling Agent 40 gal HTAGA at$50/gal 15 gal HTAGA at $50/gal 0.38
Totsl Cost (per Mgel) $4,975 $3,850 0.77

HACl=High-AlloyCorrosionInhibitor OACl=Organic Acid-CorrosionInhibitor HAll=High-AlloyInhibitorIntensifier

HTAGA=High-TemperatureAcid GellingAgent

526
SPE 30419 MARY S. VAN DOMELEN, ALFRED R. JENNINGS 5

typical conditions for both fracture and matrix acidizing.

Descriptions of the two metals tested (N-80 and 13Cr) are given
in Table 4. The acid formulation is given in Table 5.
Two theories exist regarding the appropriate temperature
I “N’+xA.’ to use when the required inhibitor concentrations are deter-
mined. The conservative approach is to inhibit based on the

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anticipated maximum temperature encountered, usually the
BHT. The other approach is to base inhibitor concentrations on
temperatures encountered during the treatment because sig-
nificant cooldown will occur. This cooldown results in lower
inhibitor loadings and subsequently, lower chemical costs.
The latter practice is dangerous. If an unplanned shutdown
occurs while the treatment is being pumped, temperatures in
the t,lhlll nrc Wi 11 rice Tf t~e temm?rat~~~ are Signifi-
.,,W .“” ---- . ...’ ..”-. -- . .
~nc~e&Ises
- .-.. ----- .

cant, the amount of inhibitor used will not be adequate. This

Fig. 2—Arun field Iocetion.
increased temperature could result in increased corrosion rates
that would cause high weight losses and possibly reduce
deliverable wells?4 The trees are trimmed with stainless steel
mechanical strength.
to handle 14 mole % COZand as much as 100 ppm H2S. Some
wells are completed with N-80 tubulars. Other wells are
completed with mixed s’tiiigs consisting of N-%3 aid 13Ci.
I TASLE 4-DESCRIPTION OF METALS TESTED
Although Arun wells typically produce 40 to 100 MMscf/D
currently at 1,300 to 1,400 psi lTP, many of the wells have Chemical Analyeia N-SO 13Cr
positive skin, indicative of near-wellbore formation damage. In 0.300 0.020
Carbon
most of the field, the lower portion of the Arun has less effective
In fithar .,,-11. oh-rwrrnp. 5; Sulfur 0.007 0.002
pSimi3Mkj bii dl~ il~~i?i ZLYRS. u, V...WI “w..., . .~..-yw . . ..w

ability zones are interdispersed among more massive, low- Phosphorous 0.027 0.017
permeability intervals. Well stimulation by acid fracturing and Silicon 0.170 0.330
high-volume matrix acidizing effectively removes the damage
Manganese 0.960 0.800
and provides highly conductive flow channels for improved
production from both low- and high-permeability zones?s Chromium 0.040 13.120
Protection of production equipment is the greatest concern Nickel 0.020 0.036
during and after acid stimulation. The average reservoir tem- Molybdenum 0.000 0.030
perature in the producing wells is 350°F. Severe temperature
Vanadium 0.003 0.070
cycling of the tubulars and the wellhead occurs at 80”F during
treatment and at 325°F when the wells are flowing. The thermal Copper 0.010 0.079
growth associated with the high range of temperature cycling Aluminum 0.270 0.000
is accommodated by an external flowline loop downstream
Boron 0.001 0.000
from the wellhead. The use of the flowline loop combined with
ths h; “h
U,w 1,15,,
r+wwI@i
y “u w..
~m w=.lm-itiec
”.. . -,”...--”
ad
----
temm?mture.c
.-...y-. . . . . ..-.
ma~~~
---
~~&gt Iron Balance Balance
corrosion a concern during cleanup both after an acid treatment
and during normal production.
Because of corrosion observed in the wellhead equipment
and tubulars in some wells after early matrix treatments with I FormulationTABLE 8-ARUN ACID FORMULATION

HC1, organic acid blends were selected over HC1 for stimula- Description
(per Mgal)
tion in the Arun. Another reason for this choice was the
common belief that chlorides in the returned spent acid can I 140ga195%AceticAcict 13% Acetic Acid
contribute to erosion corrosion in wells that are completed with
low-alloy tubulars and wellheads.
I 85 gal 90% Formic Acid 9’7. FormicAcid

I 30 gal Acid GellingAgent

Arun Corrosion Studies I 3 gal NonionicSurfactant

Test parameters for this series of corrosion tests were selected

to simulate the Arun stimulation program. Acid type, strength,
I 50 lb
] 5 gal
Iron-ControlAgent
Mutual Solvent
additives, tubular types, and contact times are consistent with
I 0.5 gal Bactericide

527
6 ALTERNATE ACID BLENDS FOR HPHT APPLICATIONS SPE 30419

TABLE 6-ARUN CORROSION TESTS

●
a temperature-stable viscous gel pad (HPG/titanate-
ACID SYSTEM: 13”AACETIC-9% FORMIC; TEST TIME: crosslinked gel) to fracture the formation and generate
4 HOURS; PRESSURE: 14.7 psi at 120”F, 600 psi at 350”F created fracture area
7 .
Inhibitor
first increment of gelled, organic acid with inhibitors and
Test Temp. Matsl Weight Loss fluid-loss additives
Concentration

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Number “F Type lb/# .
0/0 viscous gel spacer
●
a second increment of gelled organic acid
1 120 0.20 N-80 0.006
●
an overflush to displace acid into the formation and leave
2 120 0.20 13Cr 0.001 noncorrosive fluid in the wellbore
3 350 0.20 N-80 0.517
4 350 0.20 13Cr 0.044
Flowback was initiated on the wells through a high flow-
rate test tree following a temperature logging run to determine
5 350 2.00 N-80 0.032
apparent vertical fracture height.
6 350 2.00 13 Cr 0.017 Table 7 summarizes the pre- and post-stimulation produc-
tion rates and the skin values calculated from pressure buildup
Results of selected weight-loss corrosion tests performed tests. The 17 acid-fracturing treatments conducted in the 350”F
for the Arun project are given in Table 6. Test procedures are Arun formation resulted in a sustained increase in the ability to
described in Appendix A. Tests 1 and 2 use standard recom- deliver more 350 MMscf/D. Although the wells were stimu-
mended inhibitor concentrations for N-80 and 13Cr at 120”F lated in 1990 and 1993 and reservoir pressure continues to
(0.2% organic acid corrosion inhibitor). Tests 5 and 6 use decline with depletion, the sustained productivity of the frac-
standard concentrations for the 350°F. Tests 3 and 4 are tured wells demonstrates the effectiveness of the organic acid
included to illustrate what could happen if the corrosion- blend (13% acetic - 9% formic) used in the acid-fracturing
inhibitor loading was based on cooldown temperatures (120”F) treatments. No significant corrosion problems or well failures
and a premature shutdown allowed the tubulars to heat up to were attributed to the stimulation treatments in any of the wells.
bottomhole temperature (350”F).
As mentioned previously, the industry considers a corro- TABLE 7—ARUN ACID FRACTURING RESULTS
sion loss of less than 0.05 lb/ft2 acceptable. In Tests 1, 2, 5, and Well Pm-acid Poet-acid
6 (which used standard corrosion-inhibitor loadings based on ‘r-acid ‘oat*cid Q/Ql
Number MMscf/D MMscf/D Skin Skin
temperature), the weight losses were well below the acceptable
limit. Results of Tests 3 and 4 illustrate the danger of inhibiting CI-03 49 84 1.71 4.5 -1.0
based on cooldown temperature if heatup occurs. In these tests, CI-05 53 73 1.38 4.5 -1.0
the amount of corrosion was greatly enhanced over the corre- CI-07 32 40 1.25 0.7 -2.0
sponding rests at lower temperature or with higher inhibitor
CI-09 50 60 1.20 3.4 -2.4
loadings. Weight losses of 0.54 and 0.04 lb/ft2 were recorded
for the N-80 and 13Cr samples, respectively. CI-14 44 72 1.64 18.0 -2.2
CI-15 81 73 0.90 -1,3 -0.5
Arun Stimulation Techniques and Results ~;~-~~ 5.2 ~~ *, .“”
nn 19 .! jj?
, .&
The first large-scale acidizing treatment performed in the Arun
Field was pumped in April 1990 on an injection well. The first CII-13 49 56 1.14 1.8 -1.9
treatment on a production well was pumped in July 1990. In the CII-15 71 101 1.42 -0.3 -2.3
3 years that followed, a total of 17 large acid fracs and a similar CII-16 52 58 1.12 1.5 -2.2
number of matrix-acidizing treatments have been performed
C1l-ol 55 100 1.82 22.6 -1.2
successfully. A good review of the philosophies for the treat-
ment design and execution was given by Cannan, et al.zs CIII-03 55 68 1.24 -1.0 0.2
Although the service company performing the work was changed Clll-lo 25 65 2.60 1.4 -1.4
during the Arun stimulation campaign, few changes to the job
CIV-05 42 81 1.93 6.9 -1.6
procedures were made.
The acid-fracturing treatments conducted consisted of the Clv-1 o 40 82 2.05 2.3 -2.5
following: Clv-11 42 79 1.88 6.0 -1.0
-,. ,.,. . fin
blv-lo 49 80 L.w 1.1 -2.9
●
a prepad to establish the rate and provide some initial
Average 1.55 4.3 -1.6
formation cooldown

528
SPE 30419 MARY S. VAN DOMELEN, ALFRED R. JENNINGS 7

Conclusions sented at the 1982 57th Annual Technical Conference, New

●
Protection of completion and production equipment is a Orleans, Sept. 26-29,.
primary concern during HPHT acidizing operations. This 10. McLeod, H.O., Ledlow, L.B., and Till, M.V.: “The Planning,
Execution and Evaluation of Acid Treatments in Sandstone
concern increases when the wellbore contains high-alloy
Formations,” paper SPE 11931 presented at the 1993 59th
metals, such as stainless and duplex steels, that are suscep-
Annual Technicrd Conference, San Francisco, Oct. 5-8.
tible tOhydrogen enibr%tiermmt tiid diiGtid~ Sti~SS-CiWk-

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11. Gidley, J. L.: “Stimulation of Sandstone Formations with the
ing. Acid-Mutuat Solvent Method,” .fPT (May 1971) 551-558.
●
A combination of organic acids (acetic and formic) can be 12. Hall, B. E.: “The Role of Mutual Solvents in Sandstone
used instead of HCI in HPHT applications to minimize Acidizing,” paper SPE 5377 presented at the 1975 California
corrosion problems. Dissolving power equivalent to 15% Regional Meeting, Ventura, CA, April 2-4.
,,-1 :. _--: L1-. .:.I. ,.:.-.:r:an”,,., _A,.,.aA,,n-n.; n 13. Harris, F.N.: “Applications of Acetic Acid to Well Completion,
I-M ISpUSMUiG WUIISIgIIIllVallL1y r=uue~u ~ullu.lun rates.
●
Some of the gelling agents developed for HCI yield higher Stimulation and Reconditioning;’ .lPT (July 1961) 637-639.
14. Smith, C.F., Crowe, C. W., and Weiland, D. R.: “Fracture
viscosities in organic acids on the basis of equivalent
Acidizing in High Temperature Limestone,” paper SPE 3008
polymer loading.
presented at the 1970 45th Annual Technical Conference, Hous-
✎
Although the base cost of an organic acid blend is higher ton, Oct. 4-7.
than that of HC1, reductions in inhibition and gelling agent 15. Chatelain, J.C., Silberger, I. H.,and Schechter, R. S.: “Thermo-
costs result in a final acid blend that is both technically and dynamic Limitations in Organic Acid-Carbonate Systems,”
economically more attractive than an HC1-based system. paper SPE 5647 presented at the 1975 50th Annual Technical
●
The use of organic acid blends to stimulate the high- Conference, Dallas, Sept. 28- Oct. 1.
deliverability Arun limestone has been proven effective in 16. Dill, W.R. arsd Keeney, B.R.: “Optimizing HC1-Formic Acid
terms of both well response and protection of the produc- Mixtures for High-Temperature Stimulation; paper SPE 7567
tion equipment. presented at the 1978 53rd Annual Technical Conference, Hous-
:Gn, ~~:, i .3.
17. Paccaloni, G., Tambini, M., and Galoppini, M.: “Key Factors
Acknowledgments for Enhanced Results of Matrix Acidizing Stimulation Treat-
The authors thank the management of Mobil E & P Technology ments;’ JPT (March 1993) 256-263.
Center and Halliburton Energy Services for permission to 18. Hill, A.D. and Rossen, W.R.: “Fluid Placement and Diversion in
publish and present this information. The contributions of Matrix Acidizing;’ paper SPE 27982 presented at the 1994
Mobil Oil Indonesia are also acknowledged. Centenial Petroleum Engineering Meeting, University of Tulsa,
Tulsa, OK, Aug. 29-31.
References 19. Jones, A.T., Dovle, M., and Davies, D.R.: “Using Acids
1. Murali,J.: “13Cr Stands Above Low-Alloy Steel OCTG,” Oil & Viscosified with Succinoglycan Could Improve the Efficiency
Gas Y. (July 9, 1984) 56-58. of Matrix Acidizing Treatments,” paper SPE 30122 presented at
2. Murali, J.:”13Cr Tests High Against C02 Corrosion: Oil& Gas the 1995 European Formation Damage Conference, The Hague,
J. (July 23, 1984) 66-69. May, 15-16.
3. Murali, J.: “13Cr Stainless Proven in Field Use; Oil & Gas J. 20. Chatterji, J. and Borchardt, J. K.: “Application of Water-Soluble
(August 6, i984 56-6% Polymers in the Oilfield,” paper SPE 9288 presented at the 1980
4. McDermQu,J,R, and Manin, B.L.: “Completion Design for 55th Annual Technical Conference, Dal!as, Sept. 21-24.
Deep, Sour Norphlet Gas Wells Offshore Mobile, Alabama,” 21. Norman, L.R., Conway, M.-W., and ‘wiison, J.M.: ‘-Tempera-
paper SPE 24772 presented at the 1992 67th Annual Technical ture-Stable Acid Gelling Polymers: Laboratory Evaluation and
Conference, Washington, DC, Oct. 4-7. Field Results: paper SPE 10260 presented at the 1981 56th
5. Crolet, J.L.: “Acid Corrosion in Wells (COZ, H2S): Metallurgi- Annual Technical Conference, San Antonio, TX, Oct. 5-7.
cal Aspects: JPT (August 1983) 1553-1558. 22. Anderson, M.S. et.al.: “Stimulation in the Tommeliten Field,”
6. Garber, J.D. and Kantour, M.: “How High-Alloy Tubulars React Paper OTC 6463 presented at the 22nd Annual Offshore Tech-
in Acidizing Environments; Pet. Eng. (July 1984) 60-68. nology Conference, Houston, TX, May 7-10, 1990.
7. Kolts, J. and Corey, S.M.: “Corrosion and Stress Corrosion 23. Johnson, D.E. et.at.: “Carbonate Production Decline Rates Are
Cracking of High Performance A1ioys in Simuiateci Acidizing Reduced ~rough Improvements in Gelled Acid Technology:
Environments to 350”FV paper Corrosion/84 No. 217, presented paper SPE 17297 presented at the 1988 Permian Basin Oil and
at the 1984 National Association of Corrosion Engineers, Hous- Gas Recovery Conference, Midland, TX, March 10-11.
ton, March 14-17, 24. “Mobil Indonesia Installs Giant 9-in. Bore Production Trees,”
8.
mr~,l.--
W dsKer,
.’ 1
lV1. L.
.
dnu
J lz.-fl..
Ivlmuy
.
,
T u
n...
1
tfmc+-a.-., .,
rzllc%lanu llU1l
,4
UILIU1lu,
I..l.:i.:,:,... ,.t- Pet. Eng. M. (June 1992) 15.
Stimulation Acids on Corrosion-Resistant Alloys: paper Cor- 25. Cannan, W.L., Jennings, A.R., Husaini, S., Bordelon, T.P., and
rosion/86 No. 154 presented at the 1986 National Association of Sardjono, S.: “Increasing Arun Deliverability Through Effec-
Corrosion Engineers, Houston, March 17-21. tive Acid Fracturing; paper SPE 22397 presented at the 1992
9. Crowe, C.W. and Minor, S.S.: “Effect of Acid Corrosion Inhibi- SPE International Meeting on Petroleum Engineering, Beijing,
tors On Matrix Stimulation Results,” paper SPE 11119 pre- China, March 24-27.

529
8 ALTERNATE ACID BLENDS FOR HPHT APPLICATIONS SPE 30419

Appendix A: Corrosion Test Procedures

All samples were prepared from commercially available field-
grade tubular goods. Test coupons were obtained from 2 3/8-in.
OD tubulars with wall thicknesses of 0.254 in. for 13Cr tubulars
and 0.190 in. for N-80 tubulars. The coupons used were

Downloaded from http://onepetro.org/SPEOE/proceedings-pdf/95OE/All-95OE/SPE-30419-MS/1967233/spe-30419-ms.pdf/1 by Halliburton Energy Services Group user on 08 August 2021
approximately 1 1/4 in. by 1 1/4 in., which corresponds to a
4.555-in.2 surface area. All coupons were sand-blasted and
rinsed with acetone before initial weighing and testing.
Corrosion weight-loss tests were conducted in autoclaves
manufactured from Hastelloy Alloy B-2. All test specimens
were hung in glass cells, which isolated them from galvanic
contact with the autoclave body. Autoclaves were filled with
kerosene that acts as the heat-transfer and hydraulic fluid. In all
tests, a 100-mL volume of acid solution was used to provide a
volume-to-surface-area ratio of about 22 mL/in.2 of exposed
metal. No precautions were taken to exclude oxygen.
m.—-
1ne metdl., LXJupum
----------- Welt.-...IGIWVGU - ●l.a .;A ~... ;..-.mm
-.-.,.. A+-.,,
MUII1 Lll= aUJu -n+.. v,,ldt
after exposure for the designated test time. They were immedi-
ately rinsed in water and then with acetone. The coupons were
then scrubbed lightly with a soft brass bristle brush and a mild
cieansing powder, rinsed with hot water and acetone, and then
reweighed. Corrosion losses were reported in lb/ft2 removed for
the stated exposure time. These values may be multiplied by
1,380.3 for conversion to roils per year (mpy).