SPE 107296

Single Step Matrix Acidising With HFEliminating Preflushes Simplifies the Process,
Improves the Results
Phil Rae, InTuition Energy Associates, and Gino Di Lullo, BJ Services

Copyright 2007, Society of Petroleum Engineers

This paper was prepared for presentation at the European Formation Damage Conference
held in Scheveningen, The Netherlands, 30 May1 June 2007.
This paper was selected for presentation by an SPE Program Committee following review of
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Abstract
For over 50 years, mixtures of hydrochloric and hydrofluoric
acids have been used for the removal of near-wellbore damage
in sandstone formations. Such mixtures dissolve many
siliceous minerals, including clays and quartz fines, the
materials most frequently associated with particulate plugging
of the formation pores. Unfortunately, the dissolution of these
minerals is not a simple process and various chemical
reactions can result in the generation of voluminous solid
precipitates or colloidal gels. The appearance of such
precipitates in the near-wellbore, can ultimately cause further
formation damage and negate the benefit of the acid treatment.
Other byproducts can be formed in sandstones containing
carbonate minerals that react with acid and fluoride ions to
produce the very insoluble calcium fluoride, CaF2, which is
another potential source of formation damage. For this reason,
traditional HCl:HF matrix treatments in sandstone formations
are always preceded by a preflush, usually consisting of HCl
to dissolve these carbonates.
This approach is not always successful and adds to the
complexity of the operation. The situation is worse in
multistage treatments, which traditionally involve many repeat
stages of preflush, main HF-stage, overflush and diverter. In
such situations, it is difficult to ensure that the correct acid
stage is always entering the appropriate zone and encountering
the appropriate mineralogy. The result can be poor zonal
coverage, poor damage removal, creation of unexpected
damage due to acid/rock incompatibilities and, ultimately,
poor stimulation results.
This paper presents the results of a new acidising technique
that eliminates the need for preflushes, across a wide range of
mineralogies. It describes the background to this approach and
reviews the results of laboratory testing and field treatments.
It concludes with a matrix acidising methodology that can

improve logistics, reduce cost and improve results while,

simultaneously, making treatments easier to implement and
control, at the field level.
Introduction
Will we run out of oil and gas anytime soon? No, probably
not, but we will need to come up with some innovative
solutions to meet increasing world demand and ensure that
hydrocarbons remain affordable. While new discoveries in
challenging environments, such as deepwater and HPHT, are
exciting, a significant amount of hydrocarbon remains in
older, mature fields. Production in such fields is usually far
below peak values, and many problems, like rising water cut
and scaling, are common. Yet, appropriate treatments, can
often restore production rates and extend economic field life
by many years, thereby improving ultimate recovery.
One of the most economical means of increasing production
for the industry is matrix acidising, a stimulation technique
that has been in use in the petroleum industry since the early
1900s. It is one of the simplest operations, both for the
operators and service companies, in terms of logistics in
remote areas i.e. land and offshore. When properly applied, it
is also an effective way to reduce the environmental impact of
our industry, ensuring that reservoir drainage is efficient by
optimising productive capacity from previously damaged
wells.
Matrix Acidising Revisited
In the course of drilling, or during production or workover, the
vast majority of oil and gas wells are exposed to conditions
that ultimately lead to formation damage, a phenomenon that
limits the productive (or injective) capacity of the well. This
reduction in well performance is generally due to changes in
near-wellbore permeability, caused by rock crushing, invasion
of drill solids, swelling of pore-lining clays, migration of
mobile fines and changes in wettability, amongst other things.
Traditionally, many of these causes of permeability
impairment have been found to be removable by injecting acid
formulations containing HF. The latter is capable of attacking
and dissolving many siliceous minerals including clays and
quartz fines, the materials most frequently associated with
particulate plugging of the formation pore spaces.
Unfortunately, the process of dissolving these minerals is not a
simple one and numerous chemical species are generated by
the interactions between the initial reactants and their first,
second or third stage reaction products. Driven by the unstable

nature of many of these chemical equilibria, the result is often

the generation of voluminous solid precipitates or colloidal
amorphous gels, in the reaction mixture. The appearance of
these secondary and tertiary precipitates at inopportune times,
or in critical locations like the near wellbore, can ultimately
cause further formation damage and negate the benefit of the
acid treatment. In an effort to mitigate these problems, the
industry has adopted several different approaches, as detailed
below:
1) The use of HF formulations containing excess HCl, a
strategy that lowers the pH of the HF mixture to levels at
which some of the reaction products have higher
solubility. This is the basis of the well-known Mud Acid
(RMA) a combination of HCl:HF in a 4:1 ratio, and of
more recent formulations, championed by Gdanski and
others, which feature even more extreme ratios of 9:1.
2) The use of delayed acid formulations that generate HF
only slowly, generally due to hydrolysis of one or more
components, thereby allowing deeper penetration of the
HF into the formation and effectively diluting the reaction
product concentration. This helps minimise precipitation
and is the approach used in systems like Clay Acid
(Fluoroboric Acid, HBF4) or SGMA (Self-Generating
Mud Acid).
3) The use of half-strength Mud Acid, another strategy that
dilutes the concentration of reaction products per unit
volume of acid treating solution.
4) The use of Buffered Acid systems that, essentially, limit
the availability of hydrogen ions for generation of HF.
This allows deeper penetration due to lower reactivity but,
since the pH of these systems is high, additional measures
must be adopted to prevent the appearance of siliceous
precipitates. The incorporation of additional materials like
phosphonates can inhibit the appearance of precipitates
and this is the approach used in one commercial HF-based
acid system.
5) The use of overflush fluids, usually dilute HCl or
ammonium chloride brine, to push the HF-containing acid
stage, along with its load of unstable, dissolved reaction
products, away from the critical near-wellbore region,
before any precipitation occurs.
6) The instigation of rapid flowback techniques to bring the
treating solutions back out of the formation and out of the
well, as quickly as possible, usually while the systems are
still at low pH and less likely to precipitate.
Unfortunately, the secondary and tertiary precipitates
generated by the interaction of HF with siliceous minerals are
not the only problematic byproducts encountered when acid
formulations containing HF enter a sandstone rock matrix.
Most sandstones contain varying quantities of carbonate
minerals (calcite, dolomite, etc) along with the quartz, clays
and feldspars that usually form the bulk of the rock. In the
presence of acids, the carbonate minerals dissolve to release
calcium ions that, in turn, react with fluoride ions to produce
the very insoluble calcium fluoride, CaF2, which precipitates
very quickly, and is another potential source of formation
damage. For this reason, traditional matrix acid treatments in
sandstone formations have traditionally almost always been

SPE 107296

preceded by a preflush, usually consisting of HCl, or other

non-fluoride containing acid, to dissolve these carbonates.
This is pumped in sufficient volume to theoretically remove
all carbonates within a radius of 2-3 ft from the wellbore,
thereby reducing the risk that the main, HF-containing acid
stage will contact any carbonate minerals.
While this is a good idea, in theory, it is not always as
successful as one might hope, in practice. The very reactive
preflush can open up preferential flow paths into the rock, due
to dissolution of carbonate, potentially bypassing other
damaged zones. Subsequently, the main HF-containing acid
can follow these same flow paths and may not contact the
plugging clays and other siliceous minerals that it is designed
to dissolve. The situation is probably worse in multistage
treatments, featuring sequential diversion, for example. These
treatments are very complex, involving many repeat stages of
preflush, main HF- stage, overflush and diverter and it is
difficult to ensure that the correct acid stage is always entering
the appropriate zone and encountering the appropriate
mineralogy. The result can be very poor zonal coverage, poor
damage removal, creation of unexpected damage due to
acid/rock incompatibilities and, ultimately, poor stimulation
results.
Matrix Acidising Revised.Not Just Revisited!
The problems detailed above are common to the majority of
commercial, HF-containing, acid systems but the listed
strategies for addressing these problems have not met with
universal success. However, we believe that we have
identified a method to solve these problems in the majority of
cases while, simultaneously, improving the success ratio and
safety of matrix acid treatments. Using novel high pH HFbased acid systems offers a potential method to circumvent
most of the problems and completely change the modus
operandi of acidising, in the process. As noted above, these
novel acid formulations are buffered, high pH acid systems
being generally in the range of pH 3.2 4.8, whereas most
traditional systems, like Mud Acid, have low pH (typically pH
0 - pH 1, depending on HCl:HF ratio). Yet, these novel high
pH systems have the same dissolving capability with respect
to siliceous minerals. The elevated pH has obvious advantages
in terms of corrosion and general reactivity, allowing deeper
matrix penetration of live acid and reduced requirements for
corrosion inhibitors. There are numerous other advantages of
this high pH including, but not limited to:
i)
reduced risk to surface equipment including pipelines
ii)
reduced risk to the environment and personnel
iii)
reduced chemical requirement for neutralisation
iv)
reduced risk of creating sludges and emulsions
v)
reduced risk of upset to process facilities.
Critically, because of the high-pH of these systems, they
attack calcium carbonate only slowly (when compared with
conventional systems) and therefore are much less prone to the
release of calcium ions and subsequent precipitation of
calcium fluoride. Combining such high-pH buffered systems
with certain scale inhibitors and anti-precipitants, enhances
their properties by minimising or preventing the risk of
secondary precipitates while further inhibiting dissolution of

SPE 107296

carbonates. Thus, such systems can, potentially, be used with

no preflush and with minimal risk of untoward reactions with
reservoir rocks. Such an approach greatly simplifies matrix
acidising procedures in sandstone reservoirs, eliminating the
need to pump multiple fluids in a carefully choreographed
sequence.
Pumping these systems, either alone or with a simple NH4Cl
overflush, potentially improves acid placement and
distribution and reduces equipment requirements, in terms of
tankage, etc. It improves logistics, reduces cost and improves
results while simultaneously making treatments easier to
implement and control, at the field level.
Eliminating Iron-Based Precipitates
One final benefit from the use of this technique should be
neither underestimated nor overlooked. Iron is ubiquitous in
the oilfield due to the use of steel tanks, lines and well tubulars
and, while iron is not necessarily a problem in HF-containing
systems, due to the formation of soluble hexafluoroferrate
complexes, it is very much a problem in conventional HCl,
used in the preflush.
It is widely recognised that iron-based precipitates are
responsible for many problems associated with acid
stimulation treatments. Steel, consisting mainly of iron, is
readily dissolved by strong mineral acids to produce ferrous
(Fe 2+) ions. Contact with atmospheric oxygen readily
transforms these to ferric (Fe 3+) iron, which can precipitate
very easily from acid solutions, even at low pH. Contact with
steel reverses this oxidation effect, to some extent, reducing
ferric iron back to the ferrous state. However, depending on
circumstances, the ferric iron concentration in HCl can be
extremely high due to the dissolution of the ferric oxides (rust)
that quickly form when steel is exposed to air. For this reason,
it is very much preferred that the well tubulars be pickled
with a suitable rust dissolver ( eg. dilute acid) and the string
contents reversed out, ahead of any acid treatment on the
formation. Failure to do so results in the injection of extremely
high levels of (mainly) ferric iron into the formation with a
very high probability of plugging the zone. Even when using
pickled tubulars, however, the level of iron in a mineral acid
preflush can still reach several thousand mg/litre, necessitating
the incorporation of high levels of iron-control agents to avoid
precipitation.
By eliminating the use of a mineral acid preflush, as described
above, and using a buffered HF-containing acid system, the
problems of iron dissolution and its subsequent precipitation
are largely mitigated. Such an approach, when coupled with a
tubing pickle, preferably using a neutral chelant pickling
agent, could significantly improve acidising results in many
formations. Incidentally, it would be particularly beneficial,
operationally, to be able to inject the neutral chelant pickling
agent, containing the dissolved and complexed iron, etc.,
directly into the formation without having to reverse it out
ahead of the acid treatment.
Laboratory Testing
Preliminary laboratory testing of this approach was
undertaken, just to show "proof of concept". As can be seen in
Figs. 1-3 and in Table 1, the Mud Acid system immediately
attacked and dissolved calcite chips, even at room

temperature, with violent effervescence and the generation of

a cloudy, white calcium fluoride (CaF2) precipitate. The high
pH, buffered acid system, on the other hand, did not react with
the calcite, at rrom temperature, and there was no
effervescence or precipitate. Even at 180 deg.F, after three
hours, there was no reaction between the high pH system and
the calcite, demonstrating, rather conclusively, that such an
acid system could, in principle, be pumped, with no preflush,
into relatively carbonate-rich sandstone without the risk of
generating calcium fluoride precipitation. Given such
encouraging initial results, a few core flow tests were
performed to confirm these findings. The results of these tests
are presented in Table 2 & Table 3. In cores with reasonable
carbonate content, the use of the high pH, buffered HF system
with no preflush caused no problems and gave essentially the
same permeability increase as pumping a traditional sequence
of HCl followed by HF. In cores with high carbonate content,
the high pH buffered HF system gave a meaningful increase in
permeability, with no untoward reactions while the
conventional HCl, HCl:HF combination caused core
disintegration and collapse due to the excessive dissolution of
cementitious carbonate by the aggressive preflush, mainstage
combination.
Field Results
The approach of using an HF-based system, with no preflush,
potentially in carbonate-containing rock, met with some
incredulity, initially. However, at the time of writing, more
than 35 jobs have been performed in several different parts of
the world with positive and encouraging results. The first 23
are summarised in Table 4.
Conclusions
1) Traditional sandstone matrix acidising techniques are often
successful in recovering productivity in wells damaged by
near-wellbore permeability reduction. However, the logistical
and HSE challenges, implicit in such acid treatments, often
discourages their wider use.
2) Traditional treatments require complex sequences of fluids
(preflush, main stage, overflush) to be pumped, along with
serial diversion, in an attempt to accomplish zonal coverage
while mitigating untoward mineral reactions with the acid
treating solutions.
3) Distribution of the acid system in such complex fluid trains
is unlikely to be efficient resulting in unwanted reactions and
less than optimum stimulation results.
4) The use of carefully designed high pH buffered acid
systems can eliminate many of the problems associated with
conventional sandstone matrix acidising.
5) Use of such systems can eliminate the need for preflushes
and overflushes, across a range of mineralogies, thereby
reducing acid volumes and tankage and dramatically
improving the logistics and safety of such operations.
6) High pH buffered acid systems can be pumped as single
stage treatments, thereby improving zonal coverage of the acid
system, simplifying the pumping schedule, reducing the cost
and, ultimately, improving the results of the treatment.
7) To date, 35 Single Step Sandstone Acid treatments have
been pumped with good results across a range of mineralogies.

References
1. Williams, B.B., Gidley, J.L., Schechter, R.S. Acidizing
Fundamentals Monograph Volume 6, chapters 3, 4, 8 and
9, SPE 1979
2. Kalfayan L, Production Enhancement With Acid
Stimulation Pennwell Corporation (2000) 51
3. Smith C.E. and Hendrickson AR Hydrofluoric Acid
Stimulation of Sandstone Reservoirs JPT (Feb 1965)
215
4. Crowe C.W., Precipitation of Hydrated Silica from Spent
Hydrofluoric Acid: How Much of a Problem Is It? JPT
(Nov 1986) 1234
5. Gdanski R.D., Fluosilicate Solubilities Impact HF Acid
Compositions SPE 27404, Symposium on Formation
Damage Lafayette Feb 7-10 (1994)
6. Di Lullo, G. and Rae, P. A New Acid for True
Stimulation of Sandstone Reservoirs, paper SPE 37015
presented at the 1996 SPE Annual Technical Conference
and Exhibition held in Denver, CO, 6-9 October
7. Ross, D. and Di Lullo, G. HV:HF Acid Treatments,
Proven Successful in South America, paper IBP-SE076/98 presented at the 1998 Rio Oil & Gas Conference
held in Rio de Janeiro, Brazil, 5-6 October
8. Ely J., Stimulation Treatment Handbook, PennWell
Books (1987)
9. Ali A. Syed, Sandstone Diagenesis, Applications to
Hydrocarbons Exploration and Production, USA (1981)
10. Gdanski R.D. and Shuchart C.E.: Advanced SandstoneAcidizing Designs With Improved Radial Models SPE
52397, San Antonio, Texas 5-9 October 1997
11. Martin A.N. and Smith K.L., New HF Acid System
Produces Significant Benefits in Nigerian Sandsones,
SPE Paper 38595, presented at SPE Annual Technical
Conference & Exhibition San Antonio, Texas 5-8 October
1997
12. Nasr-El-Din H.A., Al-Dahlan M.N., As-Sadlan A.M., AlZamil H.A., Iron Precipitation During Acid Treatments
Using HF-Based Acids presented at SPE Internation
Symposium and Exhibition, Lafayette, February 20-21,
2002
13. P. Rae and Di Lullo G.: Achieving 100 Percent Success In
Acid Stimulation Of Sandstone Reservoirs, SPE 77808,
Melbourne, Australia, 8-10 October 2002
14. Nasr-El-Din H.A., Al-Mutairi S.H., Al-Driweesh S.M.:
Lessons Learned from Acid Pickle Treatments of
Deep/Sour Gas Wells SPE 73706, Lafayette, Louisiana
20-21 February 2002
15. Crowe C.W., Evaluation of Agents for Preventing
Precipitation of Ferric Hydroxide from Spent Treating
Acid JPT (April 1985) 691-695
16. Thomas R.L., Nasr-El-Din H.A., Lynn J.D. and Mehta S.:
Precipitation During the Acidizing of a HT/HP Illitic
Sandstone Reservoir in Eastern Saudi Arabia: A
Laboratory Study SPE 71690, New Orleans, Louisiana
30 September-3 October 2001
17. Thomas R.L., Nasr-El-Din H.A., Mehta S., Hilab V. and
Lynn J.D.: The Impact of HCI to HF Ratio on Hydrated
Silica Formation During the Acidizing of a High
Temperature Sandstone Gas Reservoir in Saudi Arabia

SPE 107296

SPE 77370, San Antonio, Texas, 29 September-2 October

2002
18. Hashem M.K., Nasr-El-Din H.A., Hopkins J.A.: An
Experience in Acidizing Sandstone Reservoirs: A
Scientific Approach SPE 56528, Houston, Texas, 3-6
October 1999
19. McLeod H.O.: Matrix Acidizing, Journal of Petroleum
Technology (Dec. 1984): 2055-69
20. Abrams A., Lybarger J.H., Neasham J.W. and Richardson
E.A.: The Development And Application Of A High pH
Acid Stimulation System For A Deep Mississippi Gas
Well, SPE 7565, Houston, Texas, 1-3 October

SPE 107296

ACID SYSTEMS

OBSERVATIONS

High pH HF System

No effervescence or precipitation even after 24 hrs

Regular Mud Acid

Strong effervescence and formation of white precipitate

Table 1: Comparative Observations on the Reaction of Calcium Carbonate with Conventional Mud Acid
(12:3 HCl:HF) and a High pH HF System

Fig. 1: Solubility of 20 Mesh Calcite Chips In Mud Acid

@ Room Temperature
INITIAL @ 15 MINUTES

AFTER REACTION @ 180F (L) & ROOM TEMP

AFTER 3 HOURS

SPE 107296

Fig 2: Solubility of 20 Mesh Calcite Chips in Novel High pH HF Acid

@ Room Temperature

INITIAL @ 15 MINUTES

AFTER 3 HOURS

SPE 107296

Fig 3: Solubility of 20 Mesh Calcite Chips in Novel High pH HF Acid

@ 180 Deg. F

INITIAL @ 15 MINUTES

AFTER 3 HOURS

SPE 107296

Table 2: X-Ray Diffraction Analysis of Cores for Core Flow Testing

MINERALOGY

APPROXIMATE WEIGHT %
TEST 1

TEST 2

TEST 3

TEST 4

BEREA

BEREA

030950F

030950G

QUARTZ

98%

98%

65%

66%

CALCITE

2%

2%

DOLOMITE

18%

18%

SIDERITE

3%

1%

PLAGIOCLASE FELDS

2%

3%

ILLITE

5%

5%

TRACE

TRACE

6%

7%

TEST #/ CORES

KAOLINITE

Table 3: Core Flow Analysis Comparing Results of High pH HF System with and without
an HCl Preflush on Final Permeability

TEST #

ACIDS

INITIAL
PERM, md

REGAIN
PERM, md

RESULTS

Novel High pH HF
NO PREFLUSH

7.55

17.96

138% increase

Novel High pH HF
HCl PREFLUSH

7.80

17.96

130% increase

Novel High pH HF
NO PREFLUSH BJ

2.69

4.73

76% increase

Novel High pH HF
HCl PREFLUSH

3.0 1

Fines plugging

(BEREA)

2
(BEREA)

3
(#030950F)

4
(#030950G)

SPE 107296

Table 4: Jobs Summary

Country

Well

Well Type Completion

Acid
Concentration
(Half/Regular/S
trong)

Volume
(Gal)

Peru

Producer

Vertical

Peru

Producer

Peru

Pickling
Post Job Post Job
(Yes/No) Gain BOPD
Gain BWPD

Casing

Regular

5670

Yes

4000

N/A

Vertical

Casing

Regular

7140

No

699

N/A

Producer

Vertical

Casing

Regular

9660

Yes

2100

N/A

Peru

Producer

Horizontal

Casing

Conform Acid
Regular

2730

No

-300

Peru

Producer

Horizontal

Casing

Conform Acid
Regular

2100

No

N/A

Nigeria

Producer

Vertical

Gravel

Half

~250

Yes

417

Nigeria

Producer

Vertical

Gravel

Half

~250

Yes

Nigeria

Producer

Vertical

Gravel

Half

~250

Yes

727

Nigeria

Producer

Vertical

Gravel

Half

~250

Yes

N/A

Russia

Producer

Vertical

Fractured

Regular

No

40

El
Geothermal
Salvador
Injector
Argentina
Injector

Vertical

Strong

13209

Yes

Vertical

Slotted
Casing
Casing

Half

1717

Yes

1440

Argentina

Injector

Vertical

Casing

Half

1060

Yes

Argentina

Injector

Vertical

Casing

Half

2325

Yes

Brazil

Producer

Vertical

Casing

Half

1490

Yes

1800

Brazil

Producer

Vertical

Casing

Regular

2025

Yes

20

Brazil

Producer

Vertical

Gravel

Regular

210

Yes

350

Brazil

Producer

Vertical

Gravel

Regular

420

Yes

280

Brazil

Producer

Vertical

Gravel

Regular

420

Yes

210

Brazil

Producer

Vertical

Casing

Regular

2100

Yes

2500

Brazil

Producer

Vertical

Casing

Regular

1500

No

20

Brazil

Producer

Vertical

Casing

Regular

880

No

4800

Ecuador

Producer

Vertical

Casing

Regular

1135

Yes

600

7528