Matrix Treatment

Stimulation
Field
Guidelines
by G. Nitters
SIPM, EPD/411
Contents
1 Introduction 1
2 Damage removal techniques 3

2.1 Matrix acidising 3
2.2 Acid wash (perforation wash) 4
2.3 Chemical flushes with surfactants, solvents,mutual solvents, etc. 4
2.4 Skinfrac 4
3 Damage removal design process 7

3.1 Problem well identification 9
3.2 Analysis of the skin factor 10
3.3 Damage classification 11
3.4 Treatment selection 12
3.5 Treatment design 12
4 Matrix acidising of sandstones 15

4.1 Introduction 15
4.2 Acid type, - concentration and - volume 15
4.3 Pumping schedule 20
4.4 Method based on experimental acid responsecurves 20
4.5 Alternative design methods 21
4.6 Paccaloni's prediction curves 24
4.7 Design recommendation 24
5 Matrix acidising of carbonates 27

5.1 Acid/carbonate rock reactions 27
5.2 Wormholing 30
5.3 Treatment design 32
5.4 Acid wash or soak 33
5.5 Matrix acidising 34
34
35
6 Non-acid matrix treatments 37

Field Guidelines for Matrix Treatments Contents  i
6.1 Wax and asphaltene removal treatments 37
6.2 Hot oil treatments 38
6.3 Solvent treatments 38
6.4 Dispersant treatments 39
6.5 Chemical and electrical heat treatments 39
6.6 Removal of emulsions, pipe dope, etc. 40
6.7 Scale removal 42
6.8 Carbonate scale 42
6.9 Calcium sulphate scale 43
6.10 Barium sulphate 43
6.11 Scale removal recommendation 43
6.12 Enzyme treatments 44
6.13 Hypochlorite treatments 45
7 Additives for matrix treatments 47

7.1 Introduction 47
7.2 Corrosion inhibition 48
49
7.3 Sequestering agents 49
50
50
7.4 Solvents 51
7.5 Surfactants 53
54
54
7.6 Clay stabilisers 55
55
7.7 Additive summary 55
8 Placement techniques 57
8.1 Introduction 57
8.2 Mechanical techniques 58
8.3 Packer and bridge plug arrangements 58
8.4 Selective Placement Tool (SPT) 58
8.5 Ballsealers 59
8.6 Use of solids to alter the effective zonal permeability 59
8.7 Use of fluids to alter the effective zonal viscosity 61
61
62
9 Laboratory experiments 65
9.1 Introduction 65
9.2 Fluid compatibility tests 66
9.3 Standard test procedures for stimulation core flow tests 67
67
67
68
68
68
ii  Contents Field Guidelines for Matrix Treatments

69
69
70
9.4 Corrosion tests 70
9.5 (De-)emulsion tests 71
9.6 Strength measurements. 72
10 Special applications 73
10.1 Gravel-packed wells 73
73
74
75
75
76
10.2 Summary 76
10.3 Horizontal wells 77
10.4 Naturally fractured sandstones 78
10.5 Exploration wells 79
10.6 High temperature/high pressure wells 81
81
82
Appendix 84
Check list for the selection of stimulationcandidates 84
84
84
85
85
86
E.1. Hydraulically fractured wells 86
E.2. Matrix treatments 86
86
86
Field Guidelines for Matrix Treatments Contents  iii

CONFIDENTIAL
1 Introduction
Soon after the first wells were drilled, people started to look for methods to
improve the production of new and existing wells. In 1895 for the first time a well
in Ohio, USA, was successfully treated with hydrochloric acid. Lack of good
corrosion inhibitors prevented widespread application of acid to stimulate wells
until the early thirties, when arsenic inhibitors emerged. The use of "mud acid"
was introduced (by Dowell) for sandstone wells. In subsequent years further
development of techniques, materials and equipment lead to the present
widespread stimulation activity: world-wide probably several thousand treatments
per year with a total expenditure of many millions of US dollars.
Why is stimulation so popular? Quite simply, because it is a cheap way of
generating extra production capacity. Within the Shell group (excl. Shell Oil) in
1993 nearly 400 matrix treatments were carried out with a total gain of 16610
m3/d at a total cost of US $ 28 million. Although it is difficult to estimate how
long the productivity improvements last, the unit technical cost is estimated to be
less than US $ 0.40/bbl.
The flow of hydrocarbons from a well can be described by the general inflow
equation:
Kh ( P - Pwf )
Q =
mB0 ( ln ( re / rw ) + S )
The parameters, that can be influenced to some extent by matrix treatments, are:
 The skin factor S;
The skin may be dissolved or removed by acid or organic solvents
dependent on the composition of the impairing material and the nature
of the formation.
 The formation capacity Kh;
Effectively more informatior height may be connected with the
wellbore, showing up as an increase in kh in a well test interpretation.
Field Guidelines for Matrix Treatments Introduction  1

CONFIDENTIAL
2 Damage removal techniques
The most commonly used damage removal techniques are:

 Matrix acidising
 Acid washes
 Chemical flushes with surfactants, solvents, mutual solvents, etc.
 (Skinfrac)
2.1 Matrix acidising

This technique aims at the removal of impairing material near the wellbore by
injection of acid - at a pressure below fracturing pressure - into the porous matrix
of the reservoir. It can be applied in both sandstones and carbonate reservoirs, but
the methods, objectives and mechanism for each of these two types of rock are
completely different. Volumes are typically in the range of 0.3 - 2 m3/m of
perforated interval. It is the most widely applied stimulation technique, covering
some 90% of the total stimulation effort in the Group.
For sandstones the objective is almost always the removal of formation fines,
clays, damage, etc. from the near wellbore area, although occasionally acidising
can serve to establish a connection between the wellbore and natural fractures
(e.g. Southern North Sea gas fields). Damage removal is accomplished by
injection of acids (mostly mixtures of HCl and HF, often called mud acid) to
dissolve the siliceous fines. Over the years many alternatives to mixtures of HF
and HCl have been proposed and experimented with. In general, no satisfactory
alternative to mud acid has been found.
For carbonates matrix acidisation is usually carried out with HCl only. Here the
mechanism is the enlargement of pores, natural fractures, etc., thus allowing
impairing fines to be flushed out rather than dissolving them. The use of mud acid
is not recommended in view of the potential precipitation of calcium fluoride
(CaF2) when HF reacts with calcium carbonate.
In general, matrix acidising is not effective as a means to increase the
productivity in low permeability reservoirs, but should primarily be applied for
the removal of (acid soluble) damage. Only in exceptional cases is it effective as
Field Guidelines for Matrix Treatments Damage removal techniques  3
CONFIDENTIAL
a primary stimulation treatment, such as in naturally fractured formations (as is

quite common in carbonates), where it may connect separated fissures.
The acids are usually formulated with a number of additives aimed at combating
various problems. A wide range of additives is commercially available. Although
the usefulness of some of these additives can be questioned, the acid should at
least contain a corrosion inhibitor. Otherwise, the strong acid will attack the
tubular goods, well-head, etc. Furthermore, pure HCl flushes should almost
always contain a sequestering agent. This will prevent precipitation of iron
hydroxide (from iron dissolved from the tubing and certain iron containing
minerals) as the acid is spending inside the pores of the formation rock. Mud acid
flushes are self-sequestering and, in general, do not need a sequestering agent.
2.2 Acid wash (perforation wash)

This involves the use of small volumes of acid, usually HCl, to remove scale and
other acid soluble material from plugged perforations. The volume is limited to
0.1 - 0.2 m3/m. Depending on the type of scale, a sequestering agent may be
added to avoid precipitation of iron hydroxide. However, this type of treatment is
not intended to significantly penetrate the formation rock and, hence,
precipitation of iron inside the pores of the formation rock should not occur.
2.3 Chemical flushes with surfactants, solvents,

mutual solvents, etc.
Acid will only dissolve acid soluble materials. Other forms of damage, such as
emulsion blocks, precipitation of organic material, asphalt, etc. will not respond
to treatment with acid. In fact it may be exacerbated. A large number of different
treatments have been proposed to solve these problems. Unfortunately, this group
of damage removal treatments is not supported by a great deal of science.
Successful treatment design is usually found by trial and error.
2.4 Skinfrac
In some wells the damage due to e.g. clay swelling, may have penetrated so deep
into the formation that it cannot effectively be cured by acid or any other solvent.
Also sometimes the damage is caused by materials that have no solvent such as
some lost circulation materials, bitumen, ferric asphaltenes, etc. In such cases,
rather than trying to dissolve the damage, small hydraulic fractures to by-pass the
damage zones should be applied: Skinfracs. For application and design of this
technique, the reader is referred to the "Field Guidelines for Hydraulic Fracturing
Treatments" (Report EP 93-1170).
4  Damage removal techniques Field Guidelines for Matrix Treatments

CONFIDENTIAL
3 Damage removal design process
The well and reservoir requirements for successful stimulation are dictated by
economical constraints, which may be translated into the following rules of
thumb:
Minimum requirements for successful matrix treatments
Hydrocarbon saturation 30 % or more
Water cut 40 % or less
Gross reservoir height no limit
Permeability Gas > 1 mD, Oil > 20 mD
Reservoir pressure Gas: two times the abandonment pressure

Oil 80 % depletion
Production system Current production not more than 80 % of maximum

capacity of facilities
Figure 1 - Minimum requirements for successful matrix treatments
Field Guidelines for Matrix Treatments Damage removal design process  5

CONFIDENTIAL
The decision to stimulate a well can be made using the chart depicted in Figure 2.
In this chart the potential production of a well refers to the production to be
expected based on general information on the reservoir quality, i.e. permeability,
thickness, porosity, saturation, etc. Several reservoir engineering models exist to
calculate this potential production, ranging from simple application of Darcy' law
to more complicated reservoir simulators. Often the potential is simply judged on
the basis of a comparison with neighbouring wells. The Production Analyst is
very suitable for this. Use of the "bubble display" allows the production rate and
cumulative production of wells to be compared on a field wide basis. Although in
many cases this may be acceptable, it can lead to erroneous conclusions.
Reservoir parameters (permeability, saturation,
Well input data Stimulation Treatment

(Q,S,WIQI, etc.)
Selection
Depleted or Yes Not a stimulation
highgas/ water candidate
cut?
No
K<20 mD (Oil) Yes No Major hydraulic
Natural fracs? fracturing treatment
K<1mD (Gas)
No Yes
Slanted /horizontal
No
Skin>5 and/orW IQI<0.9 sidetrack with acid
treatment
Yes
Investigate other
No measures
S dam >20% of total S?
(e.g. reperforation)
Yes
No Yes
Yes
Sand problems? Sandcontrol in place? Completion fit for fracs? Skinfrac treatment
(Frac&Pack)
No Yes No
Yes
W orkover justified?
Matrix treatment
Low chance of
Cause of damage No success
No
known?
Matrix treatment
Yes
High chance of
success
Figure 2 - Stimulation Treatment Selection Chart
etc.) may vary considerably between wells whilst, on the other hand, all wells
may be damaged e.g. due to impairing drilling practices applied throughout the
field! Only if impairment exists, a damage removal treatment will result in a
substantial improvement in production.
As with any well treatment, matrix treatments require a number of steps to be
taken. The complete process is depicted in Figure. 3. The remainder of this report
6  Damage removal design process Field Guidelines for Matrix Treatments
CONFIDENTIAL
describes, step by step, the selection and design process for matrix treatments. It
will enable the production technologist in the field to select and design the best
suitable treatment to improve the productivity of a damaged well. Theoretical
details are limited as much as possible. Readers interested in such details are
referred to the Well Stimulation Manual Vol. III ( EP 92 - 0323), which in turn
contains a large number of references to specific topics.
Damage removal treatment process
Problem well
identification
Diversion,
Damage Operational
additives,
classification constraints
etc.
Operational Scheduling
Treatment Treatment Site
stimulation and
selection design preparation
program logistics
Treatment
result
prediction
Evaluation cycle Job execution
Figure 3 - Damage removal design cycle
3.1 Problem well identification

Sooner or later during the lifetime of almost any well, production problems will
occur. Production may decline due to natural (produced fines, wax, etc.) or
induced (e.g. mud remnants) near wellbore permeability damage. Also the natural
production may be low due to disappointing reservoir properties (e.g. low
permeability).

CONFIDENTIAL
The parameter that is mainly influenced by matrix stimulation is the skin factor S.
The skin is an important factor to decide whether or not to stimulate a well and
what generic type of treatment would be best suitable. For clearly damaged wells
(high skin factor) matrix treatments are normally the first choice. However, the
skin factor is a dimensionless, mathematical concept and represents the combined
effect of a number of parameters of which formation damage is only one. For a
proper interpretation of the skin (and hence for the determination of the
appropriate remedial action), the contribution of each factor needs to be analysed.
3.2 Analysis of the skin factor

The skin factor (S) is a measure for the ease with which fluids flow from the
undisturbed reservoir to the wellbore. It represents the pressure drop due to
additional resistance to flow of reservoir fluid in the near well bore region.
Note that a negative value of S will result in a pressure drop less than may be
expected on the basis of the reservoir permeability, i.e. it means that the well has
been stimulated or that natural fractures exist.
The skin factor is frequently determined by means of the so called "Horner plot"
of the pressure data from of a pressure build-up test. As already indicated above,
the skin comprises all the factors that hinder (positive value of S ) or stimulate
(negative value of S) the (natural) flow of fluids to the wellbore:
Stot : Total skinfactor ("Horner" skin)

Sdam : Skin due to formation damage, positive. This is what we are trying
to remove by a matrix treatment.
Sperf : Skin due to limited perforation height, positive. This results from
the well not being perforated over the complete reservoir height,
e.g. to minimise gas or water coning
Sturb : Skin due to turbulent (non-Darcy) flow (mainly applicable to gas),
positive. This is often caused by flow convergence due to an
inadequate number and dimensions of perforations.
Sdev : Skin due to wellbore deviation, negative. At high deviation angles
the increased effective length of the reservoir section open to flow
increases the "natural" well productivity.
Sgravel : Skin due to gravelpacking, usually positive. However, in principle
underreamed, open hole gravel packed wells might have a negative
skin due to the increased effective wellbore radius.
Sstim : Skin due to stimulation, negative. This is in particular true for
hydraulically/acid fractured wells.

CONFIDENTIAL
Stemp : Skin due to temperature transition in water injectors, usually

positive, due to lower mobility of the cold injection water compared
to the hotter formation water*.
Sfiss : Skin due to the near wellbore presence of natural fissures, negative.
This can greatly enhance well productivity.
The real skin due to damage (that portion of the total skin that can be removed by
matrix treatments) can thus be isolated from this total skin using the following
formula:
Sdam = Stot - (Sperf+ Sturb+ Sdev+ Sgravel+ Sstim+ Stemp+ Sfiss)
For each of these skin components formulae have been derived by various
authors. Details may be found in the Production Handbook. The common systems
programme HORVIP can also be used to determine Sdam.
3.3 Damage classification

If the well appears to suffer from near-wellbore damage (i.e. removable by matrix
treatments), the reader may continue the selection procedure by trying to classify
the nature of the damage. In principal formation damage is classified according to
the process or operation which caused the damage to develop:
 Impairment related to drilling, completion and workover operations.
 Impairment induced by the produced fluids (or in case of injection
wells, by the continuously injected fluids).
 Impairment as a result of injected fluids during specific operation, such
as (re)perforation, stimulation, gravelpacking, etc.
A damage classification check-list has been prepared. This check-list, shown in
Appendix A, is probably not complete, but does cover 80 - 90 % of all cases of
damage. For a detailed discussion on damage classification, the reader may
consult the Well Stimulation Manual Vol. III ( EP 92 - 0323).
3.4 Treatment selection

Once the most likely source of damage has been established, a specific treatment
may be selected using the chart given in Figure 4.

CONFIDENTIAL
Matrix treatment selection

Cause of damage Damage type Type of treatment
Solids Acid
Drilling, invasion treatment
completion, (HF/HCl)
etc.
Specific well Acid
Precipitates,
treatment* treatment
Chemical Clay swelling
(HF/HCl)
interaction Solvent
Emulsions treatment
*Stimulation, gravelpacking (re-)perforation, etc.
(Surfactants)
Solvent
Wax,
treatment
Produced asphaltenes
(Surfactants)
fluids
Formation Acid
fines treatment
Acid
Precipitates, treatment
scale (HCl)
Water
Acid
Clay swelling treatment
Injected fluids
(HF/HCl)
Solvent
Oily/inhibitor
Gas treatment
residues
(Surfactants)
Figure 4 - Matrix treatment selection
3.5 Treatment design

Having selected the type of treatment, the next step is to formulate a design. In
the following chapter we will discuss the design procedure of the following types
of treatment:
 Matrix acidising of sandstones
 Matrix acidising of carbonates
 Solvent treatments
 Treatment with surfactants, enzymes, etc.

CONFIDENTIAL
4 Matrix acidising of sandstones
4.1 Introduction
Improving the natural productivity of a well by increasing the permeability of a
large area around the wellbore would require a large treatment. This would
dissolve virtually all cementing pore-fill material and even part of the quartz
matrix in the vicinity of the well. It is obvious that the integrity of the formation
would be affected. Sand production might be the result. The main application of
acidising is therefore limited to damage removal. Hence the term "matrix
acidising" is somewhat misleading. However, its use has become so widespread
that we will continue to use the term also in these guidelines.
Only when the pre-treatment productivity is high, will a normally sized matrix
treatment of an undamaged well be economically justifiable. This is particularly
true for gas wells where high velocities can lead to significant non-Darcy flow
effects (Sturb). These can be reduced by increasing the near wellbore porosity
with a matrix treatment.
4.2 Acid type, - concentration and - volume

Traditionally, the majority of the acidising treatments of sandstones have been
carried out with a standard mixture of 12% HCl and 3% HF, irrespective of the
chemical nature of the damaged formation. This mixture is generally known as
regular mud acid (RMA). A typical job comprises of the injection of 0.2 -1.8
m3/m of perforated interval of mud acid preceded by an HCl preflush of
approximately half that volume. The preflush is used to dissolve any carbonates
present as these could cause precipitation calcium or magnesium fluoride upon
contact with HF. Sometimes, 6% HCl + 1.5% HF is used (half-strength mud acid,
HMA), for instance when formation competence problems are expected with the
use of stronger acids. Shell oil developed even weaker alternatives by replacing
HCl with organic acids, such as formic acid or acetic acid. On the other hand also
double strength mud acid (DMA, 24/6 HCl/HF) or even stronger have been
promoted by some service companies, but their use has never become
widespread.
Field Guidelines for Matrix Treatments Matrix acidising of sandstones  11

CONFIDENTIAL
Both field experience, laboratory work as well as theoretical calculations have

shown that clays and feldspars have a large influence on the reactivity of a
formation rock with acid. Chemical simulations, for instance, support the
occurrence of "secondary precipitates" from the reaction of potassium rich
feldspars and clays, observed in core flushing tests.
The interfering reactions that can occur when acidising clay and feldspar rich
sandstones have prompted various experts and authors to produce charts and
tables with specific treatment suggestions for the different minerals. Figures 5 and
6 show a compilation of the various recommendations.
From all naturally occurring clays, chlorite is probably the most difficult one with
respect to acidising. It usually contains calcium, magnesium and iron (III). As a
result, upon dissolution it is very sensitive to precipitation of calcium and
magnesium fluoride and ferric hydroxide.
Formations containing chlorite should therefore be treated with low
concentrations of hydrofluoric and hydrochloric acid. Contrary to the normal
recommendation, also the mainflush should contain a sequestering agent (e.g.
citric acid, see Chapter xxx). Alternatively, hydrochloric acid may be replaced by
acetic acid. In line with this suggestion, Shell Oil recommends the use of BRMA
(Buffer regulated Mud Acid), a mixture of an organic acid, e.g. acetic acid, and
hydrofluoric acid. For details on this Shell Oil development, see the Well
Stimulation Manual Vol. III ( EP 92 - 0323).
12  Matrix acidising of sandstones Field Guidelines for Matrix Treatments

CONFIDENTIAL
Sandstone Acidising Selection

Shallow damage
Main Mineral Clean

Feldspar Smectite Kaolinite (Fe-) Chlorite
Sandstone
Type of
acid
RMA, HMA,
SFMA    
BRMA/Acetic
acid (SFMA) 
SGMA
Claysol
Clay Acid
RMA : Regular Mud Acid - 12% HCl + 3% HF

HMA : Half -strenght Mud Acid - 6% HCl + 1.5% HF
SFMA : Specially Formulated Mud Acid, 5 - 20% HCl + 0 - 5% HCl
BRMA/Acetic acid ; Buffer Regulated Mud Acid, mixture of Acetic acid and HF
SGMA : Self Generating Mud Acid, mixture of organic ester and NH 4F
Claysol : Sequential NH 4F and HCl flushes, developed by Halliburton
Clay Acid : Mixture of HCl and Fluoboric acid, developed by
Schlumberger-Dowell
Figure 5 - Sandstone acidising selection chart - Shallow damage

CONFIDENTIAL
Sandstone Acidising Selection

Deep damage
Main Mineral Clean
Feldspar Smectite Kaolinite (Fe-) Chlorite
Sandstone
Type of
acid
RMA, HMA,
SFMA
BRMA/Acetic
acid (SFMA)   
SGMA

Claysol
Clay Acid
RMA : Regular Mud Acid - 12% HCl + 3% HF

HMA : Half -strenght Mud Acid - 6% HCl + 1.5% HF
SFMA : Specially Formulated Mud Acid, 5 - 20% HCl + 0 - 5% HCl
BRMA/Acetic acid ; Buffer Regulated Mud Acid, mixture of Acetic acid and HF
SGMA : Self Generating Mud Acid, mixture of organic ester and NH4F
Claysol : Sequential NH4F and HCl flushes, developed by Halliburton
Clay Acid : Mixture of HCl and Fluoboric acid, developed by
Schlumberger-Dowell
Figure 6 - Sandstone acidising selection chart - Deep damage
Even when the above rules are followed, the results of matrix treatments are
sometimes disappointing; secondary impairing mechanisms can nullify the
beneficial effects of mud acid. KSEPL developed a procedure to determine
optimum acid formulations based on an analysis of the chemistry of the
acid/formation (including damage) reaction. This method is being referred to as
"the SFMA concept". The method simulates the invasion of acid in the rock
matrix and determines the optimum compromise between the power to dissolve
clay components and the potential to impair by precipitation of reaction products.
It also takes into account loss of formation integrity due excessive dissolution of
minerals. The calculations produce a SFMA contour plot, showing the theoretical
productivity improvement as a function of the HF and HCl (or organic acid)
concentrations. An example is shown in Figure 7. The method can also be used to
estimate the required volume.

CONFIDENTIAL
SFMA diagram (example)

HF (%w)
5.0 1.50
2.0
4.0 Severe loss of
2.5 formation strengh
Operationally
3.0 not applicable 3.0
2.0
Preferred
compositions
1.0 2.5
2.0
1.5
2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0
HCl (%w)
Figure 7 - SFMA contour diagram
Combined with acid response tests, the SFMA concept is particularly valuable for
the ranking of suitable acid formulations. The following procedure is
recommended:
1. Determine the mineral composition of the formation.
2. Establish the (most likely) nature of the damage.
3. Run the SFMA program (N.B. Currently, this program can only.be run
at KSEPL, a user-friendly version for use in OPCO's is being made). If
the use of organic acid might be useful, based on the formation and/or
impairment composition and using Figures 5 and 6, formic or acetic
acid can be included in the calculations.
4. Carry out (a limited number of) acid response tests with suitable core
material, using a number of acid compositions selected from the SFMA
contour plot.

CONFIDENTIAL
5. Select the most appropriate acid composition using the acid response
test results.
4.3 Pumping schedule

At this point it is possible to formulate a design in terms of volume and HCl/HF
concentrations, i.e. the first two elements of the total design. Following this, a
pumping schedule has to be determined. In the literature, different methods are
found to do this. They range from relying on field experience (Paccaloni's on-site
design method) to using design curves based on generalised core flushing tests
(SPE Monograph method). Neither of these methods directly apply the results of
laboratory testing.
We will first discuss the preferred method based on acid response curves,
followed by a short description of some alternatives if such experimental data are
not available.
4.4 Method based on experimental acid response

curves
The prevailing experimental conditions in an acid response test deviate in many
ways from the actual conditions during a field acidising treatment. Nevertheless it
is often the only information available as to how the permeability of the
(damaged) formation responds to treatment with acid. The total acid volume
required amounts to:
Vtot = {Varc* (Rd/Rw) + pf(Rd2 - Rw2)} * h, (1)
Vtot = total acid volume (m3)
Varc = acid volume per unit length, determined from the acid
response curve (m3/m)
f = porosity (fraction)
h = height of perforated interval (m)
Another important factor in the treatment design is the maximum injection rate at
which acids can be injected without fracturing the formation. By expressing the
skin factor S in terms of Rd and kd, the maximum pump rate at any moment
during an acid treatment can be written as:

frac  p res  p hyd  pfric 
(t)  p

2 pk 0 h
R 1  R
Q
max
ln    
K
   
 1 ln
e o d
R 2 K
w d
(t)
R w

CONFIDENTIAL
with kd(t) defined as the permeability of the damaged zone during the injection of
acid at time t.
Hence, Qmax(t) denotes the maximum injection rate at time t. By splitting up the
total volume (Vtot) derived from the acid response curve into small increments
and taking the corresponding permeabilities, a set of maximum injection rates as
a function of pumped volume or time is obtained, i.e. the use of acid response
curves for the design enables a detailed pumping schedule. This method has been
computerised and is available as MATACID through ICEPE.
Appendix B shows an example of the input and output of this program. Since this
method is primarily written for use with the standard KSEPL acid response
curves, the method cannot directly be applied to curves determined at other
laboratories, unless they follow the KSEPL procedures. All major contractors
agreed to do so upon request. To facilitate the use of other laboratories for this
type of tests, a standard test procedure is described in chapter 9. If it is not
possible to apply the given procedure(s), SIPM (EPD/41) or KSEPL (RR/56)
should be contacted for assistance.
4.5 Alternative design methods

Frequently, experimental data cannot be obtained. Hence, the formulation of a
pumping schedule follows directly after identification of the damage and pre-
selection of the acid recipe using Figures 5 and 6. In that case the following
procedure is suggested:
1. Determine of the fracture initiation gradient of the well or field. If no
accurate measured data are available, Figure 8 might be used to
estimate the fracturing gradient.

CONFIDENTIAL
Estimated
Estim ated fracture gradient
- depth trend -
Depth (m )
5500
5000 Hydrostatic
gradient
4500
4000 Overburden
gradient
3500
3000
2500
2000
1500
1000
500
0
0 20 40 60 80 100 120
Fracture gradient (M pa)
Figure 8 - Fracture gradient trend
This empirical correlation has been derived from data from the US Gulf
coast, South east Asia and the North Sea. They are thought to be
acceptable for other areas throughout the world (if more specific
information is not available).
2. Calculate the maximum possible injection rate and/or pressure without
fracturing the well, using the fracture gradient calculated above:
4.197 *10 -6 * k av H net * (0.9 * FG * D - Pres )
Q max =
m av ln (R i / R w )
in which
µav = viscosity averaged between at bottomhole and at
reservoir conditions and Ri= 100 ft.
3. Determination of the required volume of mud acid using the following
chart:

CONFIDENTIAL
Matrix Acidising Volume Guideline
Formation temperature
<150 F o 150 - 250 oF >250 oF
Permeability
( K < 20 mD 100 gal/ft 50 gal/ft 50 gal/ft

)*
K = 20 - 100 mD 150gal/ft 100 gal/ft 100 gal/ft
K >100 mD 200gal/ft 150gal/ft 100 gal/ft
* Consider fracturing for low permeabilities!

See Figure 2
Figure 9 - Acid volume selection chart
4. Finally, a complete acid treatment is specified:

 A preflush volume, usually a minimum of 40 % of the mainflush
volume increasing to 100 % in the presence of significant quantities of
carbonates
 A mainflush volume, established using the above chart.
 A postflush volume, ranging from 10 gal/ft in case of immediate
resumption of the production to 200 gal/ft if the well cannot be brought
back to production within four hours.
 Tubing displacement volume
 Pump rate and corresponding pumping time.

CONFIDENTIAL
4.6 Paccaloni's prediction curves

Paccaloni followed an approach, similar to that applied in design method based
on acid response curves to construct graphs of the calculated tubing head
pressures during the treatment vs. the injection rates for various values of S*. The
initial acid injection pressure can be used to determine the initial (pre-acid) value
of S. Alternatively, an injection test with an inert fluid would enable a quick
determination of S. By monitoring the pressures and rates carefully during the
treatment and comparing it with the theoretical suite of curves, a fair estimate of
the effect of the treatment is obtained. In fact, Paccaloni uses this technique on
site to decide when the treatment should be terminated, i.e. to stop pumping when
there is no further reduction of the skin value. The procedure excludes the use of
diverting agents, since such chemicals cause a temporary increase of the Skin
factor. To promote even distribution of acid over the entire interval to be treated,
Paccaloni suggests to apply the maximum allowable pump rate that just prevents
fracturing.
Whether or not this approach can be followed depends very much on the local
operational conditions. For instance, wells in depleted areas may go on vacuum or
local experience may indicate that good productivity improvements do occur
regardless of the injectivity behaviour during the treatment. Furthermore,
terminating the job with formulated acids remaining in the tanks presents a
disposal problem.
An example calculation is given in Appendix D. Since this prediction/ design
method applies the same simple reservoir engineering concepts as in the design
method based on acid response curves, the combination of the two methods might
be used to determine field correlation between acid response curves (on impaired
core samples) and actual treatments.
The major service companies supply similar programs from their execution
control vans (or vessels). Dowell Schlumberger have based their program on
transient flow equations rather than the steady state approach of Paccaloni. The
results are similar, given that it is only used to qualitatively identify reductions in
skin values during the treatment.
4.7 Design recommendation

In summary, we recommend to base the design on acid response tests using acids
selected with the SFMA concept. It is further recommended to use the "Paccaloni
method" as an aid in the execution of the treatment (if no diversion is applied). As
indicated, the latter will enable the optimisation of treatments based on field
results, through the correlation of acid response curves and actual treatments.
The other options mentioned are primarily included here in view of their,
reportedly, frequent use by stimulation contractors.

CONFIDENTIAL
5 Matrix acidising of carbonates
As in sandstones, the primary objective usually is to remove or by-pass damage.

However, both chemical and physical aspects of carbonate acidising are very
different from sandstone acidising. The different composition of the rock causes
the reaction rate to be much faster in carbonates. It also prohibits the use of
hydrofluoric acid, since it may cause precipitation of calcium fluoride. The
different nature of porosity and permeability (e.g. vuggy, fractured porosity vs
(usually) intergranular porosity in sandstones) causes the acid to follow
preferential flowpaths - worm-holing, thus by-passing rather than dissolving
damage. This demands a different injection procedure.
5.1 Acid/carbonate rock reactions

It is often difficult to determine the exact nature of the rock. Inclusion of iron
minerals and siliceous material may have complicated the structure of carbonates.
Depending on the concentration of siliceous components, such rocks are known
as sandy or shaly limestones. Pressure solution processes may lead to the
formation of silica rich streaks in the rock, i.e. stylolites. Figure 10 shows a
schematic classification of carbonates as a function of the composition.
Field Guidelines for Matrix Treatments Matrix acidising of carbonates  21

CONFIDENTIAL
Impurities (Clay, silt, etc)
Non-carbonates
50 % 50 %
Impure Impure Impure limestone

Impure dolomite calcareous dolomitic
dolomite Limestone
10 % 10 %
Calcareous dolomite Dolomitic Limestone
100 % Dolomite 50 % 100 % Limestone
Carbonate rocks
Figure 10 - Classification of carbonates
Although a wide variety of carbonates are found in nature, their reactions with
HCl - and other, organic acids - is governed by a simple ionic reaction¹:
CO3-- + 2H+-> CO2 + H2O
Apart from the formation of ferric hydroxide (due to the pick-up of iron from the
tubing), there are no complicating precipitation reactions, as is the case with
sandstones. However, the type and amount of insoluble compounds affects the
acid composition. Figure 11 summarises some guidelines with regard to the
choice of acid with respect to the type of carbonate rock.
22  Matrix acidising of carbonates Field Guidelines for Matrix Treatments

CONFIDENTIAL
A c id S e le c tio n
Type of
a c id M
Muudd A
Accid
id O
Org
rgaannicic R
Reeta
tard
rdeedd
2288%
%HHC
CLL 1155%
%HHC
Cll
(S
(SFFMMAA)) aaccid
id HHCCll
M a in M in e ra l
c o m p o s tio n
( <<1100%
% ccaarb
rboonnaate
te  *)
1100 -- 5500%
%
ccaarb
rboonnaatete 
Im
Imppuure
re ddoolo
lom
mite
ite
 
Im
Imppuurere ccaalc
ddoolo
lom
lcaare
mite
reoouuss
ite 
Im
Imppuure
lim
re ddoolo
limeessto
lom
mitic
tonnee
itic

Im
Imppuure
re lim
limeessto
tonnee 
PPuure
re ddoolo
lommite
ite 
C
Caalclcaare
ddoolo
reoouuss
lom
mite
ite 

DDoolo
lommitic
itic
lim
limeessto
tonnee
PPuure
re lim
limeessto
tonnee 
Legend  : P re fe rre d : R e a s o n a b le : Poor
* E s s e n tia lly s a n d s to n e a c id is in g
Figure 11 - Acid selection chart for carbonates

The dissolving power of the acid is entirely determined by the stoichiometry of
the applied acid/rock reaction.

CONFIDENTIAL
A c id /c a r b o n a te d is s o lv in g p o w e r
A c id /r o c k c o m b i n a t io n A c id c o n c e n t r a t i o n
5 % 10 % 15 % 30 %
H C l/ L i m e s t o n e 0 .0 2 6 0 .0 5 3 0 .0 8 2 0 .1 7 5
F o r m ic a c id / L i m e s t o n e 0 .0 1 2 0 .0 2 0 0 .0 2 4 0 .0 4 3
A c e t ic a c i d /L im e s t o n e 0 .0 1 4 0 .0 2 7 0 .0 4 2 0 .0 8 4
H C l/ D o lo m i t e 0 .0 2 3 0 .0 4 6 0 .0 7 1 0 .1 5 2
F o r m ic a c id / D o lo m i t e 0 .0 1 2 0 .0 1 9 0 .0 2 2 0 .0 3 5
A c e t ic a c i d /D o lo m it e 0 .0 1 2 0 .0 2 4 0 .0 3 6 0 .0 7 2
* D a t a f o r o r g a n i c a c id s h a v e b e e n a d ju s t e d f o r s im u l a t e d
d o w n h o le c o n d it io n s ( 9 0 o C , 1 4 0 b a r )
Figure 12 - Dissolving power of various acids

Figure 12 lists the dissolving power of different acids and concentrations for
limestone (simple carbonate) and dolomite (mixed carbonate). It is useful when
comparing the maximum dissolution of rock of the different acids and may be
used to estimate the total amount of acid required. However, in practice for
organic acids it may take long before the total dissolving power is reached, i.e.
their reaction rate with carbonates may be relatively low. The effect is enhanced
if CO2 is held in solution due to the pressure downhole. Also the presence of oil
can reduce the reaction rate.
5.2 Wormholing
Another complicating factor is the formation of wormholes rather than uniform
dissolution of the rock matrix. In the presence of fractures, these worm-holes tend
to follow the fractures. Whether or not worm-holes are desired, depends on the
objective of the treatment. The number and extent of the worm-holes is
determined by:
 The reaction rate; high reaction rate promotes the formation of a few,
but long worm-holes.
 The injection rate into the matrix.
 The presence of vugs, fractures, high permeability streaks, etc., which
determines the preferred direction of the worm-holes.

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Figure 13 shows the optimum pump rate (i.e. creating maximum wormhole
length) as a function of the perforation density. Also indicated is the value for
open hole completion. This graph is valid for calcite reacting with HCl and
mixtures of HCl and acetic or formic acid and also for dolomite reacting with HCl
above 60 °C. At lower temperatures higher rates are required to reach optimum
wormhole length. Also, if the carbonate is inhomogeneous, the formation of
worm-holes may primarily take place in the high reactive layers.
It is important to realise that the above flow rates for maximum wormhole length
are real optimum rates. At both lower and higher rates the wormhole length
decreases; at lower rates wormholing virtually disappears, while at higher rates
the length decreases with the third power root of the rate.
A lot of different acid formulations have emerged (and disappeared again) over
the years. The principal acid has always been (and still is) hydrochloric acid.
Most "new" acid formulations were aimed at retardation of the fast acid/carbonate
reaction by the addition of weaker acids, creating acid/oil emulsions, etc. By
reducing the reaction rate the tendency to worm-holing is reduced. Regardless
whether or not this is an advantage, significant effects have only been observed
by.extreme reduction of the reaction rate, which is not achieved for most of the
systems. Just adding some acetic or formic acid does not help. Studies by Shell
Oil indicated that significant reduction of worm-holing was only possible by
increasing the pH of the fresh acid from the value of -0.5 to -1 for HCl to 4 to 5,
using for instance, Buffer Regulated Organic Acids (BROA).
Also service companies have marketed a number of alternatives for pure HCl.
These acids can be divided into two groups:
 "Chemically" retarded acids.
 Emulsified acids.
As the primary (claimed) effect of these acid formulation is retardation, they are
mainly applicable if worm-holing needs to be reduced. In general this is the case
for the removal of near wellbore damage, in which case they form an alternative
to high rate matrix acidising with HCl; for instance, if high rates cannot be
applied for operational reasons. Information on practical experience within Shell
is not available. More details can be found in the Well Stimulation Manual Vol.
III ( EP 92 - 0323)

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In je c tio n r a te fo r m a x im u m w o r m h o le le n g th
In je c tio n r a te (m 3/m in /m p e r fo r a te d )
0 .0 0 7
0 .0 0 6 P e rfo ra te d
0 .0 0 5 O p e n h o le
0 .0 0 4
0 .0 0 3
0 .0 0 2
0 .0 0 1
0
0 10 20 30 40 50
S h o t d e n s ity (s h o ts /m )
Figure 13 - Injection rates for maximum wormhole length
5.3 Treatment design

Damage is usually limited to the first few inches around the wellbore. In
carbonates the radial distribution of such damage may be affected by the presence
of vugs, fractures, etc. As indicated in the introduction impairment removal in
carbonates hinges on by-passing, rather than actual removal of the damage by
dissolution. The above considerations lead to a number of different treatment
procedures, depending on the extent of the damage and the type of formation.
Figure 14 indicates the preferred type of treatment for the different situations.

CONFIDENTIAL
Carbonate treatment selection chart
*)
Type of rock/damage Acid wash/soak Matrix treatment CFA Acid frac (MHF) Wormholes
low rate high rate required
Plugged perforations * * No
Shallow damage,
no vugs or fracs * * No
Deep damage,
no vugs or fracs (*) * Yes
Shallow damage,
vugs or fracs * (*) Yes
Deep damage,
vugs or fracs * Yes
Deep or shallow damage,
low permeability with natural fracs * * (*) No/(n.a.)
Deep or shallow damage,
low permeability, no natural fracs * * n.a.
* CFA (Closed Fracture acidising, acid fracturing and MHF (Massive hydraulic
Fracturing) are discussed in the Field Guidelines for Hydraulic fracturing (EP 93-
1170)
Figure 14 - Carbonate treatment selection
This selection chart is valid for both calcite and dolomite. However, if the
treatment temperature in dolomites is less than 60 °C, typical values for "low
rate" and "high rate", will shift to higher values.
5.4 Acid wash or soak

The primary use of an acid wash or soak is to breakdown perforations in new
completions or after workovers. A soak should allow enough time for the acid to
penetrate the perforations and to disperse (or in some cases dissolve) plugs caused
by mud, filtercakes, cement, etc. Worm-holing should be avoided. Due to the
stationary character of the treatment, the rate at which the impairment is removed
is slow. Applying some pressure can be used to invoke some fluid movement.
However, keep in mind a maximum injection rate of some 0.0002 m3/min/m to
prevent worm-hole formation. The following treatment guidelines apply:
1. Use 28% w HCl to maximise the dissolving power, if corrosion aspects
permit.
2. Volume of acid approximately equal to the casing volume across the
perforated zone.

CONFIDENTIAL
3. Acid preferably spotted across the perforated zone using coiled tubing.
4. Pre-clean tubing, if no coiled tubing can be applied, by circulating two
times the tubing content of 12 % w HCl.
5. Add an iron sequestering agent to the acid
6. If the presence of oil-based mud cake is suspected, an alcohol (e.g.
isopropyl alcohol), a mutual solvent or a dispersing surfactant should be
used.
7. Soaking time should be 12 hr or longer.
Laboratory experiments may help to find optimum fluid composition and soaking
times. The corrosion inhibition schedule should be adapted to these long exposure
times.
5.5 Matrix acidising

Matrix acidising is the most commonly used remedial treatment, also in
carbonates. The intention should be to inject acid below fracturing pressure.
However, in practice, in many cases the formation will be fractured or natural
fractures opened, albeit not on purpose. Such treatments are still considered as -
high rate - matrix treatments to differentiate them from purposely designed acid
fractures.
In fact, some controversy exists on how to perform a matrix acidising treatment in
carbonates: at low, sub-fracturing, pressures, i.e. at low injection rates, similar to
the treatments carried out in sandstones, or at high injection rates, regardless of
the fracture propagation pressure. The difficulty is that both methods have been
applied with success. The success or otherwise of either method probably
depends on the local situation with regard to type of damage, presence of vugs,
natural fractures, etc.
The different approaches are discussed below:
5.5.1 Approach 1 - low rate, small acid volume,

low concentration
This method typically involves using 0.2 - 0.4 m3/m of 15% w HCl at a pump
rate of 0.004 m3/min/m (possibly somewhat higher in dolomites) or less if the
fracturing rate would be lower. The low pump rate provides a long near-wellbore
contact time, but, at the same time create long wormholes. Any damage will be
by-passed rather than removed; hence the procedure is particularly suitable to
remove shallow damage in homogeneous carbonates, i.e. without vugs and
natural fractures, whilst the damage itself is insoluble in acid.
Placement of such a treatment in long intervals is difficult. The method is,
therefore, only suitable for short intervals, say 3 - 10 m.
CONFIDENTIAL
5.5.2 Approach 2 - high(er) rates, large volume,

high concentration
Here typically 1.2 - 2.0 m3/m of 15 - 28 % w HCl is injected at rates of 0.015 -
0.030 m3/min/m. The high rate reduces the tendency to form long worm-holes.
The increased volume and concentration will, however, compensate for the
reduced worm-hole penetration depth. In practice, this method is likely to actually
remove the damage by dissolution or by creating a high effective porosity near
the wellbore which would make the damage mobile. Back-production will then
flush out the damage.
If the injection rate, indicated above, exceeds the fracture propagation rate,
fractures will be created effectively by-passing the damage. In sufficiently
inhomogeneous carbonates, differential etching will provide enough post
treatment conductivity of the fractures for improved productivity. Hence, the
treatment in essence becomes a acid fracturing treatment. However, if fracturing
occurs in reservoirs of limited thickness, the fracture might grow out of zone
which would reduce the effectiveness of the treatment or might, for instance,
induce water production.
The higher rates increase the effectiveness of diverting agents, specifically ball
sealers. Hence, the treatment is more suitable in longer zones with acid soluble
forms of damage. However, the higher rates and concentrations involved create
some drawbacks, increased potential for emulsion formation, fines generation,
etc.
The method is also suitable if vugs and natural fractures are present, since they
form a natural, preferential flow path for the acid, from which (small) sideways
branching worm-holes may be formed. In fact the treatment then becomes similar
to the Closed Fracture Acidising technique (CFA), originally developed as a
remedial fracturing technique. The latter technique is discussed in the stimulation
guidelines part II - Hydraulic fracturing.

CONFIDENTIAL
6 Non-acid matrix treatments
Some forms of damage cannot be removed by acid or might even be intensified

by the use of acid. Wax and asphaltene problems need treatment with
hydrocarbon solvents rather than acids, for instance. In this paragraph we will
briefly discuss some aspects of non-acid treatments. Depending on the type of
damage, the following treatments may be used to remove non-acid soluble
damage:
 Wax and/or asphaltene removal treatments.
 Surfactant/solvent treatments for the removal of emulsions, pipe-dope
deposits, water blocks, etc.
 Removal of polymer residues, etc.
 At this point it is emphasized that we will only discuss the removal of
such materials from within the pores of the formations or the
perforations.
6.1 Wax and asphaltene removal treatments

Wax and asphaltenes are mostly mentioned together, as if they were the same
problem. However, the chemical and physical nature of wax is quite different
from that of asphaltenes. Wax consists of a mixture of high molecular weight
aliphatic hydrocarbons, which, when cooling down, can solidify. In principal,
this is a reversible process: heating the crude tends to dissolve the wax again.
Successful in-situ heat generation or electrical heating has been reported. Other
methods include the use of (aliphatic) solvents.
Asphaltenes are more aromatic in character and also contain resin type
compounds. In practice, they are defined as the high-molecular weight fraction of
a crude oil, that is insoluble in n-heptane. Asphaltene precipitation is a rather
complex process. During depressurisation of the crude oil (near the wellbore and
in the tubulars) the solubility of asphaltene decreases until the bubble point is
reached; further depressurisation generally causes the solubility to increase again.
Asphaltenes generally have a low solubility in light crudes and, as a consequence,
these have a low asphaltene content. On the other hand, in light crudes that are
Field Guidelines for Matrix Treatments Non-acid matrix treatments  31

CONFIDENTIAL
undersaturated with gas, a small pressure decrease quite easily creates extremely
high super saturations with respect to asphaltenes. Hence, asphaltene precipitation
often occurs when light crudes that are highly undersaturated with gas, are
depressurised. Heavy crudes are seldom supersaturated with asphaltene and,
therefore, are much more tolerant with respect to asphaltene precipitation, in spite
of their (generally) high asphaltene content.
Once precipitated, asphaltenes are difficult to dissolve again in the crude. Being
the result of destabilising supersaturation, it is a more or less irreversible process.
Usually (aromatic) solvents are the only solution to asphaltene problems.
6.2 Hot oil treatments

Injection of heated crude oil ("hot oiling") is often used to remove wax
deposition. The success of such treatments is hampered by the presence of other
organic solids, e.g. asphaltenes, that will not so easily redissolve in the crude.
Moreover, heating might result locally in over saturation of the crude with respect
to wax, resulting in in-depth formation damage. When cooling down it may result
in even more severe wax problems.
Heat treatments have virtually no effect on asphaltene precipitates.
6.3 Solvent treatments

Wax and, to a lesser extent, asphaltenes are soluble in a variety of organic
solvents. Wax is more soluble in aliphatic solvents, such as kerosene; asphaltenes
require more polar solvents, such as xylene. Since the dissolution is often a
reasonably slow process, fairly long soaking times may be required; upto 48
hours is not uncommon. The selection of the solvent, or mixture of solvents,
should be based on laboratory experiments to determine potentially good
solvents. Some commonly used fluids include:
 Kerosene,
 Toluene,
 Xylene,
 Diesel.
Practical experience with a number of solvents should then indicate the optimum
treatment, both in terms of ultimate solvent selection and required soaking times.
The volumes to be applied depend in principle on the extent of the damage. In
practice it is often not easy to determine this. Therefore, as a general guide-line
the following volumes are recommended:
Wax: 0.10 - 0.20 m3/m (8 - 16 gal/ft)
Asphaltenes: 0.30 - 0.40 m3/m (24 - 32 gal/ft)
32  Non-acid matrix treatments Field Guidelines for Matrix Treatments
CONFIDENTIAL
6.4 Dispersant treatments

Some stimulation contractors market special water-based dispersants (e.g.
Halliburton's Parasperse). Dispersants do not dissolve organic deposits but tend to
break them up in very small particles, which can be produced with the formation
fluids. Their application for formation damage removal is limited; the particles
have to be smaller than, say 1/7 th of the pore size, which in practice may be
difficult to achieve. Mutual solvents have also been proposed for this purpose, but
the success is limited.
6.5 Chemical and electrical heat treatments

A typical chemical heat treatment, known as the "CHANGE" process, is based on
the heat generated in the highly exothermic reaction between sodium nitrite (
NaNO2) and ammonium nitrate (NH4NO3):
NH4NO3 + NaNO2 2H2O + NaNO3 + N2(g) + Heat
The amount of heat generated is proportional to the concentration of the salts. The
treatment involves the following steps:
1. Establish injection rate and pressure using filtered NH4Cl brine.
2. Design the required solution pH, based on the injectivity determined in
step 1. To this end computer programs are available through Baker
Sand Control (licensee of this process originally developed by Shell
Oil).
3. Inject a Xylene preflush, 0.6 m3/m (50 gal/ft) at the determined
injection rate.
4. Inject the NaNO2 and NH4NO3 solutions at 50% of the pre-determined
rate.
5. Shut-in the well for 24 hours.
6. Resume production slowly, until the treating fluids have been
recovered.
Also electrical heating of well bores has been applied with some success.
However, installation of the equipment is rather expensive. It is seen more as a
tertiary recovery method to lower the viscosity of the crude oil by (continuous)
heat injection than as a stimulation treatment.
6.6 Removal of emulsions, pipe dope, etc.

Some forms of damage are practically insensitive to any of the treatments
discussed so far. Emulsions, pipe dope, paint (from packers and other tools), lost

CONFIDENTIAL
circulation materials (sawdust, mica), etc. have been found to hinder the free flow
of oil in and just outside the perforations.
If such damage is suspected, treatment with surfactants is an option. In fact, the
dispersant treatments described above also fall under the heading of surfactant
treatments. A surfactant might be applied as a stand alone treatment, or in
combination with acidising, for instance.
The only way to select a surfactant for a particular problem is through laboratory
testing. Such tests, to be performed on samples of the damage to be removed,
should be aimed at:
 Optimum dispersion of the material to be removed.
 Minimisation of adverse effects, such as incompatibility with the
formation rock fluids.
Chemicals used in this type of treatment include:
 Mutual solvents - e.g. EGMBE1
 Alcohols - e.g. Methanol
 Micellar solvents - e.g. Cellosolve
 True surfactant solutions - e.g. Dobanic acid .
 Xylene (strongly promoted by Shell Oil as a preflush to an acid
treatment).
As indicated in the introduction of this chapter, a variety of chemicals is offered
by the different service companies. Figure 15 shows a list of some commercial
products. Application guidelines are given Figure 16. Application of solvents has
serious environmental consequences. It complicates the disposal of back
produced fluids.
1Ethylene Glycol Mono Butyl Ether

CONFIDENTIAL
Common comercially available solvents
Brandname Chemical class Manufacturer Claims

Claims
Musol EGMBE Halliburton

Musol A EGMBE derivative “ improved action
U-66 EGMBE Schlumberger Dowell
J-40 EGMBE BJ
WSA-1 EGMBE (?) Western
Cellosolve EGMBE Nowsco
A-sol series Alcoholic mixtures Welchem better than EGMBE
in most applications
MAS Micellar solvent Western prevents emulsions
Figure 15 - Some commercially available solvents

CONFIDENTIAL
Solvent selection chart
Aromatic Kerosene/ Alcoholic Mutual

Surfactant
solvent Diesel solvent solvent
Wax 
Asphaltene 
Emulsions  
Scale/
sludge 
Waterblock   
Pipe dope 
Oil based
mud 
Paint, etc.
Legend  : Preferred
: Reasonable
: Poor
Figure 16 - Solvent selection chart
6.7 Scale removal

Scale deposition often takes place inside the tubulars or surface facilities and, to a
lesser extent, in the pores of the near well bore formation. We will discuss briefly
the treatments aimed at removal of scale from the formation.
6.8 Carbonate scale

This type of scale may be removed by hydrochloric acid. Since scale is usually
located very near the well bore, small volumes (0.2 - 0.6 m3/m) of 15 % w HCl
pumped at low rates are sufficient. In fact this treatment resembles matrix
treatments described earlier in this chapter. In view of the often recurrent
character of scale, treatments are often combined with inhibitor squeezes.
Successful application of non-acid treatments - chelating agents - has been
reported by Exxon. A typical treatment could be:

CONFIDENTIAL
1. m3/m of an almost saturated EDTA solution, followed by,

2. An inhibitor squeeze equivalent to 3 - 10 kg/m of inhibitor (e.g.
phosphonic acid solution).
6.9 Calcium sulphate scale

Calcium sulphate scale is not directly soluble in HCl. Hence, a "scale converter"
is applied prior to treatment with acid. This scale converter, e.g. ammonium
carbonate converts the scale into calcium carbonate, which can subsequently be
dissolved in acid.
Although this procedure is rather popular in the U.S.A., it is doubtful how
effective this conversion within the pores of the formation is. A better option
might be the use of EDTA as described above, the more so because frequently,
the actual scale is a mixture of calcium sulphate and carbonate.
6.10 Barium sulphate

Probably the most difficult scale to remove is barium sulphate. Some success has
been reported using EDTA (and similar complexing agents) or "crown ethers".
The latter chemicals are not yet available on a commercial basis due to the high
costs.
An additional problem is caused by the natural presence of radioactive radium
sulphate in barium sulphate scales. Scale produced to surface, either solid or
dissolved in e.g. acid, must be treated as radio-active waste material.
Perhaps the most effective way is to by-pass, rather than remove, the scale by a
small hydraulic fracture, which also avoids the potential hazardous handling of
radio-active waste. In principle such a treatment could be applied for all types of
scale. Theoretically it may be carried out in any well. However, at high
permeabilities, excessive fluid-loss may hamper its application. For details on the
design we refer to the "Field Guidelines for Hydraulic Fracturing Treatments"
(Report EP 93- 1170).
6.11 Scale removal recommendation

Figure 17 shows a survey of possible treatments and their typical area of
application. For more details on scale and its removal and inhibition see the water
injection manual (Report EP 93- 2900).

CONFIDENTIAL
Scale remover selection chart
Converter Chelating
HCl Skinfrac
+ HCl agents*
Carbonates   
Iron
compounds 
Calcium
sulphate  
Barium
sulphate 
Mixed
scales   
Legend  : Preferred
: Reasonable
: Poor
Figure 17 - Scale remover selection chart
6.12 Enzyme treatments

A rather common type of damage is formed by the remnants from polymers used
in workovers, gravel packs, fracturing treatments, etc. These residues are often
sensitive to acid and oxidising agents (breakers), but effective treatment is
hampered by placement problems.
Enzymes have proved to be a viable alternative in such cases. The catalytic nature
of the action of enzymes makes them less sensitive to placement problems. The
enzyme tends to "eat" its way into the polymer residue, provided the reservoir
temperature is not too high. Currently commercially available enzymes can be
applied upto 70 °C.
Enzymes can be specifically tailored to the polymer to be degraded. Hence, for an
enzyme treatment to be successful, the nature of the impairing polymer residue

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must be known. Optimum treatment design, i.e. type and concentration of enzyme
can then be established in laboratory tests. A typical design for the enzyme
treatment to CMC impaired gravel packed wells may be as follows:
1. Perform pressure build-up survey to establish skin before the treatment
if required.
2. Place one gravel pack volume of an aromatic solvent preflush, e.g.
xylene, at low flow rates and at sufficient back pressure in the tubing
annulus to enable good placement. Inject two to three gravel pack pore
volumes solvent at minimum overpressure.
3. Shut in the well for two hours.
4. Place one gravelpack pore volume of enzyme solution, containing 10
l/m3 of liquid SP 359 (a Novo Nordisk product, contact SIPM/KSEPL
for more information). The pH of the enzyme solution should be around
8.0 or below. Low flow rates should be used during the placement of
the enzyme solution while maintaining sufficient back pressure.
Squeeze one to two gravelpack pore volumes of enzyme solution into
the formation at minimum overpressure.
5. Shut in the well for 2-4 hours.
6. Back produce the well for clean up.
7. Evaluate success of treatment e.g. perform pressure build-up survey to
determine skin.
6.13 Hypochlorite treatments

Some impairment, (e.g. bacterial slime in water injectors, but also water soluble
polymers (HEC, CMC, etc.) can be removed by strong oxidising agents, such as
hypochlorite or chlorine dioxide. These two products can, besides degrading the
CMC, also remove other potential impairing materials present in the near
wellbore region. The drawback of these materials is that they are strong oxidative
chemicals and, specifically in the case of chlorine dioxide, specific safety
precautions have to be taken. For details we refer to the Well Stimulation Manual
Vol. III ( EP 92 - 0323).

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7 Additives for matrix treatments
7.1 Introduction
The use of acid in sandstones (and to a lesser extent also in carbonates) can create
a number of problems. Acids can:
 release fines that can plug the formation pores,
 form stiff emulsions, which can severely restrict the flow of oil,
 create asphaltenic sludges when mixed with certain reservoir oils,
 corrode the tubulars,
 induce secondary precipitation e.g. ferric hydroxide or potassium fluoro
silicate,
 stimulate only the more permeable zones, leaving the poor (target)
zones unstimulated.
Over the years, both oil companies and stimulation contractors have developed
procedures aimed at combating one or more of the above problems. In many
cases the solution was found in the application of additives.
Know-how on the application and function of additives is, in essence, the domain
of service companies. They give practical advice on the use of additives. This
chapter gives an overview of currently available additives. We will consecutively
discuss:
1. Corrosion inhibitors
2. Sequestering agents
3. Solvents
4. Surfactants
5. Clay-stabilisers
Of these additives the corrosion inhibitor is the only one that should always be
applied. Also a sequestering agent is often required. The rest should only be used
if there is a demonstrated need for them.
Field Guidelines for Matrix Treatments Additives for matrix treatments  41
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The use of diverting agents will be discussed in chapter x Placement techniques.
7.2 Corrosion inhibition

The acid corrosion reaction may be described by the following reactions:
Fe + 2H+  2H + Fe++
2H  H2 (g)
As with any chemical reaction, the reaction rate, i.e. the corrosion rate, rapidly
increases with temperature: each 10 °C increase in temperature will increase the
corrosion rate by a factor 2 to 3. Moreover, corrosion inhibitors loose their
effectiveness at higher temperatures, causing an extra increase in corrosion rates
above 100 to 150 °C.
Modern corrosion inhibitors can give adequate protection upto temperatures of
approx. 100 °C. For protection at higher temperatures salts with reducing
properties (cupro-iodide, potassium iodide, etc.) are added as intensifiers. The
use of these intensifiers is a point of concern, since their solubility in acid at
lower temperatures is sometimes poor. Moreover, they hamper environmentally
acceptable disposal of spent acid.
Addition of other additives can have a great impact on the inhibitor performance.
The use of silt suspending agents or mutual solvents blended into the acids, for
instance, can reduce the corrosion inhibitor effectiveness dramatically.
The use of corrosion inhibitors is imperative. The required concentration,
however, depends on the degree of corrosion that can be tolerated. Generally, a
maximum weight loss of 0.05 lbs/ft2 of tubular steel (equivalent to a thickness
reduction by 0.001 inch) is considered to be acceptable during a single treatment.
Hence, the longer the duration of the treatment, the lower the actual corrosion
rate should be. Figure 18 shows the acceptable corrosion rate as a function of the
expected duration of the treatment for the most commonly used types of steel.
42  Additives for matrix treatments Field Guidelines for Matrix Treatments

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Allowable corrosion rates for acid treatments
Corrosion rate
(mm/yr)
60
50
40
30
20
10
0
5 10 15 20 25 30
Expected duration of the treatment* (hrs)
Figure 18 - Allowable corrosion rates for acid treatments
7.2.1 Recommendation
Normal steels (e.g. N80) : all major service companies have inhibitors satisfying
the above criteria up to 120 °C and for a duration of 16 hrs.
High alloy steels (e.g. 13Cr): Only HAI 85 (Halliburton) and WA211 (Welchem)
satisfy the criteria upto 120 °C and for a duration of 16 hrs.
7.3 Sequestering agents

Acid, being a powerful solvent for a variety of inorganic materials also dissolves
iron scale from the tubulars and iron containing minerals. However, as the acid is
spending the pH increases, which may eventually result in reprecipitation of
dissolved iron in the form of iron hydroxides. Such precipitates can cause serious
impairment, particularly at the radially extending acid front, where the pH is
highest.
More or less regularly applied chemicals to prevent precipitation by forming
soluble complexes with iron, include:

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 Citric acid,
 Acetic acid,
 EDTA, Ethylene Diamine Tetra Acetic acid
 Lactic acid,
 NTA, Nitrilo Tri Acetic acid.
Of these, citric acid is recommended as a general purpose sequestrant. It prohibits
precipitation of ferric hydroxide under most conditions upto a pH of 4 - 5,
without serious side reactions unless large quantities of calcium (e.g. calcite) are
present. A computer program, SEQUES, is available to calculate the amount of
sequestrant required to keep iron in solution.
The concept of using a reducing agent was (re-)introduced by DS, who promote
the use of erythorbic acid (trade name L58). Erythorbic acid is a stereo isomer of
ascorbic acid, more commonly known as vitamin C, which would be almost
equally effective. The performance is at least comparable with that of citric acid.
Since the operating principle of reducing agents like erythorbic acid, is very
different from complexing sequestering agents, it cannot be incorporated in
SEQUES in its present form (SEQUES is based on calculation of ionic equilibria
of chemical complexes). However, the underlying (electro)chemistry is relatively
simple: reducing agents should be applied in stoichiometric proportions. For
erythorbic acid this is a molar ratio of 1 Mole on 2 Moles of iron(III), i.e 1.6
Kg/M3 of erythorbic acid per Kg/M3 of iron(III) present.
7.3.1 Application guide-lines for SEQUES

The basic input for SEQUES is rather simple. The main complication is to find a
proper estimate of the concentrations of the various metal ions in the spent acid.
Two methods to arrive at such an estimate are available:
1. Analysis of the effluent of acid response tests.
2. Analysis of back produced acid after a field treatment.
The second procedure may be regarded as supplementary to the first one, since it
includes any iron pick-up from the tubing.
7.3.2 Recommendations
1. Both laboratory and field experience indicate that hydrochloric acid
should always contain a minimum amount of sequestering agent,
irrespective of the iron content of the formation rock. In practice a
significant amount of iron will be picked up from the tubular goods. In
general, no sequestrant is required for mud acid flushes.

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2. Citric acid is recommended as a general purpose sequestrant. It

prohibits precipitation of ferric hydroxide under most conditions upto a
pH of 4 - 5, without serious side reactions unless large quantities of
calcium are present.
3. SEQUES can successfully be applied to determine the required type
and concentration of sequestrant. The input data, the expected metal ion
concentrations, can be obtained from acid response tests initially.
4. Sampling and analysis of back produced acid should be carried out to
check (and if necessary, adjust for subsequent treatments) the applied
type and concentration of sequestrant.
5. Based on the available laboratory data, the use of reducing agents, such
as erythorbic acid (L58 from DS) in stoichiometric proportions,
provides adequate protection against ferric iron precipitates.
7.4 Solvents
Solvents are added to acids for various reasons. When used as a mixture with
acids, special surfactants are blended in, to disperse the solvent in the acid. Such
blends are often marketed as special formulations, e.g. BJ's "One-shot acid".
Most service companies claim an impressive list of advantages, which might
suggest that using a - mutual - solvent is almost imperative. Indeed, some
companies do use them in all acid treatments. However, there are some serious
adverse effects:
1. Some solvents can create very stable emulsions.
2. The miscibility of mutual solvents is limited. Under most conditions
only 2 - 5% v/v can be mixed with acids as a single phase liquid.
3. The solvents always reduce the effectiveness of the corrosion inhibitor.
4. It can interfere with the solubility of some other additives, e.g. reduced
solubility of intensifiers for corrosion inhibitors.
5. Some solvents can undergo chlorination by hydrochloric acid. The
resulting chlorinated hydrocarbons act as refinery catalyst poisons.
In general, it is recommended to apply solvents as a preflush, since this would
eliminate some of the drawbacks. Chlorination may be avoided by adding the
solvent to acetic acid, rather than hydrochloric acid.
However, the use of solvent as an additive to acid can only be justified if
laboratory experiments demonstrate the need for a solvent by answering three
questions:
 Is their a problem that can benefit from a solvent?
 If so, which solvent is the best solution?

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 At what stage, preflush, mainflush or postflush, should it be used?

Figure 16 in chapter x outlines the general application areas of the various types
of solvents. It serves as a guide-line to set up the laboratory experiments. Figures
19 and 20 show a selection procedure for oil wells and gas wells respectively.
For further details of the laboratory tests, see chapter x.
S c re e n in g c o m p a ta b ility te s t O il w e lls
S o lu tio n 1 S o lu tio n 2 S o lu tio n 3
A c id + c ru d e o il
A c id + S o lv e n t C ru d e o il + s o lv e n t + s o lv e n t
S in g le p h a s e ? S in g le p h a s e ? S in g le p h a s e ? C la s s 1
Yes Yes Yes
No No No
E m u ls io n ? E m u ls io n ? E m u ls io n ? C la s s 2
B re a k in g B re a k in g B re a k in g
S ta b le S ta b le S ta b le
C la s s 3 C la s s 4 C la s s 5
C o re flu s h in g te s t w ith a c id + s o lv e n t a n d k e ro s e n e
A c id flu s h In c re a s in g O il flu s h In c re a s in g
p e rm e a b ility (K w ) p e rm e a b ility (K o rw ) S o lv e n t a c c e p te d !
N e u tra l o r N e u tra l o r
d e c re a s in g d e c re a s in g
S o lv e n ts c la s s 1 , 2
S o lv e n ts c la s s 3 , 4 , 5 S o lv e n t re je c te d !
Figure 19 - Selection criteria for (mutual) solvents (Oil wells)

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S c re e n in g c o m p a ta b ility te s t
G a s w e lls
S o lu tio n 1
A c id + S o lv e n t
S in g le p h a s e ? C la s s 1
Yes
No
E m u ls io n ? C la s s 2
B re a k in g
S tab le
C la s s 3
C o re flu s h in g te s t w ith a c id + s o lv e n t a n d g a s (N 2 )
A c id flu s h In c re a s in g G as In c re a s in g
p e rm e a b ility (K w ) p e rm e ab ility (K o rw ) S o lv e n t a c c e p te d !
N e u tra l o r N e u tra l o r
d e c re a s in g d e c re a s in g
S o lv e n ts c la s s 1 , 2
S o lv e n ts c la s s 3 S o lv e n t re je c te d !
Figure 20 - Selection criteria for (mutual) solvents (Gas wells)
7.5 Surfactants
Surfactants are chemicals composed of an oil soluble group (lipophilic group)
and a water soluble group (hydrophilic group). These chemicals lower the
interfacial tension of liquids by adsorbing at the fluid/fluid, fluid/gas or fluid/rock
interfaces. Surfactants can be classified into four major groups, depending on the
nature of the hydrophilic group:
1. Anionic surfactants; major applications include demulsifiers, retarding
agents and cleaning agents.
2. Cationic surfactants; the main applications in the petroleum industry
are demulsifiers, corrosion inhibitors and bactericides.
3. Nonionic surfactants; these are mainly used as non-emulsifiers and
foaming agents.
4. Amphoteric surfactants; these products find application in some
corrosion inhibitor blends and as foamers.
All surfactants influence to some extent the wettability of the formation rock.
Cationic surfactants tend to change the wettability to oil wet. Anionic surfactants

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are electrostatically repulsed from the surface and leave the silica minerals in the
natural wetting state. In limestones, dolomites, etc., anionic surfactants will be
adsorbed and tend to oil wet the carbonate formation.
The more oilwet the formation is the lower the relative permeability to oil will be.
Even though changing the wettability during treatments may be a temporary
effect, surfactants that tend to leave the formation water wet are preferred. If this
is not possible, for instance in the case of corrosion inhibition, it is important to
reduce the concentration to a minimum. Alternatively, chemicals (solvents) may
be used to enhance the desorption of the corrosion inhibitor.
7.5.1 Application areas of surfactants

 Emulsion prevention
 Wetting agents
 Anti-sludge agents
 Penetrating agents
 Foaming agents
 Corrosion inhibitors
A number of other applications for surfactants, such as acid/solvent dispersants,
mud dispersants, etc. are sometimes advocated, primarily by service companies.
We will not discuss these here, but stress that the use of surfactants should be
limited.
As for all additives, the use of surfactants as additives to acid can only be justified
if laboratory experiments demonstrate the need for a surfactant by answering
three questions:
 Is their a problem that can benefit from a surfactant?
 If so, which surfactant is the best solution?
 At what stage, preflush, mainflush or postflush, should it be used?
It is our general experience that many times surfactants can be left out without
any noticeable effect on the results of the treatment.
7.6 Clay stabilisers

Clays will expand when exposed to water with a low salinity. This includes acids.
Swelling of clays reduces the area open to flow and, hence, the permeability.
Montmorillonite type clays are notorious in this respect.
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Fortunately, not all clays are equally susceptible to swelling. The ability of a clay
mineral to expand depends on its chemical composition and on its structure. In
decreasing order of sensitivity to fresh water, expanding clay minerals include:
 Montmorillonite or smectite
 Illite
 Mixed layer clays, strongly dependent on the composition.
 Kaolinite, very limited swelling.
A number of additives are available to combat the negative effects of clay
swelling caused by contact between clays and water based fluids. They range
from simple cations such as K+, NH4+ and Ca++ to cationic polymers.
General rules for application cannot be given. A "Panacea for all evils" does not
exist: an excellent product for one treatment may be out performed by a
competitive product in a different situation.
Selection of a clay stabiliser for a specific treatment can only be done after
laboratory (core flow) experiments, applying the product recommendations for
use given by the stimulation contractors.
7.7 Additive summary

The different service companies offer a large suite of acid additives. If the
decision to use additives is left to the service company, one might end up with an
expensive mix of, sometimes superfluous, chemicals and in the worst case,
incompatible materials. Often the mutual compatibility of the various additives is
overlooked. So, although the know-how on the chemicals is very much the
domain of the stimulation contractors, their recommendations should always be
checked critically.
In essence, only one class of additives are required in every treatment: the
corrosion inhibitor. Sequestering agent (in hydrochloric acid flushes only) are
also often required, but their use should be justified on the basis of tests or
calculations. All other additives are optional and should only be used if specific
well conditions require their use and only after thorough testing for compatibility.
One of the most common mishaps in acidising is additive overdose. Figure 21
lists some of the problems that can occur in the well and surface equipment
during and after an acid job.

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Harmful effects of additive overdose
Additive Effect of overdose
Corrosion inhibitor Sludge, emulsions, facilities upsets

Oil wetting formation rock reducing
effective permeability
De-mulsifier Formation of stable emulsions in

facilities, well and near well bore
region
Silt suspending agent Emulsions and foaming problems
Clay stabilisers Loss of effective permeability
Figure 21 - Harmful effects of additive overdose
If the need for a particular additive cannot be clearly demonstrated, its use is not
justified. Also, if the stimulation contractor or manufacturer of an additive does
not wish to disclose basic information about its chemical nature, it should not be
used.

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8 Placement techniques
8.1 Introduction
In any stimulation treatment, placement is an essential part of the treatment. If
e.g. the acid is not directed to the intended interval, the treatment objective,
production improvement, may be missed all together. This does not mean that in
each stimulation diverters need to be used. The objective of stimulation should
be clearly defined before deciding on the specific diversion technique. Figure 22
may be used as a guideline to select the appropriate type of diversion.
D iversion selection guideline
G ood vertical Y es N o diversion

perm eability? needed
No
Foam
Re-establish Thief zone Polym er
natural profile or D eviated well? Yes Film form ing
shut off thief zone? (e.g. fine grade O S R)
SPT tool
Natural profile No
Ballsealers
Foam
No Polym er
G ravelpack? Film form ing
(e.g. fine grade O S R)
SPT tool
Yes
Yes Foam
Polym er
G ravelpack? Film form ing
(e.g. fine grade O S R)
No
C ake form ing
(e.g. B enzoic acid)
Foam
P olym er
S PT tool
Figure 22 - Diversion selection chart
Field Guidelines for Matrix Treatments Placement techniques  51

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Diversion techniques can be divided into three classes as follows, each with
specific applications:
8.2 Mechanical techniques

These techniques use mechanical means to isolate a particular zone for injection
of stimulation fluids. Except perhaps for ballsealers, mechanical diverting
methods are usually more reliable than other diversion techniques, albeit at high
costs. A big disadvantage is that they are not applicable to gravel-packed wells
and wells where zonal isolation has not be achieved through effective
cementation of the production casing.
8.3 Packer and bridge plug arrangements

Complete zonal isolation is obtained by packing-off a section of the completion
interval, for instance by a combination of a retrievable packer and a retrievable
bridge plug. This effective method is however very expensive and requires a rig.
Also the perforation intervals should include blanch sections to allow setting of
packers. In most cases this is not an economically viable system.
8.4 Selective Placement Tool (SPT)

A straddle-packer selective placement tool has been developed that is run on
coiled tubing, can pass through production tubing and can be repeatedly set in
casing. It is fitted with high-expansion straddle-packers. Nowsco UK Ltd. was the
first company to bring such a tool on the market; several other companies
followed.
The current tool has the following limitations that need to be borne in mind.
 It has a maximum operation temperature of 110 degrees C (230 F).
 The rubbers applied in the tool are extremely sensitive to most solvents,
particularly those with a high aromatic hydrocarbon content.
A number of applications for the SPT have been identified. In the context of this
manual the most relevant applications are:
 Acid stimulation of specific intervals with optimum volumes of fluid.
 Treatment of highly inhomogeneous formations (e.g., to prevent mud
acid from coming into contact with carbonates).
In most cases of chemical treatment, the SPT is the most economical means of
ensuring 100% selectivity.
52  Placement techniques Field Guidelines for Matrix Treatments

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8.5 Ballsealers
Ballsealers are small rubber lined plastic balls. They are available in a density
range of 0.9 - 1.4 g/cm3. In deviated or horizontal wells the ballsealers tend to
travel along the top side of the deviated well bore, thus reducing the chance of
seating on perforations other than those on the topside. (Buoyant) ballsealers may
therefore be less applicable in deviated wells, particularly with zero degree
phased perforations.
The quality control on the density of commercial ballsealers is rather poor. On
average, 20 - 30 % of the ballsealers deviate more than the 5 % scatter, specified
by the manufacturers. Also for special grade ball sealers, such as Exxon's high
accuracy ball sealers, similar deviations were observed. Especially for the 0.9 -
1.0 density ballsealers such deviations cannot be tolerated. It is therefore
suggested for field treatments, to check the densities of the ball sealers on-site by
immersing them in fluids with the desired densities (upper and lower
specification limit, e.g. methanol/water mixtures). Only ballsealers that float in
the high density fluid and that sink in the low density fluid should be accepted.
KSEPL has developed a design method for the use of ballsealers, which is
currently available as an Excel Macro. It is suggested to contact SIPM for
application of this design method.
8.6 Use of solids to alter the effective zonal

permeability
This technique uses chemical diverters, e.g. benzoic acid and its derivatives, to
create a diverter cake, either at the perforation or at the sandface. Chemical
diverters fall into two types:
1. Those forming a thin, but very low permeability film on the sandface.
They can effectively plug off the high injectivity or thief zone.
However, there is the risk of almost total injectivity loss if too much
diverter is used. Examples are fine grained oil soluble resins (particle
size < 10 micron) and "liquid diverters", e.g. Halliburton's MMOWG.
2. Those creating a relatively high-permeability diverter cake, usually by
filling up the perforation. Once the diverter cake is formed, distribution
of the stimulation acids is controlled by the resistance of the cake rather
than the varying resistance of the formation. All zones will receive
similar volumes of stimulation fluids. Examples are commercial grades
of benzoic acid (e.g. TLC-80, Halliburton), salts of benzoic acids (J
363, DS or DIV II, Nowsco, both sodium benzoate; see remarks below)
and coarse grades of oil soluble resins (> 50 micron).
Neither types of chemical diverters require zonal isolation to work. However, the
main disadvantage is that, if they are not removed by the produced fluids, they
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can cause impairment too. In most cases clean-up is rather slow. Many cases of
slow clean-up after diverted acid stimulation treatments may be attributed to the
diverter not (completely) dissolving in the back-produced fluids.
Nevertheless, chemical diverting agents, in particular benzoic acid can be used
successfully provided a number of design rules are observed:
1. In general we suggest to use straight benzoic acid (rather than salts of
benzoic acid), since it is soluble in formation water and oil and
sublimates in gas.
2. The effective downhole particle size of benzoic acid is influenced by
the type and order of addition of surfactants and inhibitors. The
preferred order of mixing is surfactant, inhibitor and finally, the
diverter. Acidic slurries prepared in this way show reasonably stable
particles for 1 - 2 hours.
3. In order to maintain the permeability of the diverter cake continuous
addition of benzoic acid throughout the treatment is preferred. Figure
23 shows the minimum concentration to be applied for effective
diversion.
4. Cake build-up is a function of concentration, inflow profile, length of
perforated interval, shot density, injection rate, etc. Note that benzoic
acid is slightly soluble in acid: at concentrations less than 1 kg/m3 no
cake will be formed. This solubility increases with temperature. At
temperatures above 90 oC (200 oF) the solubility of benzoic acid is so
high that its use becomes impractical.
Based on the experimental work KSEPL is formulating a computer model for the
design of chemically diverted treatments.

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Stable diverter cake build up

(B enzoic acid in Hydrocloric
(Benzoic H ydrocloric acid)
Av. particle size (µm )

600
500
No cake build up
400
300
200 Stable diverter cake
100
2 4 6 8 10 12
Concentration (kg/m 3 )
Figure 23 - Stability of benzoic acid diverter cake in hydrochloric acid
Other types of chemical diverting agents, e.g. Oil soluble resins, anthracene, etc.
follow similar rules as far as cake build-up is concerned. However, their solubility
in crude oil should be checked carefully in core flushing experiments.
8.7 Use of fluids to alter the effective zonal viscosity
8.7.1 Viscosified fluids

In this technique, a viscous pills, e.g. polymer solution, are injected in between
acid flushes. In order to work a number of prerequisites should be fulfilled:
 An adequate volume of polymer must be placed in the unimpaired zone.
 The subsequent acid must have direct access to the impairment.
 The polymer must not cause impairment and must be easily removed by
the produced fluids.

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In practice, these requirements, especially the latter, are difficult to meet.

Currently available products, (Temblock systems (Halliburton), Protectozone
(D/S), Rigid Gel P-5 (Nowsco) have been used with limited success.
A better alternative is to gel the acid to be injected. The requirements for
successful application of acid gels are:
 The acid gel should have sufficiently high viscosity at the treatment
temperature for a sufficient length of time.
 The acid gel should lose its viscosity after the treatment to promote
rapid clean-up.
Biopolymer (Shellflo-S)/ acid gels satisfy both criteria and act as "self-diverting"
acid systems.
For Shellflo-S, the transition temperature at which the gel looses its viscosity, is
65°C, but this can be adjusted over a fairly wide range of temperature with
various chemicals, including some acids. For instance, addition of 5 % formic
acid increases the transition temperature 65° C to 73 - 74° C. Gelation of acid
with Shellflo-S is sensitive to iron (III) ions. Therefore a reducing agent (e.g.
erythorbic acid or vitamin C has to be added. N.B. An ordinary sequestering
agent, such as citric acid, is not effective here. Contrary to the non-acid Shellflo-S
gels, the acid gel loses its viscosity permanently, due to rapid chemical
degradation of the polymer, which takes place above the transition temperature.
These properties make the system particularly useful for the removal of shallow
damage, e.g. caused by mud remnants.
The following procedure has been applied successfully:
1. Run coiled tubing to below the perforated interval; if a large sump is
present a bridgeplug might be placed to reduce the dead volume.
2. Inject the required volume of gelled acid by pumping through both the
coiled tubing and the coiled tubing/tubing annulus, maintaining the
same rate through both conduites.
3. Displace the acid with a suitable brine.
4. Close the well in for 12 -24 hours to allow for sufficient reaction time
(depending on the type of acid and damage) and proper breakdown of
the viscosity.
8.7.2 Foamed fluids

Foam can be injected as a spacer between treatment stages (multi-stage process)
or, alternatively, part or all (one-stage process) of the treating acid can be injected
as foam. Foam diversion has the potential for wider application than any of the
above diversion methods. However, it is probably the least understood method. A
foamed acid stimulation pumping schedule for shallow damage may read as
follows:
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(Adapted from Shell Oil procedures, exact operational procedures should be

established locally based on the specific well conditions.)
1. Prepare the well and well site for the treatment by rigging up the coiled
tubing unit and pumping equipment. Pressure test the surface lines and
the blow out preventer, tubulars to the required pressure.
2. Run the coiled tubing in the hole and clean the perforations with foam.
Spot 0.12 m³/m (10 gal/ft) of foamed HCl , while pulling the coiled
tubing up at a velocity of 1 m/min. Maintain pumprate at 159 l/min (1
bbl/min).
3. Run the coiled tubing back to original depth. Spot 0.24 m3/m (20 gal/ft)
of foamed mud acid. Pull the coiled tubing at 0.5 m/min while pumping
at 159 l/min (1 bbl/min).
4. Inject 0.12 m3/m (10 gal.ft)of unfoamed 3% NH4Cl brine, while
lowering the coiled tubing at 1 m/min and pumping at 159 l/min (1
bbl/min). An additional volume of NH4Cl brine should be injected after
running in the coiled tubing to total depth.
5. Displace the tubing/coiled tubing annulus and while pulling the coiled
tubing, the tubing with filtered water, suitable brine, oil, etc. Keep the
well full with displacement fluid to avoid swabbing acid foam into the
well bore while pulling. Research at KSEPL to provide a more
sophisticated appplicate- procedure for form is an going.

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9 Laboratory experiments
9.1 Introduction
Various laboratory test procedures are available to support the design of matrix
treatments. They range from simple beaker tests (for instance, to check the
compatibility of different fluids) to complicated core flow tests. In general, doing
such tests are aimed at:
 Identification and quantification of damage.
 Determination of the most suitable removal treatment in a semi-
quantative sense.
 Determination of some key parameters required to formulate apractical
design.
 Checking the necessity for and the applicability of additives, solvents,
etc.
The following tests will be discussed:
1. Fluid compatibility tests.
2. Stimulation core flow test, including some supporting analysis.
3. Corrosion tests.
4. Emulsion tests.
5. Reaction rate measurements - Rotating disk experiments.
6. Strength measurements (Brinell Hardness, Thick walled cylinder, etc.).
Some of these tests are derived from API recommended practices. Note that all
bottle and test tube tests involving hydrofluoric acid can only be carried out with
plastic bottles and tubes!
Field Guidelines for Matrix Treatments Laboratory experiments  59

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9.2 Fluid compatibility tests

Impairment is often caused by incompatibility between different fluids, either
chemically (precipitates) or physically (emulsions). These effects can been
studied qualitatively by mixing various fluids, to which the well has been exposed
during drilling, completion, etc., in test tubes and examining the effects3.
In general, the following fluids should be tested:
 Mud filtrate
 Cement filtrate
 Completion brines
 Acid formulations
 Formation water
 Crude oil (condensate)
Fluids 1 - 3 should be made up according to information from drilling reports, etc.
or from samples of actually used fluids. The acid formulations may be derived
from some of the other tests mentioned in this chapter or from contractor
recommendations. The formation fluids (water, 5, and crude oil, 6) should
preferably be actual samples from the field, although formation water may also be
reconstituted.
In principle, no precipitates, (stable) emulsions or other incompatibilities should
be observed. The fluids should either form a single phase fluid or unstable
emulsions that quickly separate into two phases. The tests may be carried out at
ambient temperature and pressure.
In case a (black) precipitate is observed when mixing crude oil and acid, an
additional test to verify the occurrence of sludge should be carried out. In this test
acid and crude oil are thoroughly mixed (e.g. using a high speed mixer) and
subsequently aged for 24 hours. Then the mixture is poured out through a 100
mesh stainless steel wire screen. If no solids remain on the screen no sludge was
formed. If there are solids, these may either be stiff emulsions, paraffins or
sludge. To separate out sludge, the screen should be washed alternately with
warm water and a suitable solvent(e.g. Shellsol T). This will remove the
emulsions and paraffins, but not the sludge. If sludge is observed the test may be
repeated with acids containing anti-sludge agents.
60  Laboratory experiments Field Guidelines for Matrix Treatments

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9.3 Standard test procedures for stimulation core

flow tests
The objective of the core flow test is to determine the effect of the various fluids
used in the well on the permeability of the formation rock and to identify
potential remedial treatments. In many cases, these remedial fluids are acids.
Therefore these tests are often referred to as acid response tests, but applying such
tests is certainly not restricted to the use of acid. Apart from KSEPL, all major
service companies can carry out such tests, but their standard test procedures may
deviate from those applied at KSEPL. However, on request these companies will
perform the tests according to the standard procedure outlined below. The
"KSEPL procedure" has been discussed with the following companies:
 Dowell Schlumberger, Tulsa and Aberdeen
 Halliburton, Duncan, Leiderdorp (Holland) and Aberdeen
 BJ Services, Tomball (USA) and Aberdeen
 Nowsco Calgary, Great Yarmouth
 Core Labs, Dallas, Calgary and Aberdeen
9.3.1 Selection of samples

The core material for acid response studies should preferably be taken from a
preserved core. The standard size of the plugs for core flow samples is one inch
(2.54 cm) in diameter and a minimum length of 2.5 cm. Samples should be taken
along side the bedding plane, as this is usually the preferential direction of flow
of injected fluids.
Samples from oil-bearing zones should be cleaned prior to the tests with a
chlorothene/methanol mixture to remove all hydrocarbons and dried under
vacuum. In case of poorly or unconsolidated samples cleaning should be carried
out by careful flushing with the cleaning fluid, rather than by extraction as is
routinely done. Samples from (dry) gas wells and water bearing intervals do not
need to be cleaned. It is advised to measure porosity, air permeability and
(Brinell) hardness on the cleaned and dried samples prior to further testing.
9.3.2 Auxiliary analytical techniques

Throughout a study, the rock matrix should be examined applying various special
analytical techniques. The results of these techniques aid in the assessment of the
core flushing results. The following techniques may be considered:
 Hardness (BHN) measurement.
 Porosity and permeability measurements.

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 Viscosity measurements of the fluids to be tested (at relevant

temperatures), required for calculation of permeabilities during the
various flushes.
 X-ray dispersion (XRD) analysis or "MINERALOG", to determine the
mineralogy of the rock samples.
 Scanning electron microscopy (SEM), including Energy dispersive X-
ray (EDX) analysis, to obtain detailed information on mineralogy and
morphology.
 Computer tomography (CT-scanning).
 Effluent analysis by X-ray fluorescence (XRF), Atomic absorption
(AA), etc.
9.3.3 Core flushing tests

The test conditions depend on the objectives for the tests. The following guide-
lines should be followed:
9.3.4 Core holder

Hassler sleeve type, preferably with axial and radial pressure on the sample. A
minimum difference of 5 bars should be maintained between confining pressure
and injection pressure to avoid by-passing of the fluids to be injected along the
sleeve.
9.3.5 Flow rate

Simulating the actually planned pump rate, i.e.
Test flow rate = 0.25*(d)²*Q/(H*D),
in whichd = core plug diameter
Q = treatment pump rate
H = treatment interval
D = wellbore diameter
If no rates are known in advance, a rate of 5 - 10 ml/min is recommended,
corresponding to 0.8 - 1.6 M3/min (5 - 10 BPM) for a 50 M interval and a 9.625"
well bore.
9.3.6 Pressure
The pressure at the core outflow end is to be kept constant at a minimum of 50
bar.

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9.3.7 Temperature
All tests should be carried out at treatment temperature. If no shut-ins are applied,
the average between surface and reservoir temperature should be applied. During
shut-ins the reservoir temperature is recommended.
The sequential flushes involved in an acid response tests comprise in principal:
1. A 3%w ammonium chloride (NH4Cl) brine to determine the initial
fluid permeability (Ki).
2. An hydrochloric acid flush to remove all soluble carbonates.
3. A mud acid mainflush.
4. A 3%w ammonium chloride overflush to determine the final fluid
permeability (Kf).
The above test procedure will show the effect of a treatment on virgin core
material. If the effect of potential impairing mechanisms and the subsequent
removal of impairment should be included in the study, the following sequence is
recommended:
1. A 3%w ammonium chloride (NH4Cl) brine to determine the initial
fluid permeability (Ki).
2. A flush of potentially impairing fluids, either directly (e.g. mud filtrate
or injection water), or by flowing e.g. mud along the core face, while
maintaining a pressure difference over the core sample*.
3. An hydrochloric acid flush to remove all soluble carbonates.
4. A mud acid mainflush.
5. A 3%w ammonium chloride overflush to determine the final fluid
permeability (Kf).
If non-acid soluble damage is suspected, e.g. remnants from oil based mud or
asphaltene precipitation, flushes 3 and 4 should be replaced by suitable candidate
solvents.
The volumes of the different flushes should simulate the actually planned
maximum volumes, but should be kept the same within one series of tests to
allow comparison of test results on different core samples. All flushes should be
carried out under conditions that simulate injection. However, if the effect of
clean-up will be studied the direction of the flow should be reversed.
Initially all core flow tests on the selected core samples should be carried out
under single-phase flow conditions. This is to ensure that the permeability
responses obtained are truly representative of only rock/fluids interactions, rather
than the result of uncontrollable two-phase flow effects. The tests should
therefore preferably employ successive flushes of solutions, which are completely
miscible. When the required and suitable additives have been identified, acid

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response tests using fully formulated acids can be carried out to determine the
effect of the additives on the performance of the acid, keeping in mind that two-
phase flow effects may influence the results. Also, when studying the clean-up
with hydrocarbons, the effects of two-phase flow should be included in the
interpretation of the results.
During the tests samples of the effluent should be taken at regular intervals.
Analysis of the samples will aid in the interpretation of the results, especially in
case unexpected phenomena are observed.
9.3.8 Reporting of results:

Proper monitoring of the pressures, flow rate and temperature during the
experiments (i.e. as a function of throughput) is vital for meaningful
interpretation of the results. These "raw data" should be made available for
interpretation, along with the results of auxiliary analysis. Also any anomalies
observed during the tests should be reported.
9.4 Corrosion tests

The required concentration of corrosion inhibitor is normally determined by the
service company on the basis of charts showing weight loss vs time for different
types of steel and a range of temperatures. Recently, KSEPL has developed a
corrosion test cell, which measures the actual corrosion rate (Figure 22). The
equipment is simple to operate and can also be used on-site as a quality control
tool.

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Figure 24 - Corrosion test cell

The primary aim is to verify that the corrosion rate of a particular acid
formulation does not exceed the limit.
9.5 (De-)emulsion tests

To identify the need for demulsifiers and their effectiveness, the following test
procedures are recommended:
1. Make up a series of water based fluids according to the following
scheme:
Formation brine Test fluid
90 10
80 20
. .
. .
10 90
In this context the test fluid can be any of the following fluids:
 Acids, both live and spent

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 Fracturing fluids
 Broken fracturing fluids.
2. Add one or more selected demulsifiers to the above mixtures and mix
each of the prepared fluids with crude oil (50:50), using a high shear
blender at treatment and/or formation temperature. Since solids tend to
stabilise emulsions it is also recommended to add 2.5 g/l of solids; silica
flour or formation fines (e.g. kaolinite) for acids.
3. Only mixtures that show 90% separation within 10 min and complete
separation (> 99%) within 4 hours, should be accepted.
The above test is designed for use in production chemistry laboratories of
operating companies or in service company laboratories.
9.6 Strength measurements.

Acidising, specifically of sandstones, attacks the integrity of the formation rock.
Although this may not be too dramatic in many cases (to our knowledge, no well
has been made a sand producer by treating it with acid), it sometimes is a
concern. As a general rule those acid formulations that have the smallest effect on
the strength of the sandstone are preferred, provided that they are equally
effective in achieving the objective of the treatment
A number of methods are available to measure the reduction in strength as a
result of acidising. The most commonly applied methods are:
 Brinell Hardness (BHN),
 Thick walled cylinder and
 Triaxial compression strength.
The BHN test is the only (more or less) non-destructive test and as such, is the
only test that can be performed before and after acidising on the same sample.
The other test methods require twin samples, of which one is acidised prior to the
strength test. Details of the testing procedures can be found in the Rock
Mechanics Manual.

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10 Special applications
10.1 Gravel-packed wells

This section presents a discussion on maximising gravel-packed well productivity
through tailored stimulation methods. In a gravel-pack, the most critical areas for
impairment, and hence for stimulation, are:
1. The screen,
2. The perforations,
3. The gravel,
4. The gravel/sand interface,
5. The near well bore formation.
In practice it is often difficult to determine the exact location of the damage.
Ideally, one should aim at developing stimulation treatments that can
simultaneously remove damage from many locations. Even when a stimulation
treatment is designed to deal with a specific identified form of impairment, care
should be taken that the procedure employed does not negatively influence the
remainder of the gravel-packed well.
10.1.1 The screen

A remedial treatment based on a soak with a fluid that can dissolve the plugging
material, should restore the flow capacity of the screen. The preferred method is
to spot the acid with coiled tubing at the bottom of the well and subsequently
pulling up the C.T. while pumping. This will ensure coverage of the entire screen
and, hence, maximise the chance of establishing inflow across the total length. To
avoid possible adverse reactions in the pack or formation, treatment volume
should not exceed the capacity of the completed section of the wellbore by more
than, say, 1 - 2 m3.
Field Guidelines for Matrix Treatments Special applications  67

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The fluid should:

 Dissolve the plugging material,
 Be compatible with the gravel and formation and
 Be non aggressive to the combination of carbon steel and high quality
steels used in the screens.
10.1.2 The perforations

Many publications on both laboratory and field studies¹, indicate that perforations
in gravel-packed wells are often responsible for poor well performance.
Frequently encountered problems are:
 Perforations contaminated with debris, paint, pipe dope, etc.
 Perforations filled with precipitates from incompatibility between
completion brine and formation fluids.
 Contamination with mud remnants.
 Perforations filled with formation sand/gravel mixtures.
The first three types of impairment occur prior to the actual placement of gravel.
Hence they are best treated before gravel-packing. Five commonly used
techniques are available:
 Perforation washing
 Backsurging
 .Pre-gravel-pack acidisation
 Underbalanced (tubing conveyed) perforating.
 Pre-packing of perforations.
The latter two techniques aim at prevention of damage and as such fall outside the
scope of this manual.
Perforation washing is generally considered to be an effective way of removing
any impairing material from the perforations. Perforation washing should be done
with a clean, non-damaging (compatible) fluid. Circulation rates should be 2 to 3
bbl/min. Care should be taken with strongly laminated sands to prevent
intermixing of sand and shales.
Backsurging is another method to obtain clean perforations prior to gravel-
packing. Usually, backsurge tools are designed such that the perforated interval is
exposed to a reduced pressure for a short period. It is applicable to most wells,
but is specifically beneficial in depleted reservoirs where perforation washing
may not be possible.
68  Special applications Field Guidelines for Matrix Treatments

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Pre-gravelpack acidisation is in principal also a good method to obtain clean

perforation tunnels. However, several potentially negative effects, such as fines
generation, secondary precipitates, emulsions, etc. may nullify the effect of the
acid, especially when post-acid/pre-pack well clean-up is not feasible. On the
other hand it has proven its use in removal of lost circulation materials e.g. graded
calcium carbonate or removal of perforation debris. To minimise negative effects,
the pre-gravel-pack acid job should be limited in size such that essentially only
the perforation area is treated, i.e. total volumes limited to 0.08 -0.16 m3/m (10 -
20 gal/ft).
10.1.3 The gravel

Assuming that the correct size of gravel has been placed, the bulk of the gravel
usually does not create a significant productivity reduction, provided that the
gravel is clean and free of dirt, cement dust, etc., i.e. the gravel should satisfy the
API requirements for good quality gravel. Occasionally, intermixing with e.g.
shales from other zones due to poor placement techniques, has been reported.
Depending on the nature of the contamination, treatment with HCl or HF/HCl can
alleviate such problems. Such a treatment would also help in case dirty (off-spec)
gravel has been applied. If iron pick-up from the tubulars (rust, scale) is suspected
it is advised to add a sequestering agent to the acid, specifically when HCl alone
is used. Normally 10 -20 Kg/M3 citric acid will suffice. The treatment volume
should be geared to the approximate volume of the gravel-pack.
If the size of the gravel is too large and formation sand has invaded the gravel-
pack, a similar treatment with HF/HCl may have some effect. If, on the other
hand, the gravel size would be too small, stimulation would not have an
appreciable effect on productivity. A re-gravel-packing treatment under fracturing
conditions, "Frac&Pack", could be considered.
10.1.4 The gravel/sand interface

Two main problems may occur at the gravel/sand interface:
1. Just prior to and during the placement of the gravel-pack the formation
face may be stirred up. Remixing of sand, shale, feldspar, etc. creates a
new surface of reduced permeability. This defect is best cured by an
acid treatment using an appropriate mix of HF and HCl.
2. Incompatible fluids can create an impaired zone at and/or near the
formation face (filter cake). The effect is intensified if the fluids contain
solids or if the viscosifier leaves a residue behind (e.g. poorly mixed,
unsheared and unfiltered, partially broken HEC). Subject to the type of
damage, usually an HCl treatment will alleviate the problem. If the
impairing solids are due to precipitation 15 % wt HCl is suggested. If,
however the problem is related to the presence of polymer (HEC)
residue lower concentrations, say 2 - 3 %w of HCl should be used.
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Recent laboratory and field work has shown that HEC breakdown by
strong acids creates a significant amount of insoluble residue.
Alternatively, treatments with enzymes (if reservoir temperature is 65°
C or lower) or hypochlorite may be applied. Laboratory tests should be
carried out to establish the applicability of a particular treatment.
3. Again the volume of the treatment should be restricted to the zone to be
treated, say, 1.1 times the volume of the pack. To promote complete
coverage of the entire zone a diverting agent that filters out at the
formation face may be used. Also gelled acid or foam might be applied.
10.1.5 The near-wellbore formation

The formation rock near the well-bore may have been damaged during drilling,
cementing, perforation and preparing the well for gravel-packing. As such gravel-
packed wells do not differ from perforated wells, but it is more difficult to direct
the stimulation fluids to the impaired region in gravel-packed wells than it is in
conventionally completed wells.
10.2 Summary
Figure 25 shows a treatment selection chart based on the arguments described
above.

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Gravel-pack stimulation selection chart
Most likely location of damage preferred treatment
Screen, slotted liner Acid/solvent soak
Blocked perforations
Perforation debris, precipitates,etc. Backsurging
Perforation washing
Pre-gravel-pack acidisation
Formation sand/gravel mixtures Post gravel-pack acidisation, small
volume HF/HCl, spotted or diverted
Gravel
Contamination with shale, etc. HF/HCl post gravel-pack acidisation
Gravel too large " " " "
Gravel too small Squeeze pack or Frac & Pack
Gravel/Formation interface
Remixing of sand, shale, feldspar. HF/HCl
Solids 15 %w HCl
Polymer residue (HEC) 3 %w HCl, enzymes or hypochlorite
treatment
Near well-bore formation Various matrix treatment techniques

as applied in normally completed
wells (diversion more important)
Figure 25 - Gravel-pack stimulation selection chart
As in any acid stimulation treatment a number of additives are required to combat

a number of side effects inherent to the use of acid In relation to gravel-packing,
special attention should be given to corrosion aspects. Often screens are
manufactured using high alloy steels. Particularly, the points where the screen is
welded to its support, are sensitive to corrosion.
Currently available corrosion inhibitors are in principal designed for use in
normal steels, although most contractors claim that they are also effective in high
alloy steels, albeit in higher concentrations. Service companies should be
requested to carry out corrosion tests using the steels applied in the well. As a rule
of thumb, it is suggested to use twice the concentration recommended for
normally completed wells.
10.3 Horizontal wells

Damage removal in horizontal wells is not different from that of vertical wells as
far as selection of candidates and treatment fluids is concerned. Apart from the
(usually) large fluid volumes involved, the design procedures follow the guide-
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lines given in the relevant sections of this manual. The major difference lies in the
placement of the treatment.
Effective removal of damage in long horizontal sections requires optimum
placement techniques. However, "conventional" means, such as ball sealers or
granular diverters are not applicable. Depending on their densities, they tend to
shut-off either the top part or the bottom part of the horizontal section. Some
mechanical alternatives have been cited in the literature, such as special
application of coiled tubing (DS), the FO tool (Halliburton) or the PCS tool
(Baker).
Apart from the above mechanical devices, and possibly in addition to them,
diverting agents can be applied. To this end, non-solids systems, such as foamed
or gelled acid are to be preferred. In long horizontal sections the use of foam may
become impractical in view of the large volumes required to cover the entire
zone. In those cases the choice of a diverting agent is narrowed down to the use
of gelled acid.
10.4 Naturally fractured sandstones

Many reservoirs around the world contain natural fractures. These fractures are
frequently rather permeable and form the main flow path for the hydrocarbons
from the reservoir into the well.
Stimulation of such wells should be aimed at:
 Removal of the damage induced by the high fluid losses and the
measures taken to cure those losses and
 Further increase of the conductivity of the natural fractures by
dissolution of the (natural) minerals present in the fractures.
For a proper selection of a stimulation fluid for naturally fractured reservoirs the
following guide-lines can be given:
1. Determine the most likely source of damage, by studying the drilling
and completion reports.
2. Get a clear description of the type of fractures and their possible
contents. This involves core studies (mineralogy) and geological
advice.
3. Apply the selection chart given in Figure 26 to determine the most
appropriate type of acid.
4. If core samples are available perform core flushing tests to confirm the
applicability of acids selected on the basis of Figure 26.

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Acid selection chart for naturally fractured formations
Formation Fractures
open or filled with filled with filled with mud

calcitic material siliceous fines remnants, etc.
Calcite HCl (10 - 15 %) HCl (10 -15 %)+ HCl (10 - 15 %) +

silt suspending silt suspending
agent agent, small
volume
Dolomite HCl (10 - 15 %) HCl (28 %) + HCl (28 %) +

silt supending silt supending
agent agent, small
volume
Sandstone HCL (10 - 15 %) Mud acid (SFMA) Mud acid (SFMA),

small volume
Figure 26 - Acid selection chart for naturally fractured formations
Also with regard to injection rates, treatment of fractured rocks involves a

compromise between two options. Removal of a mud cake inside the fractures
near the well bore, is enhanced by a low pump rate (longer contact time, no by-
passing). On the other hand, effective removal of fracture filling minerals as deep
as possible, is promoted by pumping fast, possibly even exceeding the fracturing
limit. It depends very much on the local situation, whether to use a low or high
pump rate or possibly a combination of both, i.e. initially pumping at a low rate to
effectively dissolve a mud cake, followed by continued injection at a high rate.
10.5 Exploration wells

Often production technologists or stimulation engineers are asked whether
stimulation of a particular exploration well is useful.
The main objective for a stimulation treatment in an exploration well is, from a
petroleum engineering point of view, to establish that producible hydrocarbons
are present and, if possible, produce at a rate sufficient to obtain a good well test.
It is not the intention to optimise the treatment so as to maximise the
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productivity. With this in mind the following guide-lines have been compiled in
discussions with engineers from various operating companies:
1. For a successful stimulation a minimum hydrocarbon saturation of 25%
is required. Stimulation cannot create gas or oil.
2. Selection of type of stimulation.
For gas wells: Fracturing if the permeability is less than 1 mD.
For oil wells: Fracturing if the permeability is less than 50
mD, but to some extent dependent on the
viscosity.
3. Perforation policies or exploration wells should be such that only a
limited length of the zone of interest is perforated. This minimises the
risk of water or gas influx after stimulation. This is particularly
important in case a well is likely to be fractured. Additional perforation
can always be done after stimulation, if required.
4. Every effort should be taken to gather data relevant to the design of a
(possible) treatment. Whenever possible, time should be taken to
perform leak-off tests, to take side-wall samples for mineralogical
analysis (Mineralog, SEM study)*, etc.
5. Prior to drilling of the exploration well a scheme of action should be
made (and agreed on by all parties) with respect to the likelihood of
successful stimulation. Approval for the additional costs and time
involved should be obtained to ensure management commitment. Such
a plan could, for instance, be as follows:
1) Confirm hydrocarbon shows during the drilling phase.
2) If information from other sources, e.g. other wells in the area indicates
that fracturing might be required, perform microfrac to obtain important
data for possible fracturing treatment.
3) Take oriented core of the microfrac.
4) Repeat these steps as appropriate.
5) Run logs over target interval and determine reservoir quality,
hydrocarbon saturation, etc.
6) Take side wall samples, if step 3 was omitted and determine some basic
properties, such as formation composition, porosity, strength, etc.
7) Run casing and perforate a limited interval over the first zone of
interest.
8) Carry out initial production test to obtain preliminary data on
permeability, skin, etc.

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9) Decide on the basis of the log interpretation and initial production test
whether or not stimulation is feasible (apply guide-line No. 2).
10) Perform acid or other damage removal treatment.
11) Carry out a production test.
12) In case of low production run FRACJOB (or ACIDFRAC in case of
carbonates) using data from e.g. microfrac tests to assess the prospects
for fracturing.
13) Design and perform fracturing treatment if warranted.
14) Carry out production test.
15) If necessary, additionally perforate.
16) Repeat production test.
Following a plan like the above, ensures that every possible and necessary step is
taken to prove the existence of producible hydrocarbons or otherwise.
10.6 High temperature/high pressure wells
10.6.1 High pressure

Most wells are drilled upto depths of 3000 - 4000 m (9000 - 12000 ft) in
hydrostatic reservoirs. Pressures and temperatures encountered in those wells fall
in the ranges covered by the specifications of the equipment and products
provided by the major stimulation contractors. Equipment usually has a pressure
rating upto some 1300 bars (20000 psi), while most products have been designed
for use upto 120° C (250° F).
High pressure wells require a surface treating pressure of, say, a thousand bars or
more. Usually this is not a problem because the tubulars, etc., are designed for
high pressure service. However, occasionally the injection pressure during
stimulation may considerably exceed the static well-head pressure. From an
operational point of view this presents the following potential problems.
1. The well-head may not be rated upto such high pressures. This problem
may be overcome by the use of a well-head isolation tool. These tools
are offered by all major stimulation contractors. They have the added
advantage that high quality steel components of the Christmas trees are
protected from contact with corrosive acids.
2. The tubing string may not be suitable for such high pressures. This can
be overcome (to some extent) by pressurising the tubing/casing
annulus.
3. The high pressure may prohibit the use of coiled tubing.

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4. In many cases, the pump rate has to be limited to ensure that the
maximum allowable pressure is not exceeded. The span between
reservoir pressure and fracturing pressure tends to be small in high
pressure areas. Therefore, in many cases the treatments will have to be
carried out at a maximum pressure, with a variable injection rate,
depending on the effect of the treatment.
5. The reduction in injectivity, inherent to the use of diverting agents, ball
sealers, etc., may result in extremely low pumprates and eventually in
premature termination of the job. Hence, diversion should be
considered carefully and only applied if it is vital for the success of the
treatment.
10.6.2 High temperature

The influence of high temperatures on the design, execution and performance of
matrix treatments is perhaps more drastic than the effect of high pressures.
1. Reaction rates are faster, resulting in a limited penetration depth of live
acid. To combat this retarded acids may have to be applied. A number
of options are available:
 SGMA Self Generating Mud
Acid,Shell Dev. Co.
 BRMA Buffer Regulated Mud Acid,
Shell Dev. Co.
 Clay acid Fluoboric acid, Dowell
Schlumberger
 Clay Sol Sequential HCl/NH4F,
Halliburton
 AlHF Retarded Mud acid,
Halliburton
Whether or not retardation is required depends on the type of damage and
the radius of the affected zone.
Alternatively, cool-down preflushes could be applied. A drawback of this
procedure is substantial amounts of water may have to be injected, which
can adversely affect the clean-up after the treatment.
2. Corrosion of tubulars at high temperatures is much more severe than at
low temperatures for two reasons:
 being a chemical reaction, its rate approximately doubles every 10° C
temperature increase and
 current commercial inhibitors start to decompose at temperatures above
100 - 120° C.
CONFIDENTIAL
The current way to combat this higher corrosion is to add high

(excessive?) concentrations of corrosion inhibitors and intensifiers.
Also here cool-down preflushes will help to reduce the corrosion
problems. However, it should be borne in mind that return acid,
although spent, is hot and still very corrosive and should therefore
contain sufficient corrosion inhibitor. Unfortunately corrosion inhibitors
tend to stay behind in the formation. Therefore, an overdose might be
required to compensate for loss of inhibitor through adsorption on the
formation. Overdisplacement of the acid deep into the formation will
alleviate the problems. In any case, it is strongly recommended to
include corrosion tests with (simulated) spent acid in the corrosion test
program.

CONFIDENTIAL
Appendix
Check list for the selection of stimulation

candidates
The following list of questions should be addressed for the identification and
classification of formation damage. Depending on the local situation part of the
list may be omitted. It is stressed that some of the questions can only be answered
after careful scrutiny of well histories and/or after laboratory testing. Often at
least confirmatory testing is required.
A. General information required

1. Reservoir characteristics (production mechanism, pressure,
permeability, porosity, etc.).
2. Geological information (mineralogy, etc.).
3. Well completion (gravel-packed, perforated hole, type and size of
tubing, casing, perforation details, etc.).
4. Cores available?
B. Pre-selection of possible source of damage

1. What is the skinfactor?
2. Is the recorded value essentially due to formation damage or should it
be corrected for partial completion, well deviation, etc.?*
3. Has the value of the skin factor changed during the life of the well?
4. Can any change in skin factor be related to changes in GOR, watercut,
rate, drawdown, etc.?
5. Can any change in skinfactor be related to one or more of the following
activities:
Field Guidelines for Matrix Treatments Appendix  79

CONFIDENTIAL
 Completion/workover?
 Perforation?
 Previous stimulation?
 Gravelpacking?
C. Check on damage due to produced (injected)

fluids
1. Is the crude asphaltic or waxy?
2. Is the water cut low and/or more or less constant?
3. If water is being produced.
4. Did (sudden) changes in water cut occur during production?
Is the water self-scaling under the pressure and temperature in the near
well-bore region?
Are injection and formation water being produced and are they
compatible?
5. In case of injection wells, are the injected fluids compatible with the
formation fluids and/or formation rock?
6. Are the injected fluids on-spec - what is the frequency of plant up-sets?
7. In case of a gas injector, what lubricants, inhibitors, etc. are applied?
D. Check on damage due to (additional)

perforation
1. Was the well perforated under drawdown?
2. What type of perforation gun was applied?
3. What is the perforation density and phasing?
E. Check on damage due to previous

stimulation treatments
E.1. Hydraulically fractured wells
1. What type of fluid has been used?
2. What type and size of proppant has been used?
3. What is the (estimated) closing stress?
80  Appendix Field Guidelines for Matrix Treatments
CONFIDENTIAL
4. Could the injected fluid have cooled the reservoir enough

(during the treatment) to induce precipitation of organic
solids?
5. Was proppant over-displaced?
E.2. Matrix treatments

1. What type of acid was applied?
2. Was the tubing cleaned prior to the treatment?
3. What diversion techniques were applied to ensure adequate
coverage of the stimulation interval?
4. Was there any pressure response during diverting?
F. Check on damage due to gravelpacking

1. What is the type of gravelpack: IGP, OHGP or EGP?
2. Was the gravel size correct (acc. Saucier criterion)?
3. Was the gravel upto specification?
4. Any chance of mixing the gravel with e.g.. shale cavings,
also from other intervals?
5. Were the perforations prepacked?
G. Check on damage due to the application of

incompatible fluids
(These questions should be answered for each of the above
activities separately)
1. Is there any evidence (e.g. from lab tests) of interaction
between injected fluid and reservoir fluids?
2. Any indication of precipitates being formed, either due to
instability of the treatment fluid or caused by reaction
with other fluids?
3. To what extend have the fluids been filtered?
4. Any evidence of fluid/rock interaction?
5. If in any of the above cases particles were generated or
present in the fluids, was their size in the critical range of
1/7 - 1/3 of the average pore size?*
Field Guidelines for Matrix Treatments Appendix  81

CONFIDENTIAL
6. Have samples been taken during the initial backflow and

analysed for:
 Total iron.
 Acid strength (pH).
 Precipitates on standing.
 Total solids.
 Presence of emulsions.
 Bacterial mass, slime, etc.?
82  Appendix Field Guidelines for Matrix Treatments

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Stimulation

2 Damage removal techniques 3

3 Damage removal design process 7

4 Matrix acidising of sandstones 15

5 Matrix acidising of carbonates 27

6 Non-acid matrix treatments 37

7 Additives for matrix treatments 47

ii  Contents Field Guidelines for Matrix Treatments

Field Guidelines for Matrix Treatments Contents  iii

Field Guidelines for Matrix Treatments Introduction  1

2 Damage removal techniques

The most commonly used damage removal techniques are:

2.1 Matrix acidising

a primary stimulation treatment, such as in naturally fractured formations (as is

2.2 Acid wash (perforation wash)

2.3 Chemical flushes with surfactants, solvents,

4  Damage removal techniques Field Guidelines for Matrix Treatments

3 Damage removal design process

Minimum requirements for successful matrix treatments

Hydrocarbon saturation 30 % or more

Water cut 40 % or less

Gross reservoir height no limit

Permeability Gas > 1 mD, Oil > 20 mD

Reservoir pressure Gas: two times the abandonment pressure

Production system Current production not more than 80 % of maximum

Figure 1 - Minimum requirements for successful matrix treatments

Field Guidelines for Matrix Treatments Damage removal design process  5

Well input data Stimulation Treatment

Figure 2 - Stimulation Treatment Selection Chart

Damage removal treatment process

Evaluation cycle Job execution

Figure 3 - Damage removal design cycle

3.1 Problem well identification

Field Guidelines for Matrix Treatments Damage removal design process  7

3.2 Analysis of the skin factor

Stot : Total skinfactor ("Horner" skin)

8  Damage removal design process Field Guidelines for Matrix Treatments

Stemp : Skin due to temperature transition in water injectors, usually

3.3 Damage classification

3.4 Treatment selection

Field Guidelines for Matrix Treatments Damage removal design process  9

Matrix treatment selection

Figure 4 - Matrix treatment selection

3.5 Treatment design

10  Damage removal design process Field Guidelines for Matrix Treatments

4 Matrix acidising of sandstones

4.2 Acid type, - concentration and - volume

Field Guidelines for Matrix Treatments Matrix acidising of sandstones  11

Both field experience, laboratory work as well as theoretical calculations have

12  Matrix acidising of sandstones Field Guidelines for Matrix Treatments

Sandstone Acidising Selection

Main Mineral Clean

RMA : Regular Mud Acid - 12% HCl + 3% HF

Figure 5 - Sandstone acidising selection chart - Shallow damage

Field Guidelines for Matrix Treatments Matrix acidising of sandstones  13

Sandstone Acidising Selection

RMA : Regular Mud Acid - 12% HCl + 3% HF

Figure 6 - Sandstone acidising selection chart - Deep damage

14  Matrix acidising of sandstones Field Guidelines for Matrix Treatments