9 Stimulation by Acidizing BP PDF

RO-EP-DA-PO-06-POL-001-02 OMV Petrom Exploration Production
Revision 1 2012 OMV Petrom Workover Best Practices

9. STIMULATION BY ACIDIZING
Contents
EXECUTIVE SUMMARY ......................................................................................................................... 9-1

9. STIMULATION BY ACIDIZING ............................................................................................................ 9-3
9.1 Introduction ............................................................................................................................. 9-3
9.1.1 Objectives of Well Stimulation by Acidizing ...................................................................... 9-4
9.2 Well Acidizing Stimulation Technology.................................................................................... 9-4
9.2.1 Total Skin factor and its use in OMV Petrom for Making Decision for Acidizing .............. 9-5
9.2.2 Best Candidate Selection Process for Acidizing ................................................................. 9-7
9.2.3 Review of the Most Frequent Damages in OMV Petrom and General Selection of
Treatment .......................................................................................................................... 9-7
9.3 Well Acidizing Methods Applied in OMV Petrom .................................................................. 9-10
9.3.1 Sandstone ........................................................................................................................ 9-13
9.3.2 Carbonate ........................................................................................................................ 9-15
9.4 Technology Workflow of Best Practices for Fluid Selection, Treatment Design and Job
Execution ............................................................................................................................... 9-18
9.4.1 Sandstone Matrix Acidizing Treatment ........................................................................... 9-18
9.4.2 Applied Sandstone Design Procedure ............................................................................. 9-29
9.4.3 Carbonate Acidizing Best Practices.................................................................................. 9-36
9.4.4 Planning and Job , Execution of Acidizing Treatment...................................................... 9-45
9.4.5 Job Evaluation and Control .............................................................................................. 9-48
9.5 Configuration of Surface Equipment for Acidizing............................................................... 9-52
9.6 Fluids and Materials Used for Acidizing ................................................................................. 9-53
9.6.1 Additives (corrosion inhibitors, Iron-Control Agents, Clay Stabilizers etc)...................... 9-53
9.7 Quality and Safety Requirements for Acidizing ..................................................................... 9-54
9.7.1 Quality Control................................................................................................................. 9-54
9.7.2 Health, Safety and Environmental Aspects of Acidizing .................................................. 9-57
9.7.3 Personnel (Training, Supervision) .................................................................................... 9-59
Appendix 9-A Commercially Available Acid Systems Specification Details.................................... 9-60
Appendix 9-B Commercially Available Additives and Solvent Specifications ................................ 9-66
List of Figures ................................................................................................................................. 9-70
List of Tables................................................................................................................................... 9-72
OMV Petrom Exploration Production RO-EP-DA-PO-06-POL-001-02
OMV Petrom Workover Best Practices Revision 1 2012
References ...................................................................................................................................... 9-74

EXECUTIVE SUMMARY
EXECUTIVE SUMMARY: 9. STIMULATION BY ACIDIZING

No. Strongly Recommended
Review the well logs, reservoir characteristics and previous workovers to identify shortlist
candidates with damage to the wellbore, in the perforations and / or within the formations.
1.
Clarify the factors causing skin damage on shortlist candidates and determine which near
wellbore flow restrictions can be removed by acid treatment.
Involve careful consideration of fluid selection, the pumping schedule, acid placement
2.
techniques and on-site treatment monitoring.
Use developed workflows (Figure 9-10 to Figure 9-16) for proper fluid selection required for
sandstone acidizing.
Mineral Composition > 100 mD 20-100 mD < 20 mD
3. <10% Silt and < 10 % Clay 15% HCl 10% HCl 7.5% HCl
>10% Silt and >10 % Clay
>10% Silt and < 10 % Clay 10% HCl 7.5% HCl 5% HCl
>10% Silt and > 10 % Clay
Reduce the concentration of the HCl if the formation is partially or totally dolomite and
4. should be lowered wherever silicate content of the dolomite is high in order to avoid
precipitation. Follow selection workflow in Figure 9-20.
In case of high bottomhole temperatures use slower reacting weak organic acids. Special
5. attention should be paid to the concentrations of formic acid to avoid precipitation of
calcium formate.
Use retarded HCl (by gelling or emulsifying the acid), or organic acids if bottomhole
6.
temperature is high (>120 oC).
The cleanliness of all tanks that will hold water or acid should be verified and the acid tank
7.
must be circulated before pumping.
8. Mix chemicals in recommended sequences.
9. Always keep foam quality above 70%.
10. Carry out acid pickling of tubing string for all important (costly) jobs.
11. Put the well into production immediately (no reaction break) in high temperature wells.
12. Use nitrogen displacement for gas wells.
13. Use diverting for long (> 25 m) perforated intervals.
Use HBF4 when problems with migrating fines exist, what is often case in the maturated
14.
wells completed with gravel pack.
Verify availability and specifications of all fluids (additives, acid, surfactants, diverters)
15.
required to complete the stimulation job
The injection rate and pressure is to be monitored and the pressure kept below predefined
16.
levels (especially breakdown pressure in sandstone).
Fluids pumped during the stimulation job are to be sampled and analysed for post-
17.
treatment review.
Real-time formation response to stimulation fluids should be recorded in a Field-Acid-
18. Response-Curve (FARC) to enable swift corrective action to be undertaken during the
treatment job.
Use standardized treatment report which describes fluid QC data, pump rates, tubing and
annular pressure measurements, types and volumes of fluids and diverters, deviations from
19.
the program, pumping interruptions and any other problems which influenced the execution
of the treatment job.
http://www.petrom.com 9-1
EXECUTIVE SUMMARY: 9. STIMULATION BY ACIDIZING

No. Not Recommended at All
1. To exceed frac pressure during treatment operation.
2. To use HF + KCl or formation brine.

If doing foam injection frac pressure is reached do not decrease foam quality, just stop
3.
nitrogen.
To start treatment if all fluids which are pre-blended at the service company facility are not
4.
subjected to quality checks.
5. To use diverting for short (< 25 m) perforated intervals.
6. To use mud acid to treat formations if HCL solubility is > 20%.
7. To start acidizing treatment if sufficient injectivity is not obtained.
8. To use of HCl preflush after dry tests in exploratory/wildcat wells.

To continue the treatment if the surface pressure rises sharply or rises continuously for
9.
certain volume of acid (0.5-1m3).
To delay the well shut-in time after acidizing treatment in order to minimize precipitation
10.
of reaction product.
To use NaCl, KCl, or CaCl2 brines in any HF treatment stages or in any stage immediately
11.
preceding or following HF stages.
9-2 http://www.petrom.com
9.1 Introduction
There are two basic stimulation methods which can be used to eliminate formation damage and
increase well productivity: matrix acidizing and fracturing (hydraulic and acid).
Matrix stimulation by acidizing is injecting an acid/solvent at below the fracturing pressure of the
formation in order to dissolve/disperse materials that impair well production in sandstone reservoirs
or to create new unimpaired flow channels in carbonate reservoirs.
In the case of injecting acid below the fracturing pressure the injected acid dissolve some of minerals
present, and hence, reestablish or increase the permeability inner-wellbore vicinity (not deeper than
0.1 to 0.3m in sandstone reservoir and 1 to 3 m in carbonate reservoirs). Matrix acidizing can
significantly enhance the productivity of a well when near-wellbore formation damage is present,
and conversely, is of little benefit in an undamaged well. Thus, matrix acidizing should generally be
applied only when a well has a high skin effect that cannot be attributed to partial penetration,
perforation efficiency, or other mechanical aspects of the completion.
The most common acids used in OMV Petrom are hydrochloric acid (HCl), used primarily to dissolve
carbonate minerals, and mixtures of hydrochloric and hydrofluoric acids (HF/HCl), for attacking
silicate minerals such as clays and feldspars. Other acid formulations, particularly some weak organic
acids, are used in special applications.
Acid fracturing, resulting from the injection of fluids at pressures above the formation
fracture/parting pressure, is intended to create a path of high conductivity by dissolving the walls of
the created fracture in a non-uniform way. Acid fracturing is sometimes used to overcome formation
damage in relatively high-permeability formations. However, carbonate reservoirs of relatively low
permeability may also be candidates for acid fracturing. In acid fracturing, the reservoir is
hydraulically fractured and then the fracture faces are etched with acid to provide linear flow
channels to the wellbore.
Acid fracturing of relatively homogenous carbonates will produce smooth fracture faces that will
retain little fracture flow capacity when treating pressure is released. Acid fracturing of
heterogeneous carbonates can develop non-uniform etching of the fracture face. The area that is not
etched acts as a support for the etched areas, thus providing flow channels in the fracture and
significant increases in well productivity. It is suggested that laboratory tests be conducted on cores
to determine the etching characteristics of the rock before treating a well. In some instances, the
non-etched area of a heterogeneous carbonate will be softened by acid and will not support the
fracture when treating pressure is released. The only alternative would be hydraulic fracturing and
propping with sand. Two other problems can exist in acid fracturing: (1) Un-dissolved fines can
significantly reduce fracture flow capacity if not removed with spent acid and suspending agents,
usually surfactants or polymers will materially aid in the removal of these fines (2) Emulsions can
block the etched fracture. API RP 42 tests should be performed to select an emulsion preventing
surfactant for the acid treatment.
Acid fracturing is rarely used in the treatment of sandstones, because acid, even hydrofluoric acid
(HF), does not adequately etch these fracture faces. However, treatments have been successful in
some sandstone formations containing carbonate-filled natural fractures. Removal of these
carbonate deposits often results in sufficient conductivity to yield excellent treatment results.
The results of field studies in Sotanga Meoian, Targoviste Rsvad Gura Ocnitei Meoian III, Calinesti
Dacian, Moreni, Gura Ocnitei and South Dacian, which are in an maturated/advanced stage of
production consisting mostly of high permeability sand layers with high variation of stability (good to
poor ) have been used in formulating the stimulation acidizing best practices in OMV Petrom.
9.1.1 Objectives of Well Stimulation by Acidizing
The key objectives of well acidizing in OMV Petrom are to:

Remove near wellbore formation damage and decrease skin factor
Restore damaged matrix permeability in near well-bore reservoir area
Improve matrix permeability in near well-bore reservoir area
Maximize well productivity
Remove deposits from well tubular/wellbore cleanout.
The improvement in productivity of wells that can be realized with matrix stimulation as shown in
Figure 9-1 The plot shows that acidizing is more effective in restoring the original permeability by
removing formation damage, than in increasing permeability over its original value. This is used as
principal guidance in the company for selecting the best well candidate for application of stimulation
by acidizing.
9.2 Well Acidizing Stimulation Technology
In sandstone formations, acid treatments aim to remove near-wellbore flow restrictions and
formation damage. The goal of these treatments is to return the near-wellbore area to its natural
condition. In carbonates, dissolving matrix is one of the objectives, but bypassing a damage of the
nearwellbore by creating new channels is the primary target.
Usually, wellbore damage is caused by drilling or completion operations, fines migration, clay
swelling or polymer plugging. To select an optimized fluid system for effective stimulation, the type
of damage and the formation mineralogy must be known. The structured process of the design of a
well acidizing stimulation job the following main phases:
1. Candidate selection and proper diagnosis of damage type - The best candidate well for a
stimulation treatment is selected, regardless of the type of stimulation/remediation needed.
Candidates are wells with damage to the wellbore, in the perforations and / or within the formations
which is acid-removable. If the damage is not acid-removable, then it should not be acidized and is
not a candidate. During this phase, the best treatment for the type of damage must be determined
by assessing and, ideally, measuring the skin. The economically most attractive candidate is then
selected based upon expected production gains.
2. Fluid selection - The appropriate fluids, acid types, concentration, treatment volumes and
additives are selected. Careful thought should be given to the determination of appropriate
additives and combinations for each case.
3. Pumping schedule and execution sequences - The number of stages and how much to pump in
each stage (volumes, rates and time) are determined.
4. Acid placement and techniques - detailed simulation of the acidization process using the planned
pumping schedule should be undertaken, including diversion. A major reason for unsuccessful acid
treatments is that the acid does not go where it needs to go. Determination of the proper fluid
placement method is thus a key factor in acid treatment design in both carbonates and sandstones.
5. Treatment monitoring, quality control and on site evaluation -The actual skin changes resulting
from the stimulation treatment are compared to the predicted results. Quality control steps (during
rig-up, before pumping, during pumping and flowback) should be implemented.
9.2.1 Total Skin factor and its use in OMV Petrom for Making Decision for Acidizing
The skin is an important factor to decide whether or not to stimulate a well and what generic type of
treatment would be most suitable. Since it represents the total additional pressure drop as compared
to ideal conditions, in the near-wellbore region, its value is the combined effect of several
parameters, including formation damage. To properly interpret the skin and therefore determine the
appropriate remedial action, field engineers must analyze the contribution of each factor. This
analysis should involve identifying skin damage which could be removed by stimulation and may
result in additional opportunities for production improvement such as re-perforating. Candidate
identification therefore requires an understanding of the various skins and recognizing skin damage.
The production of newly completed well or worked-over well may be lower than expected, due to
wellbore damage from the drilling/completion/workover process, or by mechanical difficulties in the
overall completion process. All of these problems will result in an additional pressure drop near the
wellbore, and thus affect the skin factor. Therefore, the key to candidate selection lies in the analysis
of the various skin components. In Table 9-1 these skin component characteristics are summarized.
Table 9-1 Summarized skin components
Skin Components Characteristics

S Total skin factor (Horner skin)
Skin caused by formation damage (positive). It is the component that needs
Sdam to be removed with the matrix treatment.
Skin caused by limited perforation height (positive). It results from the well
not being perforated over the complete reservoir height, such as to minimise
Spart gas or water coning.
Skin caused by wellbore deviation (negative). At high deviation angles, the
increased effective length of the reservoir section open to inflow increases
Sdev the natural well productivity.
Skin caused by the presence of small perforations (positive or negative). The
Sperf skin depends on the perforation size and phasing.
Skin caused by reduced crushed-zone permeability around perforations
(positive). Difficult to estimate due to many parameters that cannot be
estimated reliably, like permeability of crushed zone, actual depth of
Sd,perf penetration.
Skin caused by gravel packing (usually positive). Theoretically, it may have a
negative value in underreamed, open hole, gravel packed wells because of
Sperf the increased effective wellbore radius.
Skin caused by turbulent (non-Darcy) flow, mainly applicable to gas
(positive). It is often caused by flow convergence because of inadequate
Sturb dimensions and an inadequate number of perforations.
Figure 9-1 illustrates how the skin factor varies with the damage ratio, kd/k, and damage zone radius,
rd, for a vertical well with a radius of 0.0762 m. These variables determine the magnitude of the skin
factor and control the well productivity. For instance, a reduction in permeability to less than one
tenth of the initial value within 0.6 m of the wellbore axis results in a skin factor of approximately
18.7.
Figure 9-1 Skin factor as a function of damage radius and damage ration (kd/k)
The skin effect is a composite variable. The following sources of the nonideal flow should consider:
Formation damage,
Limited entry completions effects,
Perforation effects,
Saturation blockage near the wellbore, and
Gravel-pack completion effects.
The composite skin factor can be calculated from well test data. It is very important to separate the
observed skin factor into its components and to establish which near-wellbore flow restrictions can
be removed by stimulation treatment and which require workover or recompletion. For good
understanding of the skin related concepts it is enough to consider pseudo-steady flow only.
Figure 9-2 Pressure profile of damaged and undamaged well
Skin, S, is the composite of all non-ideal conditions affecting flow into the wellbore, and may
generally be written, with its main components, as:
= + + + ++ + (9-1)
The last term in the above expression represents an array of pseudoskin factors. These pseudoskin
effects are generally mechanical, resulting from obstructions to flow or because of turbulence effect
and additional pressure drop. The real skin due to formation damage is that portion of the total skin
that can be removed by matrix treatments. Sdam describes the permeability of the damaged to
undamaged zones and the damaged radius, as shown on Figure 9-2.
9.2.2 Best Candidate Selection Process for Acidizing
Despite the extensive research efforts done by the industry on the root cause of formation
impairment and its remediation by matrix treatment, the failure rate of matrix acidizing treatments
today is estimated at 60 to 70%. Worldwide, this failure rate represents a loss of millions of dollars in
wasted stimulation expenditure and missed production. The primary causes for failed treatments
have been poor candidate selection and poor treatment design with respect to fluid selection and
placement. Another reason for the high failure rate of matrix acidizing treatments is the lack of
proper technology transfer to the field. Because the industry often sees matrix treatments as low-
technology treatments, little attention is given to design.
Many candidates are normally selected by each Asset and they are sending for evaluation. The
process of candidate selection applied in Assets includes:
Prepare list of candidate wells,
Review of well logs/records, reservoir characteristics and information on the
completion/previous workovers,
Map the productivity of each well,
Establish reasonable upper production potential for matrix stimulation techniques,
Evaluate potential mechanical problems, and
Focus on wells with the highest reward and lowest risk.
The candidate wells are then analyzed by Stimulation Team in Production Engineering according
to the following six criteria:
1. PVT matching in order to select the best PVT correlation to simulate well behavior when
acid is injected.
2. Verification of the remaining reserves and the current water saturation.
3. Evaluation of an approximate damage type from history well data and skin factor using
an analytical model (Resestim 7 in house made software or licensed software Prosper
for integrated system analysis).
4. Predict well productivity index (PI) increase after stimulation job based on new skin.
5. Make production forecast using material balance equation for oil and gas wells.
6. Estimate NPV and Cash Flow based on production forecast.
All economically feasible wells are candidates. The design of the stimulation is made for the
economically most attractive candidates. A system for the selection of the acid should be used and
the calculation of the other design parameters is based on models/algorithms that will be explained
later.
9.2.3 Review of the Most Frequent Damages in OMV Petrom and General Selection of
Treatment
Once damage has been characterized in a well, its origin must be ascertained to help determine the
correct remedial action. Various types of damage can exist since almost every operation performed
on the well is a potential source of damage. The physical characteristics of the damage are an
essential parameter since this determines the desired characteristics of the treating fluid. The
physical characteristics of the damage are the main criterion adopted to categorize the various types
of damage indicated in Figure 9-3 (seven basic types of damages).
Emulsions
The intermixing of oil- and water-base fluids in the formation often results in the formation of
emulsions. Emulsions can have high viscosity, particularly water-in-oil emulsions. Typically, they are
formed due to invasion of drilling/completion filtrate or treatment fluids into the formation. High pH
filtrates from mud or cement slurry or low pH filtrate from acidizing can emulsify some formation
oils. Similarly, hydrocarbon filtrates from oil-based drilling or stimulation fluid can form emulsions
with some formation brines. Emulsions are stabilized by surface active materials (surfactants) and by
fines, which are either present in the "treating" fluids or are generated through the fluid/rock
interaction. Generally, mutual solvents with or without demulsifiers are used for treating such
problems.
Figure 9-3 Formation damage types
Wettability Change
Partially or totally oil wetting a formation reduces the relative permeability to oil. This may occur due
to adsorption of surface active materials from oil-based drilling, workover or completion fluids on the
rock. This type of damage is removed by the injection of mutual solvents to remove the oil wetting
hydrocarbon phase, followed by the injection of strongly water-wetting surfactants.
Water Block
A water block caused by an increase in the water saturation near the wellbore decreases the relative
permeability to hydrocarbons. Waterblock can form either during drilling and completion operations
through invasion of water-base filtrate, or during production through fingering or coning of
formation water. The formation of a water block is favored by the presence of pore lining clays such
as illite. The hairy shape and large surface area of these clays increase the adsorption of water on the
pore wells.
A water block is usually treated by reducing the surface tension between water and oil (HF acids).
Nonaqueous acids (such as alcoholic acid) are particularly suitable in (gas) wells where a water block
problem is suspected because they also increase the vapor pressure and reduce the surface tension
between water and gas.
Scales
Scales are precipitated mineral deposits. They can precipitate in the tubing, perforations and/or
formation. Scale deposition occurs during production because of the lower temperatures and
pressures encountered in or near the wellbore. Scales can also form by mixing of incompatible
waters: formation water and either fluid filtrate or injection water. Various solvents can be used to
dissolve scales, depending on their mineralogy. The most common types of scales encountered in a
well are:
Carbonate scale (CaCO3 and FeCO3): CaCO3, is the most common scale, occurring in
reservoirs rich in calcium and carbonate and/or bicarbonate ions. Hydrochloric acid will radial
dissolve all carbonate scales.
Sulphate scales occurring mainly as gypsum (CaSO4, 2H2O) or anhydrite (CaSO4). The less
common barytine (BaSO4) or strontianite (SrSO4) is much more difficult to remove but, their
occurrence is more predictable. EDTA will dissolve calcium sulphate. Barium and strontium
sulphates can also be dissolved with EDTA provided the temperature is high enough and the
contact times sufficiently long (typically 24 hr soaking period is required for a 4000m well
with a BHST of about 100oC
Chloride scales such as sodium chloride: These are easily dissolved with fresh water or very
weak acidic (HCl, acetic) solutions.
Iron scales such as sulphide (FeS) or oxide (Fe2O3): Hydrochloric acid with reducing agents
and sequestrant will dissolve such scales and prevent the reprecipitation of by-products such
as iron hydroxides and elemental sulphur.
Silica scales: Generally occurring as very finely crystallized deposits of opal or chalcedony.
Hydrofluoric acid can dissolve silica scales.
Hydroxide scales such as magnesium (Mg[OH]2) or calcium (Ca[OH]2) hydroxides:
Hydrochloric acid or any acid that can sufficiently lower the pH and not precipitate calcium or
magnesium salts can be used to remove such deposits.
Contact time is a very important factor to consider in the design of a scale removal treatment. The
major problem when treating scale deposits is to allow sufficient contact time for the acid to reach
and effectively dissolve the bulk of the scale material. The treating fluid must contact and effectively
dissolve most of the scale in order for the treatment to be successful.
Organic Deposits
Organic deposits are precipitated heavy hydrocarbons (paraffin or asphaltenes). They are typically
located in the tubing, perforations and/or the formation. Although the mechanisms of creation of
organic deposits are numerous and complex, the principal mechanism is a change in temperature or
pressure near the wellbore during production. The heavy hydrocarbon fractions do not remain
dissolved in the oil and begin to crystallize. Cooling down the wellbore or injecting of cold treatment
fluids has the same overall effect as a temperature drop during production.
The deposits are usually re-dissolved by organic solvents. Blends of solvents can be tailored to a
particular problem, but an aromatic solvents is an efficient, general purpose solvent, particularly for
paraffins. The addition of a small amount of alcohols is often beneficial when dissolving asphaltenes.
Organic deposits must not be confused with another type of deposit called sludge. This deposit is a
reaction product between certain crude oils and strong inorganic acids. Once formed, sludge cannot
be dissolved.
Mixed Deposits
Mixed organic/inorganic deposits are a blend of organic compounds and either scales or silts and
clays. When migrating fines associated with an increase in water production in a sandstone reservoir
become oil-wet, they act as a nucleation site for organic deposits. This type of combined deposits
requires the use of a mixed solvent.
Silts and Clays
Damage due to silts and clays includes the invasion of the reservoir permeability by drilling mud, the
swelling and/or migration of reservoir clays. Clays or other solids from the drilling, completion or
workover fluids can invade the formation. When the differential pressure is sufficiently large and the
size of the particles is smaller than the pore throat openings, they are forced into the pore network
and tend to plug the network, resulting in damage.
When water-based filtrate from drilling, completion, workover or treating fluids invades the porosity
of the reservoir, it can disturb the equilibrium between the clays and formation water. This is
normally due to a change in salinity, which creates imbalances in the forces between clays. Smectite
clays can swell and drastically reduce permeability. Flocculated aggregates of kaolinite can be
dispersed, and subsequently block pore throats. This disturbance of native clays is the most common
and, probably the most important cause of damage.
During production, particles can become dislodged and migrate with the produced fluids. The
particles can bridge near the wellbore resulting in reduced productivity. When the damaging
particles come from the reservoir rock, they are usually referred to as "fines". This is a generic term
that includes clays (phyllosilicates with a size of typically less than 4 micrometers) and silts (silicates
or aluminosilicates with a size between 4 and 64 micrometers). These particles are soluble in
hydrofluoric acid mixtures.
Damage due to fines is located in the near wellbore area within a 0.9 m to 1.2m radius. Damage may
also occur in a gravel pack in sandstones it is removed by treatment with an acid containing HF: Mud
Acids of various strengths or Clay Acid systems. An HCl system is normally used to remove fines
damage in a carbonate formation. Since the fines are not dissolved, yet are dispersed in the natural
fractures or in the wormholes just created, nitrogen is normally recommended when the well has low
bottom pressure. The nitrogen will enhance fines removal.
Due to the complexity of the fines problem and its impact on treatment design this manual contains,
in the following two chapters, detailed information on the removal of fines damage in sandstones
and carbonates respectively.
9.3 Well Acidizing Methods Applied in OMV Petrom
There are two principal matrix acidizing treatment methods used in OMV Petrom in which applied
treatment pressure at the bottom is lover than formation fracturing pressure are:
1. Sandstone acidizing, and

2. Carbonate Acidizing
Matrix acidizing of sandstones with mud acid is directed at silt and clay damage removal. A treatment
may also be designed to remove other types of damage, such as: emulsion, wettability change,
water block, organic deposits, and mixed deposits. Samples of the formation, produced fluids, and
possibly even tubing, are important to ascertain formation damage type and well condition. The
sensitivity of the formation to a treating fluid may result in deconsolidation due to dissolution of the
cementing material. Precipitates may form from Fe, Na, K dissolved by mud acid. Fines released
during HCl or Mud Acid stages may create damage. Low permeability wells are very susceptible to
this damage mechanism.
The primary objective of matrix acidizing in carbonates is to dissolve the matrix, but most of all, to
bypass damage, by creating wormholes and thus to increase the effective wellbore radius and its
average effective permeability. The formation is therefore actually stimulated (unlike in sandstone
reservoirs), and the skin value is decreased, often to negative values.
Considering the main types of potential damages the general best practice workflow of well
stimulation by acidizing is shown on Figure 9-4.
Figure 9-4 Formation damage types and treatment selection
The final fluid selection for treatment
The first step in planning to acidize any type of formation (sandstone and/or carbonate) is to use key
reservoir characteristics like gross lithology, mineralogy composition and temperature for fluid
selection. The general workflow applied in OMV Petrom for basic fluid selection is shown in Figure
9-5.
Figure 9-5 Basic Fluid Selection for Well Acidizing
9.3.1 Sandstone
Treatment fluid selection in sandstone formations is highly dependent on the mineralogy of the rock
as well as the damage mechanism. Hydrofluoric (HF) acid is typically used to dissolve the damaging
silicate particles (Figure 9-6). Nonacid systems are sometimes used to disperse whole mud and allow
it to be produced with the treating fluid. The criteria for selecting the treating fluid for any treatment
stage are mineralogy (solubility of minerals in acid, clays/silt, iron and zeolites content and other
lithology criteria such as chlorite and glauconite content), petrophysical properties (permeability)
and well conditions (temperature, formation damage mechanism).
Figure 9-6 Constituents of sandstone which are soluble in HCl/HF acid systems
HF Reactions in Sandstones
The reaction of HF acid with the damaged matrix occurs in three steps. Live HF reacts with sand,
feldspar and clays, which results in silicon fluorides and some aluminum fluorides as reaction
products. The HF acid provides the greatest dissolving power during this phase, while only a small
amount of HCl is consumed. The depth of invasion of the live HF acid is normally 5-15 cm from the
wellbore. The primary stage is the stage that removes skin damage. The reaction of hydrofluoric acid
(HF) on the pure quartz component of sandstone described by the equations 9-2 and 9-3 results in
silicon tetrafluorid (SiF4) and water:
4HF + SiO 2 SiF 4 + 2 H 2 O (9-2)
SiF4 + 2HF H2 SiF6 (9-3)
The stoichiometry of this reaction shows that 4 moles of HF are needed to consume one mole of
SiO2. However, the produced SiO4 may react with HF to form fluosilicic acid (H2SiF6) resulting in the
silicon hexafluoride anion SiF62-.
If the reaction goes to completion, 6 moles of HF, rather than 4, will be consumed to dissolve 1 mole
of quartz. A complication is that the fluosilicate may exist in various forms, so that the total amount
of HF required to dissolve a given amount of quartz depends on the solution concentration.
The most common primary reactions involved in acidizing are summarized in Table 9-2.
Table 9-2 Primary chemical reaction in acidizing
HYDROFLORIC ACID - HF
Quartz:
4HF + SiO2 SiF4(silicon tetrafluoride) + 2H2O
SiF4 + 2HF H2SiF6 (fluosilicic acid) or SiF4 + 2F- SiF62- (Silicon hexafluoride anion)
Albite (sodium feldspar):
Na AlSi3 + 14HF + 2H+ Na+ + AlF2+ + 3SiF4 + 8H2O
Orthoclase (potassium feldspar):
KAlSi3O8 + 14HF + 2H+ K+ + AlF2+ + 3SiF4 + 8H2O
Kaolinite:
Al4Si4O10(OH)8 + 24HF + 4H+ 4AlF2+4SiF4 + 18H2O
Montmorillonite:
Al4Si8O20(OH)4 + 40HF + 4H+ 4AlF2+ + 8SiF4 + 24H2O
Calcite:
2HF+ CaCO3CaF2 + CO2 + H2O Note: CaF2 is very low soluble
FLUOBORIC ACID HBF4
HBF4 + H2O HF +HBF3OH rapid response
HBF3OH + HF + H2O HBF4 slow reaction
Fluoboric acid-based solution (Clay Acid)
One of the key problems that can occur after acidizing is migration of fine particles in both,
unconsolidated and consolidated sandstones causing the blockage of the pores, and in some cases
increasing the tendency of forming viscous stabilized emulsions. Migration of fine particles after
reaction with HF is primarily related to the concentration of HF and its reaction speed. To avoid
undesirable precipitations of secondary products of reaction, rock deconsolidation and migration of
fine particles, some special acids compositions have developed that can help in avoiding a problems.
The most frequent used is Fluoboric acid (HBF4)
Fluoboric acid (HBF4) is used to produce HF through the hydrolysis according to the chemical reaction
shown in Table 9-2. At any time there is only a limited amount of HF acid available and the
probability of forming precipitates of fluosilicates, fluoalumintes or silica is decreased significantly..
The acid is consumed by reaction on clay surface minerals followed by hydrolysis to produce more
HF. Because of this, HBF4 is considered as acid with delayed reaction (retarded acid). If the
temperature is higher than 95 oC, the kinetic of the hydrolysis is rapid. The reaction of fluoroboric
acid with silica is approximately 10 times lower if temperature is less than 65 oC. A major advantage
of HBF4 is its ability to inhibit the migration of fines present in sandstone by coating the initial surface
with borosilicate as a product of reaction during treatment. Experimental results showed that when
the cores containing pore lining illite have been treated by HBF4, the poorly crystallized precipitate of
KBF4 has been observed at the outlet of cell and it does not have a damaging effect. The positive
effects of using HBF4 and major advantages of its application are:
The dissolving potential of clay acid is still high (for example, 8% of HBF4 is approximately
equal to 2%HF).
The borosilicate coating stabilizes fines and makes them less sensitive.
Because of these HBF4 is recommended always when problems with migrating fines exist, what is
often case in the maturated wells completed with gravel pack.
Precipitation of reaction product
When the live HF has been consumed, the secondary reaction proceeds as the reaction of dissolved
silicon fluorides on clay and feldspar. This reaction releases a large amount of aluminum and other
cations into solution, consumes a large amount of HCl, and forms silicon precipitates and sodium and
potassium fluosilicates, which can precipitate if the selected HF concentration is too high relative to
the minerals that contain sodium and potassium. The reaction is complete when the silicon fluorides
are no longer present, which is normally within 1.2 m from the wellbore. The precipitation of
fluosilicates can be very damaging, and is one of the main causes of HF treatment failures,
particularly in formations containing large amounts of K-feldspar. However, it is not really a problem
if the fluid is kept in motion. If live HF is shut in during an acid job, severe and permanent damage to
the matrix permeability can result from silica gel precipitation.
Reaction with feldspar, chert, mica and clay components of sandstones also results in SiF62-anion,
but, in addition, produces a range of aluminum complexes: AlF2+, AlF+2, AlF3, AlF4-, AlF52- and AlF63s-.
The concentration of each aluminum complex depends on the concentration of free fluoride ions in
the dissolving solution. Some of these products combine with free sodium, potassium, and calcium
ions to produce four compounds with varying degrees of solubility in the spending acid:
Sodium fluosilicate ( Na2SiF6),
Sodium fluoaluminate (Na3AlF6),
Potassium fluosilicate ( K2SiF6), and
Calcium fluosilicate ( CaSiF6).
Matrix treatments are always designed to prevent the formation of these compounds in order to
remove any risk of precipitation.
The tertiary reaction proceeds as the reaction of dissolved aluminum fluorides on clay and feldspar.
The tertiary reaction is slower than the secondary reaction and it is much faster on clays than on
feldspars. However, it is an important reaction that must be considered, because it causes further
reduction in the HCl content of the spent HF. Once the acid is consumed, alumino-silicate scaling
occurs, within a distance of 1.2 m to 1.8 m from the wellbore.
There are many precipitation reactions that take place during an HF sandstone acidizing job. These
reactions are unavoidable, but their effect on stimulation response can be minimized with proper
fluid selection and treatment design
In Table 9-3 damaging HF reactions in sandstones resulting in precipitation are summarized.
Table 9-3 Damaging HF reactions in sandstones
Reaction Precipitate(s)
HF + carbonates (calcite, dolomite) Calcium and magnesium fluoride (CaF2, MgF2)
HF + clays, silicates Amorphous silica (orthosilicic acid) (H4SiO4)
HF + feldspars Sodium and potassium fluosilicate (Na2SiF6, K2SiF6)
HF + clays, feldspars Aluminum fluorides (AlFn3-n) Aluminum hydroxides
HF + illite clay Na2SiF6, K2SiF6
Spent HF + formation brine, seawater Na2SiF6, K2SiF6
HCl-HF + iron oxides and iron minerals Iron compounds
HF + calcite (calcium carbonate) Calcium fluosilicate
9.3.2 Carbonate
There are two basic types of acid treatments applicable to carbonates in OMV Petrom. They are
characterized by injection rates and pressures. Acid treatments with injection rates below formation
fracturing pressure, called matrix acidizing and acid treatment with injection rates above fracturing
pressure (called acid fracturing, see Chapter 11). Matrix acidizing is applicable only to formation
exhibiting formation damage. In the case of naturally fractured formations acidizing at matrix rates
even in an undamaged carbonate formation may result in an acceptable stimulation response.
Whereas the purpose of sandstone acidizing is to dissolve the damage, the primary objective of
matrix acidizing in carbonates is to dissolve the matrix, but most of all, to bypass damage, by creating
new channels and thus to increase the effective wellbore radius and its average effective
permeability. The dissolution of carbonate rocks by acid results in rapid generation of irregularly
shaped and empty channels called wormholes, as shown in Figure 9-7. Because of the randomness of
porous media, it had been shown that during dissolution two neighboring pores can coalesce if
sufficiently enlarged. It is difficult to model or predict the development of wormhole formation in a
real rock as the mineralogy will never be 100% carbonate.
Figure 9-7 Various Wormhole structures
The formation is therefore actually stimulated (unlike in sandstone reservoirs), and the skin value is
decreased, often to negative values.
Acids used in carbonate acidizing and chemistry of reactions

Commonly used acids to stimulate carbonate formation are:
Hydrochloric (HCl),
Acetic (CH3COOH)/ week organic acid, and
Formic (HCOOH)/week organic acid.
Carbonate acidizing solely with HCl, is not complicated by a tendency for precipitates to form, as is
the case for sandstone acidizing. The reaction products CaCl2, MgCl2 (dolomites) and CO2 are readily
soluble in water. Therefore, the formation of a precipitate or a separate CO2-rich phase is generally
not a problem.
Under comparable conditions weak organic acids react more slowly than hydrochloric acid and they
can be used instead of HCl when high bottomhole temperatures (above 200oC) prevent efficient
protection against corrosion. Acetic acid is easier to inhibit than formic acid and is used more often.
Table 9-4 illustrates the maximum protection times with corrosion inhibitors at various temperatures
and acid concentrations.
Table 9-4 Maximum protection time for different acids and temperatures
The following factors affect the spending rate of acid in carbonate formations: temperature,
pressure, acid type, acid concentration, acid velocity, reaction product and formation composition
(structure and mineralogy). Acetic and formic acids react with CaCO3 to form calcium acetate and
formate.
The formic acid concentration must be limited to about 10% as calcium formate precipitates above
that level. Acetic acid can be used at higher concentrations, as calcium acetate remains soluble, but
best practice is to use not more than 10% acetic acid. None of the organic acids react appreciably
with SiO2. They react with iron compounds or minerals containing iron. Acetic acid forms a complex
with iron in solution and helps prevent iron precipitation up to 60oC. In reservoirs with high iron
content, it is necessary to cut back on HCl concentration or substitute part or all the HCl with acetic
acid.
Chelating agents, such EDTA (ethylendiaminetetraacetic acid), are even weaker acids than acetic and
formic acids. For example, 9% disodium EDTA solution has the approximate dissolving power of 2.2%
HCl. It is not common to use chelating acid in matrix acidizing because of their cost relative to the
common acids (HCl, acetic and formic acid) and lower dissolving power.
The summarized chemical reactions of HCl and organic acids with carbonate are shown in Table 9-5.
Table 9-5 The reaction of HCl with carbonates
HYDROCHLORI AClD
Calcium carbonate :
2HCl + CaCO3CaCl2 + CO2 + H2O
Dolomite:
4HCl + CaMg(CO3)2 CaCl2 + MgCl2 + 2CO2+ 2H2O
Siderite:
2HCl+ FeCO3 FeCl2 + CO2 + H2O
Organic Acids
Calcium carbonate and Acetic Acid :
2CH3COOH + CaCO3Ca(CH3CO2)2 + CO2+ H2O
Dolomite and Acetic Acid:
4CH3COOH + CaMg(CO3)2Ca(CH3CO2)2 + Mg(CH3CO2)2 +2 CO2+ H2O
Calcium carbonate and Formic Acid :
2HCOOH + CaCO3Ca(HCO2)2 + CO2+ H2O
Dolomite and Formic Acid:
4HCOOH + CaMg(CO3)2Ca(HCO2)2 + Mg(CH3CO2)2 + 2CO2+ H2O
However, despite the simplified chemistry, HCl acidizing of carbonates is a difficult process to model.
The reason for this is the high rate at which the reactions take place as compared with that of HF
with the various minerals prevalent in sandstones.
Wormhole growth depends on the acid injection rate, the diffusion rate and the formations surface
reaction rate. Wormholes will only form if the diffusion rate determines the overall spending rate,
which happens if the acid/rock reaction rate is high. The diffusion rate determines the rate at which
acid travels from the bulk of the fluid to the rock surface as shown on Figure 9-8.
The treatment objective is to form the longest and deepest penetrating wormholes as possible.
Wormholing efficiency under expected downhole and surface treating conditions is a major criterion
in fluid selection.
Images shown in Figure 9-9 are neutron radiographs of cores acidized under different conditions.
Experiments have shown that the quantity of rock dissolved, i.e., the acid penetration depends on
acid velocity. One advantage of wormhole formation is that the near-wellbore damage can be
bypassed and the effective treated zone becomes much larger than in sandstone acidizing (for the
same amount of rock dissolved) or in matrix acidizing of carbonates using slow reacting acids when
the kinetics is limited by surface reactions. In addition, problems of deconsolidation in the near-
wellbore area are less severe.
Figure 9-8 Wormholing controlled by diffusion
Major wormhole structure possibilities can be categorized, as a function of injection rate and
acid/rock reactivity, as follows:
Face dissolution (no Wormholing),
Conical (single channel with limiting branching),
Dominant wormholes (primary channels with some branching),
Ramified wormholes (extensive branching), and
Uniform dissolution.
Figure 9-9 Various Wormhole structures (Fredd and Fogler, SPEJ, 1998, 1999; Hoefner and Fogler, AlChEJ, 1998)
9.4 Technology Workflow of Best Practices for Fluid Selection, Treatment

Design and Job Execution
9.4.1 Sandstone Matrix Acidizing Treatment
Fluid Selection for Acidizing Treatment
Fluid selection for each stage of the treatment must take account of all of the parameters previously
discussed: dissolution of damage, compatibility with rock minerals and reservoir fluids and potential
damaging reaction products. Since silts and clays are the component minerals that react with HF acid
to cause potentially damaging precipitates, the higher the silt and clay content, the greater the risk of
precipitation. Increasing the HCl:HF ratio is one way to retard precipitation. HCl increases the
dissolving power of the HF and low-HF content reduces the precipitation of silica. Therefore, as the
silt and clay content of the formation increases, the recommended HCl: HF ratio also increases. The
presence of HCl sensitive clays will also affect the type of acid chosen. X-ray diffraction (XRD) analysis
is the most common test used to determine formation mineralogy.
In OMV Petrom two different models for acidizing fluid selection are in use:
Model 1: Use mineralogy composition and rock/reservoir permeability.
Model 2- Use mineralogy composition and temperature.
Formation solubility in both HCl and HCl: HF can be used to approximate the total silt and clay
content. The difference in these solubilities correlates well to silt and clay content by XRD analysis as
seen in Table 9-6. Solubility information, however, does not indicate the type of clay present.
Table 9-6 Solubility of Common Minerals in Acid
*Insoluble (IS), High (H), Moderate (M), Low (L), Very Low (VL),
Model 1-Sandstone Acidizing Workflow
Model 1- Preflush/Overflush stage Fluid Selection
Using mineralogy composition and reservoir permeability workflow for selecting the best fluid for
pre-flush treatment is shown in Figure 9-10 and summarized Table 9-7 if the content of carbonate is
less than 20%, HCl is used as a preflush to an HF acid. Normally the greater the permeability, the
lower the chance of creating fines migration damage during the HCl preflush.
Since clay and silt type materials may react with HCl to produce mobile fines, the HCl concentration
decreases with increased fines content. The clay content is the dominating species due to its large
surface area and cation exchange capacity (CEC).
Figure 9-10 Model 1 Preflush/Overflush Fluid Selection
Table 9-7Model 1 Preflush Fluid Selection

<10% Silt and < 10 % Clay 15% HCl 10% HCl 7.5% HCl
>10% Silt and >10 % Clay
>10% Silt and < 10 % Clay 10% HCl 7.5% HCl 5% HCl
At the presence of HCl sensitive minerals, like chlorite, glauconite and zeolites it is advisable to keep
the pH low to so all reaction products dissolved and the selected fluid for preflush should be
corrected according to the following practices shown in Table 9-8.
Table 9-8 Model 1 Preflush /Overflush fluid selection including presence of HCl sensitive minerals
Lithology Criteria (%)

Zeolites Chlorite+Galuconite Silt and Clay Permeability (mD) Acid Concentration (%)
>2 Any Any Any 10% Acetic
>=2 >6 Any Any 10% Acetic
<=2 3-6 >10% Silt and >10 % Clay Any 5%HCl+5%Acetic
<=2 3-6 <10% Silt and < 10 % Clay Any 7.5%HCl+5%Acetic
0-2 <=3 >10% Silt and >10 % Clay >100 10%HCl+5%Acetic
0-2 <=3 <10% Silt and < 10 % Clay >100 15%HCl+5%Acetic
0-2 <=3 >10% Silt and >10 % Clay 20-100 7.5%HCl+5%Acetic
0-2 <=3 <10% Silt and < 10 % Clay 20-100 10%HCl+5%Acetic
0-2 <=3 >10% Silt and >10 % Clay <=20 5%HCl+5%Acetic
0-2 <=3 <10% Silt and < 10 % Clay <=20 7.5%HCl+5%Acetic
0 <=3 >10% Silt and >10 % Clay >100 10%HCl
0 <=3 <10% Silt and < 10 % Clay >100 15%HCl
0 <=3 >10% Silt and >10 % Clay 20-100 7.5%HCl
0 <=3 <10% Silt and < 10 % Clay 20-100 10%HCl
0 <=3 >10% Silt and >10 % Clay <=20 5%HCl
0 <=3 <10% Silt and < 10 % Clay <=20 7.5%HCl
Summarizing the previous table, the following rules/best practices have been using:
If 4-6% chlorite/glauconite then use <20md Guidelines with 5% Acetic Acid
If 6-8% chlorite/glauconite then use only 10% Acetic Acid preflush to Mud Acid
If <2% Zeolite then use 5% Acetic Acid in all HCl systems
If 2-5% Zeolite then use only 10% Acetic Acid preflush
Model 1 Main Treatment Fluid Selection

Silt and clay content and permeability are used as selection criteria. Silt and clay percentages are
calculated internally from the input lithology. The total of mica and feldspars are considered to be
silts. The total of kaolinite, mixed layer, illite, smectite, glauconite, chlorite, and zeolites are added
for clays.
The permeability of the formation influences the selection of the treating fluid in two ways. First,
permeability affects the type and extent of damage. A highly permeable formation can easily be
penetrated by foreign solid particles of fluids, and the depth of the damage can be large. On the
other hand, low permeability sandstone will merely be damaged by invasion of foreign particles.
However, this type of formation can be more sensitive to the invasion of foreign fluids because the
small pores often contain a large quantity of clays that have a high reactivity toward fluids. The
permeability also influences the amount of damage caused by precipitates. A low permeability
formation is more severely damaged by precipitates than a formation of high permeability. The
same is true for damage resulting from water block. In some cases, the type of produced fluids
precludes the use of some treating fluids. This applies to gas wells, where it is preferable to minimize
the use of purely water based fluids. Agents that lower surface tension (surfactants, alcohols) and/or
gases (foams) are recommended. In other cases, adverse reactions between acids and formation oils
or formation waters dictate the use of only specific acid formulations. Figure 9-11 and Table 9-9
show mud acid fluid selection best practice workflow for sandstone acidizing treatment.
Figure 9-11 Model 1 Main/Base Treatment Fluid Selection
Table 9-9 Model 1 Main/Base Treatment Fluid Selection

<10% Silt and < 10 % Clay 12% HCl +3%HF 8% HCl +2%HF 6% HCl +1.5%HF
>10% Silt and >10 % Clay 13.5% HCl +1.5%H9% HCl +1%HF 4.5% HCl +1%HF
>10% Silt and < 10 % Clay
12% HCl +2%HF 9% HCl +1.5%HF 6% HCl +1%HF
If 4-6% chlorite/glauconite then use <20md Guidelines with 5% Acetic Acid

If 6-8% chlorite/glauconite then use 10% Acetic Acid preflush to Mud Acid plus 5% acetic acid
If chlorite/glauconite > 8%, then use 10% acetic acid and organic mud acid
If <2% Zeolite then use 5% Acetic Acid in all HCl systems
If 2-5% Zeolite then use 10% Acetic Acid preflush and overflush to mud acid containing 10% acetic
acid
If > 5% Zeolite then use 10% Acetic Acid preflush and overflush to 10% citric acid / HF.
Formations with more than 2% zeolites are considered sensitive and use the above flowchart for acid
selection.
For moderate zeoloite compositions, acetic acid is used as the acid preflush and overflush and is
added to the conventional mud acid formulations with the HCl. The organic acid is to keep the pH
low, acting like a buffer in these acid solutions. Reaction products are more soluble in low pH.
For higher zeolite compositions, acetic is also used for the preflush and overflush, but organic mud
acids made with citric acid are recommended.
The workflow (Figure 9-12, Figure 9-13 and Figure 9-14) and Table 9-10 lists the recommendations
based on these parameters.
Figure 9-12 Main Treatment Fluid Selection including presence of high sensitivity Clays and Zeolites
Figure 9-13 Main Treatment Fluid Selection including presence of high sensitivity Clays, Chlorite and Glauconite
Figure 9-14 Model 1 Main/Base Treatment Fluid Selection including presence of high sensitivity Clays, Zeolites and
Glauconite
Table 9-10 Model 1 Main/Base Treatment Fluid Selection including presence of high sensitivity Clays, Zeolites and
Glauconite
Model 2-Sandstone Acidizing Workflow
Model 2- Preflush/Overflush stage Fluid Selection
The formation temperature is an important factor because it influences the efficiency of corrosion
inhibitors and the reaction rates. Several treating fluids decrease reaction rates at high temperatures
and provide deeper live-acid penetration. The workflows shown in Figure 9-15 and Figure 9-16 as
well as in Table 9-10 and Table 9-11 can be used as guidance for fluid selection for Preflush/Overflush
and Main treatment.
Figure 9-15 Model 2 Preflush/Overflush Fluid Selection including presence of high sensitivity Clays, Zeolites and
Glauconite
Table 9-11 Preflush /Overflush fluid selection including presence of HCl sensitive minerals and temperature
Model 2 Main Treatment Fluid Selection
Figure 9-16 Model 2 Main Treatment Fluid Selection including presence of high sensitivity Clays and reservoir
temperature
Table 9-12 Main Treatment Fluid Selection including presence of HCl sensitive minerals and temperature
9.4.2 Applied Sandstone Design Procedure
A sandstone acidizing design procedure in OMV Petrom consists of the following distinct stages:
1. Tubing pickling stage/wellbore cleanup
Wellbore cleanup is commonly used to remove scale, paraffin, bacteria or other materials from the
tubing, casing or gravel-pack screen. The injection string (production tubing, drill pipe or coiled
tubing) should be cleaned (pickled) prior to pumping the acid treatment. The pickling process may be
multiple stages, consisting of solvent and acid stages. An acid pickling job of tubing/casing can be
done by simply spotting around 2.4 bbl/1000 feet (1.2 lit/m) of 3-20% HCl down the tubing and up
the annulus. A typical pickling solution is a 7.5% HCl solution containing an iron control agent and
corrosion inhibitor. Often the same acid mixed for use in the HCL preflush may be used as the
pickling solution.
2. Preflush
Non-Acid
A water displacement stage, consisting of 3-5% NH4Cl solution, depends on concentration of
smectite, illite, kaolinite, chlorite and feldspar, according to:
Concentration%=3+(%smectite*0.3+%illite*0.12+%kaolinite*0.08+ %chlorite*0.12+%feldspar*0.05)
This is considered to displace formation water containing bicarbonate and sulfate ions. Typical
volumes are 500 to 1000 l/m (40 to 80 gal/ft)
Acid preflush
The main purpose of the standard preflush with 5%-15% HCl is to dissolve carbonate constituents of
the reservoir. This is to prevent the possibility of forming CaF2 as a mud acid precipitation product.
Numerous acidizing jobs in OMV Petrom have proved that the best practices is to execute pre-flush
with at least 50% of the volume of acid fluid for base/main treatment.
Typical volumes are 620 to 1240 l/m (50 to 100 gal/ft) and it is preferable that the preflush
penetrates the same distance as the HCl/HF mixture.
Organic acids, such as acetic and formic, should be used in conjunction with, or instead of, HCl in
sensitive formations the. Although they will dissolve the carbonate, they work more slowly and are
especially applicable for high temperature conditions. When pumping organic acids as stand-alone
fluids, they should be mixed in ammonium chloride rather than fresh water. Organic acids also act as
a low-pH buffer and chelating agent that helps minimize the tendency of iron compounds to
precipitate as the acid spends. However, they do not dissolve iron scale or prevent clay swelling.
If iron and carbonate contents are high, both an acetic acid and HCl preflush can be used. If
carbonate content is not high (less than 5%), then the organic acid can be applied only, without using
HCl preflush. The best practice in OMV Petrom is to use 10% acetic acid contain 5% NH4Cl.
Ammonium chloride is added for clay stability as use of acid without the addition of NH4Cl could
cause clays swelling.
3. Main Treatment
The main acid phase is commonly a mixture of HCl/HF. Volumes may range from 120-3000 l/m (10-
250 gal/ft) and more common volumes used in OMV Petrom are in the range 120 to 240 l/m (10 to
20 gal/ft). Volume is somewhat arbitrary, but should have a logical dependence on formation
permeability, acid sensitivity, type and severity of damage and length of the treated interval. Risks
associated with acidizing-such as fines migration, precipitation of reaction products, and rock
deconsolidation-normally can be controlled (if not minimized or eliminated) by use of proper
volumes and concentrations of acids.
Mud Acid should not be used in formations with > 20% HCl solubility. Pore lining clays will be
dissolved by mud acid. Thus, an abundance of chlorite in the pore throats may result in iron control
problems. High permeability formations may experience deep invasion of particulates (drilling mud,
barite, etc.).Low permeability formations will not experience severe particle invasion but will be
more sensitive to damage by precipitates. Sludge or emulsion tendency of crude will dictate the use
of a specific acid system. Treatments in gas wells include mutual solvents or alcohols. High
temperature decreases live acid penetration and increases corrosion rates. Wells with low bottom
hole static pressure (BHSP) should be treated with energized/foamed fluids.
The well shut-in time after treatment should be minimized to reduce precipitation of reaction
product. It is mandatory to avoid using NaCl, KCl, or CaCl2 brines in any HF treatment stages or in any
stage immediately proceeding or following HF stages.
4. Overflush/Aterflush
Overflush (or afterflush) is an important part of a successful acidizing treatment. The purposes of the
overflush are:
Displace nonreacted mud acid into the formation,
Displace mud acid reaction products away from the wellbore,
Remove oil-wet relative permeability problems caused by some corrosion inhibitors,
Redissolve HF precipitates, if an acidic afterflush is used.
Typical overflushes for mud acid treatments are:

Water containing 3 to 8% ammonium chloride,
Weak acid (3 to 10% HCl) in the cases when HCl is used as preflush fluid.
Acetic acid in the same concentration as HCl if formation mineralogy and temperature do not
allow application of HCL. Alternatively, 3-8% of NH4Cl solution can be used.
Nitrogen (gas wells only and only following a water or weak acid overflush).
Usually, the Overflush/Afterflush treatment can be performed with the same fluid concentration as
used in the preflush. The typical volumes of 360 to 1200 l/m (25-100 gal/ft) are also very similar to
those used in the preflush. The same fluid and concentration can be used in most cases. In gas wells,
and sometimes in extremely water-sensitive formations, nitrogen is an effective overflush. The
afterflush should occur immediately after the main acid injection in order have the most beneficial
effect and to minimize precipitation of Si (OH)4.
Wells should be put on production immediately after the treatment. In such case, the afterflush
volume should be at least the same as the main HCl/HF volume. In cases when wells have to stay
closed in for some time (which is to be avoided), the afterflush volume should be at least twice the
HCl/HF volume in order to displace the reaction products to a distance where their influence is
negligible (1 to 1.5m radial penetration).
Certain chemicals (additives, inhibitors, iron complexing agents) may be used in addition to the basic
solution of acid or NH4Cl in order to reduce problems with emulsion and sludge formation or prevent
corrosion and scale precipitation.
A large overflush is necessary to prevent the near-wellbore precipitation of amorphous silica. At
formation temperatures of 95 C or higher, amorphous silica precipitation occurs when the mud acid
is pumped into the formation. The precipitate is somewhat mobile at first, but may set as a gel after
the flow stops. It may be diluted and dispersed far enough from the wellbore to reduce its harmful
influence if it is kept moving by the overflush.
Diversion techniques
One of the main reasons that acid treatments fail is that the injected acid is not correctly placed and
does not have full contact with the damage. Selection of the proper fluid placement method is a key
success factor in acid treatment design in both sandstones and carbonates and acid diversion is a
challenge that has to be faced in either lithology.
As acid is pumped, it flows preferentially along the most permeable path into the formation. The
treated zone is commonly not adequately converged by the injected acid due to significant zone
heterogeneities caused by big variations in zone properties. The acid opens high permeable zones
even more, and less permeable, damaged zones are almost guaranteed not to receive adequate
treatment. Some technique to divert the treatment fluid toward more damaged formation or
damaged perforations is therefore mandatory. To approach full damage removal, acid must be
diverted to the sections that accept acid the least that is, those are most damaged
There is a variety of diversion techniques, but there are three basic methods of acid placement
(diversion techniques) as shown in workflows (Figure 9-17 and Figure 9-18 ):
Mechanical placement
o Packer isolation system ,
o Ball sealers (Not used in OMV Petrom)
o Coiled tubing
Chemical diversion
o Bridging and plugging agents (inert materials in the of large sized particles from 10-
100 mesh, such as silica sand, water soluble agents like rock salt and benzoic acid,
oil-soluble agents such as resins etc.)
o Particulate diverters (small particle size, commonly below 0.1 mm and those can be
water-fine grade of benzoic acid and oil soluble- blends of hydrocarbon resins)
Foam Diversion (The most useful in gas well acidizing, in gravel pack completions and
generally more effective in higher-permeability formations with deeper damage)
Gels (more reliable than foam, but could be damaging, because higher concentration, gels
will stay unbroken and therefore will not be completely cleaned up causing. This will damage
the perforations. Commonly used is Hydroxyethylcellulose-HEC).
Figure 9-17 General Workflow for choosing a diversion method for matrix acidizing
Treatment fluid can be directed exclusively toward a low-permeability zone using injection string
(tubing, drillpipe or coiled tubing equipped with mechanical packers). Flow can be blocked at
individual perforations taking most of the treatment fluid by injecting ball sealers that seat on the
perforations. In sandstone, microscopic agents such as oil-soluble resins can create a filter cake on
the sand face. Chemical diverters such as viscous gels and foams created with nitrogen are used to
block high permeability pathways within the matrix. The requirements on any diverting agent are
stringent. The agent must have limited solubility in the carrying fluid, so it reaches the bottom of the
hole intact, it must not react adversely with formation fluids, it must divert acid. Also, the used
diverter agent must be able to cleaned up rapidly and thereby avoid harming production. Ball sealers
drop into the rathole as soon as injection halts or, if they are of the buoyant variety, they are caught
in ball catchers at the source. Benzoic acid flakes dissolve in hydrocarbons. Oil-soluble resins are
expelled or dissolved during the ensuing hydrocarbon production. Gels and foams break down with
time.
In practice, acid and diverting agents are pumped in alternating stages: first acid, then diverter, then
acid, then diverter, and so on. The number of stages depends on the length of the zone being
treated. Typically, one acid diverter stage combination is planned for every 5-8 m of formation.
The current diverter technologies work sporadically and many times do more harm than good.
Recent work shown that even when a diversion technique such as ball sealers is applied properly,
over one third of the perforation become permanently blocked because the balls become lodged in
the perforation. Chemical diverters often misused or do not meet expectations rock salt is
sometimes used by mistake with HF acid producing plugging precipitates, and so-called oil-soluble
resins are infrequently only partially soluble in oil. It is necessary to choose properly the non-
damaging diversion techniques whose effectiveness can be proved and documented. Foam and the
use of inflatable packers on coiled tubing are viable techniques for positive diversion.
Figure 9-18 Diversion selection workflow
Injection pressure and rate strategy- Design model
Additional reservoir parameters (fracture gradient, porosity, height, etc.) are required to
calculate/estimate injection pressure and rate constraints for the acid.
The acid use for the main treatment stage should be injected at a pressure that will not cause
fracturing of the formation. In cases of very severe damage, the pressure may need to be increased
above the fracturing pressure for a short period of time, but should be returned below fracturing
pressure as quickly as possible. Application of this injection strategy during any treatment stage will
allow removing damage more successfully. Maximum allowable injection pressure at the surface to
avoid formation breakdown is defined by Eq. 9-4.
Pinj max = ( FG H mp ) - Ph + P fr(i, j,k) - FS

(9-4)
And maximum required hydraulic power of pump (Eq. 9-5) unit for performing acid treatment job is:
P = 1.67 Qi max Pinj max (kW) (9-5)
Where:
FG- Formation fracture gradient (bar/m)
Hmp- Mid perforation depth (m)
Ph Hydrostatic pressure of fluid treatment column (bar)
Pfr Pressure drop due to friction (bar)
FS- Engineering design safety factor, usually can be taken in the range 20-30 bar
Pi - Injection pressure (bar)
P Pumping unit required power (kW)
The mMaximum injection rate that could be achieved, according to the Paccaloni model is defined by
Eq.9-6.
3.72105
= (9-6)

Where:
Qimax maximum injection rate of acid (m3/min)

K reservoir permeability (mD)
Hmp average well depth (m)
injfl viscosity of injection fluid (mPas)
rb radius of injected fluid bank* (m)
rw well radius (m)
Radius of injected fluid bank can be roughly calculated from the amount of stimulating fluid injected
and the available pore space, using the following equation (Eq.9-7):
= (1 , ) 2 2 (9-7)
Where:
porosity (frac)
So,g r- residual saturation of oil or gas (frac)
Sowc connate water saturation (frac)
Normally, the volume of treatment fluid pumped during matrix acidizing is not large and it is
sufficient if the fluid penetrates the formation about 1-1.4 m, for which can assumed that rb changes
only slightly. From numerous acidizing jobs it was found that for practical and quick estimation, an
arbitrary rb =1.2 m (assuming that acid penetration will be under steady-state flowing conditions)
Acid treatment volume and rate guidelines

Table 9-13 Acid treatment guideline
Table 9-14 Recommended volume of treatment fluid
Additives
Additives are added to the different stages of a treatment to prevent excessive corrosion, sludging
and/or emulsions, provide a uniform fluid distribution, improve clean-up and prevent precipitation of
reaction products. Additives are used not only for the main treatment but also, in pre-flushes and
over-flushes to stabilize clays, disperse paraffin or asphaltenes and inhibit scale or organic
deposition. Additive selection is primarily dependent on the treating fluid, the type of well, type of
damages, bottomhole conditions, the type of tubular and the placement technique.
Since there is a large number of an additive available, which vary between contractors, the choice of
additives can be rather difficult. Additives are always required, but it is important that only necessary
additives be used. Of all these additives, a corrosion inhibitor is the only one that should always be
applied. Also, a sequestering agent, for the prevention of iron hydroxide precipitation is often
required.
Although proper fluid selection is critical to the success of a matrix treatment, the treatment may be
a failure if the proper additives are not used.
The most frequent additives used in OMV Petrom are:

Corrosion Inhibitors,
Surfactants (Emulsifiers, Deemulsifiers, Nonemulsifiers),
Clay Control/Stabilizers,
Fines-Fixing Agent (FFA),
Mutual Solvents,
Iron Control Agents,
Alcohols,
Anti-sludge Agents,
Friction Reducers,
Non-Emulsifiers, and
Foaming Agents.
9.4.3 Carbonate Acidizing Best Practices
Fluid Selection for Carbonate Acidizing
As the physics of carbonate matrix acidizing is complex and considering the complex nature of
wormhole formation, a proper selection of the acidizing system and concentration is very important
in the first step in designing carbonate acidizing. There is an optimum combination of acid (or
reactive fluid) injection rate and degree of reactivity (or retardation) for each formation. The key
criteria for proper acid system selection for carbonate acidizing are temperature, mineralogy and
petrophysics/reservoir properties. The goal of proper acid system selection is to optimize of acid
penetration and the structure of the newly created channels.
Temperature strongly influences inhibition of the acid. At high temperature (150 oC), organic acid are
preferred because they are less corrosive than HCl.
Mineralogy refers to whether the carbonate formation is pure limestone or partially (or totally)
dolomite. Greater than 20 % HCl must be avoided in dolomites due to the potential precipitation of
by-product. In case where silicates (quartz, feldspars or clays) content in the dolomite is high (up to
50%, as shown in Figure 9-19 then the HCl should be inhibited with HF.
Figure 9-19 Impure dolomite: Quartz grains (white crystals) scattered in the dolomitic matrix (brown crystals of dolomite)
When the insoluble minerals are class or fines, dissolution of the rock matrix will result in the release
of insoluble fines and a special blend of 7.5% - 15% inhibited acid special clay dispersing, suspending
and chelating agents should be applied. In dolomite carbonate formations containing anhydrate
(anhydrous calcium sulfate), anhydrite will first dissolve in HCl but gypsum (hydrated calcium sulfate)
will quickly reprecipitate because of its low solubility. In such formations, the best practice is to use
an acid system with good chelating properties in order to minimize problems (inhibited blend of HCl
with good chelating properties or non-acid system with chelating and clay suspending agents).
Diversion is required to improve fluid placement. Apart from small treatments to remove near-
wellbore damage, for which neat HCl acid (with necessary additives) can be used, (lightly) gelled acid
is used in most carbonate matrix treatments. This is done to improve zonal coverage of the acid, to
retard the acid reaction rate, or to improve its fines-suspending properties. Some relevant aspects of
the various acid systems are discussed below.
Petrophysics/Reservoir Properties such as distribution, type of porosity and reservoir permeability

have a strong influence on the extent of the damage and on penetration of acid. Reservoirs with high
permeability (K>50 mD) can be severely damaged by the invasion of solid particles and inhibited HCl
with HF intensifier or emulsified HCl acid (70% of HCl and 30% of oil/diesel) can be used to remove
damage. In naturally fractured carbonate formations, damage by solid particles occurs in the
fracture. A proper acid treatment fluid enlarges the fractures and allows clean-up of the fracture
network. An inhibited blend of HCl with good chelating properties could be an appropriate solution
for this application due to its good suspending properties.
Lightly gelled acids various strengths of HCl with low concentrations of gellant (< 0.5%) for friction
reduction. Gelling provides a viscosity of 1-3 cp at ambient temperatures. These systems are
applicable for high-rate matrix treatments.
Gelled acid systems various strengths of HCl with higher concentrations of acid gelling agents (2-
3%) to provide higher viscosity. These might range from 30 to 40 cp at ambient temperatures,
resulting in an enhanced zonal coverage and reduced fluid loss. Systems that contain HCl, a gelling
agent and a pH-sensitive crosslinker are called in-situ crosslinked acid. These are marketed as Zonal
Coverage Acid (ZCA) by Halliburton and Self-Gelling Acid Diverter (SGAD), by Schlumberger. After
crosslinking at a pH of 2-3, the gel will break upon further spending of the acid at pH values above 4.
The systems can be built to work in HCl acid at strengths from 5-28% acid. The self-gelling acid
system is particularly suited for treatments in horizontal wells.
Emulsified acid systems oil outside phase acid systems have been successfully used in situations
where a retarded reaction rate is needed to create deeper acid penetration and wormholes. Because
of their retarded nature, they can be pumped at low rates, which is beneficial in heterogeneous
formations. Also their high viscosities result in better zonal coverage.
Energized and foamed acid systems in reservoirs where the reservoir energy is low, some form of
additional energy may assist in the unloading of the fluids introduced into the formation.
The physics of matrix carbonate acidizing is more complicated than in sandstone because of the
wormholing phenomena. Development of a simplified workflow that could cover all possible
variations is difficult and the proposed workflow is intended as an initial guide. Best practice is that
fluid selection for carbonate acidizing is be made for each individual treatment. In general, the fluid
that gives the deepest penetration for the expected pumping and reservoir conditions is the fluid
that should be used.
Selection of a base acid in an integrated approach requires consideration of some of the key
parameters (permeability, type of carbonate ,Fe content, bottomhole temperature in relation to
corrosion and reactivity of the formation) influencing on physics and chemistry of carbonate matrix
acidizing, as shown on Figure 9-20.
Carbonate Acidizing Fluid Selection Workflow
Figure 9-20 Fluid selection workflow for carbonate acidizing
Design procedure for Carbonate Acidizing

For a carbonate matrix stimulation treatment to be successful, it is important to acidize under
conditions that will lead to the formation of deep penetrating wormholes that bypass formation
damage, whilst using minimal acid volumes at optimal injection rates. Results from studies on
efficient wormhole formation indicate that the injection rate should be increased, or the overall
dissolution rate decreased (by changing the fluid type) as the depth of penetration increases. If such
detailed planning is not feasible, then it is recommended to pump acid at the highest possible rate
and pressure, whilst staying below fracturing conditions. Table 9-15 shows a schematic of dissolution
as a function of surface reaction and diffusion rate as well as of acid injection rate.
Table 9-15 Wormhole structure
Common sequences for performing carbonate matrix acidizing are:

1. Pickling of the injection string,
2. Preflush,
3. Main Treatment, and
4. Overflush.
Pickling
The injection string usually should be picked prior to pumping of acid. The best practice for pickling
injection string in OMV Petrom is to use acid of 5-15% HCl containing an iron control agent and a
corrosion inhibitor. If there are some organic deposits in the injection string then pickling of injection
string can be done with acid and an aromatic solvent and surfactant.
Preflush
If there are organic deposits (such as paraffins and asphaltenes with high molecular weight) in the
wellbore tubular and near-wellbore zone then a carbonate preflush with an solvents (xylene or
another) should be applied to remove organic deposits. In a limited number of cases in OMV Petrom,
the preflush also served to displace oil from the near-wellbore and to prevent the formation of
emulsion or sludge. Mutual solvents such as EGMBE (ethyleneglycol monobutylether) or others that
are in liquid state and are water-and oil-miscible should be used. The common practice in the gas
wells is to use various surfactants (anionic, cationic, nonionic, amphoteric) up to a maximum
concentration of 1.5% in order to reduce the surface tension between acid solution and gas.
Main Treatment
The main treatment stage is commonly performed with 15% - 28% HCl. Selection of the treatment
volumes depends upon the anticipated depth of damage and reservoir porosity. The recommended
volume of treatment fluid varies within a broad range (1203700 lit/m) whereas most treatments
involve volumes is in the range of 310-1850 lit/m. The radius of acid penetration can be estimated
using formation porosity and the injected volume of acid. The penetration of acid in carbonate
formations is not uniform due to the heterogeneous nature of the depth of acid penetration and the
required fluid volume has to be estimated by matching numerical model and laboratory test results.
Overflush
The purpose of the overflush is to displace the acid. Fresh water (additivated with NH4Cl) is the most
common overflush fluid. Filtered crude oil and diesel may also be used in oil wells but are not
preferable because of possible incompatibilities with acid. Nitrogen gas is an effective overflush,
especially in gas wells.
Diversion Techniques for carbonate acidizing
Successful matrix treatments require uniform vertical distribution of the treating fluid. Improper
placement exacerbates heterogeneity, as shown in Figure 9-21. Good placement is particularly
difficult in carbonates because acid can bypass damage relatively easily. This damage bypass can
result in negative skins, thus any pathway that preferentially attracts acid to begin with (such as
natural fractures, high permeability thief zones, or depleted zones) will become an even stronger sink
for acid as that zone becomes highly stimulated. Moreover, in wells with long openhole intervals,
spending of acid along the wellbore will partially spend the acid that reaches the extremes of the
openhole section, thus, jeopardizing the objective of achieving good zone coverage with acid.
Figure 9-21 Improper acid placement in carbonate formation
In carbonate reservoirs, in principle, two main diversion techniques (mechanical and chemical) can
be used to improve fluid placement.
Mechanical
Packers,
Ballsealers (Not used in OMV Petrom),
Coiled tubing.
Chemical
Chemical diverters (insoluble in acid but soluble in oil, in powder state-benzoic acid,
rock salt, polymer systems, ).
Foam diversion (foam agent with acid foamed with nitrogen).
Self-diverting acid (chemicals which transform into gel in the consumed acid solution,
thus preventing the channeling of acid in layers with maximum permeability).
In situ-crosslinked acid (Not used in OMV Petrom)
The technique is often applied in conjunction with coiled tubing and specific for carbonate
formations. It consists of bullheading stages of HCl acid alternated with in-situ crosslinked
diverter stages. During such treatments, pump rates should be kept at a maximum, but below
fracturing values. The combination of CT, for accurate placement, and in-situ crosslinked acid,
for diversion, has also been successfully applied in carbonate formations.
Retarded HCl (by gelling or emulsifying the acid), or organic acids (At high
bottomhole temperatures).
Problems during and after acidizing in sandstone and carbonate
The use of acid in sandstones and carbonates could result in various potential problems. The results
of statistical analysis (Paccaloni) of more than 650 stimulation jobs in various type of formation
(sandstone, poorly consolidated sands and carbonates) performed in wild cat, appraisal,
development and injection wells (water and gas) are summarized in Table 9-16.
Table 9-16 Statistical analysis of well-documented matrix stimulation treatments
Apparent
Matrix Documented
Well Status Formation success ratio
stimulation failure
(%)
Sandstone 56 10 82
Wildcat Limestone and
140 13 91
dolomite
Poorly
consolidated 32 7 78
Appraisal and sand
development Sandstone 120 18 85
Limestone and
216 21 91
dolomite
Poorly
consolidated 15 3 80
Water injection sand
wells Sandstone 50 8 82
Limestone and
33 3 91
dolomite
Total: 662 82 88
Table 9-17 shows the main reasons for the failures. The table shows that 73% of the failures were
due to incorrect field stimulation procedures, whereas 27% were attributed to poor selection of
stimulation-fluid types, volumes, additives, and sequences. This means that priority must be given to
improved job supervision, real-time evaluation, and on-site quality control.
Table 9-17 Main Reasons for failures
Reason Failures Failure %
Incorrect field procedures 60 73
Wrong stimulation fluid 22 27
Total: 82 100
Table 9-18 gives the reasons for failure for wildcat, development, and water (or gas) injection wells in
sandstones, carbonates and corrective actions done to improve poor results of the 1st acidizing job.
In the most cases, the second successful stimulations were designed and supervised by stimulation
experts.
Bullheading the Stimulation Fluids

Bullheading the stimulation fluids, often leaving mud below the packer, was the most common
reason for failures. The use of coiled tubing for downhole cleaning and circulation of the acid mixture
to cover all perforations resulted in success in wildcat wells, development wells and water injection
wells. The use of coiled tubing in conjunction with matrix stimulations is recommended whenever
technically feasible. To avoid pump-rate limitations owing to fluid friction pressure, the fluid could be
pumped down simultaneously through the tubing/CT annulus and the coiled tubing, joined at surface
with a Y-connection.
Table 9-18 Reasons for failures and corrective actions
Reasons (R) for Failure of Matrix Acidizing Treatment Poorly

Sandstone Carbonate Consolidated
and
Sand
Corrective Actions (CA) Done to Eliminate Poor
WC DEV/ INJ WC DEV/ INJ DEV/ INJ
Results of 1st Acidizing AP AP AP
R Bullheading of stimulation fluids; mud left below packer X X X X
R Bullheading of stimulation fluids X X
CA Wellbore cleaned with coiled tubing X X
CA Stimulation fluids circulated to cover all perforation and X X X X X
correct acid placement
R 15% HCl preflush used X X
CA Preflush avoided; 12% HCl/3%HF used X X
R Injection pressure and rate too low X X X
CA Maximum p, maximum i (m3/s) technique used X X X
R Insufficient acid volumes used X X
CA Corrected acid volumes used X X
R Perforation breakdown not attempted; injectivity never X
obtained X
CA Formation initially fractured, then matrix conditions
restored
R Injection pressure too high (fracturing conditions) X X X X
CA Job performed in matrix conditions X X X X
R Use of wrong or not properly selected stimulation fluids X X X X
CA Use correct stimulation fluids and fluid selection guide X X X X
R Injection tests with heavy mud; injectivity with acid X
couldnt obtained
CA Formation was reperforated before the second acid job X
R Wrong sequence of stimulation fluids X
CA Redesigned sequence of stimulation fluids X
R Old strings not cleaned previously X
CA Pre-job cleaning with 15% HCl/Tubing Pickling X
R Coiled tubing not properly positioned X
CA Coiled tubing properly positioned X
R Circulation of stimulation fluids through tailpipe not X
properly performed
CA Efficient acid contact with unstimulated zone X
R Ineffective chemical diverting agents X
CA Maximum p, maximum i (m3/s) technique used X
WC Wild Cat DEV/AP - Development / Apprasial Wells INJ- Injection wells (water and gas)
The second stimulations were successful because:

(1) The postjob inflow either was significantly improved or was very close to ideal;
(2) Postjob skin factors were remarkably reduced, most often down to 0 to 5 in sandstones and -
2 to -5 in limestones; and
(3) Dry tests in exploratory wells become continuously flowing tests. Because of these
indications both the technical and economic objectives were achieved.
Use of 15% HCl Preflush
The use of 15% HCl preflush after dry tests in wildcats and in severely damaged development wells
resulted in failures caused by total, permanent block of injectivity. The preflush subsequently was
circulated out of the well, and the most efficient stimulation fluid (3% to 4% HF acid) was spotted
directly in front of the perforations. The dry wildcat wells became discoveries, and the development
wells had low final skin factors. The success rate of acidizing jobs have increased considerably by
simply avoiding the use of HCl preflush after dry tests in wildcat wells. The mistake of using an HCl
preflush in severely damaged wildcat wells is very common and has led to frequent erroneous
statements of low (or no) production potential for the formations thus treated. The economic
implications of such incorrect evaluations in exploratory wells are severe.
The success rate can be increased by applying the following best practices with dry or partially
flowing exploratory wells.
1. Avoid the use of HCL preflush.
2. Select the most effective stimulation fluid for the expected damage type (3% HF in most
cases).
3. Design the simplest stimulation procedure; avoid stage treatments, diverting agents,
chemical retarders, etc.; and include only corrosion inhibitors and an effective mutual
solvent.
4. Establish a target injectivity index in matrix conditions. Once it is reached, flow the well back
immediately.
5. Stop injection upon reaching the productivity target.
As far as development wells are concerned, the severely damaged sandstones containing 5% to 15%
carbonates first are treated with 0.124 to 0.248 m3/m of 3% HF solution to reduce the skin factor
and to guarantee sufficient injectivity. The regular sequence (HCL preflush, HF treatment, and then
overflush) follows immediately only if the target injectivity index (directly related to the target PI)
was not reached.
Insufficient Injection Pressure and Rate
Insufficient bottomhole injection pressure (BHIP) caused several failures in thick, multilayered
reservoirs whereby only a small part of the exposed pay was stimulated. Comparison of pre- and
postjob pressure-buildup analyzes indicated a slight decrease in damage. Less than 20% to 40% of
the total pay was producing after the stimulations, even in the two cases where chemical diverting
agents were used. Accurate postjob evaluation indicated that only 150 to 373 kW was used instead
of the required 1492 to 2238 kW.
The stimulations (all in development wells) were repeated with the same stimulation fluids, but the
"maximum p, maximum i" technique was used. The concept supporting this technique is that, at the
maximum allowed BHIP (in matrix conditions), it is always possible to calculate a maximum injection
rate resulting in the complete removal of damage (s=0) across the whole exposed pay.
In the all analyzed cases, flow-meter surveys, combined with pressure-buildup analyzes, validated
the effectiveness of the maximum p, maximum I technique. The producing pay was 70% to 85% of
the total perforated pay. Although diverting agents were never used, the final skin factors decreased
from the initial 59 to 112 range to as low as 4 to 7. The total production increase obtained from
second stimulations was 1908 m3/d oil; as compared with 143 m3/d oil after the first stimulations.
The maximum injection rate (in matrix conditions) reached during the second stimulations was 2.86
m3/min, which is significantly higher than 0.3 m3/min used during the first stimulations.
The real challenge in the stimulation of carbonate rocks is to remove/bypass damage from both
primary and secondary porosity efficiently. The presence of natural fractures in the exposed pay
causes a very high permeability contrast and insufficient injection pressure and rates cause very
small portions of the exposed pay to produce or to take fluid. Using chemical diverters (benzoic acid)
did not improve these results.
Perforation Breakdown Not Attempted
Several stimulations after dry tests in wildcat wells failed because a perforation breakdown was not
attempted. The jobs were over after 1 or 2 hours of no injectivity, with 3% HF in front of the
perforations. The previous dry drillstem tests were justified by a lack of permeability rather than
severe formation damage. Because of the importance of the exploratory target, the two jobs were
repeated and the fracture pressure was exceeded to clean the perforations and to obtain injectivity.
Matrix conditions were then restored and damage was effectively removed. As a result, two
important discoveries were claimed.
Fracture Pressure Exceeded
Failures also resulted from poor job supervision whereby the jobs were carried out in fracturing
conditions until the end. No improvement in the production/injection inflow performance was
observed in some cases while a deterioration of the production parameters (with postjob skin factors
higher than pre-stimulation ones) was detected by pressure-buildup in the remaining two cases. The
same fluids pumped in matrix conditions resulted in complete success when the stimulations were
repeated (final skin factor ranging from one to four).
Use Incorrect Stimulation Fluids.
The wrong choice of stimulation fluids caused several documented failures. In one case, acetic acid,
selected on the basis of laboratory tests on cores, caused the initial skin factor (+35) to double
towards the end of the job. The stimulation was repeated with 3% HF, and the final skin was less
than five.
Another well initially produced 350 m3/d oil, but production declined over 6 months to only 64 m3/d
oil. Production increased to 318 m3/d oil after reperforation, but declined with the some trend. An
HF job was attempted, which again improved production for only a few months. This behavior
suggested that formation damage was probably caused by migratory fines, and a different acid
formulation, fluoboric acid (HBF4), that had been studied especially for stabilizing shaly fines was
used. This well produced 302m3/d oil for 5 years after the HBF4 job.
A water injection well was stimulated with an HCl preflush followed by HF to increase the very poor
injectivity observed a few days after the wells transformation from produced to injector. No
improvement was obtained, and the skin factor remained as high as 62. A second stimulation was
designed including a massive cushion of aromatic solvents as the first step in the same sequence of
fluids used previously. This treatment removed the damage very efficiently; the final skin factor was
2.7, derived from pressure-falloff test interpretation.
One-half of the recorded failures (5 out of 10) in poorly consolidated sands pertain to use of
improperly tailored stimulation fluids, such as HCL/HF at various low concentrations (7.5% to 1.5%;
7.5% to 0.5%) or just 7% to 15% HCL. A careful laboratory investigations suggested the use of low-
power acids, such as EDTA (two cases) or formic acid (three cases). Matrix stimulations with these
fluids allowed efficient damage removed, while fluids in previous jobs tended to cause more damage.
Wrong Sequence of Stimulation Fluids
Table 9-18 indicates that some failures of acidizing jobs in development wells were caused by
incorrect type or sequence of stimulation fluids. The reservoirs were not over pressured and the
formation fluids were heavy crudes, forming sludge and strong emulsions with HCL. Additives for
preventing or minimizing these problems were used, but the jobs failed. The jobs were repeated,
adding Steps 1 through 3 to the sequence and doubling the volume in Step 4.
1. Aromatic solvent was added to remove any damage caused by precipitated asphaltenes
2. Nitrogen was added
3. Diesel commingled with nitrogen was added.
4. Diesel (twice the acid volume) was added.
5. 28% HCl was added containing anti-sludge additives.
6. Diesel was added (twice the string capacity).
7. Nitrogen (string capacity) was added.
The described procedure was successful where previous stimulations failed, and it has since been
adopted for stimulating heavy oils in carbonate reservoir that are not overpressured. Obviously, Step
1 can be omitted if asphaltene deposits do not form part of the damage. A blend of alcohols has been
used instead of diesel when some diesel/crude-oil incompatibility is detected.
Incorrectly Positioned Coiled Tubing
The documented failures in wildcat wells were caused by incorrect positioning of coiled tubing
(above the top of the perforations rather than at the bottom, as planned). Both jobs with 28% HCl
resulted in negligible improvement, yet surface production was not obtained. The importance of the
exploratory targets made further attempts advisable. The stimulations were repeated with the same
fluids, but more attention was given to the correct circulation of 28% HCl and the coiled tubing was
positioned below the bottom perforations. Both wildcat wells produced spontaneously at
economically significant production rates after the second stimulation.
Incorrect Acid Circulation
A tailpipe was sometimes used to circulate HCl in front of the perforation pay in deep wells with a
high bottomhole static temperature (150oC). Before stimulation, the well produced around 50 m3/d
oil with very high skin (s>200). Stimulation results were below expectations, and a residual skin factor
of 45 was detected from a pressure-buildup interpretation. Careful analysis showed that circulation
had been stopped prematurely and that the acid mixture did not come out of the tailpipe. This led to
the conclusion that only the lower part of the perforated interval was contributing to production. The
tailpipe was released mechanically and dropped into the rathole. A 28% HCl was then bullheaded to
stimulate the upper part of the perforations. A second pressure-buildup interpretation provided a
zero skin factor and production was almost ten times higher.
9.4.4 Planning and Job , Execution of Acidizing Treatment
Matrix Acidizing Planning and Scheduling
Planning, execution and evaluation of a stimulation treatment requires a significant amount of time,
even in the case of routine jobs. Proper planning is the only way to achieve optimum results and
structured improvements in job results (in case of field wide campaigns). Therefore, when starting
stimulation campaigns, it is suggested to treat the first wells as one-off treatments and adjust
subsequent treatments based on proper evaluation of these initial treatments (pilot campaigns).
Planning should not only look at the execution (to be discussed in the next chapter), but should
include sufficient time for design and evaluation. A time table for planning different phases of matrix
acidizing stimulation is given below in Table 9-19 and shown in Figure 9-22.
Table 9-19 Matrix Acidizing Planning Schedule
Figure 9-22 Matrix Acidizing Planning Schedule
The above table and chart have been made with a number of assumptions:
Direct availability of stimulation contractors, specifically in the case of one-off jobs.

All times indicated refer to the time required for an individual well. Proper planning for a
field campaign may require up to one year including laboratory testing, depending on the
situation. Usually, tendering is done for a complete campaign, hence the time per well can be
very short.
One or more stimulation contractors are active in the area; otherwise considerably longer
time for arranging equipment and materials is required.
Once the contractor has been selected, work should start to determine logistics and to finalize
designs. Finalisation of designs can be completed once all laboratory testing is completed and the
well parameters are known. In practice, it is rarely possible to determine the exact design until a very
short time before the treatment is carried out. As soon as the contract has been awarded, a meeting
should be held with the contractor to outline the location, the timing, the well configuration, the
fluid pumping schedule, the on-site quality control and other operational aspects or problems that
may exist. Any special or unusual aspects should be discussed the onset to allow the contractor
sufficient time to prepare for the treatment. The more time that is allowed for preparation, the more
it will be ensured that all specifications of fluids and equipment can be met to successfully perform
the treatment. One Petrom OMV representative is assigned as project coordinator, who will have the
authority to liaise both technically and operationally with the contractor. The contractor should also
appoint a project coordinator who will liaise with the operator and will act as coordinator within the
contractors organization to ensure that the specifications of the treatment are met. The more lead
time available to the contractor, the more thoroughly the contractor will be able to consider all
possibilities regarding the stimulation treatment.
Site preparation
Just prior to the treatment, the wellsite needs to be prepared for the treatment. The equipment of
the stimulation company has to be rigged up. In many cases, third party equipment also needs to
be on location, such as logging tools, wireline rig, coiled tubing unit, etc. The various stimulation
equipment should be rigged up such that other equipment can easily be installed as required. If a
service rig is on location, equipment should be spotted out of the fall line of the rig mast. Care should
also be taken to the placement of the high-pressure pumping equipment, where personnel will not
be exposed to the fluid end of the pump. If equipment for N2 or CO2 is on location, it should be
spotted at least 20 m from other equipment and the wellhead.
Matrix Acidizing Job Execution
Successful job execution depends on good planning, preparation, supervision, and attention to
details, quality control, and communication. It is well worth the cost to select well-trained, dedicated
personnel, well-maintained equipment, well organized crew and good-quality materials. A lack of
one of these prerequisites will often result in an unsatisfactory stimulation job and therefore a lower
return on investment, even though the costs of a poorly executed treatment may be substantially
lower.
The most common process in matrix treatments is for the fluids to be preblended at the service
company facility, and then transported to the location. This allows blending small volumes
accurately, controlling environmental hazards. The fluids are then pumped with little effort or quality
risk. The operator should carry out regular quality control checks at the service company facility.
Wellbore preparation is especially critical for acid treatments. When key steps of preparing the
wellbore for the acidizing process are left out (e.g. not pickling the tubing, not removing the gas lift
valves, not removing the rods or an electrical submersible pump), the prospects for ultimate success
are reduced. Injection of tubular debris into the formation can be disastrous and rust and mill scale
must be removed, even with new pipe. In this connection the best practice always involves an acid
pickling job of tubing prior to carrying out the acid stimulation job. This can be done by simply
spotting 15-20% HCl down the tubing and up the annulus.
When executing a mud acid treatment in sandstones, significant changes in the flow distribution of
the injected fluids may occur during the treatment as pore-plugging materials are dissolved. Because
the acid does not follow the ideal mode, adjustments to the injection volumes must then often be
made. Significant changes in the fluid can also occur in the tubulars, before the fluid reaches the
formation. The dilution of stage composition and spending are just some of the complications that
must be addressed by the designer. The use of smaller tubulars, such as coiled tubing, especially
during acid treatments in horizontal wells, can contribute to a better acid job by facilitating the
maintenance of stage integrity and reducing displacement volumes. Mechanical limitations
associated with artificial lift (e.g. gas lift) are more easily overcome by the use of coiled tubing. The
risks of leaking valves, undiluted acid remaining in the mandrels and acid leaking into the
tubing/casing annulus are thus avoided. The limited injection rate coincidentally controls the contact
time. However, the pump rate and extraction out of the tanks holding the acid can create a
bottleneck during execution. A complete understanding of these operational aspects is necessary for
proper execution.
At the end of a matrix treatment in carbonate formations, the acid should be flushed into the
formation with water (or KCl or NH4Cl brine if the formation contains swellable clays), and the well
can be immediately returned to production. For sandstones, where HF systems have been used, to
minimize the impact of precipitation, it is mandatory that an afterflush be employed and that the
well is returned to production immediately. The afterflush can be diesel oil, nitrogen, HCl, or
ammonium chloride brine, and its use will tend to ensure that precipitation from spent acid solutions
is prevented, or will occur away from the critical region very near to the wellbore.
The additives used in acid systems, such as corrosion inhibitors, mutual solvents, clay stabilizers, etc.,
are water soluble or at least water dispersible. This characteristic maximizes the efficiency of the
acid. However, since consumption of these additives in the formation cannot be quantified
accurately, many of the additives are added in excess, to assure an adequate concentration is
present in the formation to function effectively. Consequently, a significant amount of the additives
that are injected, are produced back with the water phase and they show up in the oil/water
separation system, where they can cause system upsets (i.e. emulsions) and often result in downtime
for the individual well, as well as the entire production installation. Delays in returning the stimulated
well to production have reduced the stimulation effectiveness. Furthermore, environmental
compliance on permitted produced water overboard discharge locations, has been difficult to attain
in such cases. Preventing disturbance in the functioning of the system requires optimizing the fluid
design to minimize or eliminate the formation of precipitates or micro emulsions. The evaluation of
the optimal demulsifier is critical due to the potential for emulsion formation by the aqueous phase
of the acid stimulation and is described in API RP 42 (1977). Apart from proper demulsifier selection
and use of acid additives, separate facilities for isolating flow returns from the normal dehydration
train could also be used for minimizing facility processing disturbances, as well as filtration of the
produced fluids through specially designed media.
9.4.5 Job Evaluation and Control
The Company Assigned Representative (CAR) prepares the matrix acidizing stimulation activity
reports, to be communicated to the appropriate office, including the treatment report. To facilitate a
proper evaluation and ensure the proper feedback into subsequent treatments, it is absolutely
essential to produce high quality stimulation treatment reports. The treatment report must
incorporate fluid QC data, pump rates, tubing and annular pressure measurements and clearly
identify which fluid or diverter was pumped, together with cumulative volumes. It is essential that
the report also identifies all deviations from the program, pumping interruptions and equipment
problems which influenced, directly or indirectly, the treatment operation.
Matrix Acidizing Control
Real Time Skin Evaluation
In recent years, technology to determine real-time skin effect evolution during a treatment has been
developed. Although this technology is not practiced routinely, it can be a useful diagnostic tool. For
example, if the skin effect is decreasing during an HCl stage, an acid-soluble species (e.g. calcium
carbonate/oxide, iron carbonate/oxide) created the damage. This information should be
complemented by the well history and laboratory testing to improve the understanding of the causes
of the present problem and assist future work.
The use of reliable methods for real-time control, and post-stimulation evaluation allowed
stimulation specialists to recognize the failed jobs, to identify the reasons for the failures, to optimize
the stimulation design, and to achieve a very high success rate.
The evaluation method used to record formation response to stimulation fluids is the Field --Acid -
Response Curve (FARC) proposed by Paccaloni (ref). The developed technique is based on the use of
a steady-state equation of radial flow. The model has proved to be easy, fast, and simple enough to
be used and appreciated by field personnel. Field supervisors can make better decisions on how to
manage treatment jobs by using FARC during these jobs. Real time management of acidizing jobs
depends heavily on an accurate knowledge of reservoir parameters. The absence of such data during
matrix stimulation jobs, makes injectivity tests before treatment necessary in order to estimate
starting reservoir permeability and skin factor. The linear nature of the Pacalloni curves in the
prediction diagram shown in Figure 9-23 can be used for this purpose. These curves illustrate the
relationship between injection pressure and rate for various skin factors and an assumed
permeability (K) and reservoir thickness (h).
The apparent skin is then plotted on the type curves at several injection rates below the fracturing
pressure, i.e. within Darcy low radial flow regime. The calculated skin values, S(t) using Eq.9-8 at
various injection rates are then compared, and Kh is changed until a reasonable fit is achieved
(marked in red ( ), as shown in Figure 9-23. If fit gives low skin factor, then the well is a poor
stimulation candidate. In the example shown in the Figure below, the estimated skin factor after
matching with injection data is 90.8. This value is used further for calculating Field Acid Response
Curve (FARC), i.e., change of skin factor during acidizing job.
( pi( t ) - p R + p h - p fr ) k w h
S(t ) = - ln r b (9-8)
26879.6 i( t ) w rw
Figure 9-23 Evaluation of matrix stimulation using prediction diagram and injection test
The obtained fit also gives a starting point for tracking the skin values over time according to
equation 9-8, using acid injection data marked in green in Figure 9-23( ) which essentially represent
FARC, as shown in Figure 9-24.
To obtain FARC it is required to know the bottom hole pressure (BHP) which can be calculated by
using algorithms for calculating pressure drop due to friction and the properties of the acid (density).
The supervisor of an acidizing treatment job, having FARC curve, as shown on figure above, could
make decision to stop injection before the planned volume of treatment fluid was injected.
Figure 9-24 Field Acid Response Curve
In another case (Figure 9-25 Acid Injection Data vs. time and Figure 9-26 FARC), the formation
clearly did not respond to the treatment as expected. The initial skin factor value of 20 increased as
the acid was injected to the value of 70 at the end of the job. The wrong acid recipe was used and a
2nd job must be performed with another type of treatment fluid.
Figure 9-25 Injection rate and pressure during job in Well 2
Figure 9-26 Field Acid Response Curve
The general workflow for real time monitoring and control of matrix acidizing is shown in Figure 9-27.
Figure 9-27 Workflow of matrix acidizing control in real time
Post-treatment Data Evaluation and Control
Careful recording should be made while bringing a well on production following stimulation. Early
indications of success can be found in the ease of initiating production and higher flow rates and
flowing tubing head pressures. Early production problems may indicate an incompatibility between
treating fluids and the produced oil. Flowback fluid samples should be acquired, regardless of the
volume of the treatment. These samples should be marked, with the date and time, total volume
recovered to that point and other pertinent data, such as choke size, flowing tubing pressure, water
cut and produced quantities. The analysis of water samples may indicate problems with the treating
fluid selection (e.g. precipitation problems with HF acidizing). Monitoring the ionic content of
returned fluids following acidizing treatments can provide insight into the actual chemical acid-
spending processes downhole. The mass balance of the injected and returned fluids and the relative
percentage of silicate reprecipitation allow the determination of relative spending levels of various
acids on the formation and well scale. Stimulated wells should be subjected to pressure buildup and
pressure transient analysis following a treatment. These data are the basis for a quantitative
assessment of the well and reservoir characteristics. Comparison of these results to pre-treatment
buildups can provide the best assessment of the success of the stimulation treatment. Ultimately, a
treatment should be evaluated on the basis of the well performance and economic parameters to
justify the treatment.
9.5 Configuration of Surface Equipment for Acidizing
The equipment needed for matrix treatments is, in general, relatively simple. The main items
required are:
Storage vessels for acids, solvents, etc.
Low-pressure suction lines and manifold.
Blending equipment for on-the-fly addition of additives, such as surfactants, use of
high-pressure pump units, at least one more unit than is strictly required for the
treatment (based on horsepower requirements).
High-pressure line to the wellhead.
Adequate measurement and control equipment, such as pressure sensors, flow
meters, densitometers, recording equipment, etc.
Waste disposal tank(s) or similar facilities (see also chapter 9.8.2 with environmental
aspects).
Figure 9-28 is a schematic for typical equipment layout for a matrix acidizing stimulation treatment
Figure 9-28 Typical Surface Equipment Layout for Standard Matrix Acidizing without using foam
In case the acidizing job will be performed with foamed acid (with N2 or CO2) the equipment which
has been utilized in OMV Petrom is shown in Figure 9-29.
The main component that needs to be added as compared with the typical equipment layout is a
nitrogen converter.
Figure 9-29 Typical Surface Equipment Layout for Matrix Acidizing with Foamed Acid
9.6 Fluids and Materials Used for Acidizing
9.6.1 Additives (corrosion inhibitors, Iron-Control Agents, Clay Stabilizers etc)
Corrosion Inhibitors
Acid corrosion inhibitors reduce the corrosion of well tubulars by acids. They adsorb on the surface of
the pipes to form a protective film, thus reducing the reaction rate of acid with steel.
As with any chemical reaction, the corrosion rate increases rapidly with temperature: each 10 C
increase in temperature will increase the corrosion rate by a factor 2 to 3. Moreover, corrosion
inhibitors lose their effectiveness at higher temperatures, causing an extra increase in corrosion rate
above 100 to 150 C. Corrosion inhibitors can give adequate protection to temperatures up to
approximately 100 C and Table 9-20 shows the temperature limits for efficient application of some
corrosion inhibitors.
For protection at higher temperatures, as shown in Table 9-20 below, salts with reducing properties
(cupro-iodide/sulfate, potassium iodide, etc.) are added as intensifiers.
Table 9-20 Temperature limits for corrosion inhibitors
The main factors affecting corrosion are metallurgy, acid type and concentration, agitation,
temperature, pressure, inhibitor solubility and concentration i.e. the ratio of metal area to acid
volume contact time, presence of inhibitor aids and the influence of other additives. Chemical
providers gives recommendations for their particular product, as shown in Appendix 9-B.
Surfactants
Surfactants, or surface active agents, are chemical containing both oil and water soluble groups, as
shown in Figure 9-30, with the ability to alter liquid-liquid or gas-liquid interfacial properties.
The reasons for using surfactants in acidizing are to:
Reduce surface and /or interfacial tension and capillary forces,
Alter and/control wettability,
Break undesirable emulsions,
Speed cleanup,
Disperse additives,
Disperse/suspend fines
Prevent sludge formation, and
Prevent/break water blocks.
The use of surfactants requires careful selection of an appropriate molecule. Remarkably, in the
design of most well treatments, surfactants are selected with little or no laboratory data to support
the choice and sometimes without full knowledge of their properties at the conditions where they
will be applied.
Figure 9-30 Dipolar surfactant composition
9.7 Quality and Safety Requirements for Acidizing
9.7.1 Quality Control
Incorporation of Quality Control (QC) measures during all aspects of an acid job can make the
difference between success and failure. QC is the process of ensuring that the materials and
equipment meet specifications and are delivered in proper condition to the well-site.
The execution of matrix acidizing must be performed as specified in the treatment schedule or by the
operator on location. During this process, QC and data collection is important. The operational
objective is defined by the design.
Quality control monitoring only during the actual pumping of the treatment is not sufficient. In
addition, quality control steps must be planned and executed during rig-up of equipment, before
pumping, and after pumping.
Laboratory check
The laboratory testing is to be carried out in the field prior to, and during the treatment. Although
perhaps more difficult because of poorer working conditions, it is most important to ensure that the
fluids prepared on location and pumped into the well, have similar properties to the fluids selected
on the basis of the initial laboratory tests and to the parameters used in the design. Failure to carry
out those quality control checks will almost certainly result in the treatment not being pumped
exactly as designed. These tests should be performed on samples of the chemicals supplied to the
field. This will initially certify that each individual material meets the specifications laid down and will
pass the final quality control check. After each material has been tested individually, they should
then be tested as acollective fluid using location water. Field testing will identify any incompatibilities
due to contamination.
For matrix stimulation operations, useful QC measures include:
During rig-up of equipment:

o It is mandatory to inspect all tanks that will be used to hold acid or water. The tanks
must be clean. Small amounts of dirt, mud, or other debris can easily ruin an acid job.
o Make sure the service company has the equipment to circulate the acid tank prior to
pumping.
o The line to the pit or tank should be laid and ready to connect to the wellhead so the
acid can be back-flowed immediately after the end of the overftush.
o Calibration of all measuring devices, such as transducers and flowmeters, should be a
regular part of maintenance procedures. Calibration conditions should mimic
operating conditions to the extent required to properly calibrate the equipment.
Sufficient inventories of spare parts should be available to make maintenance repairs
quickly. Calibration tests should be conducted routinely and the results documented.
Quality control before pumping

o Check the service company tickets to be sure all additives for the job an on location.
It is important to make sure that additives included in the treatment design are
included among the chemical components delivered for on-site mixture and use. Not
only do additives once in a while fail to show up, sometimes an incorrect additive, or
at least an unacceptable substitute, may be delivered instead of what had been
requested or specified.
o Circulate the acid storage tank(s) just before the acid is injected into the well. It is
known that certain additives, particularly corrosion inhibitor, can settle to the top of
the acid tank, leaving the body of acid inadequately inhibited. It is important to mix
acid on deliveryand if possible, continuously, up to injection. If that is not possible,
then acid should be mixed immediately prior to injection.
o On-site titration of acids to verify the concentration.
o Verification that surface-active agents are supplied in the specified concentration. It
is important to stay below the maximum surface pressure during injection, for
consideration of equipment safety limits. Also, in sandstones, it is necessary to stay
below fracturing pressure. It may be that changes need to be made as the treatment
is being pumped. If any changes are in order, they must be well understood by all
personnel beforehand and during treatment, while they are made.
o Regular QC testing of each batch or lot of corrosion inhibitor by the service company
o On-site testing of gel viscosity for diverters (carbonates)
o Make sure the service company personnel know the maximum surface pressure and
stay below that pressure.
o Check the pressure-time recorder or any other on-site treatment monitoring or
evaluation mechanism, to ensure proper operation.
o Acid-clean (pickle) the tubing. If the tubing is not pickled, debris, iron scale, pipe
dope, and other solids can be injected into the formation at the very beginning of an
acid treatment. This can irreparably damage the near-wellbore formation, ruining an
otherwise well-designed treatment. If possible, always include a pickling
pretreatment.
Quality control during pumping

o Control injection rate, maintain surface annulus pressure at or below certain level
(30-35 bars) during treatment and monitor the pressure response when acid reaches
the formation. The surface pressure should slowly decrease if the rate is held
constant, indicating skin removal. If the surface pressure rises sharply or rises
continuously for certain volume of acid (0.5-1m3), the acid may not be removing the
damage or maybe damaging the formation. Acid injection should be stopped, and
the well should be flowed back immediately, no matter what objections there may
be. Samples of the back-flowed acid should be sent to the service company
laboratory for analysis
o Sampling of fluids pumped during the stimulation treatment, with samples retained
until the treatment has been evaluated.
o Regular testing of particle size and solubility of particulate diverters
o Note the pressure response when the diverting agent reaches the formation. The
surface pressure should rise slightly, if there is no diverter response, more diverter or
a different diverter may be needed in the future. If diverter response is not noted,
the injection rate may be increased, if the pressure limit permits, to enhance zone
coverage. This should be considered only if it does not compromise other aspects of
the design.
o Never exceed the breakdown pressure of the formation in a sandstone acidizing
treatment, unless absolutely necessary initially to break down the perforations (with
a perforation -wash tool) or to bypass severe damage to initiate inactivity. Once
fracture pressure was exceeded, injection pressure remained virtually unchanged,
suggesting an absence of effective diversion and zone coverage.
o In the final flush, make sure acid is displaced from the wellbore. The full overflush
should be pumped as designed. Spent acid, especially in sandstone, must be
sufficiently displaced from the wellbore to reduce the damaging effects of
precipitation of acid reaction products. In carbonate stimulation, it is desirable for
acid to be fully spent before it flows back, to avoid possible corrosion problems on
flowback of return fluids.
Quality control after pumping

o Do not shut the well in after acid injection. Flow the well back to the tank or pit as
soon as the flow line is connected. Flowback immediately following acidizing is not
normal production, and if care is not taken, severe damage can be caused during this
initial period. Three of the most common problems during flowback are:
Fines migration (to avoid potentially damaging effects, the flow rate should
be set low at first. Then, after spent acid is produced back, the flow rate
should be gradually stepped up to planned production conditions).
Re-precipitation of acid reaction products (In sandstone acidizing, the only
way to minimize the problem once the acid treatment has been pumped is
to return the well to production as soon as possible. The process of flowing
spent acid back must be initiated immediately. Shutting the well in an HF

treatment is the worst course of action, with respect to damage caused by
reprecipitation of HF reaction products).
Back-production and processing of additives (most additives included in acid
mixtures are produced back after treatment. They can cause upsets to
production equipment and facilities. Depending on the circumstances, spent
acid must be collected and properly disposed of).
o Collect at least three one-quart samples of back-flowed acid for analysis. Sample the
acid back-flow at the beginning, middle, and near the end of the flow. If on swab, get
a sample from every other swab run. This information can indicate the nature of acid
spending, whether overtreatment or undertreatment occurred, and whether iron
and potential precipitation of reaction products are a concern. It also can indicate if
acid mixtures injected might have been incompatible with formation fluids. It is
imperative to patiently evaluate return samples before drawing any potentially
incorrect conclusions about the treatment pumped. If possible, get a laboratory
analysis for the following:
Amount, size, and type of solids,
Strength of returned acid,
Total iron content,
Presence of emulsions and/or sludges, and
Formation of any precipitates (besides iron).
o A complete analysis of acid returns, using spectroscopic methods can be performed

by specialized laboratories. Concentrations of the following ions should be
determined: Aluminum (Al3+), Magnesium (Mg2+), Chloride (Cl-), Barium (Ba2+),
Potassium (K+),Fluoride ion (F-), Calcium (Ca 2+), Sodium (Na+), Iron (Fe2+, Fe3+) and
Silicon (Si2+, Si4+). Spectroscopic analysis can indicate on what the acid stages spent
themselves and whether the spent acid stages produced back in the expected and
desired manner. This information can be important for designing future treatments
in the same field. For example, perhaps spent HF returns in a sandstone acidizing
treatment showed high Ca2+content. This might indicate the need for a larger acid
(HCl) preflush. Alternatively, it might indicate the need to back off on the HF stage.
High Si/Al ratios suggest reprecipitation of aluminum fluoride salts, indicating that
the designed HCl/HF ratio should be modified. Other potential modifications include
lowering the HF concentration and using a special HF system designed to minimize
the reprecipitation of such reaction products.
o Take the treatment report and the pressure charts to the office for evaluation and
placement into the well file. Both the operator and the service company must make
an effort to exchange and discuss all relevant treatment information, to give each
other the best chance for future success.
9.7.2 Health, Safety and Environmental Aspects of Acidizing
In any well operation, including acid stimulation, safety must be designated as a crucial quality
control measure and job safety is of utmost importance. Awareness of the importance of health,
safety and environmental, (HSE), issues has become more and more central to the thinking of the
E&P industry and regulators in the last decades. The implementation of HSE management systems
(HSE-MS) of Petrom OMV and Service providers to control these aspects in acidizing operations are
no exception.
Accomplishing successful well acidizing is of high importance, but, all is greatly diminished in
importance when compared to safety concerns.
HSE Aspects of Acidizing
The pre-job safety meeting is the most important part of the treatment. In this meeting, all safety
considerations should be discussed in detail. The main purpose of the meeting is to ensure that each
individual present at the job site knows his or her responsibility and what to do at all time during the
job. The following topics should at least be covered during this meeting:
Job details and contingency procedures (sudden leaks, etc.).

Chemical hazards, i.e. actions required if hazardous contact occurs.
Required protective clothing, goggles, gloves, etc. for working with the chemicals on location.
Applicable smoking, drinking and food limitations.
Sampling procedures.
Communication lines between contractor and OMV Petrom personnel (all individuals present
should be familiar with the service company's mode of communication. Service company
representatives should report their means of communication to the OMV Petrom company
representative during the treatment. They should plan appropriate action to take if that line
of communication fails.
Maximum allowable treating pressure.
Responsibilities of each individual on location.
Do a complete head count of all personnel on location? It is best practice for the leads to
have an idea of where everyone is at all times? Personnel should inform the leads of their
whereabouts when leaving the site temporarily.
Check if the place of a fire extinguisher on the ground is easy for access.
Check if reserve a vehicle is ready for transporting eventually injured personnel in the case of
catastrophic event.
Give two individuals the responsibility of transporting eventually injured persons to the
nearest clinic/hospital.
Gathering area in case of emergencies/disasters. Disaster, such as an explosion or a major
equipment failure or leak, may require evacuation to a safe area. By contrast, in the event of
an accident, the gathering area may be more immediately accessible.
Location of First Aid facilities and first aider in charge.
Materials Safety Data Sheet (MSDS). Basic information on the nature of chemicals handled,
precautions to be taken and actions to be taken in the event of a fire, spillage or accidental
contact should be available at locations where chemicals are handled and also at first aid
stations.
Safe Handling of Chemicals (SHOC) instructions should be on site. As to safe handling of
chemicals (SHOC), especially in matrix treatments, whenever in doubt, the manufacturers
instructions should be consulted for advice on the handling of chemicals. In general,
precautions should be taken to avoid skin contact and inhalation and, in any event where
contact is possible:
o Hands should be washed before eating, smoking or using the toilet, food should be consumed
in areas free from dust and fumes,
o Contaminated clothing should be removed before eating.
o Personnel handling acid or caustic substances should wear gloves, boots, face shields and
acid/alkali resistant coveralls or aprons.
o During all stimulation jobs, there is a risk of splashing or contact with dangerous chemicals.
Therefore an emergency shower and/or eye wash facility should be installed within 20
meters.
Rest area.
General HSE guidelines for acidizing
A stimulation treatment involves the handling, injection and back production of potentially
hazardous chemicals and during the operation high injection pressure will be needed. Therefore, the
strict and precise HSE requirements must be followed and applied. To ensure a safe and
environmentally acceptable execution of a stimulation treatment, the following rules apply:
Design the treatment with chemicals which have the smallest possible environmental impact.
Make sure that for each chemical used, a instructions and a Material Safety Data Sheet
(MSDS) are available on site.
For critical jobs, or with new, relatively inexperienced crews, hold dry runs on critical
operations.
Pressure tests all lines prior to the treatment.
Determine the position of all valves and sequences of opening and closing of the valves.
Make sure that all lines are secured and anchored.
Check the monitoring equipment prior to the main treatment.
Make sure that adequate (in accordance with the requirements on the SHOC or MSDS cards)
first-aid facilities, including qualified personnel, are available on-site.
Establish prior to the treatment handling and disposal procedures for chemicals, empty
containers and back-produced fluids.
9.7.3 Personnel (Training, Supervision)
Properly trained personnel are the keys to success. The wellsite personnel must understand the
fundamentals of the stimulation technique that will be used and must know how to use the
equipment, software and techniques. Two main keys to effective QC are communication and
documentation. The designer must communicate the design expectations to the material suppliers.
Because these expectations must be consistent with the supplier or manufacturers specifications,
the specifications should be available to the designer.
Appendix 9-A Commercially Available Acid Systems Specification Details

Table 9-21 Commercial Sand Acid 1
General Fluid Description Halliburtom Energy Services BJ Services Schlumberger Dowell

Half strength Mud Acid
6% HCl-1.5% HF 6% HCl-1.5% HF 6% HCl-1.5% HF
(H948)
7.5% HCl 7.5% HCl 7.5% hydrochloric acid Regular Acid (7.5%HCl)
10% HCl-1% HF 10% HCl-1% HF 10% HCl-1% HF Custom Blend
Regular Mud Acid
12% HCl-3% HF 12% HCl-3% HF 12% HCl-3% HF
(H949)
13.5% HCl-1.5% HF 13.5% HCl-1.5% HF 13.5% HCl-1.5% HF Custom Blend
15% HCl 15% HCl 15% hydrochloric acid Regular Acid (15% HCl)
Gelled Acid, LT-100, DGA 100, DGA 200, DGA
15% HCl with gelling agent 15% HCl + SGA-HT
HT-200 300, DGA400
Regular Acid (28% HCl)
28% HCl 28% HCl 28% hydrochloric acid
(H28)
Acetic - HF system None Acetic:HF Organic Mud Acid
CLAYFIX 5, 2% Ammonium
Ammonium chloride Chloride, 5% Ammonium Ammonium chloride J285
Chloride
Generic Fluid Description Halliburton Energy BJ Services Schlumberger

Services Dowell
Aromatic solvent Paragon Xylene A26, P121
Aromatic solvent that Paragon 100E+ Envirosol XS P129
does not contain xylene,
benzene, toluene or
Asphaltenic compatible Carbonate Completion One Shot Plus MISCA
acid system for acidizing Acid
of sandstone and
carbonate reservoirs
Biodegradable, non- Paragon EA P130
aromatic solvent
CO2 conditioning system Gidleys CO2
Conditioner (No
competive equivalent -
HES exclusive patent
Diesel Diesel Diesel U051
Emulsified acid Carbonate Emulsion Emulsified Acid Super X Emulsion,
Acid Super X Emulsion
HT, Dowell Acid
Dispersion (DAD)
Foamed acid Fines Recovery Acid Foamed Acid Foamed acid
Formic - HF system None Formic: HF Organic Mud Acid
(H954)
Gelled acid Carbonate Stimulation Gelled Acid, Gelled DGA 100, DGA 200,
Acid Acid 100, Gelled Acid DGA 300, DGA400
200, Gelled Weak Acid
HCl based, iron control Fe Acid, Double Ferrotrol Agents Micellar Iron and
acid system (non-H2S Strength Fe Acid Sludge Control
environment) Agent (MISCA)
HCl-HF system for use in Silica Scale Acid BJ Sandstone Acid
geothermal wells
HCl-HF system with Sandstone Completion BJ Sandstone Acid
surfactant and aluminum Acid
scale inhibitor
Hydrochloric acid / CLAY-SAFE H
ammonium chloride
conditioner
Hydroxypropyl guar WG-11 Hydroxy Propyl Guar J347
gelling agent Gelling Agent
Generic Fluid Description Halliburton Energy BJ Services Schlumberger

Services Dowell
In-situ gelled acid Zonal Coverage Acid Leak Off Control
Acid (LCA), Self
Diverting Acid
Low strength HCl-HF K-Spar Acid BJ Sandstone Acid Clay Acid
system for use in high
feldspar/fines applications
Nitrogen Nitrogen Nitrogen Nitrogen
Organic acid 10% Formic, 10% Organic Acid L001, L036, L400
Acetic
Organic acid / ammonium CLAY-SAFE 5, CLAY-
chloride conditioner SAFE F
Organic acid for high Hot Rock Acid Organic Acid L400, L036
temperatures
Volcanic Acid I, Acetic:HF Formic:HF Organic Mud
Organic HF system Volcanic Acid II Acid
Potassium chloride 2% KCl Potassium Chloride M117
Retarded HF system with Fines Control Acid BJ Sandstone Acid Clay Acid
surfactants
Seawater Seawater Seawater Seawater
Sour well iron control acid SWIC Acid, SWIC II Ferrotrol-HAS +
system Ferrotrol-HSB A255
Water Water Water Water
Xylene Xylene Xylene A26
Table 9-24 Commercial Carbonate Acid 1
Halliburton Carbonate 20/20 Matrix Acidising Systems

Acid Composition Adventages
Carbonate Completion Acid 10 to 28% HCl This totally soluble acid blend is
+ FDP-S562A inhibitor universally applicable to most well
+ FDP-S562B anti-sludge conditions. Designed to minimise
Optional: emulsion and sludge problems
FDP-S562C H2S scavenger even in sour wells.
FDP-S562D iron reducer
FDP-S562E dispersant
Carbonate Stimulation Acid 15% HCl Gelled acid improves stimulation
+ 2% SGA-HT results. Moderate viscosity
Optional: enhances zonal coverage and
1 to 4% gelling agent minimises fluid loss.
SGA-HT, SGA-II, SGA-III
Fines Recovery Acid 70 v/o nitrogen The system of choice for low-
30 v/o 20% HCl solubility formations. Gelling
(2.5% SGA-1 in the HCl) agent also functions as a foaming
agent and fines suspender. Foam
enhances fines carrying capacity
and aids in fluid recovery.
Carbonate Emulsion Acid 70 v/o 22% HCl Ultra-retarded acid system
30 v/o diesel enhances zonal coverage and
(2.5% AF-61 in the diesel) efficiently generates wormholes
under nearly all conditions.
Zonal Coverage Acid 15% HCl + 2% SGA-II The ultimate in-situ diversion for
+ 4.5% gal/Mgal XL-1 matrix acidising and fluid-loss
+ 2 gal/Mgal BF-1 control in fracture acidising.
+ 4 lb/Mgal Ferchek
Hot Rock Acid 9% Formic 13% Acetic The system of choice when
+ 0.5% MSA-II corrosion concerns or formation
+ 0.5% LoSurf-259 compatibility problems preclude
+ 1.5% SGA-HT the use of HCl.
Main Dowell Acid Formulations For Carbonate Matrix Acidising

Acid/Description Treatment / Reservoir Recommended Advantages
Conditions Applications
Dowell X Production restricted Matrix Acidising and Economical and
Inhibited HCl 5 to 15% due to damage or low Acid Fracturing; versatile
formation permeability Carbonate and Iron
(27 to 204 C) Scale Solvent
Super X Production restricted Matrix Acidising or Acid Greater dissolving
Inhibited concentrated due to damage or low Fracturing; removal of power than equal
HCl formation permeability formation damage or volume of Dowell X
20 to 28% (27 to 177 C) scale deposits
XX Intensified Acid Low or damaged Matrix Acidising or Acid Accelerated reaction
Inhibited HCl with HF permeability in Fracturing rate with dolomite
intensifier dolomite or siliceous and siliceous
limestone reservoirs limestone
(27 to 204 C)
Super X EmulsionSXE 27 to 150 C All applications Highly retarded with
Emulsified HCl i.e. oil outside phase
70/30 HCl/oil
MSR 100, MSR 150 Drilling muds lost to the Matrix Acidising; Acid Brings back large
Blend of 7.5 to 15% formation; or reservoir Fracturing; Formation amounts of muds
inhibited HCl and special has a high percentage Cleaning; Wellbore and clays; minimises
clay dispersing, of silts and clays (27 to Cleanup and Gravel- reprecipitation of
suspending and chelating 121 C) Pack Cleanup Fluid dissolved iron
agents
DGA100 Carbonate reservoirs Acid Fracturing; reactive Exceptional fluid-
Thickened inhibited (especially older wells) stages in DUOFRAC II loss control and
15% HCl where wider and treatments improved etch
deeper penetrating patterns; suspends
fractures are needed and removes silts
(27 to 121 C) and solids with spent
acid returns
DGA200 Low-temperature Acid Fracturing; Retarded reaction
HCl thickened up to a carbonate reservoirs Formation Cleaning of rate; reduced
maximum of 28% Fissured Reservoirs, leakoff, low viscosity
DUOFRAC II treatments when spent for good
for low-temperature cleanup; liquid
wells (66 C) additive gels up to
28% HCl
Acid/Description Treatment / Reservoir Recommended Advantages

Conditions Applications
DGA300 High-temperature Acid Fracturing; Retarded reaction rate;
HCl thickened up to a carbonate reservoirs Formation Cleaning of reduced leakoff,
maximum of 28% Fissured Reservoirs, continuous- or batch-
DUOFRAC II treatments mix applications; stable
for high-temperature at high temperatures.
wells (149 C) Gels up to 28% HCl
DGA400 Carbonate reservoirs Acid Fracturing; Reduced leakoff; batch-
HCl thickened up to a less than 149 C Formation Cleaning of or continuous-mix
maximum of 28% Fissured Reservoirs; operations; stable at
DUOFRAC II treatments high temperatures
Foamed X Low-pressure, low- Acid Fracturing and Improved leakoff
Stable inhibited HCl permeability carbonate Formation Cleaning of control and well
and foam; 55 to 85% reservoirs (27 to 121 C) Fissured Reservoirs cleanup with more
foam quality efficient return of
treating fluids
SDA (Self Diverting Carbonate reservoirs Formation Stimulation, Self diversion
Acid) less than 149 C Cleaning of Fissured mechanism, deep acid
HCl thickened up to a Reservoirs penetration
maximum of 28%
BJ Services International Matrix Acidising Systems

Type/Name Purpose/Advantages
High-rate, near-wellbore treatments.
Lightly gelled acid Excellent friction reduction.
Various strengths of HCl acid with low concentrations
of gellant (e.g. DSGA or AG-57L at 4 l/m3)
Gelled Acid 100, Gelled Acid 200, Gelled Weak Acid Enhanced zonal coverage, fines
Various strengths of HCl with various concentrations suspending and reaction rate
of gellant retardation
In-situ crosslinked acid, (Enhanced Acid System) Effective diversion for treatment of
Various strengths of HCl, 5 to 28% long intervals, horizontal wells
XL Acid III (various strengths of crosslinked HCl acid) Suitable for high viscosity diversion
stages in matrix acid treatments
Foamed acid Improved diversion, leak off control
and fines recovery
Organic acid High-temperature treatments
Specialty acid systems, e.g. One Shot Acid Plus Treatment of asphaltenes and sludges.
Blend of aromatic solvents and acid
Appendix 9-B Commercially Available Additives and Solvent Specifications

Table 9-28 Commercial Sand Additive 1
Generic Aditive Description Halliburton Energy BJ Services Schlumberger

Services Dowell
Acid corrosion inhibitor HII-124B, HII-124F, Hy Temp I, Hy-Temp A201, A153, A179,
intensifier HII-500M O A281
Additive for use in aromatic Targon II AS-32 + NE-110W U101
solvents to enhance
asphaltene dissolution
Anionic, anti-sludging AS-5, AS-9 AS-32 W035 / W60
surfactant
Anionic, de-oiling, Morflo III NE-110W
nonemulsier for aquaeous
based fluids
Antisulfide-cracking agent SCA-130 HS-2 A255

Services Dowell
Broad spectrum, anionic NEA-96M AS-32, NE-110W F104
surfactant for aqueous based
fluids
Broad spectrum, cationic 19N, 20N LT-17 F078, M38B
surfactant for aqueous based
fluids
Broad spectrum, nonionic Losurf 300, Losurf NE-118, NE-940 F75N, F103
surfactant for aqueous based 259, Losurf, 357
fluids
Cationic oligimer for clay Cla-Sta XP Claymaster 5C L055
stabilization in aqueous
Cationic liquid friction FR-28LC AG-12, Acigel J507, J313
reducer
Cationic, mineral fines and Cla-Sta FS Claymaster FSC L042
clay stabilizing additive in
aqueous fluids
Ethylene glycol mono butyl Musol US-40 U066
ether
Ferric iron reduction system FERCHEK SC Ferrotrol-200 or 210 L63, L58
for iron control in sour
environments
High temperature corrosion HAI-85M A280 / A282 with
inhibitor for use up to 500F A281
with all strengths of acid and
on corrosion resistant alloys
Hydroxypropyl guar gelling WG-11 Hydroxy Propyl J347
agent Guar Gelling Agent
Improved mutual solvent that Musol E US-2
does not contain EGMBE and
is therefore more
enviromentally friendly
Micellar surfactant system SSO-21M LT-32 + Floback-30
with foaming and fluid
recovery properties for use at
225 F and below
Micellar surfactant system SSO-21HT LT-32 + Floback-30
with foaming and fluid
recovery properties for use
above 225 F

Services Dowell
Mutual solvent composed of a Musol A US-2 U100
blend of alcohols/ethers for
acids
Nonionic blend of surfactants, Losurf 396 F103
dispersants and solvents for
use where health, safety and
environmental regulations
are concerned
Nonionic microemulsion Pen-88M LT-32
penetrating agent for use at
225 F and below
Nonionic microemulsion Pen-88HT LT-32
penetrating agent for use
above 225 F
Nonionic surfactant Sperse-All M, D-4GB F040
dispersant A-Sperse
Nonionic, anti-sludging AS-7 None W054
surfactant
Nonionic, penetrating Pen-5M LT-32 F075N
surfactant
Oil soluble non-emulsifying Hyflo IVM NE-118 F040
surfactant
Organic acid corrosion MSA-II CI-20 A186, A272
inhibitor
Organic acid used for iron Fe-1A, Fe-2 Acetic Acid, Citric L001, L400
control Acid
Organic alcohol Methanol Methanol, K046
Isopropyl Alcohol
Oxygen scavenger used for FERCHEK Ferrotrol-200 or L058
iron control 210
Sandstone acidizing additive ALCHEK BJ Sandstone Acid
for the prevention of
secondary precipitation of
aluminum
Sequestering/reducing and FERCHEK A Ferrotrol-810, L041, U042, L62
scavenging agent for iron Ferrotrol-270
control in acids &271, Ferrotrol-
Soluble corrosion inhibitor for HAI-81M CI-30NF + HyTemp A270,A280
use up to 400 F 400

Services Dowell
Soluble, enviromentally HAI-OS, HAI-NS CI-27 A259, A261, A262
acceptable corrosion inhibitor
for use up to 200 F
Surface tension reduction and Superflo III Inflo-150, Inflo-100 F075N, F103
fluid recovery surfactant
Surfactant gelling agent for SGA-1 AG-10 J508
acids
Suspending agent/foaming HC-2 FAW-21 F78, F100
surfactant for acids
Synthetic, cationic gelling SGA-HT AG-12, Acigel J507
agent for acids up to 400 F
ADDITIONS from DS Halliburton Energy BJ Services Schlumberger

Services Dowell
Environmentally acceptable W060
anionic anti-sludging agent
Environmentally acceptable J507
friction reducing agent
Environmentally acceptable A272
organic acid corrosion
inhibitor
Environmentally acceptable F100
suspending agent/foaming
agent for acids
Environmentally acceptable, F103
broad spectrum nonionic
surfactant for aqueous-based
fluids
Soluble environmentally A259 and A282
acceptable corrosion
inhibitor for use up to 400 F
List of Figures
Figure 9-1 Skin factor as a function of damage radius and damage ration (kd/k),
Figure 9-2 Pressure profile of damaged and undamaged well,
Figure 9-3 Formation damage types,
Figure 9-4 Formation damage types and treatment selection,
Figure 9-5 Basic Fluid Selection for Well Acidizing,
Figure 9-6 Constituents of sandstone which are soluble in HCl/HF acid systems,
Figure 9-7 Various Wormhole structures,
Figure 9-8 Wormholing controlled by diffusion,
Figure 9-9 Various Wormhole structures (Fredd and Fogler, SPEJ, 1998, 1999; Hoefner and Fogler,
AlChEJ, 1998),
Figure 9-10 Model 1 Preflush/Overflush Fluid Selection,
Figure 9-11 Model 1 Main/Base Treatment Fluid Selection,
Figure 9-12 Main Treatment Fluid Selection including presence of high sensitivity Clays and Zeolites,
Figure 9-13 Main Treatment Fluid Selection including presence of high sensitivity Clays, Chlorite and
Glauconite,
Figure 9-14 Model 1 Main/Base Treatment Fluid Selection including presence of high sensitivity Clays,
Zeolites and Glauconite,
Figure 9-15 Model 2 Preflush/Overflush Fluid Selection including presence of high sensitivity Clays,
Figure 9-16 Model 2 Main Treatment Fluid Selection including presence of high sensitivity Clays and
reservoir temperature,
Figure 9-17 General Workflow for choosing a diversion method for matrix acidizing,
Figure 9-18 Diversion selection workflow,
Figure 9-19 Impure dolomite: Quartz grains (white crystals) scattered in the dolomitic matrix (brown
crystals of dolomite),
Figure 9-20 Fluid selection workflow for carbonate acidizing,
Figure 9-21 Improper acid placement in carbonate formation,
Figure 9-22 Matrix Acidizing Planning Schedule,
Figure 9-23 Evaluation of matrix stimulation using prediction diagram and injection test,
Figure 9-24 Field Acid Response Curve,
Figure 9-25 Injection rate and pressure during job in Well 2,
Figure 9-26 Field Acid Response Curve,
Figure 9-27 Workflow of matrix acidizing control in real time,
Figure 9-28 Typical Surface Equipment Layout for Standard Matrix Acidizing without using foam,
Figure 9-29 Typical Surface Equipment Layout for Matrix Acidizing with Foamed Acid,
Figure 9-30 Dipolar surfactant composition.
List of Tables
Table 9-1 Summarized skin components,
Table 9-2 Primary chemical reaction in acidizing
Table 9-3 Damaging HF reactions in sandstones,
Table 9-4 Maximum protection time for different acids and temperatures,
Table 9-5 The reaction of HCl with carbonates,
Table 9-6 Solubility of Common Minerals in Acid,
Table 9-7Model 1 Preflush Fluid Selection,
Table 9-8 Model 1 Preflush /Overflush fluid selection including presence of HCl sensitive minerals
Table 9-9 Model 1 Main/Base Treatment Fluid Selection,
Table 9-10 Model 1 Main/Base Treatment Fluid Selection including presence of high sensitivity Clays,
Table 9-11 Preflush /Overflush fluid selection including presence of HCl sensitive minerals and
temperature
Table 9-12 Main Treatment Fluid Selection including presence of HCl sensitive minerals and
temperature,
Table 9-13 Acid treatment guideline,
Table 9-14 Recommended volume of treatment fluid,
Table 9-15 Wormhole structure,
Table 9-16 Statistical analysis of well-documented matrix stimulation treatments,
Table 9-17 Main Reasons for failures,
Table 9-18 Reasons for failures and corrective actions,
Table 9-19 Matrix Acidizing Planning Schedule,
Table 9-20 Temperature limits for corrosion inhibitors,
Table 9-21 Commercial Sand Acid 1,
Table 9-24 Commercial Carbonate Acid 1,

Table 9-28 Commercial Sand Additive 1,
Table 9-32 Commercial Sand Additive 5.
References
1. OMV Petrom Internal Documents

Stimulation & Fracturing Activity 2010 2011
Stimulation study 1 -Standard procedure for matrix treatment recipe formulation
Stimulation study 2 - standard procedure for design special matrix treatment
Field Cases of Application of Acidizing Workflow and Acidizing Best Practices Reports
(Well 510 A Burcioaia, G10 Lebada East, 154 Bragareasa - Foam acidizing job,
Best Candidate Selection Process for Acidizing and HDF
Acid Systems Specification Details used in Petrom OMV
Additives and Solvent Specifications/Annex with procedures for testing various additives
Technical Procedure for Acidizing. WO&WI BU
2. Bert W., Gidley J. and Schechter R.: Acidizing Fundamentals, SPE of AIME, 1979
3. Buijse M.: Mechanisms of Wormholing in Carbonate Acidizing, SPE 37283, 1997.
4. Best Practices--Carbonate matrix Acidizing Treatments; Halliburton Energy Services, Inc.
Bibliography No. H01276; ; Oct. 1998;.
5. Civan F.: Reservoir Formation Damage, Gulf Publishing Company, 2000
6. Daccord, G. Lenormand, R. and Litard, O.: Chemical Dissolution of a Porous Medium by a
Reactive Fluid, Chemical Engineering Science 1993. 48, No. 1, 169-186.
7. Daccord, G., Touboul, E. and Lenormand, R.: Carbonate Acidizing: Toward a Quantitative
Model of the Wormholing Phenomenon, SPE 16887, SPE Production Engineering, February
1989
8. Economides M.: A practical Companion to reservoir Stimulation, 1992
9. Economides M. and Nolte K.G.: Reservoir Stimulation, 3rd Edition
10. Economides, M. and Boney, C.: Reservoir Stimulation
11. Ely, J.W.: Stimulation Treatment Handbook, Tulsa, Oklahoma, USA, PennWell Publishing Co.,
1985.
12. Gidley, J. L.: Stimulation of Sandstone Formations: A Detailed Examination of Recent
Experience, paper SPE 14164, 1985.
13. Gong, M.: Quantitative Model of Wormholing Process in Carbonate Acidizing, SPE 52165,
1999.
14. Huang S. T., et al: Reaction Rate and Fluid Loss; The Keys to Wormhole Initiation and
Propagation in Carbonate Acidizing; SPE 37312,1997.
15. Mostofizadeh B., et al; Optimum Injection Rate From Radial Acidizing Experiments, SPE 2854,
1994.
16. McLeod, H. O.: Matrix Acidizing, paper SPE 13752, 1984.
17. McLeod, H.O. Jr., Ledlow, L.B. and Till, M.V.: The Planning, Execution and Evaluation of Acid
Treatments in Sandstone Formations, SPE 11931, 1983.
18. Kalfayan L., Production Enhancement With Acid Stimulation, 2008
19. Kalfayan, L.J. and Watkins, D.R.: A New Method for Stabilizing Fines and Controlling
Dissolution During Sandstone Acidizing, SPE 20076, 1990.
20. Paccaioni G., M. Tambini SPE, Advances in matrix Stimulation Technology (pp. 256-263), 1993
Journal of Petroleum technology, Feb. 1987; Role of Acid Diffusion in Matrix Acidizing of
Carbonates; M. Hoefner, et al; (pp. 203-208).
21. Paccaloni, G.: A New, Effective Matrix Stimulation Diversion Technique, SPE 24781, SPE
Production & Facilities , August, 1995.
22. Prouvost, L. and Economides, M.J.: Applications of Real-Time Matrix-Acidizing Evaluation
Method, SPE 17156, SPE Production Engineering, November, 1989.
23. Recommended Practices for Laboratory Testing of Surface Active Agents for Well Stimulation
(RP 42), second edition, Dallas, Texas, USA, American Petroleum Institute (January 1, 1977).
24. Schehter R.: Oil Well Stimulation, Prentice-Hall, Inc. 1992;
25. Wang Y. , et al: The Optimum Injection Rate for Matrix Acidizing of Carbonate Formations,
SPE 26578 1993.
26. Wang, Y., Hill, A.D. and Schechter, R.S.: The Optimum Injection Rate for Matrix Acidizing of
Carbonate Formations, SPE 26578, 1993.
27. Walsh, M. P., Lake, L. W. and Schechter, R. S.: A Description of Chemical Precipitation
Mechanisms and Their Role in Formation Damage During Stimulation by Hydrofluoric Acid,
SPE 10625, 1982.

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RO-EP-DA-PO-06-POL-001-02 OMV Petrom Exploration Production

Revision 1 2012 OMV Petrom Workover Best Practices

EXECUTIVE SUMMARY ......................................................................................................................... 9-1

References ...................................................................................................................................... 9-74

EXECUTIVE SUMMARY: 9. STIMULATION BY ACIDIZING

EXECUTIVE SUMMARY: 9. STIMULATION BY ACIDIZING

2. To use HF + KCl or formation brine.

6. To use mud acid to treat formations if HCL solubility is > 20%.

7. To start acidizing treatment if sufficient injectivity is not obtained.

8. To use of HCl preflush after dry tests in exploratory/wildcat wells.

9.1.1 Objectives of Well Stimulation by Acidizing

The key objectives of well acidizing in OMV Petrom are to:

9.2 Well Acidizing Stimulation Technology

Skin Components Characteristics

Figure 9-2 Pressure profile of damaged and undamaged well

9.2.2 Best Candidate Selection Process for Acidizing

Figure 9-3 Formation damage types

Silts and Clays

9.3 Well Acidizing Methods Applied in OMV Petrom

1. Sandstone acidizing, and

Figure 9-4 Formation damage types and treatment selection

The final fluid selection for treatment

Figure 9-5 Basic Fluid Selection for Well Acidizing

Table 9-2 Primary chemical reaction in acidizing

Fluoboric acid-based solution (Clay Acid)

Precipitation of reaction product

Figure 9-7 Various Wormhole structures

Acids used in carbonate acidizing and chemistry of reactions

Figure 9-8 Wormholing controlled by diffusion

9.4 Technology Workflow of Best Practices for Fluid Selection, Treatment

9.4.1 Sandstone Matrix Acidizing Treatment

Fluid Selection for Acidizing Treatment

Model 1-Sandstone Acidizing Workflow

Model 1- Preflush/Overflush stage Fluid Selection

Figure 9-10 Model 1 Preflush/Overflush Fluid Selection

Table 9-7Model 1 Preflush Fluid Selection

Mineral Composition > 100 mD 20-100 mD < 20 mD

Lithology Criteria (%)

Model 1 Main Treatment Fluid Selection

Figure 9-11 Model 1 Main/Base Treatment Fluid Selection

Table 9-9 Model 1 Main/Base Treatment Fluid Selection

Mineral Composition > 100 mD 20-100 mD < 20 mD

If 4-6% chlorite/glauconite then use <20md Guidelines with 5% Acetic Acid

Model 2-Sandstone Acidizing Workflow

Model 2- Preflush/Overflush stage Fluid Selection

Model 2 Main Treatment Fluid Selection

9.4.2 Applied Sandstone Design Procedure

1. Tubing pickling stage/wellbore cleanup

Typical overflushes for mud acid treatments are:

Figure 9-18 Diversion selection workflow

Injection pressure and rate strategy- Design model

Pinj max = ( FG H mp ) - Ph + P fr(i, j,k) - FS

P = 1.67 Qi max Pinj max (kW) (9-5)

Qimax maximum injection rate of acid (m3/min)

Acid treatment volume and rate guidelines

Table 9-14 Recommended volume of treatment fluid

The most frequent additives used in OMV Petrom are:

9.4.3 Carbonate Acidizing Best Practices

Fluid Selection for Carbonate Acidizing

Petrophysics/Reservoir Properties such as distribution, type of porosity and reservoir permeability

Carbonate Acidizing Fluid Selection Workflow

Figure 9-20 Fluid selection workflow for carbonate acidizing

Design procedure for Carbonate Acidizing