PERFORMANCE OF DIFFERENT ACIDS WITH VARIOUS FORMULATIONS

FOR SANDSTONE FORMATIONS (TERENGGANU SAND)

by

TIRZA HAHIJARY

(12300)

Dissertation submitted in partial fulfillment of the requirements for the

Bachelor of Engineering (Hons) Degree in Petroleum Engineering

JUNE 2012

Universiti Teknologi PETRONAS

Bandar Seri Iskandar
31750 Tronoh
Perak Darul Ridzuan
 CERTIFICATION OF APPROVAL

PERFORMANCE OF DIFFERENT ACIDS WITH VARIOUS FORMULATIONS

FOR SANDSTONE FORMATIONS (TERENGGANU SAND)

by

Tirza Hahijary

A project dissertation submitted to the

Petroleum Engineering Program
Universiti Teknologi PETRONAS
in partial fulfillment of the requirement for the
Bachelor of Engineering (Hons)
PETROLEUM ENGINEERING

Approved by,

________________
(AP Aung Kyaw)

UNIVERSITI TEKNOLOGI PETRONAS

TRONOH, PERAK
June 2012

i
 CERTIFICATION OF ORIGINALITY

This is to certify that I am responsible for the work submitted in this project, that the
original work is my own except as specified in the references and acknowledgments, and
that the original work contained herein have not been undertaken or done by unspecified
sources or persons.

______________________
TIRZA HAHIJARY

ii
 ABSTRACT

This report summarizes an experimental work about various acid used in sand acidizing
by saturating the core sample, including the literature review, the methodology, and the
result achieved from the experiment. As acidizing method has been used for many years
in oil and gas wells, it is expected to improve the performance of the core sample, which
in this case is taken from sandstone formation.

The objective of this project is to determine the most effective acid formulation that
increases the core properties the most, especially the permeability. Ten cores are
prepared from sands sample taken from Paka Beach, Terengganu, Malaysia. Analyzing
the core properties i.e. porosity and permeability will be done beforehand followed by
trial-and-error experiment in Core Analysis Lab in Universiti Teknologi PETRONAS,
Malaysia. This project only focuses in matrix acidizing method for sandstone formation,
whereby the core will be saturated with various acid formulations. The approach for the
experiment is unusual compare to common acidizing treatment as the equipments are
limited in the lab.

The literature review involved are mostly about sand acidizing, types of acids used in
general, and stages of acidizing. All is summarized from open journals found in the
internet and other sources i.e. books, thesis, etc. Methodology to achieve the project
objective is also given, which consists of research methodology, project activities,
experiment methodology, key milestone, and project Gantt chart. The result and
discussion for this project will be elaborated and conclusion will be at the end of the
report.

iii
 ACKNOWLEDGMENT

First and foremost, I thank and praise Jesus Christ for His guidance and blessings, for
without it I would not have been able to complete my final year project.

My deepest gratitude goes to AP Aung Kyaw, my supervisor who has guided me and
found time in a very busy schedule to give me knowledge and support, monitor my
progress and answer my questions.

I would also like to express my gratitude to all lecturers and friends who assisted me in
doing this project, especially Siti Nor Dahliawati bt Zulkefli for being a great partner in
this final year project.

Furthermore, I am sincerely thankful to my beloved parents, Charles C. Hahijary and

Maureen Oppier for their uncountable support and prayers during my time doing this
project.

My acknowledgement would be incomplete without giving credit to UTP, especially the

Geoscience and Petroleum Engineering Department who has allow me to use the
equipment with the assist of lab technicians guiding me through the procedures. Again,
many thanks for all of the supports received.

iv
 TABLE OF CONTENTS

CERTIFICATION OF APPROVAL .................................................................................. i

CERTIFICATION OF ORIGINALITY ............................................................................. ii

ABSTRACT ...................................................................................................................... iii

ACKNOWLEDGMENT ................................................................................................... iv

TABLE OF CONTENTS ................................................................................................... v

LIST OF FIGURES .......................................................................................................... vii

LIST OF TABLES ......................................................................................................... viii

CHAPTER 1: INTRODUCTION ...................................................................................... 1

1.1. Background .............................................................................................. 1

1.2. Problem Statement .................................................................................. 3

1.3. Objectives and Scope of Study ................................................................ 4

CHAPTER 2: LITERATURE REVIEW ........................................................................... 5

2.1. Acidizing Treatment ................................................................................ 5

2.2. Types and Stages of Acid Systems .......................................................... 7

2.3. Acidizing Damage Mechanisms ............................................................ 12

CHAPTER 3: METHODOLOGY ................................................................................... 15

3.1 Research Methodology ........................................................................... 15

3.2 Project Activities .................................................................................... 15

v
 3.3 Experiment Methodology ....................................................................... 16

3.3.1 Apparatus ....................................................................................... 16

3.3.2 Materials ........................................................................................ 16

3.3.3 Procedures ...................................................................................... 16

3.3.3.1 Preparing the sands into the core ....................................... 17

3.3.3.2 Poroperm test ..................................................................... 18

3.3.3.3 Acid Saturation .................................................................. 18

3.4 Key Milestone .......................................................................................... 19

3.5 Project Gantt Chart ................................................................................. 20

CHAPTER 4: RESULT AND DISCUSSION ................................................................. 21

CHAPTER 5: CONCLUSION and RECOMMENDATION ........................................... 26

5.1 Conclusion .............................................................................................. 26

5.2 Recommendation .................................................................................... 27

REFERENCES .................................................................................................................. 28

APPENDICES ................................................................................................................... 29

vi
 LIST OF FIGURES

Figure 1: Production improvement after hydrofluoric (HF) acid treatment

Figure 2: Paka Beach location
Figure 3: Acid flows through a sandstone matrix pore system
Figure 4: SEM micrographs
Figure 5: Project activities plan
Figure 6: PoroPerm test
Figure 7: Acid saturation process
Figure 8: Key Milestone for Final Year Project-II
Figure 9: Gantt chart for Final Year Project-I
Figure 10: Gantt chart for Final Year Project-II
Figure 11: Permeability and Porosity changes
Figure 12: Sample-6 contains HCl 12% + HF 6%
Figure 13: Sample-6 before acid saturation
Figure 14: Sample-6 after acid saturation
Figure 15: Sample-9 before acid saturation
Figure 16: Sample-6 after acid saturation

vii
 LIST OF TABLES

Table 1: Sandstone minerals solubility in HCl and HCL-HF

Table 2: Evolution of acid system guidelines for sandstone formation
Table 3: Damaging HF reactions in sandstones
Table 4: Acid concentration and perm-poro changes for each sample

viii
 CHAPTER 1
INTRODUCTION

1.1. Background

Oil and gas, known as hydrocarbons, are produced from thousands of meters
underground. They are accumulated inside a rock formation that has good porosity
and permeability. From the rock pores, they flow through the channels in between
the pores, going to the production tubing, and finally up to the surface. In the early
years of production, the flow rates of these hydrocarbons produced is promising due
to naturally high porosity and permeability of the reservoir, also because of the
pressure difference between the reservoir pressure and the bottom-hole pressure.
However, the production is going to decrease over time due to several cause i.e.
near-wellbore formation damage, clays that swells or migrates then clot the pore
spaces, reservoir pressure declines, etc.

Acidizing treatment is a common and recommended method which has been used
for many years to improve hydrocarbon production after some production time.
Figure 1 shows a graph of Nigerian oil well after mud-acid (HCl 12% + HF 3%)
and hydrofluoric (HF) acid treatment. This figure shows that mud-acid does not give
much increment in terms of production rate but on the other hand, HF gives
significant recovery for the field. This fact proves that the correct acid combination
for a particular field will increase the production of hydrocarbons.

Different types of acidizing treatments were developed i.e. matrix acidizing, fracture
acidizing, acid washing, etc. For sandstone formation, matrix acidizing should
remove the damage or plugged pores near the wellbore area so that the initial
permeability will be attained or even gets higher to produce more hydrocarbons.

1
 Figure 1: Production improvement after hydrofluoric (HF) acid treatment.

Field Overview
The cores are prepared by mixing sand sample taken from Paka Beach, Terengganu
with Epoxy Resin and Hardener (9:1 ratio). Paka area is located around 100 km
south Kuala Terengganu, the capital state of Terengganu, Malaysia, and it is facing
the South China Sea. The location of Paka Beach is shown in Figure 2 below (label
A). Although Terengganu is a well-known area for its offshore hydrocarbons
production, there is no record of oil and gas produced from Paka Beach. Yet the
project will still be continued as its main purpose is to find the most suitable acid
formulations to improve the properties of the particular formation.

2
 Figure 2: Paka Beach location

1.2. Problem Statement

The production of hydrocarbons is decreasing over time. This phenomenon may

happen because of few reasons such as near-wellbore formation damage, increased
skin factor, dissolved mineral into the pore spaces, etc. All the above reasons will
decrease the initial porosity and permeability of the formation which later on will
decline the production.

Matrix acidizing is the first recommended method to fix this problem. Yet, the
process of acidizing is unique for each formation and can’t be generalized. Factors
that affect this condition are formation history (how it was shaped), formation
location (anticline, dome, etc), and acidizing history (whether there was an acidizing
treatment had been applied into the formation or not). More damage to the
formation will occur if the acid used is not compatible with each other or with the
formation or formation fluids. By evaluating the core sample taken from the
wellbore (formation lithology, solubility, mineralogy, etc), then only we may choose
the method to optimize the production.

3
 In this project, there are constrains met along the way. The unavailability of
equipments and materials in the lab limit the experiment to be similar with ones that
have been done in the industry. Few of the restrains are the sample is not from a
real formation, there is no equipment for injecting the acids, and there is no gas
available for the SEM machine to identify the mineralogy of the cores. Yet, the
experiment will still be continued as its purpose is to find the most suitable and
effective acid formulations that increases the properties of the rocks, especially
permeability also porosity.

1.3. Objectives and Scope of Study

The main objective of this project is to determine the most effective acid
formulation that increases the core properties the most, especially permeability.
When the permeability increases, the fluid will ease to flow through the connected
pores and consequently will increase the production rate in the real formation
through the production tubing up to the surface. Yet, few prior points that have to be
taken account are:
1. To analyze the initial properties of the core (porosity and permeability).
2. To do a trial-and-error experiment that will test the effect of various acid
formulations to the core.
3. To find out the most suitable acid formulation that will increase the core
performance the most, especially permeability.

The scope of study includes:

 Conducting research, experiments, calculations and/or simulation regarding
matrix acidizing to determine acid formulations for sand formation taken
from Paka Beach, Terengganu.
 The cores are saturated with different acid formulations since there is no
equipment available for injecting the acids in the lab.
 Will be using conventional acid systems (HCl, HF, or the combination) and
boric acid only.

4
 CHAPTER 2
LITERATURE REVIEW

2.1. Acidizing Treatment

Acidizing is one of the way to optimize oil and gas production. It is now believed as
the most widely used method for stimulation and workover practices in oil and gas
industry.

Sandstone acidizing started in May 1933 by Halliburton. Hydrochloric (HCl) and

Hydrofluoric (HF) acid were pumped to 1,532 feet deep well with 11 ft of open-hole
production interval belongs to the King Royalty Company, Texas. The details of HF
composition and strength mixture are not known. Yet, the result of this acidizing
treatment was not giving good outcome and caused substantial sand production into
the wellbore.

On the other hand, Jesse Russell Wilson from Standard Oil Company of Indiana was
successfully pumping HF to sandstone formation on March 1933 which results in
more discovery of the use of HF. Based on Wilson’s findings, acid-removable
formation damage due to solids plugging is remarkable by treating the formation
with HF acid. Few experiments were conducted regarding combination of acids
used in sandstone formation, i.e. Dowell who introduced mud acid which is the
combination of 12% HCl – 3% HF in 1939, also Smith and Hendrickson who
elaborated HF reactivity and others effects in the field, etc. Since then, many matrix
acidizing treatments has been performed since the mid of-1960s. Acetic and formic
acids also have been used, in combination with HF.

There are three common methods of acidizing which are acid washing, matrix
acidizing, and acid fracturing. The main aim of these three methods is to improve
the production of hydrocarbon fluids by removing formation damage caused by

5
drilling or workover operations near-wellbore area. The mechanism of the treatment
is by pumping and injecting acid formulations to dissolve into the formations and to
achieve specific purposes i.e. penetrating the reservoir, creating wormholes,
removing near-wellbore damage, washing the reaction products, etc (different
formation has different approach and intention of acidizing treatment).

In this project, matrix acidizing method will be applied by saturating the core
sample taken from sandstone formation. In sandstone formation, matrix acidizing
treatment should be designed primarily to remove or dissolve acid-removable
damage or plugging in the perforations and in the formation pore network near the
wellbore[8]. The acid supposed to flow along and through the pores, dissolving
solids and fines occupies in the pore throats and space that restrict the flow of oil or
gas. Figure 3 shows how the acid flows in sandstone pores system. In short, matrix
acidizing is a formation damage removal treatment for sandstone formations. This
will only succeed when the formation is damaged. If it is not, the treatment cannot
be expected to increase the production significantly. Formation damage may occur
during drilling, cementing, perforating, production, workover, and stimulation.

Figure 3: Acid flows through a sandstone matrix pore system

It is important to understand the skin term occurs in the formation then followed by
the well production rate. Skin (s) is a mathematical expression of the damage
present, where flow rate (q) is expressed from Darcy’s law which is directly

6
 proportional to permeability (k). Permeability and skin factor are the most
importance variable in stimulation design. These two are preferably measured
before and after stimulation, although sometimes is not practical due to cost
constrained. Following aspects have to be investigated before treating the formation
damage:
 Reservoir geology and mineralogy
 Reservoir fluids
 Production history
 Drilling history (e.g. fluids used)
 Cementing program (e.g. cement bond logs)
 Completion and perforation reports (e.g. fluids used)
 Workover history
 Stimulation history

Skin factor: Production rate:

2.2. Types and Stages of Acid System

There are two types of acid systems which are:

1. Conventional Acid Systems (HCl, HF, CH3COOH, HCOOH, etc)
2. Retarded Acid Systems (gelled acids, chemically retarded acids, emulsified
acids).

The use of acid systems in each formation is different from one another based on
reservoir behavior and characteristic, also purposes of the treatment. For example,
the concentration of acids pumped into sandstone and carbonate formation is
different. Other example based on the types of acid systems is Conventional Acid
Systems is usually used to dissolve and react with rock matrix to achieve certain
goal i.e. increase permeability and creating flow channel for fluid to move. On the

7
other hand, Retarded Acid Systems, as it is called, is generally being applied to slow
or retard the acidizing process because the acid has penetrated too far from the
initial plan and somehow causes problems. This is usually being done by pumping
high viscosity fluid to reduce the acid transfer rate inside the rock matrix. Figure 4
is the micrographs result of pore-filling clays before and after exposure of mud acid
(HCl 12% + HF 3%) and hydrofluoric (HF) acid. It shows that after acid is being
pumped into the core sample (right micrographs), the clays that filled the pore
spaces before (left micrographs) is lessen which will increase back the porosity and
permeability, as well as the production.

Figure 4: SEM micrographs

HCl and HF have been the most common acids used in the industry. HF is the only
acid that dissolves siliceous minerals significantly. Thus mixing HF with other acid
(HCl, or boric acid) is a regular treatment to get major improvement in permeability.
The most frequent mixtures used are HCl and HF (mud acid). The concentration of

8
both acids used are varied from the low end (e.g. HCl 3% and HF 0.5%) to the high
end (HCl 12%-15% and 3%-5% HF, or more). For sandstone with high carbonate
mineral content (>15%-20%), the mixture of HCl-HF should be avoided. But,
carbonates are likely present as grain cementation in sandstones and by removing it
could diminish rock competence. Modern HF acid systems with low total acidity
(mild pH) are a good option in such cases because it reacts slowly with the
carbonates.

Besides HF, HCl is also applicable for removing certain minerals, such as CaCO3,
FeCO3, FeO2, and FeS2. Acetic acid and formic acids, which usually are called
organic acids, are sometimes used to replace HCl, especially in high-temperature
conditions, where HCl can cause severe corrosion.

For matrix acidizing, there are 3 stages involved in the treatment:

1. Pre-flush stage, to “clean and prepare” the pores without making any
damages or factures i.e. to dissolve with any carbonates if presents and to
remove formation waters with high concentration of calcium to avoid
precipitation.
2. Main stage, to remove skin damage, to prevent further fines migration, to
enlarge pores spaces, etc
3. Post-flush stage, to displace the reaction products.

In sandstone formation, there are four main categories of minerals: silica (quartz) -
the main mineral, feldspars, clays, and carbonates, whereas typical acid that are
generally used consists of 15% hydrochloric (HCl) acid as pre-flush fluid and mud
acid (HCl 12% and HF 3%). The reaction of mud acid keeps the pH low and
prevents detrimental precipitation. Mud acid also dissolves in siliceous materials
and clays. Injecting hydrofluoric (HF) acid alone is highly not recommended for
sandstone formation with high carbonate content because it can results in CaF2
precipitation.

9
Retarded hydrofluoric-based acid (RHF) is also sometimes used in stimulation for
sandstone reservoir. The goal of RHF is to decrease the reaction rate of HF with
clays and feldspars, to enhance acid penetration in the formation and to remove
deeper formation damage. RHF is usually based on three acids which are:
1. Boric Acid (H3BO3)
2. Aluminum Chloride (AlCl3)
3. Phosphoric Acid

All three listed acids above are the examples for hydrofluoric-based acid, means
they can react with sandstone formation in the stimulation. For example, boric acid
is the most common acid used to neutralize active hydrofluoric acid (HF).
Moreover, when HF reacts with boric acid (H3BO3), the outcome will be fluoboric
acid (HBF4). Equations 1 and 2 explain the reactions below.

Fast Reaction:
H3BO3 + 3HF  HBF3OH + 2H2O (1)

Slow Reaction:
HBF3OH + HF ↔ HBF4 + H2O (2)

As HF acid spends on siliceous minerals, HBF4 hydrolyzes to regenerate HF (the

[5]
reserve reaction of equation (2) . Table 1 portrays the solubility of sandstone
minerals in HCL and HCL-HF.

10
 Mineral Solubility in HCl Solubility in HCl-HF
Quartz Not Very low

Feldspars Low to moderate Low to moderate

Clays Not High

Kaolinite Not High
Illite Not High
Smectite Not High
Chlorite Low to moderate High

Carbonates High High

Calcite High High
Dolomite High High
Ankerite High High
Slderite High High
Table 1: Sandstone minerals solubility in HCl and HCL-HF[8]

Although by injecting RHF makes the process more complex, RHF is less reactive
and less damaging for the rock formation, thus results in deep penetration. From the
study that had been done, RHF acids react rapidly with clay minerals and slowly
with sand particles. The used of RHF decreases the dissolution of clays, but it also
increases the soaking time by the precipitation. Concisely, retarded acid systems
should only be used to remove deep formation damage.

Types and concentrations of acid injected into the formation depend on mineralogy
and bottomhole pressure. Thus, information such as type and extent of formation
damage, location of the reservoir, formation history, and mineralogy are very
important elements before starting the acidizing treatment.

Table 2 shows the evolution of acid system guidelines for sandstone formation from
year 1983 to 1990. From this table, the rule of acids formulations for sandstones
formations is improving from time to time, especially in currents days. More detail
guideline is available and open to the industry. Now, knowledge based systems
incorporate hundreds of rules of fluid choice.

11
 Table 2: Evolution of acid system guidelines for sandstone formation

2.3. Acidizing Damage Mechanisms

Acids combination can cause risks such as fines migration, precipitation of reaction
products, and rock deconsolidation. These risks could be minimized by pumping the
right volume and concentrations of acids.

Few mechanisms that could damage the formation are use of incompatible additives
or improper mixing, re-precipitation of acid reaction products, loss of near-wellbore
formation compressive strength, formation of emulsions and sludge, and post-
treatment fines migration. Those mechanisms can cause severe damage to the
formation and is sometimes irreversible. Thus, evaluating all formation
characteristics is very crucial before applying acidizing treatment.

12
 Precipitation usually occurs when HF is injected into the formation. This
phenomenon sometimes has to be taken account for as the precipitate(s) would
damage the formation more. Table 3 below shows the precipitation of HF in
sandstone formation

Reaction Precipitate(s)
HF + carbonates (calcite, Calcium and magnesium fluorides (CaF2,
dolomite) MgF2)
HF + clays, silicates Amorphous silica (orthosilicic acid,
H4Si(OH)4)
HF + feldspars Sodium and potassium fluosilicates (Na2SiF6,
K2SiF6)
HF + clays, feldspars Alumunium fluorides (AlFn3-n), aluminum
hydroxides
HF + Illite Na2SiF6, K2SiF6
Spent HF + formation brine, Na2SiF6, K2SiF6
seawater
HCl-HF + iron oxides and iron Iron compounds
minerals
HF + calcite (calcium carbonate) Calcium fluosilicate
Table 3: Damaging HF reactions in sandstones

Although precipitate(s) damage the formation, they are not completely avoidable,
but they can be minimized by using proper fluid selection, modern acid system use,
and treatment design.

It is also common in sandstone acidizing to have post-treatment fines migration.

New fines and mineral may be generated by HF reaction, particularly clays and
certain zeolites, although they rarely occur. The fines plug the pore throats and
reduce permeability, instead of increasing it. This mechanism can be minimized by
slowly bringing on the well and not maximizing return production right away. By

13
doing this, the fines have less chances to accumulate at pore throats and restrict the
flow of the fluids. It is called a bottleneck, or a traffic engineering problem.

Sandstone acidizing is only effective when formation is present. The right type of
acid must be used to remove the damage. For example, when siliceous fines are
present, HCl should not be used as it will not dissolve the plugging solids. On the
other hand, HF should not be used to remove calcium carbonate (CaCO3) solids or
scales other than silica.

The correct volumes or concentration of acids is also as important as the acids

choice. Some formations are very sensitive to volumes of acids, especially HF. High
clay content in sandstone could be damaged by high-strength HF solutions by the
re-precipitation of reaction products near wellbore. HCl can be very damaging to
sandstones containing high levels of iron chlorite clay and certain zeolites[8].

In conclusion, three main points that have to be followed to have a successful

sandstone acidizing treatment are:
1. Determine the correct candidate well for the stimulation.
2. Design an effective treatment.
3. Monitor the treatment for subsequent improvement.

All is begun by analyzing the well performance and reservoir properties, followed
by determining whether skin damage is present; determine the appropriate fluids,
acid types, concentrations, and treatment volumes; establish a proper treatment
additive program; determine the treatment placement method; ensure proper
treatment execution and quality control; and finally evaluate the treatment. In this
way, the acidizing can be successful and the main objectives may be achieved.

14
 CHAPTER 3
METHODOLOGY

3.1 Research Methodology

In order to achieve project objectives, some research is being done on acidizing

treatment, especially matrix acidizing method using both conventional and retarded
acid systems. Useful information is obtained from open journals and technical
papers provided in the internet.

3.2 Project Activities

The overall project activities are shown in Figure 5 below:

Figure 5: Project activities plan

During the first semester for Final Year Project (FYP-I), title selection, literature
review regarding the study, and obtaining the sand sample from Paka Beach,
Terengganu was done. The experiment starts on the second semester (FYP-II). The
sand sample was compressed to a core and was evaluated in core analysis lab for its
properties i.e. porosity and permeability.

15
 With these data, the acidizing experiment may begin. The core was saturated in
different acid formulations by trial-and-error experiment. By looking at the results
later on, the acid formulation that improve the core’s performance (especially
permeability) the most will be selected. All procedures will be recorded and written
down on the reports along the experiment and be finalized in Final Report or
Dissertation.

3.3 Experiment Methodology

3.3.1 Apparatus
Sieve shaker, PVC pipes, Laboratory Weighing Scale, Rectangle Plastic Container,
Coring Machine, Caliper, VINCI Poroperm, 50mL and 100mL plastic Measuring
Cylinders, 600ml Plastic Beaker, Clamp, Plastic Desiccators, Blue Silica Gel,
Pump, Fume Hood, Magnetic Stirrer, Hotplate, and Convection Oven.

3.3.2 Materials
Paka sands, Epoxy + Hardener (9:1 ratio), Pipe Water, Cements, Helium gas,
Distilled Water, HCl 37%, HF 48%, and Boric Acid.

3.3.3 Procedures
This experiment consists of two main parts, before and after acidizing. The first part
consists of molding the sand sample into ten cores for ten runs of experiments and
tests the core initial properties (porosity and permeability) before acid saturation.
The sand obtained from Paka is filtered using sieve shaker then 600 µm, 425 µm
and 300 µm grains are chosen to be molded. The grains are mixed in PVC pipes
with epoxy resin and hardener with 9:1 ratio, and then they are cemented to be
drilled with coring machine to get the correct core size for poroperm machine. The
porosity and permeability of all cores are tested using VINCI Poroperm apparatus
by injecting Helium (He) gas. All experiments are run in room temperature and
pressure, handled with serious precautions and personal protective equipment (PPE)
as the acids used are corrosive and dangerous for any contact with body skin.

16
The second part of the experiment is saturating the cores with different acid
formulations followed by testing the cores properties afterward. The cores are
saturated inside a desiccators placed in a fume hood for 4 hours. Total solution for
each experiment is 250ml of acid(s) including distilled water, calculated with molar
formulas:
M1V1 = M2V2 (3)

M1 = concentration of the initial acid (HCl 37% or HF 48%)

V1 = volume of acid required in the solution
M2 = concentration of the required acid in the solution
V2 = volume of total solution = 250ml
*Calculation for acid concentrations is attached in Appendix A

Scanning Electron Micrographs (SEM) is also being run before and after the
saturation process. The purposes of SEM are to observe the reaction between acids
and the core, and to analyze the permeability and porosity changes from the
micrographs image. The machine used for SEM is “LEO 1430 UP” which utilized
electric power, transferred to current, and turned into X-Ray energy. The cores have
to be crashed into very small piece of rocks and be vacuumed first before they are
put inside the SEM. The duration of SEM for each core is around 5-15minutes,
depends on how many data and how details we want to investigate the core. We can
also magnify the core in SEM for clearer and more specific picture of the grains.

3.3.3.1 Preparing the sands into the core sample

1. Dry the sands for 1 day until it feels waterless.

2. Filter the sands with sieve shaker for 10 minutes and take the 600 µm, 425 µm,
and 300 µm size grains.
3. Mix 400gr of grains with 80ml of Epoxy resin + 8ml of hardener (9:1 ratio) in
PVC pipes with diameter of 2 in. and 0.5 ft long pipe for 2 cores.
4. Repeat step-2 for another 4 pipes for total of 10 cores.

17
5. Wait until all cores harden for 2 days.
6. Cement the pipes in a square container and dry it for 2 days.
7. After the cement is hardened, take out the hardened cement, saw the PVC pipes
to release the core, and then drill and trim the cores with desired diameter and
length for Poroperm machine, which for this experiment is 1 in. diameter and 2 in.
long.

3.3.3.2 Poroperm test

1. Put the core inside the suitable core holder according to its size, in this case is 1
in. holder. Tie all screws until they are tight.
2. Open the Helium (He) gas tank valve.
3. Set the confining pressure to 300 psi.
4. Run the software and wait for the result of both properties (porosity and
permeability).
5. Write down all result.
6. Vent the confining pressure and unload the core from the holder.
7. Repeat step 1-6 to another 9 cores.
8. Close the He gas tank valve at each experiment.

3.3.3.3 Acid Saturation

1. Determine the desired volume of acid(s) and distilled water used using 50mL and
100mL plastic measuring cylinders. The total solution for each experiment is 250ml
with different combination and concentration of acids.
2. Saturate each core in a 600ml plastic beaker inside closed desiccators (with blue
silica gel at the bottom part) connected with pump in an active fume hood.
3. Turns on the pump inside fume hood for 30minutes then turn it off so there will
be no free air inside the desiccators.
4. Saturate the core for 4hours.

18
 5. Take out the core using the clamp, dry it with compressed air and put inside the
oven for 12hours.
6. Take out the desiccators with all the connected pipes and then wash it.
7. Take out the core(s) from the oven and run the porosity and permeability test
once again for after acid data.

Figure 6: Poroperm test Figure 7: Acid saturation process

3.4 Key Milestone

Figure 8: Key Milestone for Final Year Project-II

19
3.5 Project Gantt Chart

Below are the project Gantt chart for both semester of Final Year Project (FYP-I
and FYP-II).

Figure 9: Gantt chart for Final Year Project-I

Figure 10: Gantt chart for Final Year Project-II

20
 CHAPTER 4
RESULT AND DISCUSSION

This experiment does not imply common acidizing treatment, since the cores are
only saturated in acid, not injected. It also does not go through all stages of
acidizing process i.e. pre-flush, main treatment, and post-flush. As mentioned
before, the main function of matrix acidizing in sandstone formation is to remove or
dissolve acid-removable damage or plugging in the perforations and in the
formation pore network near the wellbore[8]. Permeability and skin factor are the
major aspects to be considered before and after the stimulation. Minerals and fines
migration can occur during well operations, but for this experiment the objective
that will only be considered is to determine the correct acid concentration to
increase the low permeability of the core samples.

The result for the first poroperm experiment (before acid saturation) is uncommon
compared with normal sandstone core from the real formation. The author supposes
that the mixture of sand grains and epoxy resin + hardener does not create a good
pore spaces for the core. This can be seen from Scanning Electron Micrographs
(SEM) figure later. Details reason is unknown but the author assumes that the resin
reacts as cement and closes the connection between the pores. Also because the
grain size of the cores is coarse, there are not many spaces to be occupied by fluids.
Moreover, the cores are not prepared with formation temperature or pressure, which
makes them more distinct with usual core sample taken from the wellbore. These
are few reasons why the values for permeability and porosity are very small.

Table 4 shows acid concentration used for each sample and the result after acid
saturation, which are significantly increased except for Sample-9 which was
saturated in fluoboric (boric acid + HF).

21
 Sample HCl(%) HF(%) Δф (%) Δk∞ (%)
1 12 3 -13.35 -13.39
2 12 5 86.67 409.09
3 12 6 235.97 470.87
4 12 8 172.03 582.05
5 15 3 15.33 74.32
6 15 5 17.06 603.37
7 15 8 116.29 417.02
8 15 6 66.29 301.11
9 Fluoboric Acid - -95.73 -22.73
10 15 - -57.68 23.15

Table 4: Acid concentration and perm-poro changes for each sample

From the result, the most increment for permeability is shown by Sample-6
(603.37%) which saturated in HCl 15% + HF 5%. Sample-3 increased the porosity
the most (235.97%) and increases the permeability quite high (470.87%), saturated
in HCl 12% + HF 6%. Fluoboric acid decreases both permeability (-22.73%) and
porosity (-95.73%). Figure 11 presents the graphical results of both permeability
and porosity changes.

Perm-poro change Porosity Permeability

300 700 P
P e
o 250 600 r
r m
200 500 e
o
s 150 400 a
i b
t 100 300 i
y l
50 200 i
(

t
% 0 100
y
)

-50 1 2 3 4 5 6 7 8 9 10 0
(

%
-100 -100
)

Sample

Figure 11: Permeability and Porosity changes

22
By observing the graph above, it appears that acids concentration is not necessarily
proportional with permeability and porosity increment. For example, HCl 12%
increase the porosity more than HCl 15% but not implied for the permeability.
Sample-3 and Sample-4 shows higher permeability compare with Sample-7 and
Sample-8 with the same concentration of HF. Yet, HF 8% does not yield the highest
result although it is the highest concentration of HF used. The result indicates that
the right amount and combination of acids used, HCl + HF, will result in optimum
increment, not necessarily the amount of concentration only.

Furthermore, for this experiment, hydrochloric acid (HF) gives significant effect to
the core. Based on the result, by saturating Sample-10 in a solution containing
hydrochloric acid (HCl) only will not give a good result, as the porosity is
decreasing (-57.68%) and the permeability is slightly increasing (23.15%). It can be
concluded that this type of cores does require HF to increase their properties, both
permeability and properties.

As mentioned earlier in the literature review, HF is the only acid that dissolves
siliceous minerals significantly. The concentration of HF used normally does not
exceed 3%, except under special circumstances e.g. conglomeratic sands, and other
consolidated sands. Nevertheless, HF concentration can be increased up to 5%-10%.
The only approach to prove the advantage of using a high-concentration HF mixture
in a conventional procedure is through core flow testing, which in this experiment is
being applied although not using the actual formation core of interest.

The problem with high-concentration of HF in combination with excess HCl is that

the mixture will damage the the rock competency and lead to near-wellbore
formation failure, sloughing in perforation thus to sand production.

Back to the formation characteristic itself, in certain cases, sandstone acidizing with
high-concentration of HF can be successful and will not damage the formation until
significant extent. History proved that by using HCl 12% + HF 10% created

23
channels in sandstone formation in the Cook Inlet of Alaska in the late 1960s. From
the experiment, the high-concentration HF created channels between grains, re-
precipitation and fines migration can be overcome, as evidenced in core testing.

By considering and understanding the explanation above, the result for this project
may be considered reasonable as the HF affects the permeability changes
appreciably. The permeability increases quite high when high-concentration HF is
used in the solution. Yet, this result can’t be applied directly to similar or nearby
formation because it is only done in atmospheric condition (pressure and
temperature) and not in the real formation condition (high pressure and high
temperature). Also, high-concentration of HF may lead to more formation damage.
Thus, all considerations have to be taken into account before deciding the acids
combination used.

Figure 12 shows how Sample-6, which gives the highest increment for
permeability, reacts with the acid combination. The color will turn more yellow
when the acids react with the core.

Figure 12: Sample-6 contains HCl 12% + HF 6%

24
Scanning Electron Micrographs (SEM) has been run to see the effect of
permeability and porosity changes. From the result, SEM illustrates how the acid
combinations whether opens or closes the pore spaces between the grains, depends
on what combinations of acids used. For example, SEM for Sample-3 and Sample-6
prove that the acid mixtures used (HCl + HF) successfully increases the
permeability and porosity by abundant pore spaces and channels in between the
grains. The enlarged figure of SEM also shows that the combination of HCl + HF
obliterate the sealed pore spaces thus creating channels, in contrast with fluoboric
acid. SEM for Sample-9, saturated with fluoboric acid, shows the bonding between
grains and epoxy resins + hardener doesn’t break and create no pore space there.
This is why the permeability and porosity decreases.

Figure 13: Sample-6 before acid saturation Figure 14: Sample-6 after acid saturation

Figure 15: Sample-9before acid saturation Figure 16: Sample-9 after acid saturation

25
 CHAPTER 5
CONCLUSION and RECOMMENDATION

5.1 Conclusion

In sandstone formation, matrix acidizing treatment should be designed primarily to

remove or dissolve acid-removable damage or plugging in the perforations and in
[8]
the formation pore network near the wellbore . In this experiment, the acidizing
treatment is used to increase rock properties, especially permeability, by saturating
the core samples taken from Paka Beach, Terengganu, in various acid combinations
with different concentrations. For this project, the author use and mix Conventional
acid systems e.g. Hydrochloric (HCl) acid, Hydrofluoric (HF) acid, and the most
common Retarded hydrofluoric-based acid (RHF) which is fluoboric acid. From the
results, the highest permeability is obtained by saturating the core sample in a
mixture of HCl 15% + HF 5%, whereby the highest increment for porosity is
achieved by saturating the core with HCl 12% + HF 6%. On the other hand,
fluoboric acid gives the lowest increment and decreases both permeability and
porosity. Scanning Electron Micrographs (SEM) shows the proof of permeability
and porosity increment or decrement from the figures attained.

By analyzing all results, permeability and porosity changes also the SEM figures,
the author may conclude that the amount of acids used is not necessarily
proportional with permeability increment. The proper combination and
concentrations of acids will give higher increment based on acid solubility of the
rock itself. Higher amount of acids does not always result in higher permeability.
Also for this type of sample, HF is required in order to create channels in between
the pores. Yet, it is important to be taken into account that the acids combination
may not be suitable for the real formation as the experiment was not done at real
formation condition, and the cores were only saturated in acids not injected.

26
 In conclusion, conventional acid systems are proven to increase the permeability
and porosity of the sample from sandstone formation.

5.2 Recommendation

After all work has been done and the author has come out with the result, there are
few things to be considered for improvement regarding this project. After doing this
project for two semesters, the author has obtained the importance and the effect of
matrix acidizing. The main objective of this project is to determine the most suitable
acid formulation for sandstone formation taken from Terengganu sand. It is
recommended to prepare the sand sample in formation pressure and temperature,
which can give more accurate data for permeability and porosity test. Furthermore,
the author suggested UTP to provide machines or equipment that can be used for
matrix acidizing. The tools would be very beneficial for more research that will be
held later on for the university.

27
 REFERENCES

1. Cleansorb Limited. 2006. Acidizing Oil and Gas Reservoirs: Current Practice
and Applications of the Arcasolve Acidizing Process. Arcasolve Technical
Document ATD-B1.
2. Boussa, M. Bencherif, D. and Khodja, M. 2009. “Optimization of Production
Gas Wells by Acidizing Using PLT Interpretation in Hassi R’Mel Field,
Algeria”, paper JCPT , May 2009, Volume 48, No. 5.
3. Crowe, C. Jacques, M. Touboul, E. and Thomas, R. 1992. Trends in Matrix
Acidizing. Schlumberger Oilfield Review published on October 1st 1992, Volume
4, Issue 4.
4. NN. “CHAPTER 4, RESULT AND DISCUSSION”. 2011. Masters in Petroleum
Engineering, Universiti Teknologi Petronas.
5. McBride et al., 1979; Kunze and Shaughnessy, 1980
6. LIBERTY. June 22, 2009. “MUD DISSOLVING ACID (MDA)”. Liberty
Pressure Pumping, L.P., TX 76205, 940-243-1120.
7. Al-Dahlan, Mohammed N. Nasr-El-Din, Hisham A. and Al-Qahtani, Abdulqader
A. 2002. “STIMULATION OF SANDSTONE RESERVOIRS USING
HYDROFLUORIC-BASED ACIDS”, Saudi Aramco Journal of Technology,
2002.
8. Kalfayan, Leonard. 2008. PRODUCTION ENHANCEMENT with Acid
Stimulation. 2nd Ed. Tulsa, USA.
9. www.wikipedia.org/wiki/Boric_acid

28
 APPENDICES

Table 1: Perm-poro data before acid saturation

Input
Sample d (mm) L (mm) Weight (gr) Vp (cc) kair (md) k∞ (md) Vgrain (cc) b (psi) ф (%) Vbulk (%) ρgrain (cc) ρbulk (gr/cc)
1 25.2 50.6 44.15 2.182 17.079 14.641 23.055 2.374 8.65 25.237 1.934 1.767
2 25.1 51.4 46.85 -2.441 0.064 0.044 27.874 6.704 -9.6 25.433 1.681 1.842
3 25.3 50.8 43.73 0.738 0.127 0.127 24.8 0 2.9 25.538 1.763 1.712
4 25.1 50.4 46.06 -1.275 0.043 0.078 26.214 -6.366 -5.113 24.938 1.757 1.847
5 25.1 51 45.9 -0.677 0.035 0.074 25.912 -7.571 -2.7 25.235 1.771 1.819
6 25.1 51 44.3 1.803 0.208 0.208 23.432 0 7.15 25.235 1.891 1.755
7 25.14 51.56 45.893 -2.233 0.107 0.094 27.827 2.003 -8.724 25.594 1.649 1.793
8 25.16 51.86 51.39 -2.233 0.128 0.09 28.006 5.94 -8.62 25.784 1.783 1.937
9 25.13 51.39 46.16 -1.169 0.126 0.132 26.658 -0.636 -4.586 25.489 1.732 1.811
10 25.16 51.68 48.935 -1.791 0.114 0.108 27.485 0.692 -6.931 25.694 1.78 1.905

Table 2: Perm-poro data after acid saturation

Input
Sample d (mm) L (mm) Weight (gr) Vp (cc) kair (md) k∞ (md) Vgrain (cc) b (psi) ф (%) Vbulk (%) ρgrain (cc) ρbulk (gr/cc)
1 25.2 50.6 44.49 1.891 14.887 12.681 23.346 2.48 7.495 25.237 1.906 1.763
2 25.1 51.4 46.158 -0.323 0.224 0.224 25.756 0 -1.27 25.433 1.792 1.815
3 25.3 50.8 43.261 2.488 0.826 0.725 23.05 1.984 9.743 25.538 1.877 1.694
4 25.1 50.8 45.453 0.926 0.532 0.532 24.211 0 3.683 25.136 1.795 1.729
5 25.1 51 45.73 -0.577 0.129 0.129 25.812 0 -2.286 25.235 1.772 1.812
6 25.1 51 44.198 2.112 1.567 1.463 23.123 1.02 8.37 25.235 1.911 1.751
7 25.14 51.56 45.314 0.364 0.486 0.486 25.23 0 1.421 25.594 1.796 1.771
8 25.16 52 49.501 -0.751 0.37 0.361 26.604 0.369 -2.906 25.853 1.861 1.915
9 25.13 51.39 46.089 -2.2899 0.102 0.102 27.777 0 -8.976 25.489 1.659 1.808
10 25.16 51.68 48.901 -2.808 0.127 0.133 28.502 -2.016 -10.929 25.694 1.716 1.903

Figure-1: Porosity values before and after acid saturation

29
Figure-2: Permeability values before and after acid saturation

Figure-3: Sand preparation into core in PVC pipes

30
Figure-4: After the core is hardened and taken out from PVC pipes

Figure-5: The cores are cemented in a rectangle plastic container

31
Figure-6: The cores after being drilled to a size of 1.5” diameter and 2” long

Figure-7: VINCI Poroperm machine

32
 Figure-8: Boric Acid

Figure-9: Boric Acid preparation in fume hood using warm water (50oC)

33
 Figure-10: Acids used (HCl, HF, Boric Acid)

Figure-11: SEM picture for Sample-0, Sample-3, Sample-6, and Sample-9

Sample-0 (original sample) Sample-3 (highest porosity)

Sample-6 (highest permeability) Sample-9 (lowest porosity and permeability)

34
Appendix A
Example calculation:

► To make a solution of HCl 15% + HF 3% in 250ml total solution

Initial concentration of HCl : 37% for all acids combinations, initial

Initial concentration of HF : 48% concentrations of HCl and HF are the same

HCl 15%  M1V1 = M2V2

 (37%) (V1) = (15%)(250mL)
 V1 = VHCl = 101.35mL

HF 3%  M1V1 = M2V2
 (48%) (V1) = (3%)(250mL)
 V1 = VHF = 15.625mL

Distilled water  (250-101.35-15.625)mL = 133.025 mL

~ For other acids combinations, the calculation is the same with different V 1 and M2 values ~

► To make fluoboric acid in total of 250mL solution.

Fast Reaction:
H3BO3 + 3HF  HBF3OH + 2H2O

Slow Reaction:
HBF3OH + HF ↔ HBF4 + H2O

o Boric acid is in solids form, with MW = 20.01gr/mol

o mass = Molar x Volume x MW = (1) x (0.25L) x (20.01gr/mol)
= 15.4575gr
o mass of HF 3M = 31.2656gr; ρHF(48%) = 1.15; Volume (HF 3M)
= (mass/ρ)
= 27.187mL
o mass of HF 1M = 10.4218gr; Volume (HF 1M)
= (mass/ρ)
= 9.062mL
o Volume (distilled water) = (250 – 27.187 – 9.062)mL = 213. 751mL

35
Steps:
1. Mix 3M of HF (27.187mL) with boric acid (15.4575gr H3BO3) together with
distilled water required (213.751mL) using magnetic stirrer on hotplate, placed
inside the fume hood.
2. Set the hotplate temperature to 50oC, stir for one hour until the mixture blends
and no solids can be seen.
3. Add 1M of HF (9.062mL) into the solution and stir again for one day (24hrs)
with the same temperature.
4. Saturate the core for 4-hours like other samples.

36