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CHAPTER I

THE PROBLEM AND ITS BACKGROUND

Introduction

During the late 1900s, a group of drilling crew used various muddy slurry of

water and clay as drilling mud, while drilling an oil well in Spindle Tops Texas. To

this date, drilling fluids are still the same as drilling mud, but its composition has

changed from a mixture of water and clay to bentonite clay. Engineers have

formulated compounds and mixtures with both local and foreign materials to meet

specific needs of drilling operation under various drilling conditions. Drilling mud is

mainly used in drilling oil and gas wells.

The role of drilling fluid in lubricating the drill sting tends to be overlooked,

but current trends in drilling make the function increasingly important. Friction in

high-angle hole can result in serious problems in torque and drag. Both torque and

drag are assumed to be caused entirely by sliding friction forces that result from

contact of the drill string with the wellbore. Factors affecting sliding wellbore friction

are normal contact force and coefficient of friction between the contact surfaces.

Drilling mud has a mixture of two or more phases consisting of a liquid

phase (water, oil, or other synthetic oil) and a solid phase consisting of clay mixed

with addition of certain chemical substances (additives) which can bring great

benefits to the drilling operations like it is used to control the pH level of the drilling

mud in which also affects its viscosity in response to changing conditions in the

wellbore. The pH is a value representing the hydrogen ion concentration in liquid

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and it is used to indicate acidity or alkalinity of the drilling mud. The pH is presented

in a numerical value (0 – 14), which means an inverse measurement of hydrogen

concentration in the fluid. A pH of 7.0 is neutral, a pH lower than 7.0 is in the acidic

range, and a pH higher than 7.0 is in the alkaline range. Drilling additives were

developed to be mixed with water having a pH level from 8.5 to 10 in order for the

required reaction to occur and to provide a proper yield.

A major component in drilling operation success is drilling fluid performance.

The cost of searching for hydrocarbon reserves becomes more expensive when

drilling occurs offshore, in deep water, and in hostile environments. These drilling

environments require fluids that excel in performance. Measuring fluid

performance requires the evaluation of all key drilling parameters and their

associated cost. Simply stated, the effectiveness of a fluid is judged by its influence

on overall well cost.

There are good reasons to improve drilling fluid performance and

management, not least of which is economics. Mud may represent 5% to 15% of

drilling costs but may cause 100% of drilling problems. Drilling fluids play

sophisticated roles in the drilling process: stabilizing the wellbore without damaging

the formation, keeping formation fluids at bay, clearing cuttings from the bit face,

and lubricating the bit and drillsting, to name a few. High-angle wells, high

temperatures and long, horizontal sections through pay zones make even more

rigorous demands on drilling fluids.

Furthermore, increasing environmental concerns have limited the use of

some of the most effective drilling fluids and additives. At the same time, as part

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of the industry’s drive for improved cost-effectiveness, drilling fluid performance

has come under ever closer scrutiny.

Considering the desired formation condition and reactive chemical

compounds encountered by the drilling mud during the drilling operation, it is

necessary to continually monitor the mud properties and prescribe possible

solution to keep the fluid in good condition. Properties that must be monitored

includes; mud weight, viscosity, filtration properties, and pH value. Certain

materials are used to improve these properties.

The pH of a drilling fluid may be defined as the negative logarithm of the

hydrogen ion (H+) concentration. At any particular hydrogen ion (H+)

concentration, there is a corresponding hydroxyl ion (OH–) concentration which

will result in equilibrium. The hydrogen ion represents the acidic portion and the

hydroxyl ion the alkaline or basic portion of the solution. Freshwater normally has

an equal concentration of hydroxyl and hydrogen ions and a pH near 7, which

indicates a neutral condition. Addition of a basic material such as caustic or lime

would increase (OH–) concentration and pH, whereas an acid would increase (H+)

concentration and reduce the pH. The maximum concentration of hydroxyl ions

would result in a pH of 14, whereas the maximum concentration of hydrogen ions

would result in a pH of 0.

Generally, for steel components, corrosion rate decreases as pH increases.

At ambient temperatures, as the pH increases, corrosion rates rapidly decrease.

Rates are much slower in alkaline fluids than in acidic fluids. Little reduction in

corrosion rate is obtained as pH is increased above 10.5.

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Green Mussel Shell or the Philippine Green Mussel Shell is one of the local

materials which could improve the pH of a drilling fluid or drilling mud. They grow

in brackish and salty waters with salinity of 20-35 ppt. It contains 90 to 95 wt

percent of CaCO3 (Calcium Carbonate), which is known as a pH enhancer. Its

three layers, the inner layer, mid-layer, and outer layer, is made up of aragonite,

calcite, and chitin, respectively. Green mussels are one of the most cultured

shellfish in the Philippines, with 5,890.77 metric tons produced in 2016. No wonder

green mussel shell wastes are inevitable.

The Drilling fluid or mud circulates the entire drilling system, which is mainly

made up of steel. If the drilling fluid would be acidic, it might cause corrosion to the

entire system which could result to loss of profit or even loss of workers. Continual

monitoring is required to gather information and data delivered by the drilling fluid.

Data about the formation and wellbore is carried out by the drilling fluid together

with the drilling tools.

This study is concerned with enhancing the pH of drilling mud using green

mussel shell as local additives for the substitution of imported chemicals such as

potassium hydroxide (KOH) and sodium hydroxide (NaOH). The control of pH

value is very essential in the drilling operation as most of the equipment used are

made of metal and pH is the degree of acidity or alkalinity of a substance, hence if

the drilling mud is acidic (pH less than 7.0), corrosion of the drilling equipment

bounds to take place. Therefore, when drilling operation is being performed in an

acidic formation, the drill pipe, drill collars and drill bit will corrode as a result of the

acidity of the subsurface, hence the need of enhancing or improving the pH of the

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drilling mud has to be properly taken care of using certain pH enhancers or

modifiers.

This research therefore aims to study the suitability of green mussel shell

as local additive to enhance the pH of mud. The material is easily accessible as

waste and biodegradable hence using green mussel shells will reduce cost and

also improve waste management.

Objectives of the Study

The main thrust of the study is to evaluate the Philippine green mussel shell

waste as a pH enhancer on a water-based drilling mud.

Specifically, it aims to:

1. Prepare the raw materials, Philippine Green Mussel Shells which are

samples that are free from deformation only.

2. Simulate Utilization of water-based drilling fluid

2.1 Alkalinity of the water-based drilling fluid

2.2 Acidity of the water-based drilling fluid

2.3 Calcium carbonate content of the water-based drilling fluid

3. Conduct a laboratory testing to test Green Mussel Shell as an alternative

pH enhancer into:

3.1 Size

3.2 Amount

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4. Conduct testing of the sample to establish the following parameters:

4.1 Temperature

4.2 Stirring Rate

4.3 Time

5. Evaluate the results of the laboratory testing of treating the mud with green

mussel shells, Standard for success rate of the process:

5.1 Yield a pH result which is similar or greater than the pH of water-

based drilling mud with Sodium carbonate (NaOH) as an additive

5.2 Yield a pH result which is similar or greater than the pH of water-

based drilling mud with Potassium hydroxide (KOH) as an

additive

6. Provide an experiment manual for the evaluation of waste green mussel

shell as a pH enhancer on a water-based drilling mud.

Significance of the Study

With the purpose of improving the pH of mud with use of Green Mussel

Shells, the researchers consider that this would be advantageous to the following:

Collection of Green Mussel Shell waste as a local material in improving the

pH of mud will be a great help in the economy. This will help improve the waste

management of the country.

The following other sectors will benefit from this study:

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For the environment, this research will help lessen the amount of green

mussel shell waste because accumulation of green mussel shells will be done in

this study.

To the Batangas State University, this experiment will serve as a learning

tool to educate petroleum engineering students in the field of drilling, specifically

in improving the pH of mud.

To the Philippine Government Agencies such as Philippine National Oil

Company (PNOC), the study will be a supplementary to their research on industrial

advancement.

To the Petroleum Engineering Department, this study will serve as a

reference of the students and faculty members in their field specialization by

providing understanding about the process of using green mussel shell waste as

a local material in improving the pH of mud.

To the researchers themselves, this study will serve as a guide to pursue

their line of profession in understanding and undertaking the responsibility of

passing down their knowledge to others.

To the future researchers, the development of this project may serve as a

guide and reference for their study and related researches.

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Scope and Delimitations of the Study

The study will be focusing on the evaluation of Philippine green mussel shell

as a pH enhancer on a water-based drilling mud. This experiment will pave way to

different methods of increasing the pH of mud. Specifically, this study will cover

the preparation of Philippine Green Mussel Shells, which is of good quality. The

Green Mussel Shell will be collected from Ocean Fresh Tahong Chips

Manufacturers in Bacoor Cavite. Furthermore, the study will also involve

conducting a laboratory testing on the green mussel shell that will be produced

and compare it to Sodium carbonate (NaOH) and Potassium hydroxide (KOH) as

a pH enhancer on a water-based drilling fluid to establish the best quality of

Philippine Green Mussel Shell in terms of pH enhancing properties. The

researchers will crush the samples using a mill. Moreover, the researchers will

simulate utilization of water-based drilling fluid without pH enhancer additives and

determine its pH properties using a pH meter. Finally, the researchers will conduct

a laboratory testing on the substance that will be produced regarding the pH of the

water-based drilling fluid with green mussel shells as a pH enhancer additive using

the pH meter to evaluate its effectiveness as drilling fluid additive in terms of

workability and pH as a pH enhancer.

This experiment is conducted only as an experimental sample to be utilized

as an instructional tool, together with the developed operational procedure manual,

to complement laboratory works.

However, the study will not cover the testing of drilling fluid in the actual

modern rotary drilling complex.

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Conceptual Framework

To have an outline of the concept of the study, the researchers provided a

conceptual paradigm showing the process of the evaluation of Philippine green

mussel shell as a pH enhancer on a water-based drilling mud.

As shown in Figure 1, the conceptual paradigm of the study shows the

general steps, procedures and considerations that were presented systematically

from the conceive, design, implement and operate stages of the study.

The conceive stag shows the knowledge requirements which will serve as

the foundations of the study for the evaluation of Philippine green mussel shell as

a pH enhancer on a water-based drilling mud. The knowledge requirements

include green mussel shell, pH meter, green mussel shell mill, and a container.

The study will require knowledge on drilling which will include the principle

of drilling that includes the drilling fluid and wellbore maintenance or wellbore

stability. It also requires familiarity about the drilling fluid additives and green

mussel shell. And also, the drilling fluid properties such as pH of mud and its effect

on drilling equipment.

The study will prepare green mussel shell, conduct preliminary testing for

green mussel shell by means of calcium carbonate and its pH. The study will crush

green mussel shell by means of green mussel shell mill. Then, final testing will be

conducted in terms of suitability of green mussel shell as a local material in

improving the pH of mud.

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Lastly, green mussel shell, evaluation of Philippine green mussel shell as

pH enhancer in water-based drilling mud and experimental manual will be the

output of the study.

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Input Process Output
1. Prepare the raw materials, Philippine Green
Mussel Shells which are samples that are
free from impurities only.
Knowledge on: 2. Conduct crushing of the sample into its
powdered form to determine its actual
 Drilling potentiality as drilling fluid additive when
added to:
 Drilling Fluids a. Grinding into 325 mesh size
3. Simulate Utilization of water-based drilling
o Drilling fluid major fluid
functions a. Alkalinity of the water-based
drilling fluid
 Remove Cuttings b. Acidity of the water-based drilling
from the Well fluid Evaluation of Green
c. Calcium carbonate content of the
 Cool, Lubricate, and water-based drilling fluid Mussel Shell as a pH
4. Conduct a laboratory testing in terms of
Support the Bit and a. Increase in the alkalinity of mud
Enhancer for a Water-
Drilling Assembly b. Increase in the acidity of mud Based Drilling Mud
c. Increase in calcium carbonate
 Supports Well Bore content of mud
d. Effect of the green mussel shell in
Wall the pH of mud
 Prevents entry of 5. Actual gathering of data to establish the
following parameters:
formation fluid into a. pH of mud
the Wellbore b. pH of water-based drilling fluid
with Sodium carbonate (NaOH)
o Composition or c. pH of water-based drilling fluid
with Potassium hydroxide (KOH)
Additives of 6. Evaluate the results of the laboratory testing
Drilling Fluid of treating the mud with green mussel shells,
Standard for success rate of the process:
o Properties of a. Yield a pH result which is similar
Experiment Manual
Drilling fluid or greater than the pH of water-
based drilling mud with Sodium
 pH carbonate (NaOH) as an additive
 Green Mussel Shell b. Yield a pH result which is similar
or greater than the pH of water-
Waste based drilling mud with Potassium
hydroxide (KOH) as an additive
7. Provide an experiment manual for the
evaluation of waste green mussel shell as a
pH enhancer on a water-based drilling mud.

Figure 1. Research Paradigm of the Study

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Definition of Terms

The following terms are defined operationally and conceptually for better

understanding of the study.

Mussel. It is any bivalve mollusk, especially an edible marine bivalve of the family

Mytilidae and a freshwater calm of the family Unionidae. Worldwide in distribution,

they are most common in cool seas. Freshwater mussels, also known as naiads,

include about 1,000 known species inhabiting streams, lakes, and ponds over most

of the world. (Britannica, 2015)

Additives. These are the chemical compounds that improve the lubricant

performance of base oil. The manufacturer of many different oils can utilize the

same base stock for each formulation and can choose different additives for each

specific application. Additives comprise up to 5% by weight of some oils. (OIMCS,

2018)

Drilling Fluid. Any of a number of liquid and gaseous fluids and mixtures of fluids

and solids used in operations to drill boreholes into the earth. Classification of

drilling fluids has been attempted in many ways, often producing more confusion

than insight. One classification scheme, given here, is based only on mud

composition by singling out the component that clearly defines the function and

performance of the fluid: water-base, non-water-based, and gaseous.

(Schlumberger Oilfield Glossary, 2018)

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Water-based Drilling Fluid. It is a type of drilling mud consisting mainly of water,

which has additives to modify it and make it more effective. (Collins English

Dictionary, 2018)

pH. It is the measure of the hydrogen ion concentration of a solution. Solutions

with a high concentration of hydrogen ions have a low pH and solutions with low

concentrations of H+ ions have a high pH. (Academic Dictionary, 2014)

Corrosion. It is the deterioration and loss of a material and its critical properties

due to chemical, electrochemical and other reactions of the exposed material

surface with the surrounding environment. (CorossionPedia, 2014)

pH Meter. It is an instrument used to measure acidity or alkalinity of a solution. pH

is the unit measure that describes the degree of acidity or alkalinity. It is measured

on a scale of 0 to 14. (Omega Engineering, 2016)

Alkalinity. It is the ability to buffer acids. The measure of alkalinity is crucial in

identifying the degree of buffering water has undergone against abrupt pH

changes. It identifies whether a body of water may corrode or produce scaling.

(CorrosionPedia, 2018)

Acidity. It is the amount of acid that is in a substance. (Cambridge University

Press, 2018)

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CHAPTER II

REVIEW OF RELATED LITERATURE

This chapter presents related articles and information involved in the study,

which has been the basis of its analysis. The chapter includes the conceptual

literature and the research literature.

Conceptual Literature

1. Drilling

There are hundreds of things involved in drilling just one oil well. Drilling a

borehole typically takes one to two months, although this depends on the geology

of the drill site. The drill bit, drill collars and a drill pipe make up the drill string used

to drill the well. The drill string is a hollow assembly which is lowered into the

ground and allows the circulation of the drilling fluid to the drill bit.

Circulation of drilling fluid is often referred to as mud. World Oil’s annual

classification of fluid system lists nine distinct categories of drilling fluids, including

freshwater systems, saltwater systems, oil or synthetic based systems and

pneumatic fluid systems. Drilling fluid is used to raise the cuttings made by the bit

and lift then to the surface for disposal. But equally important, it also provides a

means of keeping underground pressures in check. Hydrostatic, overburden and

formation are the pressure that needs to be maintained to avoid drilling problems

such as stuck pipe, hole cleaning and excessive torque and drag. Hydrostatic

pressure is the pressure which is exerted by a column of water extending from a

stratum to a surface, overburden pressure sometimes called load, lithostatic or

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geostatic pressure is the pressure of the weight of overburden, or overlying rock,

on formation and formation pressure is the pressure found within the pore spaces

of the formation. Knowledge of these pressures helps to prevent damaging the

formation by exceeding the fracture pressure or allowing pressures to drop too low

allowing formation fluids to flow into the wellbore.

After maintaining these pressures and achieving the pre-depth that has to

drilled, casing and cementing would follow. The well designer must design casing

to withstand a variety of forces, such as collapse, burst and tensile failure, as well

as chemically aggressive brines. Each wellbore has four main casing components:

conductor, surface, intermediate and production casings (API Energy, 2009, p. 11).

The first casing inserted is the conductor casing. The conductor casing has the

largest diameter of four casings and once driven into place, it serves as structural

piling (API Energy, 2009, p. 4). Next, the surface casing hole is drilled, the surface

casing is inserted, and cemented in place. The main purpose of this casing is to

isolate the wellbore and protect underground aquifers (API Energy, 2009, p. 11).

After the surface casing has been cemented in position, intermediate drilling takes

place. Intermediate drilling extends the wellbore towards the point where

directional drilling begins. Following the cementing of intermediate casing, the final

hole is drilled for the placement of the production casing. This casing runs the

entire depth of the wellbore “to provide the zonal isolation between the producing

zone and all other subsurface formations. It also contains the down hole production

equipment (API Energy, 2009, p. 12).” Production casing is typically five to six

inches in diameter.

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After placing each casing, the cementing follows. Cementing is the process

of mixing slurry of cement and water and pumping it down through casing to critical

points in the annulus around the casing or in the open hole below the casing ring.

2. Drilling Fluid

Drilling fluid or Drilling mud aids in the drilling of wellbores into the surface

of the earth. It is often used during drilling oil and natural gas wells and on

exploration drilling rigs, drilling fluids are also used for much simpler wellbores,

such as water wells. A type of Liquid drilling fluid is called a drilling mud. Drilling

fluid or Drilling mud has three types, namely; non-aqueous mud, also called as oil-

based mud, water-based mud (it could either be dispersed or non-dispersed), and

gaseous drilling fluid, in which wide range of gases are used.

The main functions of drilling fluids or Drilling mud include

providing hydrostatic pressure to prevent formation fluids from entering into the

well bore, keeping the drill bit cool and clean during drilling, carrying out drill

cuttings, and suspending the drill cuttings while drilling is paused and when the

drilling assembly is brought in and out of the hole. The drilling fluid used for a

particular job is selected to avoid formation damage and to limit corrosion.

2.1 Drilling Fluid Major Functions

2.1.1 Remove Cuttings from the Well

Drilling fluid carries the rock excavated by the drill bit up to the surface. Its

ability to do so depends on cutting size, shape, and density, and speed of fluid

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travelling up the well (annular velocity). These considerations are analogous to the

ability of a stream to carry sediment; large sand grains in a slow-moving stream

settle to the stream bed, while small sand grains in a fast-moving stream are

carried along with the water. The mud viscosity is another important property, as

cuttings will settle to the bottom of the well if the viscosity is too low.

2.1.2 Cool, Lubricate, and Support the Bit and Drilling Assembly

One of the primary functions of the drilling fluid is to cool and lubricate the

bit. In addition, it also lubricates the drill stem on the well bore wall. In both cases,

it reduces down hole friction. This friction is created by a combination of drill stem

strength and rotation speed. It friction is great, the bit bearing over heat and fail,

requiring bit to be replaced more often. Frequent bit replacement is costly.

2.1.3 Supports Well Bore Wall

Drilling fluid lines the wellbore sides. This walling reduces fluid loss to the

formations, contamination and sloughing. Formation requirements determine

thickness. Low porosity formation indicates thin wall cake. Wall cake thickness is

carefully monitored and controlled. If too thick, wall cake decreases wellbore

diameter, restricts circulation and increases torque and drag. In addition, it can

make tripping the bit in and out of the hole difficult.

2.1.4 Prevents Entry of Formation Fluids into Wellbore

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Hydrostatic pressure created by the weight of the fluid column presses

against the wellbore wall. The amount of pressure is determined by the fluid

density and well depth. This pressure prevents formation fluids entering the

wellbore which, if left uncontrolled, could create a kick.

2.1.5 Provides Hydraulic Horsepower to the Bit

Fluid leaving the bit under pressure removes the cuttings from the wellbore,

helping to maintain maximum penetration rates. A hydraulic program varies

depending on such variables as pump pressure, drill stem and hole diameters. If

50% or more of the available HHP output is delivered to the bit, it is said to have a

good hydraulic program.

2.2 Types of Drilling Fluid

2.2.1 Oil-based Drilling Fluids

Oil-based drilling fluids are used to drill: water soluble formation; deep, hot

hoes; to areas subject to differential pressure sticking; drilling troublesome shale

formations. They are more expensive to make and maintain, but they do not affect

water-sensitive formations and they minimize drill string corrosion.

2.2.2 Air or Gas-based Drilling Fluids

Only about 1% of all drilling fluids are air, air-mist or gas-based. The primary

advantage of air or gas-based drilling fluid is that a faster penetration rate is

achieved. In addition, compressors are used requiring less space and equipment.

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2.2.3 Water-based Drilling Fluids

The most commonly used drilling fluids which are 98% are water-based

drilling fluid. It is used primarily because it is cheaper to maintain, easier to use,

and forms filter cake to protect the hole.

Table 1

Composition of a Typical Bentonite gel Water-based

Component Quantity Mass(kg) Volume(L) %mass %volume

Water I bbl 159 1588.99 65.33 82.49

Betonite 20 ppm 9.1 9.07 3.73 4.85

Caustic 0.5 ppm 0.23 0.22 0.9 0.12

Soda

Soda Ash 0.5 ppm 0.23 0.10 0.9 0.5

High

Viscosity 1.5 ppm 0.68 0.47 0.28 0.25


cmc

Low

Viscosity 3.5 ppm 1.59 1.09 0.65 0.58

cmc

Barite 160 ppm 72.58 17.68 29.82 9.23

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2.3 Composition or Additives of Drilling Fluid

Water-based drilling mud most commonly consists of bentonite clay (gel)

with additives such as barium sulfate (barite), calcium carbonate (chalk)

or hematite. Various thickeners are used to influence the viscosity of the fluid,

e.g. xanthan gum, guar gum, glycol, carboxymethylcellulose, polyanioniccellulose

(PAC), or starch. In turn, deflocculants are used to reduce viscosity of clay-based

muds;anionic polyelectrolytes (e.g. acrylates, polyphosphates, lignosulfonatesor t

annic acidderivates such as Quebracho) are frequently used. Red mud was the

name for a Quebracho-based mixture, named after the color of the red tannic acid

salts; it was commonly used in the 1940s to 1950s, and then was made obsolete

when lignosulfonates became available. Other components are added to provide

various specific functional characteristics as listed above. Some other common

additives include lubricants, shale inhibitors, and fluid loss additives (to control loss

of drilling fluids into permeable formations). A weighting agent such as barite is

added to increase the overall density of the drilling fluid so that sufficient bottom

hole pressure can be maintained thereby preventing an unwanted (and often

dangerous) influx of formation fluids.

3. Potassium hydroxide

Potassium hydroxide, also known as lye is an inorganic compound with the

chemical formula KOH. Also, commonly referred to as caustic potash, it is a potent

base that is marketed in several forms including pellets, flakes, and powders. It is

used in various chemical, industrial and manufacturing applications. Potassium

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hydroxide is also a precursor to other potassium compounds. In food products,

potassium hydroxide acts as a pH control agent, stabilizer, and food thickener.

This ingredient has been considered as generally safe as a direct human food

ingredient by the FDA, based upon the observance of several good manufacturing

practice conditions of use. In addition to the above uses, potassium hydroxide is

also used in making soap, as an electrolyte in alkaline batteries and in

electroplating, lithography, and paint and varnish removers. Liquid drain cleaners

contain 25 to 36% of potassium hydroxide. Medically, potassium hydroxide (KOH)

is widely used in the wet mount preparation of various clinical specimens for

microscopic visualization of fungi and fungal elements in skin, hair, nails, and even

vaginal secretions. Recently, it has been studied for efficacy and tolerability in the

treatment of warts. It was determined that topical KOH solution was found to be a

safe and effective treatment of plane warts.

(Potassium hydroxide, n.d.)

Figure 1. Potassium hydroxide

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4. Sodium hydroxide

A white, deliquescent, water-soluble solid, NaOH, usually in the form of

lumps, sticks, chips, or pellets, that upon solution in water generates heat: used

chiefly in the manufacture of other chemicals, rayon, film, soap, as a laboratory

reagent, and in medicine as a caustic.

(Sodium hydroxide, n.d)

Figure 2. Sodium hydroxide

Table 2

pH of Drilling fluid Additives

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5. Green Mussel Shell

The Asian green mussel (Perna viridis), also known as the Philippine green

mussel, is a bivalve belonging to the family Mytilidae. The mussel is economically

important in several countries where it is harvested for food. It is native in the Asia-

Pacific region and was introduced in the waters of Australia, the Caribbean, Japan,

North America, and South America as invasive species via boat hulls and water

ballasts. Mussel shells are comprised of 90 to 95 wt. percent CaCO3, making this

material an excellent potential alkalinity source for drilling muds and treatment

systems (Fig. 3). The structure of the shells is comprised of three layers: an inner

layer consisting of aragonite (a natural polymorph of calcite), a mid-layer

containing both aragonite and calcite interbedded with protein molecules, and an

outer layer made of chitin, a form of polysaccharide containing nitrogen (e.g

periostracum). The average composition of minerals in the shells is approximately

90 percent calcite and 10 percent aragonite (Hutchinson and O'Sullivan 2008). The

shell material also contains up to 10 wt. percent of organic matter including

seaweed, mussel meat remnants and organic matter (within the shell). Cavite,

which is a top producer of Green Mussel Shells also has problems when it comes

to the waste management green mussel shells. The tables listed below strongly

support the Calcium carbonate and Calcium oxide content of Green Mussel Shells

which is a pH enhancer in drilling muds. Calcium carbonate and Calcium oxide is

added to the drilling fluid or mud to enhance its pH and alkalinity.

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Table 3

Compound concentration of a Green Mussel Shell in wt. %

Table 4

Calcium carbonate (CaCO3) content of Green Mussel Shell in wt. %

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Table 6

Mineral content in Mg per 100 grams of Green Mussel Shell

Table 5

Chemical composition of shellfish and commercial CaCO3

(Green Mussel, n.d)

Figure 3. Green Mussel Shell

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II. Research Literature

Presented here are the studies related to the proponent’s target at exploring

more about drilling fluid additives.

According to Zachary A. DiLoreto, in his research about “Biogeochemical

Investigations of a Full Scale Mussel Shell Bioreactor for the Treatment of Acid

Mine Drainage (AMD), the Stockton Mine, New Zealand”, February (2016), Acid

Mine Drainage (AMD) is a persistent issue and of concern for the international

mining community. In the United States alone approximately 200,000 AMD sites

exist and in Europe there are over 5000 km of AMD impacted watersheds some

predating 1000 years (Hochella et al., 1999; Ließmann, 1992; Schippers et al.

2010; Baker and Banfield 2003). To further illustrate AMD as a global issue,

Egiebor and Oni estimated that there are 15,000 ha of land in Canada

contaminated by AMD; Harries (1997) reported 54 mine sites in Australia with

significant amounts of potentially acid forming (PAF) waste and another 62 sites

with minor amounts of PAF resulting in management costs of approximately $60

million per year. A large extent of AMD has also been documented in South Korea

with 1000 abandoned metal mines (Cheong et al., 1998; Neculita et al., 2011), and

300 coal mines generating up to 48,000 tons day1 of AMD, affecting 153 km of

streams (Ji et al., 2008; Neculita et al., 2011). Furthermore, in 2003 AMD had been

observed at approximately 450 closed mines as reported by Japan's Oil Gas and

Metals National Corporation (JOGMEC) (Koide et al. 2012). Clearly AMD remains

a major issue facing the mining industry and its large extent is echoed in several

additional studies such as Alcolea et al., (2012); Hengen et al., (2014); Nieto et al,.

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(2013). This situation illustrates the need for continued research into creation and

optimization of cost-effective treatment technologies. 1.2 Acid Mine Drainage:

Causes and Reactions Acid Mine Drainage (AMD) is the result of the oxidation of

sulfide bearing minerals, mainly pyrite, within rock from overburden, tailings and

high-walls. Oxidation of sulfides results 2. in the generation of an acidic metal and

metalloid laden effluent, as well as a variety of additional products that are

detrimental to receiving environments. These include oxyhydroxides, metal-

bearing sulfates, oxides, as well as colloidal and adsorbed material (Bigham and

Nordstrom, 2000; Jamboor et al., 2000; Evangelou and Zhang 1995; Benner et al.,

1999). Sulfide oxidation, using pyrite as the main reactant, occurs in multiple steps

as described in the following reactions (Nordstrom, 1982; Akcil and Koldas, 2006;

Blowes et al., 2013): Oxidation of pyrite through interaction with atmosphere and

oxidative waters leading to the generation of ferrous iron, sulfate, and hydrogen.

(Biogeochemical Investigations of a Full Scale Mussel Shell Bioreactor for the

Treatment of Acid Mine Drainage (AMD), the Stockton Mine, New Zealand,

DiLoreto, et.al., 2016)

Moreover, in the study of Benjamin Uster, Dave Trummi, James Pope, Paul

Weber3, Aisling D. O'Sullivant, and Chris Weisener Zach A. Diloreto entitled

“Waste Mussel Shells to Treat Aciod Mine Drainage: A New Zealand Initiative”

wherein Mine-influenced water (MIW), commonly referred to as acid mine

drainage, is a significant environmental issue in New Zealand. Even though MIW

geochemistry specific to New Zealand geology and climatic regimes has been

extensively studied, little passive treatment remediation work has been fulfilled to

27
date apart from a few small-scale trial systems (Trumm 2007; Weber et al. 2008;

Trumm et al. 2008; Pope et al. 2010; Trumm and Watts 2010). The majority of

acidic MIW in New Zealand occurs on the West Coast of the South Island of New

Zealand where the main coal fields are located. The topography of the West Coast

makes remediation efforts challenging as most of the mining sites are remotely

located on high plateaus and are surrounded by thick native temperate rainforests

established on steep slopes (Fig. 1). This tough topography combined with a harsh

climate, dominated by low temperatures with an annual mean of about 9'C and

annual precipitation of 6 meters per year, results in high MIW flows and limited

space for reclamation (Davies et al. 2011). In addition, the remote mine locations

associated with a low overall population Fi Ne ev results in a contamination largely

hidden from the public view Other political reasons explaining the lack of

remediation include the absence of a specific MIW reclamation fund (no Superfund

or Abandoned Mine Land financing plan exist in New Zealand), a vague regulation

and a poor enforcement policy. Neither the Resource Management Act nor the

Australian and New a Zealand Guidelines for fresh and marine water quality (ME

1991 U ANZECC 2000) specifically addresses MIW issues and most of the

legislative and executive work is left to the regional environmental authorities.

(Biogeochemical Investigations of a Full Scale Mussel Shell Bioreactor for the

Treatment of Acid Mine Drainage (AMD), Uster et. al., 2014)

28
Synthesis

The cited research studies were relevant to the researcher as these would

greatly help the researcher understand the properties of green mussel shell and

these would also aid as a basis for determining the parameters to be used in the

study.

According to Benjamin Uster, in his research entitled “Biogeochemical

Investigations of a Full Scale Mussel Shell Bioreactor for the Treatment of Acid

Mine Drainage (AMD), the Stockton Mine, New Zealand”, Using waste mussel

shells to treat acidic MIW Because of its relative cheap price (NZ$25-30/tonne)

and the fact that it can often be sourced close to a mine site (NZ$20-30/ tonne

transport), limestone is commonly the main alkalinity generation material used in

passive treatment systems for acidic MIW. Limestone with a purity of more than

90 wt percent CaCO3, is usually used in MIW passive treatment. Similarly, mussel

shells are comprised of 90 to 95 wt percent CaCO3, making this material an

excellent potential alkalinity source for treatment systems (Fig. 3). The structure of

the shells is comprised of three layers: an inner layer consisting of aragonite (a

natural polymorph of calcite), a mid-layer containing both aragonite and calcite

interbedded with protein molecules, and an outer layer made of chitin, a form of

polysaccharide containing nitrogen (e.g periostracum) (Fig. 4). The average

composition of minerals in the shells is approximately 90 percent calcite and 10

percent aragonite (Hutchinson and O'Sullivan 2008). The shell material also

contains up to 10 wt per- cent of organic matter including seaweed, mussel meat

remnants and organic matter within the shell) This organic matter as well as the

29
nitrogen present within the shells provides an ideal source " of labile carbon and

nutrients readily available for the microbial community that operates in a bioreactor

system. The researcher will use New Zealand Mussel as an alternative substitute

to limestone as a source of alkalinity to neutralize acid mine drainage from a waste

rock dump.

Moreover, Zachary A. DiLoreto’s study entitled “Biogeochemical

Investigations of a Full Scale Mussel Shell Bioreactor for the Treatment of Acid

Mine Drainage (AMD), the Stockton Mine, New Zealand”, Chitinous waste

materials have been investigated as an organic substrate for passive AMD

treatment utilizing sulfate reduction processes (Daubert and Brennan, 2007;

RobinsonLora and Brennan, 2009; Newcombe and Brennan 2009; Robinson-Lora

and Brennan, 2009b ). These studies demonstrated high alkalinity generation in

comparison to other organic substrates of 25.2 mg CaCO3 L -1 d -1 and metal

removal of Al, Fe, and Mn, coupled to sulfate reduction rates of 185 nmol ml-1 day-

However, crab shell chitin based bioreactors have not been examined in a 9. field

setting, are more expensive to implement than traditional substrates, and have

been shown to be most effective when amended with 30% spent mushroom

compost rather than as a single substrate (Grembi et al., 2015). A similar chitinous

waste product has been examined for use in bioreactors over the last several

years. Mussel shells contain up to 5-12wt% organic content and have a structure

that consists of sheets of amorphous CaCO3 with interlamellar sheets of chitin in

a "brick and mortar" arrangement (Jacob et al., 2008; Kawaguchi and Watabe,

1993). They host both a labile and recalcitrant carbon source containing residual

30
meat and chitinous components. The remaining 88-95 wt% of mussel shell

material consists of CaCO3 which serves to generate alkalinity making mussel

shells an ideal substrate. Trials using mussel shells were first used to treat AMD

at the Stockton Coal Mine in 2007 (Weber et al., 2008). This study assessed the

effects of infiltrating rainwater through a waste rock pile. Two piles of 250 tonnes

of acid-forming overburden were placed above lysimeters that were 4m x 10m x

0.3m. One pile was underlain by 10 tonnes of mussel shell material, the other was

a control pad. It was observed that the leachate from the mussel shell padded

overburden maintained a circum-neutral pH of 6.8 compared to a pH of 3.3 from

the control pad and that acidity was 1.9 mg L-1 CaCO3 and 350.2 mg L-1 CaCO3

respectively. These preliminary experiments showed that dissolved Fe and Al

concentrations were reduced to background concentrations of 0.5 and 0.2 mg/L in

the mussel shell leachate compared to elevated concentrations of 8.5 and 54.7

mg/L in the control pad leachate. The study also noted that total organic carbon

(TOC) and carbonaceous biochemical oxygen demand (CBOD) were elevated in

the mussel shell pad compared to the control pad due to the residual biological

tissue associated with the mussel shells. These findings were encouraging,

suggesting that the shells could be used 10. as a potential source of alkalinity

generation and promote SRB activity, which was later proven in laboratory studies.

Laboratory results from McCauley et al. (2008, 2009a , 2009b , 2010) showed that

the alkalinity generation resulted in the removal of >0.8 moles of metal m-3 day-1

, as well as achieving acidity removal rates of >66 g CaCO3 m-2 day-1 , which are

31
comparable to classic vertical flow wetlands (VFWs) and SAPs using limestone as

the sole alkalinity generating source.

Therefore, despite the similarities on the cited literature, it can be said that

this study has its own identity and is not duplication of any mentioned studies.

32
CHAPTER III

RESEARCH METHODS AND PROCEDURES

This chapter presents the discussion on the experimental methods and

procedures that will be used by the researcher in the completion of this study.

Research Design

Preparation of Green Mussel Shell

Simulate utilization of Water-Based Drilling


Fluid

Determination of properties of the produced


Water-Based Drilling Fluid

Conduct testing to establish the Size and


Amount of Green Mussel Shell to be mixed
with the Water-Based Drilling fluid

Mixing of the grinded waste green mussel


shell to the Water-Based Drilling fluid

Conduct Preliminary Testing using the


Established Size and Amount to Determine
the Best Proportion of Drilling Fluid to Green
Mussel Shell

Final Testing on the Established Ratio of the


pH Enhancer Formulation

Utilization of Green Mussel Shell as a pH


enhnacer on a Water-Based Drilling fluid

Evaluation of the properties of the Water-


Based Drilling fluid with Green Mussel Shell
as a pH enhancer

Figure 4. Schematic Diagram of the Research Experimental Process

33
The study will use experimental method to produce Green Mussel Shell

powdered form from Green Mussel Shell as a local material in improving the pH of

mud.

The first step is going to be the preparation of Green Mussel Shell. This will

include the collection of Green Mussel Shell by which the Green Mussel Shell that

will be collected will be tested for the establishment of appropriate size, amount,

as well as the proportion of the drilling fluid. After the establishment of the

properties of the sample, Green Mussel Shell will be crushed using a mill into its

powdered form. Additionally, after the establishment of its properties, as well as

the crushing of Green Mussel Shell, the Green Mussel Shell will be blended to

water-based drilling fluid or mud and will be tested for the establishment of the high

quality of pH enhancing material drilling fluid additive. Moreover, the final test will

be done on the established high-quality pH enhancing material drilling fluid

additive. Lastly, the workability and effectiveness will be evaluated.

1. Preparation of Philippine Green Mussel Shell

Philippine Green Mussel Shell will be collected from the Ocean Fresh

Tahong Chips Manufacturers in Bacoor Cavite. Green Mussel Shell will be

inspected based from the given parameters and only those of good quality

will be collected. The samples were properly sealed in plastic bags and

were kept in the laboratory at room temperature.

34
A. Green Mussel Shell Pretreatment

The Green Mussel Shell samples are pre-treated in order to make

suitable and effective raw material for preparation of a pH enhancing

material. The pretreatment process of this material consists of washing,

drying, grinding, and sieving.

B. Washing

The collected samples will be washed with double distilled water in

order to remove dust particle impurities.

C. Drying

The washed Green Mussel Shell will be dried in laboratory Oven at

temperature of 60°C for 20 hours in order to remove moisture content. The

initial and final weight of Green Mussel Shell will be measured before and

after drying of samples using laboratory analytical balance.

D. Grinding of the material

The dried pre-treated Green Mussel Shell will be grinded with help

of ball mill at specific revolution speed. The waste was grinded into fine

particle size.

E. Determining the pH level of the Green Mussel Shell powder

The Green Mussel Shell powder will be tested in a laboratory in order

to determine its pH level content.

35
2. Simulation of utilizing a Water-Based Drilling fluid

A. Alkalinity of the water-based drilling fluid

The alkalinity of the water-based drilling fluid will be tested using a

pH meter.

B. Acidity of the water-based drilling fluid

The acidity of the water-based drilling fluid will be tested using a

pH meter.

C. Calcium carbonate content of the water-based drilling fluid

The Calcium carbonate content of the water-based drilling fluid will

be tested using titration method.

3. Laboratory testing of the Green Mussel Shell

A. Size

The grinded samples were sieved through RO-Tap Type Sieve

shaker at 290 rpm speed. Fine Green Mussel Shell powder (mesh 325,

Aperture 0.045 mm, wire diameter, 30 cm) was collected from

testing.

B. Amount

As for the drilling fluid to be used, the researchers will utilize water-

based drilling fluid. Preparing 3 samples of drilling fluid with a final volume

36
of 350 cubic centimeters. For the Green Mussel Shell powder as pH

enhancer, the researchers will test 3 amounts of the said powder with 0.3,

0.4 and 0.5 grams.

4. Conduct testing of the sample to establish the following parameters:

A. Temperature

The testing of the Green Mussel Shell powder to the drilling fluid

should be at a standard temperature of 25°C.

B. Stirring Rate

In the mixing process a laboratory equipped with a hydraulic mud

mixer is needed in order to achieve and ensure that the drilling fluid with the

Green Mussel Shell powder is blended properly.

C. Time

The time required to be able to finish mixing the drilling fluid is about 15

minutes to be able to get the right consistency.

5. Evaluate the results of the laboratory testing of treating the mud with green

mussel shells, Standard for success rate of the process:

A. Yield a pH result which is similar or greater than the pH of water-based

drilling mud with Sodium carbonate (NaOH) as an additive

37
The pH of the drilling fluid with green mussel shell as a pH enhancer

will be compared to the pH of the drilling fluid with Sodium carbonate

(NaOH) as an additive. This can be established by making another

laboratory testing with the utilized drilling fluid and the green mussel shell

powder as a pH enhancer additive.

B. Yield a pH result which is similar or greater than the pH of water-based

drilling mud with Potassium hydroxide (KOH) as an additive

The pH of the drilling fluid with green mussel shell as a pH enhancer

will be compared to the pH of the drilling fluid with Potassium hydroxide

(KOH) as an additive This can be established by making another

laboratory testing with the utilized drilling fluid and the green mussel shell

powder as a pH enhancer additive.

38
BIBLIOGRAPHY

Uster-et-al-2014-Waste-mussel-shells-to-treat-acid-mine-drainage.pdf
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S1516-
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https://www.researchgate.net/publication/227753812_Heat_shocking_of_Philippi
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full-html/
http://www.ijapbr.com/a-comparative-study-in-the-calcium-content-of-the-shells-
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39