1

Chapter 1
INTRODUCTION

1.1 Background of the Study

Lignosulfonate, or sulfonated lignin are water-soluble anionic

polyelectrolyte polymers. It has a wide variety of applications. The single largest

use of lignosulfonate is as plasticizer in making concrete, where it allows concrete

to be made with less water (giving stronger concrete) while maintaining the

ability of the concrete of flow. It is also used during the production of cement,

where they act as grinding aids in the cement mill and as a raw mix slurry

deflocculant (that reduces the viscosity of slurry) [1].

Being known as “The Rice Granary of Palawan”, the Municipality of

Narra is the main rice producer of the Province. One of their common agricultural

waste is rice husk also called as rice hull (RH). Local farmers previously

struggled to dispose of due to its large volume. In 2006, Phil star reported that the

local municipality of Narra committed an area to be the site for a 1.5 MW rice

husk-fired power plant project. Unfortunately, this project is still up for debate

due to some environmental concern. Agricultural wastes like rice husk are

potential source of lignin (C9H10O2) for lignosulfonate production. Utilization of

these wastes offers another option of disposing them in a more productive and

environment friendly way [2].

Rice hull is the hard protecting cover of grain of rice. It is form from hard

materials, including silica and lignin, to protect the seed during the growing

season. Each kilogram of milled white rice results in roughly 0.28 kg of rice hull
 2

as a by-product of rice production during milling. Theoretically, its volume is

about 20% of total rice crop. Common products from rice hull are: solid fuel (i.e.,

loose form, briquettes, and pellets), carbonized rice husk produced after burning,

and the remaining rice hull ash after combustion. Rice hul in its loose form is

mostly used for energy production, such as combustion and gasification. Rice hull

ash can be used as a soil amendment and as additive in cement and steel to

increase density, among others. However, only small amounts compared to the

total rice husk production are used for such purposes [3].

The chemical composition of rice hull is similar to that of many common

organic fibers and it contains of cellulose 40-50 percent, lignin 25-30 percent, ash

15-20 percent, and moisture 8-15 percent [5].

Rice hull is a potential material, which amenable for value addition. The

usage of rice hull either in its raw form or in ash form is many. Most of the hull

from the milling is either burnt or dumped as waste in open fields and a small

amount is used as fuel for boilers, electricity generation, bulking agents for

composting of animal manure, etc. [5].

1.2 Statement of the Problem

Rice hull was long considered a waste from the rice milling process and

was often burned. But because it can be easily collected and is cheap, some

amount of rice hull has always been used as an energy source for small

applications, such as brick production, for steam engines and gasifiers used to

power rice mills, and for generating heat for rice dryers [4].
 3

Based on the report of the Provincial Agriculture Office of Palawan, an

average of approximately 108,000 metric tons of rice is annually produced in the

Municipality of Narra, Palawan from 2014-2018 [6]. An average of 22,000 metric

ton of rice hull is produced annually. This result is calculated using the percentage

amount of rice hull in rice which is 20% [3]. Reportedly, these rice hull were

thrown with no further utilization. Thus, this study aims to utilize the thrown rice

hull by extracting the lignin to produce valuable lignosulfonates. With this data,

this study sought to answer the following questions:

1. What is the amount of lignosulfonate recoverable for every 20 grams of

RC-18 rice hull?

2. Is the average annual waste production of rice hull in Narra, Palawan

enough to sustain the demand of lignosulfonate on a standard oil well

cementing job?

1.3 Objectives

This study aims to utilize the rice husks by extracting the lignin to produce

lignosulfonates that can be used in several industries such as retardation in cement

job.

Specifically:

a. To determine the amount of lignosulfonate recoverable for every 20

grams of RC-18 rice hull.

 4

b. To determine the production rate of lignosulfunate in Narra, Palawan

if it can sustain the demand of a standard oil well cementing job.

1.4 Significance of the Study

The study is useful for utilizing the potential of lignin from rice hull as

cement additive which is abundant in the locality of Narra, Palawan and put it to

good use rather than disposing by carelessly burning it that will excrete more

carbon dioxide into the air that may harm the environment. Likewise, this study

outcome will also serve as reference to other researchers who would like to

conduct related study about cementing specifically in cement additive concerns.

Moreover, cementing companies can acquire reliable and effective source of

cement retarder using lignosulfonate from lignin extracted from rice husk in most

effective environmental friendly process.

1.5 Scope and Delimitation of the Study

The study only focuses in utilizing thrown rice hull in Narra, Palawan by

extracting lignin to produce lignosulfonates. Other rice hull components will not

be included during the production.

The study will be conducted in the Provincial Engineer’s Office (PEO) in

Puerto Princesa City from June, 2019 to December, 2019. The equipment’s to be

used are available for use in the said office so are some of the chemicals. For

those chemicals that are not available in the PEO, they will be acquired from

Palawan State University (PSU) Malampaya Laboratory and DKL Laboratory

Supplies in Manila. The RC-18 rice hull will be collected from certain rice mills

of Brgy. Princess Urduja, Narra, Palawan.

 5

Other varieties of rice paddy aside from RC-18, cost and expenses of the

materials and processes are not considered.

1.6 Assumptions of the Study

The rice husk collected from different variety, classes and propagation of
rice has the same characteristics and yield of lignin when extracted.

The black liquor extracted from the rice husk has the same composition
with any other result from varying classes of rice.
 6

Chapter 2
REVIEW OF RELATED LITERATURE AND STUDIES

2.1 Rice Husk

The most visible part or a rough rice grain is the husk. This is also known

as the hull. This is formed from the two leaves of the spikelet namely the palea

covering the ventral part of the seed and the lemma covering the dorsal portion.

Both parts are longitudinally joined together by an interlocking fold. This fold is a

weak point in the hull and easily breaks up when a twisting force is applied to the

grain. The upper end of the two hull sections transfers into the apiculus sections

and finally ends in the pointed awn. [7].

At the lower part, where the grain is fixed on the panicle is a tiny leaf-

shaped part called the sterile lemma and then the rachilla. Normally the panicle

breaks off during threshing, however a small part of the pedicel frequently

remains attached to the grain. The husk is formed mostly of cellulosic and fubrous

tissue and is covered with very hard glass-like spines or trichomes. The present of

this make the husk abrasive and very hard thus, they give the grain a good

protection against insects, microrganism, moisture and gases. The caloric value to

the hulls is rather high and ranges from 3000 to 3500 kcal/kg making hulls an

important source of energy in agriculture. However, the most disturbing presence

in rice hull is high proportion of silica which causes considerable damage to

processing equipment through excessive wear of machine parts and

interconnecting transfer facilities. [7].

 7

The Rice Husk is the outermost layer of the paddy grain that is separated

from the rice grains during the milling process. Around 20 percent of the paddy

weight is husk and rice production in Asia produces about 770 million tons of

husk annually. Rice husk was largely considered a waste product that was often

burned or dumped on landfills, according to Martin Gummert, postharvest expert

at the International Rice Research Institute, [8].

In Vietnam, it used to be a waste some years ago and was dumped in the

rivers, causing a big problem, but now it has a value. In fact, in most countries,

rice husk is not waste anymore. Some enterprising companies are turning it into

various products not only for the eco-conscious market place but also for

industrial sector, [9].

2.1.1 Agricultural Production of Rice

Based on the report of the Provincial Agriculture Office of Palawan, the

data below is the annual rice production in the Municipality of Narra, Palawan

from calendar year 2014-2018 [6].

Table 2.1.1: 2014-2018 Rice Production in Narra, Palawan

TOTAL (WET & DRY)

YEAR AREA PLANTED PRODUCTION AVE. YIELD
HA Metric Ton MT/HA
CY 2014 24,382.80 93,451.30 3.8
CY 2015 27,751.50 118,363.40 4.3
CY 2016 30,193.80 96,028.85 3.2
CY 2017 28,061.70 102,827.07 3.7
CY 2018 33,660.80 127,509.51 3.8
AVERAGE 28,810.12 107,636.026 3.76
 8

2.1.2 Rice kernel composition

Most rice varieties are composed of roughly 20% rice hull or husk, 11%

bran layers, and 69% starchy endosperm, also referred to as the total milled rice.In

an ideal milling process this will result in the following fractions: 20% husk,

8−12% bran depending on the milling degree and 68−72% milled rice or white

rice depending on the variety. Total milled rice contains whole grains or head

rice, and brokens. The by-products in rice milling are rice hull, rice germ and bran

layers, and fine brokens [3].

With the given data from the Provincial Agriculture Office, the estimated

rice husk produce will be determined with the equation below.

(Average Rice Production) x (Rice Husk Percentage) = Average Rice Husk

Production (1)

Average Rice Production [6] = 107,636.026 MT

Rice Husk Percentage [3] = 20%

(107,636.026) x (20%) = 21,527.2052 MT

Approximately around 21,527 MT is the average rice husk production in

Narra, Palawan from 2014-2018.

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2.1.3 Properties and Chemical Composition of Rice Husk

The chemical composition of rice husk is similar to that of many common

organic fibers and it contains of cellulose 40-50 percent, lignin 25-30 percent, ash

15-20 percent, and moisture 8-15 percent, [5].

Rice husk is a potential material, which amenable for value addition. The

usage of rice husk either in its raw form or in ash form is many. Most of the husk

from the milling is either burnt or dumped as waste in open fields and a small

amount is used as fuel for boilers, electricity generation, bulking agents for

composting of animal manure, etc, [5] The typical properties of rice husk are

indicated in Table 2.1.3 below.

Table 2.1.3: Typical Rice Husk Properties Analysis [10]

S. No. Property Range

1 Bulk density (kg/m3) 96 – 160

2 Length of husk (mm) 2.0 - 5.0

3 Hardness (Mohr’s scale) 5.0 - 6.0

4 Ash (%) 22.0 - 29.0

5 Carbon (%) ≈ 35.0

6 Hydrogen (%) 4.0 - 5.0

7 Oxygen (%) 31.0 – 37.0

8 Nitrogen (%) 0.23 – 0.32

9 Sulphur (%) 0.04 – 0.08

10 Moisture (%) 8.0 – 9.0

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2.1.4 Characterization of Rice Husk

According to a previous study, the chemical composition of rice husks is

cellulose (25 to 35%), hemicellulose (18 to 20%), lignin (26 to 31%), silica (15 to

17%), soluble (2 to 5%), and moisture ca. 7.5%. Factors affecting the

concentration of different components varied among harvesting methods, growing

area and season, and testing procedures, [11]. The composition of the rice husks

in this study is shown in Table 2.1.4.

Table 2.1.4: The Composition of Raw Rice Husks

Component Percentage (%)

(a) Solid Holocellulose 49.72

composition α-cellulose 31.13

Acid-insoluble lignin 24.89

Acid-soluble lignin 3.36

Extractives 5.01

Ash 16.50

(b)Carbohydrate Glucan 32.61

composition Xylan 17.25

Galactan 1.28

Araban 1.52
 11

Based on the analysis procedure of (Han and Rowell, 1997), the

holocellulose concentration was 49.72% of the dry biomass. By comparing the

concentration of holocellulose and carbohydrate, the difference in percentage

could be explained by the sugar degradation caused by the hydrolysis effect of

72% sulfuric acid during the total sugar analysis experiments. The α-cellulose

content of 31.13% was nearly in the middle of the 25.89% to 35.50% range that

has been reported for other lignocellulosic materials in rice husks. The 28.25%

lignin concentration, the total amount of acid soluble lignin and acid insoluble

lignin, is also in the middle range comparing with the previously reported values.

Although acid insoluble parts always considered as lignin, other possible parts

like rice grain also resist the acid treatment and effect the actually lignin content.

Because the protein portion of the rice grain would condense and become

insoluble when treated by a high concentration sulfuric acid. However, by

comparing with the lignin percentage, rice grain only comprises a tiny part of the

totally acid insoluble material.

2.1.5 Proximate Analysis of Rice Husk

Analysis of lignin and cellulose followed the method of Chesson–Datta. A

mixture containing 1 g of dried sample (a) and 150 mL of demineralized water

was heated in the oil bath at a temperature of 100 ºC for 1 hour. The mixture was

filtered and the residue was washed with hot demineralized water (300 mL). The

residue was dried in the oven until the weight was constant (b). The residue was

mixed with 150 mL of 1 N H2SO4 (Sulfuric Acid) and heated in the oil bath at

100 ºC for 1 hour. The mixture was filtered and washed with 300 mL of water
 12

demineralized and then the residue was dried (c). The dried residue was soaked

with 10 mL of 72% H2SO4 at room temperature for 4 hours. After that, 150 mL

of1 N H2SO4 was added into the mixture and refluxed in the oil bath for 1 hour.

The solid was washed with 400 mL of water demineralized, heated in the oven at

105 ºC and weighed until the constant weight (d). Finally, the solid was heated

until become ash and weighed (e), [12]. The percentage of hemicellulose,

cellulose and lignin was calculated as follows:

% hemicellulose = (c – b)/a x 100% (2)

% cellulose = (d – c)/a x 100% (3)

% lignin = (e – d)/a x 100% (4)

Proximate analysis of rice husk in this study is using Chesson-Datta

method. Proximate analysis shows that the rice husk is containing cellulose

(35%), hemicellulose (25%), lignin (20%), and ash (17%). Silica content in rice

husk ash is (98%), [14].

Table 2.1.5: Proximate analysis of rice husk using Chesson-Datta

Parameters % weight

Cellulose 32.67

Hemicellulose 31.68

Lignin 18.81

Ash 11.88

Silica (% of ash) 91.09

 13

2.2 Lignin

Lignin is one of the important chemical constituents of lignocellulosic

materials in wood and it is one of the most abundant biopolymers in nature.

Despite extensive investigation, the complex and irregular structure of lignin is

not fully understood. The physical property and the chemical characteristics of

lignin vary not only between different wood species, but also according to the

method of isolation. Moreover, the molecular structure and function groups differ

for the various type of lignin, [13].

Lignins are polymers of phenylpropane units like guaiacyl, syringyl and

phydroxyphenyl units. These precursors are derived from three aromatic alcohols

(Ramos, 2003; Whetten et al., 1998). It is relatively hydrophobic and aromatic in

nature and is known for its heterogeneity in lacking a defined primary structure. It

is synthesized from phenyl propanoid precursors by polymerization in higher

plants. There are three different types of lignin; hardwood lignin, softwood lignin

and grass lignin. Hardwood contains about 15-35% lignin and has a much more

complex lignin structure than softwood, which consists of about 20% lignin.

Lignin fills the space in the cell wall between cellulose, hemicellulose and pectin

components, especially in tracheids, sclereids and xylem. It is covalently linked to

hemicellulose and there by crosslinks different plants polysaccharides, conferring

mechanical strength to the cell wall and plant as a whole (Chabannes et al., 2001).

Lignin is formed by removal of water from sugars to create aromatic structures

through the phenylpropanoid pathway. This reaction is irreversible. Lignin

 14

polymers are cross-connected structures with molecular weights on the order of

15,000 or more.

Grass lignin is composed of all three types of units (p-hydroxyphenyl,

guaiacyl and syringyl units) interconnected by aryl ether bonds (β-O-4 linkages)

and/or resistant C-C bonds, [14]. Lignin is hydrophobic and highly branched

polymer by the oxidative polymerization, [18]. Chemical bonds have been

reported between lignin and carbohydrates (hemicellulose and cellulose). Lignin

carbohydrate complex (LCC) is the covalently bonded aggregates. The linkages

are formed by ester, ether and glycosidic types of bonds (Sjöström, 1993). This

structure gives physical strength or rigidity to plant tissue and prevents the

collapse of the water-conducting elements (Ramos, 2003). It also protects plants

from attack by microorganisms (Moore and Hatfield, 1994; Sarkanen and

Ludwig, 1971).

2.2.1 Lignin Isolation Process

Lignin isolation process is done by using an alkaline hydrogen peroxide

(H2O2) solution. A total of 20 grams of rice husk is inserted in the neck of the

500 ml flask, then add 120 mL demineralized water containing 1% H2O2

(volume/weight ratio of 6:1). Add 2N NaOH (Sodium Hydroxide) until pH of 9.

The mixture was then isolated at a temperature of 100 °C by using the heating oil

bath at a temperature of 100 ° C for 3 hours starting after the temperature reached

100 °C. After the isolation process was complete, the solution (liquor) was

separated from the solids using a filter paper [12].

 15

2.2.2 Analysis of Lignin and Silica Concentrations of Liquor

Lignin concentration of liquor was analyzed by UV-Vis Spectrophotometer

(UV-1800 SHIMADZU) with a resolution of 1 nm. Lignin concentration is done at

the wavelength of 280. Silica concentration of liquor was analyzed by AAS (AA-

6300 SHIMADZU). Analytical process was done using silica cathode lamp at the

wavelength of 251.53 nm. Burning gasses were using nitrous oxide (N2O) and

ethylene (C2H4), [14].

2.2.3 Lignin to Lignosulfonate

A 25% solids slurry of lignin was prepared by admixing the recovered

lignin with water. Sodium sulphitewas added to the slurry at a pH of about 5.0.

Formaldehyde followed the addition of sodium sulphite in close sequence. Upon

addition of both sulfomethylation ingredients, the pH of the reaction mixture was

adjusted to various levels indicated in Figure 2.2.3. The temperature of the

reaction mixture was adjusted to 70°C and maintained at such condition for 1

hour after which the temperature was raised to 140°C and maintained for 2 hours,

[15].

Figure 2.2.3: Black Liquor from Paper Industry Experiment Results

 16

Viscosity was measured by heating the sulfonated lignin solution to about

70°C and adding glacial acetic acid slowly until a pH of 8 was obtained. The

solids concentration was adjusted to 25%. A Brookfield Viscometer (model LVT)

was used for all measurements. Measurements took place at 25°C [15].

Heat stability was determined by preparing a dye composition containing

the sulfonated lignin. The dye composition was prepared by mixing 50 grams of

Red I, 35 grams of sulfonated lignin, 123 milliliters of water and 5 drops of

Ethylenediamine tetraacetic acid (EDTA) (1% solids at pH of from 8.6 to 9.2).

The pH was adjusted to 8 with acetic acid or sulphuric acid. The dye composition

was ground in a ball mill to the point where the filter test for disperse dyes was

passed.

Heat stability was measured by adding 1 gram of the solid dye

composition to 250 milliliters of water. The solution was boiled for 15 minutes

and then filtered through a tared Whatman filter paper No. 2 above a No.4 (with

vacuum) as specified in the standard American Association of Textile Chemists

and Colorists (AATCC) heat stability test. The filter paper was dried, and the

residue dye material remaining on the filter was calculated [15].

The data in Figure 2.2.2 clearly indicate that the pH of which the

sulfonation of lignin occurs in conjunction with the mole ratio of sulfonating

agents has a substantial effect on the sulfonated lignin subsequently produced

[15].
 17

2.3 Casing Strings

Since the well is normally drilled in segments, multiple concentric casing

strings are usually installed in the well. There are six basic types of casing strings:

2.3.1 Conductor Casing

The first casing installed in the well is called the conductor casing, as

shown in the figure below. Onshore this is a short segment usually around 60 ft

(20 m) long. The conductor isolates unconsolidated formations and water sands

and protects against shallow gas. This is usually the string onto which the casing

head is installed. Conductor casing is always cemented to surface. [19]

2.3.2 Surface Casing

Surface casing must be set deep enough to protect freshwater aquifers

from contamination, and prevent lost circulation. Because of this, the surface

casing is always cemented to surface. Surface casing depths typically vary

between 1000 and 3000ft (300-900 m). [19]

2.3.3 Intermediate Casing

Intermediate casing is set to isolate unstable hole sections, lost-circulation

zones, low-pressure zones, and production zones. It is often set in the transition

zone from normal to abnormal pressure. The casing cement top must isolate any

hydrocarbon zones. Some wells require multiple intermediate strings and some

other wells do not have intermediate casing string. [19]

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2.3.4 Production Casing

Production casing is used to isolate production zones and contain

formation pressures. It may also be exposed to injection pressures from fracture

jobs, gas lift, or water injection support. A good primary cement job is very

critical for this string. [19]

2.3.5 Liner

Liner is a casing string that does not extend back to the wellhead but

instead is hung from another casing string. Liners are used instead of full casing

strings to reduce cost, improve hydraulic performance when drilling deeper, allow

the use of larger tubing above the liner top, and not represent a tension limitation

for a rig. Liners can be either an intermediate or a production string. Liners are

typically cemented over their entire length. [19]

2.3.6 Typical Casing Combination Strings

For a deeper, higher pressured well a typical casing string might be:

16″ (406 mm) Conductor

13-3/8″ (340 mm) Surface Casing

9-5/8″ (244 mm) Intermediate Casing

7″ (178 mm) Production Casing

4-1/2″ (114 mm) Production Liner

 19

2.4 Well Bore Size Selection

Selecting the bore-hole size is based primarily on current practices in the

area or areas with similar lithologies. There are a number of charts and tables in

the literature, some good for some areas, but greatly lacking for other areas. The

best advice we can offer is to use what is common practice in the area, unless

there is good reason to do otherwise. No matter what specific charts we suggest

here, they are going to be wrong for some particular locale or application.

Figure 2.4.1. starts with the last string of casing or liner and works

downward to the first casing string of the well. You can see on this chart there are

many options even for those situations where the same size liner or casing is to be

run. In general, hard rock offers us more choices, and clearance between the

casing and bore-hole wall can be less than for unconsolidated wells. Figure 2.4.2

is a similar chart for unconsolidated formations.

Note, in Figure 2.4.2, there are still some options, but not as many. A few

may not be available even though shown on the chart. For instance, on the fourth

row from the top it shows that either an 8 ½ in. or 8 ¾ in. bit may be used from

9⅝ in. casing. That may be true in some cases, but if the 9⅝ in. casing string

contains any 40lb/ft or heavier pipe, then the 8 ¾ in. bit cannot be used. What is

common practice in on area may not work in another, because formation

pressures may require a heavier pipe.

The production engineers tell us they require a production casing diameter

of 7 in., so the production casing size is determined. Assume that the well is in an
 20

area of unconsolidated formations. Use the soft formation chart to determine the

intermediate casing size, the surface casing size, and the conductor casing size:

Intermediate casing = 9⅝ in.

Surface casing = 13⅜ in.

Conductor casing = 20 in.

Although not shown in the chart as a possible path, some operators in

areas where bore-hole stability is a serious problem elect an alternative for 7 in.

casing as follows:

Intermediate casing = 10 ¾ in.

Surface casing = 16 in.

Conductor casing = 24 in.

That choice would be a case where experience in a particular area might

influence the decision in order to allow more margin for the effects of anticipated

problems. [16]

Figure 2.4.1
 21

The weight per unit volume of cement slurry, usually given in units of

kg/m3 or lbm/gal. Typical oil- or gas-well slurries have densities of 1380 kg/m3 to

2280 kg/m3 [11.5 lbm/gal to 19 lbm/gal], although special techniques, such as

foamed cementing and particle-size distribution cementing, extend this range to

840 kg/m3 to 2760 kg/m3 [7 lbm/gal to 23 lbm/gal. [17]

Figure 2.4.2

2.5 Cement Slurry Density

The weight per unit volume of cement slurry, usually given in units of

kg/m3 or lbm/gal. Typical oil- or gas-well slurries have densities of 1380 kg/m 3 to

2280 kg/m3 [11.5 lbm/gal to 19 lbm/gal], although special techniques, such as

foamed cementing and particle-size distribution cementing, extend this range to

840 kg/m3 to 2760 kg/m3 [7 lbm/gal to 23 lbm/gal. [17]

 22

2.6 Lignosulfonate Retarder Concentration Percentage by Weight [20]

Figure 2.6
23
24
25
 26

2.7 Standard Oil Well Cementing Job [19]

Figure 2.7

2.8 Casing Strings COD and HD [19]

Figure 2.8
 27

2.9 Volume of Cement Slurry [21]

Volume= [(OD2 –ID2)/1024.9] (Depth)
*Volume is in barrels

2.10 Volume Conversion [22]

 Barrels to Cubic Meter

1 bbl.= 0.1589872949 m3

 Volume to Mass using Density

ρ = mass/volume
where: ρ = kg/m3; volume = m3
(kg/m3) = mass/m3
*mass is in kg
 28

Chapter 3
CONCEPTUAL/THEORETICAL FRAMEWORK

3.1 Concept of Research

The amount of produced lignosulfonates and its heat stability properties

depends on the lignin percentage of RC-18 rice hull and chemicals used in the

experiment process respectively.

3. 2 Research Paradigm

3.3 Definition of Terms

 Aryl – having or being a monovalent organic radical (such as phenyl)

derived from an aromatic hydrocarbon by the removal of one hydrogen

atom – often used in combination.

 Aromatic – characterized by increased chemical stability resulting from

the delocalization of electrons in a ring system (such as benzene)

containing usually multiple conjugated double bonds.

 Bagasse – plant residue (as of sugarcane or grapes) left after a product

(such as juice) has been extracted.

 29

 Biomass – plant materials and animal waste used especially as a source of

fuel.

 Biopolymer – a polymer substance (such as a protein or polysaccharide)

formed in a biological system.

 Briquettes – a compacted often brick-shaped mass of usually fine material.

 Borehole – a hole bored or drilled in the earth.

 Cellulose – a polysaccharide (C6H10O5) of glucose units that constitutes

the chief part of the cell walls of plants, occurs naturally in such fibrous

products as cotton and kapok, and is the raw material of many

manufactured goods (such as paper, rayon, and cellophane).

 Cementation – the process of introducing cement to the annular space

between the well-bore and casing or to the annular space between two

successive casing strings.

 Coniferyl Alcohol – an organic compound. This colourless crystalline

solid is a phytochemical, one of the monolignols. It is synthesized via the

phenylpropanoid biochemical pathway. When copolymerized with related

aromatic compounds, coniferyl alcohol forms lignin.

 Deflocculant – reduces the viscosity of a slurry.

 Degree of Milling - the extent in which the bran layers and germ have

been removed.

 Exploration – the search by petroleum geologists and geophysicists for

hydrocarbon deposits beneath the Earths’ surface, such as oil and natural

gas.
 30

 Formaldehyde – a colourless pungent irritating gas used chiefly in aqueous

solution as a disinfectant and preservative and in chemical synthesis.

 Gasify – to convert into gas.

 Glycosidic – any of numerous sugar derivatives that contain a nonsugar

group bonded to an oxygen or nitrogen atom and that on hydrolysis yield a

sugar (such as glucose).

 Hemicellulose – any of various plant polysaccharides less complex than

cellulose and easily hydrolysable to monosaccharides and other products.

 Heteropolymer – a polymer derived from two or more different (but often

similar) types of monomer.

 Hull- outermost cover of paddy. This is also known as husk.

 Hydrophobic – lacking affinity for water.

 Lignin – one of the main constituents of woody plants where it plays the

role of lining agent and is comparable in this respect to cement in steel

reinforced concrete.

 Lignosulfonate – any of various compounds produced from the spent

sulphite liquor in the pulping of softwood in papermaking and used

especially for binders and dispersing agents.

 Monomer – a chemical compound that can undergo polymerization.

 Paddy- unhulled grain of Oryza Sativa, which means, grain with the

glumes enclosing the kernel. It is also known as "palay" or "rough rice" or

"rice grain".
 31

 Phenylpropanoid – diverse family of organic compounds that are

synthesized by plants from the amino acids phenylalanine and tyrosine.

 Polymer – a chemical compound or mixture of compounds formed by

polymerization and consisting essentially of repeating structural units.

 Polymerization – a chemical reaction in which two or more molecules

combine to form larger molecules that contain repeating structural units.

 Polysaccharides – a carbohydrate that can be decomposed by hydrolysis

into two or more molecules of monosaccharides.

 Pozzolana – finely divided siliceous or siliceous and aluminous material

that reacts chemically with slaked lime at ordinary temperature and in the

presence of moisture to form a strong slow-hardening cement.

 Retarder – control the time when a slurry will set hard, keeping the slurry

viscous and pumpable in expected wellbore temperatures and for the

amount of time required to place the slurry.

 Rheology – a science dealing with the deformation and flow of matter.

 Sclereids – a variably shaped sclerenchymatous cell of a higher plant.

 Sinapyl Alcohol – an organic compound structurally related to cinnamic

acid.

 Slurry – a watery mixture of insoluble matter (such as mud, lime, or

plaster of paris).

 Syringyl Alcohol – a phenylpropanoid alcohol, one of the three precursors

of lignin.
 32

 Tracheids – a long tubular pitted cell that is peculiar to xylem, functions in

conduction and support, and has tapering closed ends and thickened

lignified walls.

 Vviscous – having a thich or sticky consistency.

 Wellbore – a hole that is drilled to aid in the exploration and recovery of

natural resources including oil, gas or water.

 Xylem – a complex tissue in the vascular system of higher plants that

consists of vessels, tracheids, or both usually together with wood fivers

and parenchyma cells, functions chiefly in conduction of water and

dissolved minerals but also in support and food storage, and typically

constitutes the woody element (as of a plant stem).

3.4 Research Hypothesis

The researchers assumed that the RC-18 rice hull used in experiment will

not vary in every concentration with addition of specific chemicals. Thus, the

researchers also assumed that the data gathered will have an increasing

percentage.
 33

Chapter 4
MATERIALS AND METHODS

4.1 Materials

Table 4.1: Materials

5kg rice husk 6.5L Sulfuric Acid

Wattman No. 4 Filter paper 1.5L Hydrogen Peroxide
ph meter 2N Sodium Hydroxide
Sodium Sulfite EDTA
Beakers 500 mL Flask
Digital Weighing Scale Glacial Acetic Acid
Container for mixing Demineralized water
Distilled water Dyes (Red)
Oven/Furnace Stirrer
Crusher Water Bath
Sieve – No. 30, No. 40 Ceramic Membrane
Ceramic Membrane Thermometer
Formaldehyde Various Volume of Volumetric Flask

4.2 Research Method and Design

Research Method

1. Preparation of Rice Hull (Anwar Ma’Ruf, 2017)

Step 1. Crush the RH to mesh size of 40-60.

Step 2. Dry the RH at 60°C for 6 hours.

2. Isolation of Lignin (Anwar Ma’Ruf, 2017)

Step 1. Prepare 20 grams of crushed RH in a flask.

Step 2. Add 120 mL of demineralized water containing 1% H2O2 with a

6:1 volume/weight ratio.

Step 3. The mixture was then added with 2N NaOH until the pH level

read 9.
 34

Step 4. Heat the mixture until temperature reads 100°C.

Step 5. Isolate the mixture in the heating oil bath at a temperature of

100°C for 3 hours.

Step 6. Filter the mixture to separate the solids.

Step 7. Purification of Lignin: The liquor was introduced to a ceramic

membrane for microfiltration.

Step 8. Precipitation of Lignin: The liquor was added with H2SO4 2N

until pH 2 was achieved.

Step 9. Stir the liquor for 4 hours.

Step 10. Dry the liquor at 60°C for 6 hours.

3. Process for producing lignosulfonate (Dilling, 1984)

Step1. Use distilled water to mix with alkaline lignin and adjust the pH of

the suspension with 50% (w/w) sodium hydroxide to pH of about 5.

Step 2. Add water to the lignin to obtain 25% solids slurry

Step 3. Add sodium sulfite to the slurry at a pH of about 5.

Step 4. Closely following the sodium sulfite, add the formaldehyde until

pH reads 8.6-9.2.

Step 5. Heat the solution to 70°C for 1 hour.

Step 6. Adjust the temperature to 140°C for 2 hours.

Step 7. Adjust the concentration to 25% solids.

Step 8. Heat the sulfonated lignin solution to 70°C and add glacial acetic

acid slowly until pH level of 8 is achieved.

Step 9. Measure the heat stability properties.

 35

Research Design

In order to achieve the purpose of this study, the researchers will be

conducting most of the activity in the Provincial Engineer’s Office (PEO) and

PSU Malampalaya Laboratory in Puerto Princesa City. The equipment’s to be

used are available for use in the said office and laboratory so are some of the

chemicals. For those chemicals that are not available in the PEO, they will be

acquired from PSU and a seller from Manila (DKL Laboratory Supply.

The rice hull will be obtained from the mills of Narra, Palawan.

4.2.1 Research Process Flowchart

CONDUCT EXPERIMENT

TABULATE GATHERED DATA

STATISTICAL ANALYSIS

DATA INTERPRETATION

CONCLUSION AND RECOMMENDATION

 36

Chapter 5
RESULTS, ANALYSIS, AND FINDINGS

This chapter deals with the presentation of data in order to answer the
stated problems.
Table 5.1: Phase 2:
Solvent/Weight of Rice Husk Ratio (ml/gr)
6:1 7:1 8:1 9:1 10:1
Concentration 120ml/20gr 140ml/20gr 160ml/20gr 180ml/20gr 200ml/20gr

Table 5.2: Phase 3:

Lignosulfonate Content of Wood and Rice Hull using Sodium Sulfite and
Formalin as Catalyst

Mole Ratio of Starting Final Heat Stability Filter Residue (mg)

Na2SO3/CH2O pH pH

LIGNIN CONTENT
Wood 20-25% Rice Hull 18.81% (6:1 ratio)
1.0/1.0 10.3 10.4 38mg 28.59mg
1.4/0.7 8.9 9.25 27.6mg 23.07mg
2.0/1.15 9.6 9.8 302mg 252.472mg
*Rice hull 18.81% lignin content is based on Chesson-Datta Method
*Wood 20-25% lignin content is approximation of hard and softwood (Chabannes
et al.,2001)

Table 5.3: Lignosulfonate Content of RC-18 Rice Hull using Sodium Sulfite
and Formalin as Catalyst
6:1 Solvent/Weight of Rice Hull Ratio
Mole Ratio of Heat Stability Filter
Starting pH Final pH
Na2SO3/CH2O Residue (mg)
1.0/1.0 10.3 10.4 28.87mg
1.4/0.7 8.9 9.25 23.53mg
2.0/1.15 9.6 9.8 260.05mg
 37

Table 5.4: Lignosulfonate Content of RC-18 Rice Hull using Sodium Sulfite
and Formalin as Catalyst
7:1 Solvent/Weight of Rice Hull Ratio
Mole Ratio of Heat Stability Filter
Starting pH Final pH
Na2SO3/CH2O Residue (mg)
1.0/1.0 10.3 10.4 33.68mg
1.4/0.7 8.9 9.25 27.45mg
2.0/1.15 9.6 9.8 303.39mg
Table 5.5: Lignosulfonate Content of RC-18 Rice Hull using Sodium Sulfite
and Formalin as Catalyst
8:1 Solvent/Weight of Rice Hull Ratio
Mole Ratio of Heat Stability Filter
Starting pH Final pH
Na2SO3/CH2O Residue (mg)
1.0/1.0 10.3 10.4 38.5mg
1.4/0.7 8.9 9.25 31.37mg
2.0/1.15 9.6 9.8 346.73mg
Table 5.6: Lignosulfonate Content of RC-18 Rice Hull using Sodium Sulfite
and Formalin as Catalyst
9:1 Solvent/Weight of Rice Hull Ratio
Mole Ratio of Heat Stability Filter
Starting pH Final pH
Na2SO3/CH2O Residue (mg)
1.0/1.0 10.3 10.4 43.31mg
1.4/0.7 8.9 9.25 35.29mg
2.0/1.15 9.6 9.8 390.07mg
Table 5.7: Lignosulfonate Content of RC-18 Rice Hull using Sodium Sulfite
and Formalin as Catalyst
10:1 Solvent/Weight of Rice Hull Ratio
Mole Ratio of Heat Stability Filter
Starting pH Final pH
Na2SO3/CH2O Residue (mg)
1.0/1.0 10.3 10.4 48.12mg
1.4/0.7 8.9 9.25 39.21mg
2.0/1.15 9.6 9.8 433.41mg
 38

Analysis of the Experiment:

Of all the results using 6:1, 7:1, 8:1, 9:1 and 10:1 ratio, we proved that
among all the experiments that are conducted, Mole ratio of 2.0/1.15 yields the
best result in producing a stable pH reading throughout the tests and the highest
heat stability filter residue by the end of the experiment.
Average Lignosulfonate Production = 21,527,000 kg x 0.021675 = 466,597.725
kg
By choosing 10:1 ratio of Solvent/Weight Rice husk ratio, with a Mole
Ratio of 2.0 Na2SO3/ 1.15 CH2O to produce the best result of Rice husk as
additive (retarder) to Standard Oil well cementing that shows a heat stability filter
residue value of 433.41mg, the highest value of all the tests conducted.

Table 5.8: Average at 8,000 ft. Total Vertical Depth

Casing String COD HD TVD 1 Well 2 Wells 3 Wells 4 Wells
Conductor 30 in N/A 60ft 29.27bbl
Surface 20 in 26 in 3000ft 791.73bbl
Intermediate 13.375 17.5 in 7000ft 497.06bbl
in
Production 9.625 in 12.25 in 7500ft 31.03bbl
Liner 6.625 in 8.5 in 8000ft 13.84bbl

Total Cement 1362.93bbl 2725.86bbl 4088.79bbl 5451.72bbl

Volume

Using mathematical computation, a General Standard Casing String and

all its components, produces a total cement volume of 1362.93bbl in 1 well.

@ 0.001% Total mass of Additives (Retarder) in 10 Standard Wells Cementing

Job @ 8,000 ft TVD = 39.653904 kg

@ 0.14% Total mass of Additives (Retarder) in 10 Standard Wells Cementing

Job @ 8,000 ft TVD = 5551.54656 kg

@ 0.30% Total mass of Additives (Retarder) in 10 Standard Wells Cementing

Job @ 8,000 ft TVD = 11896.1712 kg

 39

@ 0.001%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 10 Standard Well Cementing Job with a depth of 8,000 ft

TVD is 40kg in which each well needs at least 4kg of Additives (Lignosulfonate

Retarder).

@ 0.14%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 10 Standard Well Cementing Job with a depth of 8,000 ft

TVD is 5551.55kg in which each well needs at least 555.155kg of Additives

(Lignosulfonate Retarder).

@ 0.30%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 10 Standard Well Cementing Job with a depth of 8,000 ft

TVD is 11896.17kg in which each well needs at least 1189.617kg of Additives

(Lignosulfonate Retarder).
 40

Table 5.9: Average at 10,000 ft. Total Vertical Depth

Casing String COD HD TVD 1 Well 2 Well 3 Well 4 Well 5 Wells
Conductor 30 in N/A 60ft 29.27bbl
Surface 20 in 26 in 3000ft 791.73bbl
Intermediate 13.375 in 17.5 in 9000ft 745.59bbl
Production 9.625 in 12.25 in 9500ft 31.03bbl
Liner 6.625 in 8.5 in 10000ft 13.84bbl

Total Cement 1611.46bbl 3222.92bbl 4834.38bbl 6445.84bbl 8057.3bbl

Volume

By means of mathematical computation, a General Standard Casing String

and all its components, produces a total cement volume of 1611.46bbl in 1 well.

@ 0.001% Total mass of Additives (Retarder) in 15 Standard Wells Cementing

Job @ 10,000 ft TVD = 70.327266 kg

@ 0.14% Total mass of Additives (Retarder) in 15 Standard Wells Cementing

Job @ 10,000 ft TVD = 9845.81724 kg

@ 0.30% Total mass of Additives (Retarder) in 15 Standard Wells Cementing

Job @ 10,000 ft TVD = 21098.1798 kg

@ 0.001%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 15 Standard Well Cementing Job with a depth of 10,000

ft TVD is 70.33kg in which each well needs at least 4.69kg of Additives

(Lignosulfonate Retarder).
 41

@ 0.14%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 15 Standard Well Cementing Job with a depth of 10,000

ft TVD is 9845.82kg in which each well needs at least 656.39kg of Additives

(Lignosulfonate Retarder).

@ 0.30%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 15 Standard Well Cementing Job with a depth of 10,000

ft TVD is 21098.18kg in which each well needs at least 1406.55kg of Additives

(Lignosulfonate Retarder).

Table 5.10: Average at 12,000 ft. Total Vertical Depth

Casing String COD HD TVD 1 Well 2 Well 3 Well 4 Well 5 Wells 6 Wells
Conductor 30 in N/A 60ft 29.27bbl
Surface 20 in 26 in 3000ft 791.73bbl
Intermediate 13.375 in 17.5 in 11000ft 994.12bbl
Production 9.625 in 12.25 11500ft 31.03bbl
in
Liner 6.625 in 8.5 in 12000ft 13.84bbl

Total 1859.99bbl 3719.98bbl 5579.97bbl 7439.96bbl 9299.95bbl 11159.94bbl

Cement
Volume

By means of mathematical computation, a General Standard Casing String

and all its components, produces a total cement volume of 1859.99bbl in 1 well.
 42

@ 0.001% Total mass of Additives (Retarder) in 21 Standard Wells Cementing

Job @ 12,000 ft TVD = 113.6431894 kg

@ 0.14% Total mass of Additives (Retarder) in 21 Standard Wells Cementing

Job @ 12,000 ft TVD = 15910.04652 kg

@ 0.30% Total mass of Additives (Retarder) in 21 Standard Wells Cementing

Job @ 12,000 ft TVD = 34092.95682 kg

@ 0.001%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 21 Standard Well Cementing Job with a depth of 12,000

ft TVD is 113.64kg in which each well needs at least 5.41kg of Additives

(Lignosulfonate Retarder).

@ 0.14%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 21 Standard Well Cementing Job with a depth of 12,000

ft TVD is 15,910kg in which each well needs at least 757.62kg of Additives

(Lignosulfonate Retarder).
 43

@ 0.30%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 21 Standard Well Cementing Job with a depth of 12,000

ft TVD is 34092.96kg in which each well needs at least 1,623.47kg of Additives

(Lignosulfonate Retarder).

Table 5.11: Average at 14,000 ft. Total Vertical Depth

Casing COD HD TVD 1 Well 2 Well 3 Well 4 Well 5 Wells 6 Wells
String
Conductor 30 in N/A 60ft 29.27bbl
Surface 20 in 26 in 3000ft 791.73bbl
Intermediate 13.375 17.5 13000ft 1242.65bbl
in in
Production 9.625 12.25 13500ft 31.03bbl
in in
Liner 6.625 8.5 in 14000ft 13.84bbl
in
Total 2108.52bbl 4217.04bbl 6325.56bbl 8434.08bbl 10542.6bbl 12651.12bbl
Cement
Volume

By means of mathematical computation, a General Standard Casing String

and all its components, produces a total cement volume of 1362.93bbl in 1 well.

@0.001% Total mass of Additives (Retarder) in 21 Standard Wells Cementing

Job @ 14,000 ft TVD = 128.8280785 kg

@0.14% Total mass of Additives (Retarder) in 21 Standard Wells Cementing Job

@ 14,000 ft TVD = 18035.93099 kg

@0.30% Total mass of Additives (Retarder) in 21 Standard Wells Cementing Job

@ 14,000 ft TVD = 38648.42355 kg

 44

@0.001%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 21 Standard Well Cementing Job with a depth of 14,000

ft TVD is 128.83kg in which each well needs at least 6.13kg of Additives

(Lignosulfonate Retarder).

@0.14%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 21 Standard Well Cementing Job with a depth of 14,000

ft TVD is 18035.93099 kg in which each well needs at least 858.85 kg of

Additives (Lignosulfonate Retarder).

@0.30%

Using mathematical computations prior to Percentage of Additives,

Density and Volume of the slurry, the approximate value (kg) of the Additives

(Retarder) to be used in 21 Standard Well Cementing Job with a depth of 14,000

ft TVD is 38648.42355 kg in which each well needs at least 1840.40 kg of

Additives (Lignosulfonate Retarder).

 45

Chapter 6
SUMMARY, CONCLUSION AND RECOMMENDATION

6.1 Summary

This study aims to determine the amount of lignosulfonate recoverable to

20 grams of lignin obtained from rice husk and determine the production rate of

lignosulfunate in Narra, Palawan if it can sustain the demand of a standard oil

well cementing job. To accomplish the objectives of the study the proponents

conducted an experiment using rice hull as raw material to produced

lignosulfonate along with various chemical preparation processes.

In gathering materials, the researchers collected rice hull from

Brgy.Princess Urduja, Narra, Palawan and ordered various chemicals in DKL

Laboratory Supplies in Manila. After which, the permission to use the Provincial

Engineer’s Office Laboratory was processed along with the usage of PSU

Malampaya Laboratory. The researchers then proceeded with the stated methods

above until the final results were gathered. Finally, the papers intended to be

submitted and defended were finalized and revised for the added contents.

6.2 Conclusion

The researchers are proud to conclude that the search for viability of

lignosulfonate from RC-18 rice hull is successful. Moreover, the average

lignosulfonate produced anually from RC-18 rice hull in Narra, Palawan can

supply sustain the standard oil well cementing operations at specific depths and

number of wells as presented and fully supported by the results and resources

above.
 46

6.3 Recommendation

After analyzing the results, the researchers recommend the following:

A. Before proceeding with the lignin extraction, identify the lignin

concentration of the filtrate and liquor by using the specified

spectrophotometer from the reference that we used.

B. After the conversion of lignin to lignosulfonate, proceed with identifying

the viscosity using the specified viscometer stated above.

 47

REFERENCES

[1] Lebo, Stuart E. Jr.; Gargular, Jerry D.; McNally, Timothy J. (2001).” Lignin”.

Kirk-OrthmerEncyclopedia of Chemical Technology

[2] https://en.m.wikipedia.org

[3] www.knowledgebank.irri.org/postharvest

[4] Beagle E.C., 1978. Rice husk conversion to energy. FAC Agricultural

Services Bulletin No 31, Rome. (http://www.knowledgebank.irri.org/step-by-

step-production/postharvest/rice-by-products/rice-husk)

[5] Subramani T., Unni Krishnan G., Arumugam R., Godwyn Michael Cornelies

A., Gopu. H., 2017. Experimental Study of Quarry Sand and Rice Husk

Replacing in Concrete.

[6] Provincial Agriculture Office of Palawan

[7] Belsnio B., 1980. The Anatomy and Physical Properties of the Rice Grain.

[8] Simeon, L.M., 2016. Gov’t Promotes Rice Husk as Alternative Energy

Source.https://www.pressreader.com/

[9] Santiaguel, A.F., 2013. A Second Life for Rice Husk. https://www.eco-

business.com/news/second-life-rice-husk/

[10] Bronzeoak N.,2003. Rice Husk Ash Market Study

[11] Ludueña L., Alvarez V.A., Fasce D., Stefani P.M., 2011. Nanocellulose from

Rice Husk Following Alkaline Treatment to Remove Silica

[12] Ma’ruf A., Pramudono B., Aryanti N., 2017. Lignin isolation process from

rice husk by alkaline hydrogen peroxide: Lignin and silica extracted.

 48

[13] Jingjing L., 2011. Isolation of Lignin from Wood.

[14] Zhang S.Y., Wang C.G., Fei B.H., Cheng H.T., Tian G.L., 2013. Mechanical

Function of Lignin and Hemicelluloses in Wood Cell Wall Revealed with

Microtension of Single Wood Fiber.

[15] Dilling P., 1984. Process for Preparing Lignosulfonates.

[17] https://www.glossary.oilfield.slb.com/en/Terms/s/slurry_density.aspx

[18] https://oilfieldteam.com/

[19] https://production-technology.org/casing-specifications/

[20] Cowan K.M., Hale A.H., 1989. Process for Cementing a Well

[21] http://cem.uaf.edu/media/95030/PETE426_Sp2014_Final.pdf
[22] http://ballots.api.org/copm/comq/ballots/docs/Ch%2015.pdf
 49

GLOSSARY OF TERMS

Lignosulfonate
Lignosulfonates (often abbreviated as LS) were one of the first dispersants added
as an admixture to concrete. Lignosulfonates have been used since the 1930s as
plasticizers or water reducers. Mixed with concrete, their use has afforded the beneficial
effects of retarding the setting time and reducing the amount of mixing water required.
Furthermore, greater workability of plastic concrete during its placement in formworks
and increased air entrainment have resulted from their use. As by-product of the pulping
industry, lignosulfonates are of low price and despite their limited performance they find
a large field of applications for improving the quality of concrete .

Total Vertical Depth

This is the vertical distance from the wellhead to a point in the wellpath. This
quantity is calculated from the directional survey data. Note that a measured depth, due to
the wellbore curvature, is always greater than the corresponding true vertical depth. It is
commonly referred as TVD.

Standard Well Cementing Job

Successful primary cementing operations result in a cement sheath to bond and
support casing and provide zonal isolation. Good zonal isolation helps prevent the loss of
production, control inter-zonal flow and/or flow to the surface, reduce water production
and improve confinement of stimulation treatments. Halliburton has more than 90 years
of experience and research/development in achieving optimum cement-sheath integrity.
Halliburton has been leading the industry in delivering effective zonal isolation in oil,
gas, geothermal, offshore and hydrate wells since 1919.
 50

APPENDICES

Preparation of Crushed Rice Hull (maize 16-40) [PEO Lab]

Weighting to 20 grams of RC-18 Rice Hull

[PEO Lab]

Heating Crushed RC-18 Rice Hull

using Oven @ 60 C [PEO Lab]
 51

Solvent/Weight of Rice Hull Ratio

[PSU Malampaya Laboratory]
*Demineralized Water is our Solvent

Addition of 2N NaOH until the pH level read 9 in the mixture

[PSU Malampaya Laboratory]

Heating the Solvent/Weight of Rice Hull Ratio @100 C

[PSU Malampaya Laboratory]
 52

Further Heating Process Using Water Bath for Equal Distribution of Heat
[PSU Malampaya Laboratory]

Another Sets of Sample Introduce to Water Bath for Heating Process

[PSU Malampaya Laboratory]
 53

Purification of Lignin: [PSU Malampaya Laboratory]

added with H2SO4 2N until pH 2 was achieved.

 54

Another Heating Process for Drying Liquor

[PSU Malampaya Laboratory]

Measure Heat Stability Properties by Performing Step 9 with addition of Dye

Red 1 mix with sulfonated lignin and drops of Ethylenediamine tetraacetic
acid (EDTA)
[PSU Malampaya Laboratory]
 55

Final 3 Sets of Different Solvent/Weight of Rice Hull Ratio

10.1 Solvent/Weight of Rice Hull Ratio Heat Stability Residue

 56

Ratio and Proportion of Lignosulfonate Production

Using 10:1 Solvent/Weight of Rice Husk Ratio Heat Stability Filter
Residue (mg) which is equivalent to 433.41 mg
Conversion from mg to kg
Where 1 gram is equal to 1000 mg
433.41 mg x (1gram/ 1000 mg) = 4.3341x10-1 grams
Lignosulfonate Production Percentage out of 20 grams’ sample
[4.3341x10-1 grams/ 20 grams] x 100 = 2.16705%

Average Lignosulfonate Production out of 21,527 MT Average of Rice Husk

Production in Narra, Palawan from 2014-2018
Where 1 MT is equivalent to 1000 kg
Average Rice Husk Production = 21,527 MT x (1000 kg/ 1MT) =21,527,000 kg
Average Lignosulfonate Production = 21,527,000 kg x 0.021675 = 466,597.725
kg

Average at 8,000 ft. Total Vertical Depth

Volume of Cement Slurry

Vcon = [(302-202)/1024.9]x 60 = 29.27bbl

Vsur = [(262-202)/1024.9]x (3000-60) = 791.73bbl

Vint = [(17.52-13.3752)/1024.9]x (7000-3000) = 497.06bbl

Vpro = [(12.252-9.6252)/1024.9]x (9500-9000) = 31.03bbl

Vlin = [(8.52-6.6252)/1024.9]x (10000-9500) = 13.84bbl

Barrels to Cubic Meter

Vtotal = 13629.3bbl x (0.1589872949 m3) = 2166.88 m

 57

Volume to Mass using Density of Cement Slurry

Average Density of Cement Slurry = (2280+1380)/2 =1830 kg/m3

Mtotal = (2166.88 m3) x 1830 kg/cm3 = 3965390.4 kg

Total Mass of Additives (Retarder)

Percentage of Additives (Retarder) = 0.001%

Percentage of Additives (Retarder) = 0.14%

Percentage of Additives (Retarder) = 0.30%

@ 0.001% Mtotal = (3965390.4 kg) x (0.00001) = 39.653904 kg

@ 0.14% Mtotal = (3965390.4 kg) x (0.0014) = 5551.54656 kg

@ 0.30% Mtotal = (3965390.4 kg) x (0.003) = 11896.1712 kg

Average at 10,000 ft. Total Vertical Depth

Volume of Cement Slurry

Vcon = [(302-202)/1024.9]x 60 = 29.27bbl

Vsur = [(262-202)/1024.9]x (3000-60) = 791.73bbl

Vint = [(17.52-13.3752)/1024.9]x (9000-3000) = 745.59bbl

Vpro = [(12.252-9.6252)/1024.9]x (9500-9000) = 31.03bbl

Vlin = [(8.52-6.6252)/1024.9]x (10000-9500) = 13.84bbl

 58

Barrels to Cubic Meter

Vtotal = 24171.9bbl x (0.1589872949 m3) = 3843.02 m3

Volume to Mass using Density of Cement Slurry

Average Density of Cement Slurry = (2280+1380)/2 =1830 kg/m3

Mtotal = (3843.02 m3) x 1830 kg/cm3 = 7032726.6 kg

Total Mass of Additives (Retarder)

Percentage of Additives (Retarder) = 0.001%

Percentage of Additives (Retarder) = 0.14%

Percentage of Additives (Retarder) = 0.30%

@ 0.001% Mtotal = (7032726.6 kg) x (0.00001) = 70.327266 kg

@ 0.14% Mtotal = (7032726.6 kg) x (0.0014) = 9845.81724 kg

@ 0.30% Mtotal = (7032726.6 kg) x (0.0014) = 21098.1798 kg

Average at 12,000 ft. Total Vertical Depth

Volume of Cement Slurry

Vcon = [(302-202)/1024.9]x 60 = 29.27bbl

Vsur = [(262-202)/1024.9]x (3000-60) = 791.73bbl

Vint = [(17.52-13.3752)/1024.9]x (11000-3000) = 994.12bbl

Vpro = [(12.252-9.6252)/1024.9]x (11500-11000) = 31.03bbl

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Vlin = [(8.52-6.6252)/1024.9]x (12000-11500) = 13.84bbl

Barrels to Cubic Meter

Vtotal = 39059.79bbl x (0.1589872949 m3) = 6210.01 m3

Volume to Mass using Density of Cement Slurry

Average Density of Cement Slurry = (2280+1380)/2 =1830 kg/m3

Mtotal = (6210.01 m3) x 1830 kg/cm3 = 11364318.94 kg

Total Mass of Additives (Retarder)

Percentage of Additives (Retarder) = 0.001%

Percentage of Additives (Retarder) = 0.14%

Percentage of Additives (Retarder) = 0.30%

@ 0.001% Mtotal = (11364318.94 kg) x (0.00001) = 113.6431894 kg

@ 0.14% Mtotal = (11364318.94 kg) x (0.0014) = 15910.04652 kg

@ 0.30% Mtotal = (11364318.94 kg) x (0.0030) = 34092.95682 kg

Average at 14,000 ft. Total Vertical De

Volume of Cement Slurry

Vcon = [(302-202)/1024.9]x 60 = 29.27bbl

Vsur = [(262-202)/1024.9]x (3000-60) = 791.73bbl

Vint = [(17.52-13.3752)/1024.9]x (13000-3000) = 1242.65bbl

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Vpro = [(12.252-9.6252)/1024.9]x (13500-13000) = 31.03bbl

Vlin = [(8.52-6.6252)/1024.9]x (14000-13500) = 13.84bbl

Barrels to Cubic Meter

Vtotal = 44278.92bbl x (0.1589872949 m3) = 7039.76 m3

Volume to Mass using Density of Cement Slurry

Average Density of Cement Slurry = (2280+1380)/2 =1830 kg/m3

Mtotal = (7039.76 m3) x 1830 kg/cm3 = 12882807.85 kg

Total Mass of Additives (Retarder)

Percentage of Additives (Retarder) = 0.001%

Percentage of Additives (Retarder) = 0.14%

Percentage of Additives (Retarder) = 0.30%

@0.001% Mtotal = (12882807.85 kg) x (0.00001) = 128.8280785 kg

@0.14% Mtotal = (12882807.85 kg) x (0.0014) = 18035.93099 kg

@0.30% Mtotal = (12882807.85 kg) x (0.0030) = 38648.42355 kg