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Technological Institute of the Philippines - Manila

(ChE Research 1, First semester, 4th year - Group 1)

Production of Chalk using Calcium derived


from Tilapia Bones
[1] Keinth Joseph Pintoy Cantor, [2] Krizzia Anne Sheng Cemanes Mauricio, [3] Khim Julius De Luna Patiño,
[4] Queenie Rose Insigne Percil, [5] Ma. Stephanie Tinambunan Santos, [6] Patricia Kaye Macalindong Vidal

Key Words: chalk, calcium, fish bones, calcium oxide,


calcium carbonate, tilapia

I. INTRODUCTION
Mauricio, Krizzia Anne Sheng Cemanes,
Background of the Study Chemical Engineering Department, Technological
Institute of the Philippines, Quiapo, Manila City,
Chalk has been around since 19th century as one Phone:09272311594.
of the leading writing instruments in schools. It is (email: krizziamauricio@gmail.com )
widely used by teachers and students during class Patiño, Khim Julius De Luna, Chemical
discussions and reports. In the Philippines, both Engineering Department, Technological Institute of
private and public schools make use of the chalk the Philippines, Quiapo, Manila City,
mainly because of its affordability and effectiveness Phone:09752039488.
as a teaching tool. (email: khimtip1310081@gmail.com)
Percil, Queenie Rose Insigne,
According to an article posted by the North Chemical Engineering Department, Technological
Carolina University entitled “Mini-Encyclopedia of Institute of the Philippines, Quiapo, Manila City,
Papermaking Wet-End Chemistry”, Chalk is a form of Phone:09168206602.
calcium carbonate having the same chemical (email: inniedc14@gmail.com )
composition as ground calcium carbonate, limestone, Santos, Ma. Stephanie Tinambunan,
marble, and precipitated calcium carbonate (PCC). Chemical Engineering Department, Technological
Institute of the Philippines, Quiapo, Manila City,
Calcium carbonate is a chemical compound with Phone:09479296263.
the formula of CaCO3. This very common substance (email: stephaniesantoscloud3721@gmail.com)
is found in our natural environment and it can be Vidal, Patricia Kaye Macalindong,
found all around the world. It is one of the most Chemical Engineering Department, Technological
common compounds found from within the earth’s Institute of the Philippines, Quiapo, Manila City,
surface and it helps to make up as much as 7 percent Phone:09363398285. (email: pkmvidal@yahoo.com)
of the earth’s crust. This compound is commonly
found in rocks and many of the outer shells of marine In a study, Marine capture fisheries contribute
animals found in the ocean. Calcium carbonate in its over 50% of total world fish production, and more
pure form is odorless white powder or clear white than 70% of this production has been utilized for
crystals. It has no taste. It is created when Calcium processing. As a result, every year a considerable
ions in hard water react with carbonate ions which amount of total catch is discarded as processing
create a substance called lime scale (Chase Allen, leftovers and these include trimmings, fins, frames,
2013). heads, skin, and viscera. (FAOSTAT, FAO statistical
databases, fisheries data, Food and Agriculture
One good natural source of Calcium is the bones Organization of the United Nations, 2001)
of Tilapia (Oreochromis niloticus). It is also a good
source of protein and is popular among commercial Recent estimates revealed that current discards
fisheries. The annual production around the world is from the world’s fisheries exceed 20 million tons
about 1,500,000 tons with the approximate value of equivalent to 25% of the total production of marine
1.8 billion U. S. dollars, which is similar to total value capture fish. Therefore, there is a great potential in
of salmon and trout. (Bung-Orn Hemung, 2013). marine bioprocess industry to convert and utilize
more of these by-products as valuable products.
Cantor, Keinth Joseph Pintoy, (Won-Kyo Jung, Fereidoon Shahidi, Se-Kwon Kim,
Chemical Engineering Department, Technological 2008)
Institute of the Philippines, Quiapo, Manila City,
Phone:09274797236. The aforementioned statements served as basis
(email: keinthjoseph19@gmail.com) for the conduction of this study.
Significance of the Study million tons equivalent to 25% of the total
This study will be of great significance to a production of marine capture fisheries. Therefore,
number of people especially to teachers and students there is a great potential in marine bioprocess
who are the primary users of chalk.
The researchers believe that the results of this Industry to convert and utilize more of these by-
products as valuable products. However, most of
study will be beneficial as well to lessen the
these recycled products possess low economic value.
environmental impact by utilizing some of waste fish
Recently, bioactive compounds from remaining fish
bones disposed by commercial and household units. muscle proteins, collagen and gelatin, fish oil, fish
Furthermore, this research can also serve as future bone, internal organs, and shellfish and crustacean
reference for studies of the same interest. shells were reviewed by Kim and Mendis. Among
fish by-products, fish bone or skeleton is considered
as a potential source to obtain calcium, which is an
Scope and Delimitations essential element for the human health. However,
only few studies have been carried out to identify
The scope of this research is to evaluate the bioavailability of fish bone calcium and its potential
feasibility of producing chalk from fishbone as the applications.
main raw material. The research has also its Generally, calcium is obtained from the diet and it
limitations. The study is limited only to the existing
is severely deficient in most of the regular diets.
literature about chalk production and fishbone since
Therefore, to improve calcium intake, several calcium
there are no existing researches about the production
fortified products are in the market and demand for
of chalk from fishbone.
these products is growing continuously. It is well
It requires a deep understanding on all aspects documented that consumption of whole small fish is
underlying behind the production of chalk, and the nutritionally beneficial providing with a rich source of
fishbone as the main raw material from which calcium. Calcium in fish could be absorbed to the
Calcium carbonate will be produced. It is important to body as tested in vivo. However, very little
know all of the things involved in the process of chalk information is available on the beneficial effects of
production and it is a requirement to have enough larger fish bone and few attempts have been made to
knowledge on different parameters that is being test their usage for benefits of human health. Fish
considered. bone material derived from processing of large fish is
a useful calcium source where the quantity of calcium
II. THEORETICAL FRAMEWORK is concerned. To incorporate fish bone into calcium-
fortified food, it should be converted into an edible
Review of Related Literature and Studies form by softening its structure. This can be achieved
utilizing different methods including hot water
treatment and hot acetic acid solutions. In this study,
Chalk is calcium carbonate and has the same
it has been observed that calcium-binding activity of
chemical composition as limestone, marble, ground
the fish bone peptides (FBP) II was similar to that of
calcium carbonate and precipitated calcium carbonate. CPP. Further, the pH of the reaction system was
The most common chemical formulas for chalk are maintained at 7.8, because low pH could increase the
CaCO3 (calcium carbonate) and CaO (calcium solubility of the insoluble calcium salt. As reported by
oxide). Chalk is a soft, porous sedimentary rock that Jiang and Mine, the solubility of 36.3 mgL of Ca
is a form of limestone and is mainly composed of could be obtained at 200 mgL of the
calcite (calcium carbonate). oligophosphopeptide from egg yolk phosvitin with
35% phosphate retention, and the solubility was
Marine capture fisheries contribute over 50% of higher than that of commercial CPP II (Meiji
total world fish production, and more than 70% of
this production has been utilized for processing. As a Seika Co., Ltd., Tokyo, Japan). Furthermore, in
result, every year a considerable amount of total vivo studies with osteoporosis modeling rat have
catch is discarded as processing leftovers and these elucidated that the FBP II f ractionated in the
include trimmings, fins, frames, heads, skin, and molecular weight range of 5.0–1.0 kDa increased Ca
viscera. In addition to fish processing, a large solubility and bioavailability. Menopause is a time
quantity of processing by-products are accumulated when estrogen deficiency leads to accelerated bone
as shells of crustaceans and shellfish from marine resorption and negative bone balance. Another study
bioprocessing plants. Recent estimates revealed that has been undertaken to evaluate the beneficial effects
current discards from the world’s fisheries exceed 20 of FBP as a Ca fortifier in osteoporosis induced by
ovariectomy and a concurrent low-Ca diet. During the 1.8 billion U. S. dollars, which is similar to total value
experimental period corresponding to the menopause of salmon and trout. The whole tilapia can be
with osteoporosis disease, the loss of bone mineral processed into skinless and boneless fillets. The yield
(Ca) was decreased by FBP II supplementation in the of these processes has been reported in the range of
ovariectomized rats. After the low-Ca diet, the FBP II 30-37 %, depending on fish size and trimming
diet, including both normal levels of Ca and vitamin process. Thereafter, the left parts of fish have been
D, significantly decreased Ca loss in feces and turned to be waste or by-products. The left part
increased Ca retention as compared with the control. contains bone, skin, protein, scale, fat, and blood. In
The levels of femoral total Ca, bone mineral density, the left part, bone is the main component consisting
of 10-15% of total fish biomass. Bone is also the
and breaking strength were also significantly
source of important minerals: sodium, phosphorous,
increased by FBP II diet to a level similar to those of
and calcium. Among them, calcium ion (Ca2+) is
the CPP diet group (no difference; P < 0.05). Based on
important for development of human bone and teeth
these data, it was suggested that increased Ca retention particularly in infant. Utilization of fish bone can be a
by FBP II intake may lead to the prevention of mineral natural source of Ca2+ for being food ingredient and
loss in the osteoporosis-modeling rats. As reported by Ca2+ supplementary. It would be the strategy to
Larsen et al. [3,4], the intake of small fish with bones maximally utilize fish resource as well as to
can increase Ca bioavailability, and the small fish may effectively reduce the waste from fishery industry.
be an important source of Ca, especially in population As far as the bioavailability of Ca 2+ in the
groups with low intake of milk and dairy products. supplementary has been concerned, the bioavailability
Thus, these results prove the beneficial effects of fish should be tested. It can be performed based on the
meal in preventing Ca deficiency owing to increased enzymatic reaction. This is because Ca2+ is the
Ca bioavailability by FBP intake. Furthermore, there cofactor for several enzymes. Since the reaction is
is a potential to these fish peptides to provide a novel dependent on available Ca2+, this reaction could be
nutraceutical with a high bioavailability for Ca to used to evaluate the bioavailability of soluble Ca2+.
Oriental people with lactose indigestion and Therefore, the objective of this study was to produce
intolerance and Ca-fortified supplements, such as fruit and characterize tilapia bone powder. In addition, the
juice or Ca-rich foods, as alternatives to dairy bioavailability of Ca2+ in the tilapia bone powder
products. (Calcium from Fishbone and other Marine was also investigated, which is based on the activity
Resources) assay of crude tTGase from tilapia muscle.
(Properties of Tilapia Bone Powder and Its Calcium
Bioavailability Based on Transglutaminase Assay)
Calcium is generally obtained from dairy
products, broccoli, tofu, oysters, sardines and similar Conceptual Framework
soft sources of bone. Edible fishbone contains a high
In this research, we are going to use calcium
amount of calcium. In general, there is a lack of derive from tilapia bone to make a chalk. We decided
scientific documentation of nutritional value of marine to use tilapia fish bone instead of other fish since this
by-products. The bone fraction from fish has been is more efficient since it will yield to more product.
regarded as waste. Due to the high mineral content of
fish bones, this material can be well suitable as a In general, there is a lack of scientific
natural calcium source. Fishbone ash consists of 34- documentation of nutritional value of marine by-
products. The bone fraction from fish has been
36% calcium, particularly calcium phosphate.
regarded as waste. Due to the high mineral content of
Fishbone of Nile Tilapia (Tilapia nilotica), available fish bones, this material can be well suitable as a
as waste from a fish leather factory, should be a natural calcium source. In the present study, apparent
potentially good source of calcium. (Development of calcium absorption of different fish bone sources was
calcium supplement from the bone of Nile Tilapia tested using growing pigs. The experimental diets
(Tilapia nilotica)) consisted of boiled salmon frames, or salmon, saithe
or cod bones treated with enzymes. Calcium
Tilapia (Oreochromis niloticus) was originally found carbonate (CaCO(3)) was used as control. The
in Africa. Tilapia is the good source of protein and experimental diets were formulated to contain 0.7%
also it is popular among commercial fisheries. It can total calcium of which the added calcium source to be
be fed by algae or plant-based feed. Therefore, the tested contributed about 71% (study 1) and 86%
cost of production can be reduced practically. China is (study 2). Except for the calcium and phosphorus
the largest tilapia producer country followed by sources, the animals received similar basal diets.
Egypt. The annual production around the world is Apparent calcium digestibility coefficient was
about 1,500,000 tones with the approximately value of calculated using yttrium as indicator (both studies)
and was based on complete collection of faeces and
urine (study 2). The experimental design was parallel
and cross-over in study 1 and study 2, respectively. In
study 1, piglets getting salmon bone treated with
enzymes had significantly higher calcium absorption
than piglets getting boiled fish bone or calcium
carbonate. Therefore, in the second study only
enzymatically treated fish bones were included. The Research Paradigm
higher calcium absorption from enzymatically treated
salmon bone was also found in study 2, but this time INPUT
not significant. Calcium from boiled salmon bones in
study I, and from enzymatically treated saithe and cod A. Knowledge Requirements:
bones in study II were absorbed as well as the calcium  Chalk Properties
carbonate control. The results indicate that fish bones  Tilapia Bones Properties
may be a useful and well absorbed calcium source.  Chalk-making Procedures
Due to the high mineral content of the bone fraction, B. Hardware Requirements:
 Oven
salmon bones can be well suitable as a natural calcium
 Beaker
and phosphorus source in, for example, food, feed or  Mortar and Pestle
as supplement. (© 2010 The Authors. Journal of  Funnel
Animal Physiology and Animal Nutrition © 2010  Filter
Blackwell Verlag GmbH.)  Petri dish
 Dry ice
Chalk is formed naturally from limestone, a  Mold
sedimentary rock that is made of calcium carbonate.  Analytical Balance
Limestone deposits develop as coccoliths (minute  Blackboard Surface
calcareous plates created by the decomposition of
plankton skeletons) accumulate, forming sedimentary
layers. Plankton, a tiny marine organism, concentrates
the calcium found naturally in seawater from 0.04 PROCESS
percent to 40 percent, which is then precipitated when
the plankton dies. (Boynton, Robert, 1980) A. Collecting fish bones
B. Drying fish bones
The whole tilapia can be processed into C. Extracting Calcium from fish bones
skinless and boneless fillets. The yield of these  Alkaline Treatment with NaOH
processes has been reported in the range of 30-37 %,  Neutralization with HCl
depending on fish size and trimming process.  Filtration
Thereafter, the left parts of fish have been turned to be  Pulverization
waste or by-products. The left part contains bone, D. Converting Calcium to Calcium Carbonate
skin, protein, scale, fat, and blood. In the left part,  Oxidation of Calcium
bone is the main component consisting of 10-15% of  Hydration of Calcium Oxide
total fish biomass. Bone is also the source of  Precipitation of Calcium Carbonate
important minerals: sodium, phosphorous, and E. Making of Chalk
calcium. Among them, calcium ion (Ca2+) is  Molding of Calcium Carbonate
important for development of human bone and teeth F. Tests to be Conducted
particularly in infant. Utilization of fish bone can be a 1. Compatibility with Blackboard Surface
natural source of Ca2+ for being food ingredient and 2. Brittleness
Ca2+ supplementary. It would be the strategy to 3. Density
maximally utilize fish resource as well as to 4. Texture
effectively reduce the waste from fishery industry.
(Bung-Orn Hemung, 2013)
Chalk is usually made by stirring calcium
carbonate, color pigment, clay, and a binding agent to OUTPUT
form a doughy material, which is then pressed into Final Chalk
cylindrical shapes and cut into sticks of chalk. But for
this research, to make chalk, the researchers must first
extract the calcium from the “tilapia bones”. Then the
derived calcium from “tilapia bones” will be Evaluation of Acceptability
converted to calcium carbonate through the oxidation
of calcium.
Definition of Terms III. RESEARCH METHODOLOGY OR
OPERATIONAL FRAMEWORK
For a better understanding of this study, the following
terms are operationally defined. Project Design
Chalk. A soft, porous sedimentary rock that is a form
of limestone and is mainly composed of calcite Below is the experimental diagram of the study
(calcium carbonate).
Identify Chalk Properties
Calcium. A substance that is found in most plants and
animals and that is especially important in people for
strong healthy bones. It is well documented that Chalk Making
consumption of whole small fish is nutritionally
beneficial providing with a rich source of calcium. 1. Chalk from Tilapia Bones

Fish bones. The main component consisting of 10-


15% of total fish biomass. Bone is also the source of
important minerals: sodium, phosphorous, and Testing of the Chalk
calcium.
1. Chalk from Tilapia Bones
Calcium Oxide. A caustic solid CaO that is white Test Conducted
Compatibility with Blackboard Surfaces
when pure and that is the chief constituent of lime.
Brittleness
Density
Calcium Carbonate. A chemical compound with the Texture
formula of CaCO3. Calcium carbonate in its pure form
is odorless white powder or clear white crystals. It has
no taste. It is created when Calcium ions in hard water
Evaluation of Acceptability
react with carbonate ions which create a substance
called lime scale. 1. Chalk from Tilapia Bones

Tilapia (Oreochromis niloticus). The good source of


protein and also it is popular among commercial
Results
fisheries. It can be fed by algae or plant-based feed.

Limestone. A sedimentary rock that is made of


calcium carbonate. Proposed Testing and Operational
Procedures
Coccoliths. Minute calcareous plates created by the
decomposition of plankton skeletons Proposed Testing
We will test the product breaking strength,
Plankton. A tiny marine organism, concentrates the
how clear it writes, the dust it produces since
calcium found naturally in seawater from 0.04 percent
to 40 percent, which is then precipitated when the people nowadays prefer chalk that is dustless, its
plankton dies. effects on humans since some people are allergic
to chalk, we will also test if it is smooth and if it
Calcium Ion (Ca2+). It is mportant for development is erase cleanly. The product that we will make
of human bone and teeth particularly in infant. from this will be tested on blackboards.
Utilization of fish bone can be a natural source of
Ca2+ for being food ingredient and Ca2+
supplementary. Operational Procedure
The process of taking the calcium from tilapia of limestone necessary to make chalk suitable for
fish bones: writing purposes. Wet grinding is carried out in
Fish bone material derived from processing ball mills—rotating steel drums with steel balls
of large fish is a useful calcium source where the inside that pulverize the chalk until it is very fine.
quantity of calcium is concerned. To incorporate
fish bone into calcium-fortified food, it should be ii. Dehydrating gypsum
converted into an edible form by softening its
Gypsum, like treated fish bones, is also
structure. This can be achieved utilizing different
quarried and pulverized. The major difference in
methods including hot water treatment and hot
processing gypsum is that it must be dehydrated
acetic acid solutions. In addition, (Ishikawa et al.)
to form calcium sulfate, the major component of
used superheated steam to reduce the loss of
colored chalk. This is done in a kettle, a large
soluble components from fish tissue and that
combustion chamber in which the gypsum is
enabled better recovery of bone within a shorter
heated to between 244 and 253 degrees
period. Furthermore, the treated bones need to be
Fahrenheit (116-121 degrees Celsius). It is
subjected to saponification, degreasing, and
allowed to boil until it has been reduced by
degumming. Biological utilization and clinical
twelve to fifteen percent, at which point its water
trial showed that the bone preparation is a good
content will have been reduced from 20.9 percent
source of bioavailable calcium, much better than
to between 5 and 6 percent. To further reduce the
common calcium powders. ( Jung et al.)
water, the gypsum is reheated to about 402
Performed enzymatic degradation in acetic acid
degrees Fahrenheit (204 degrees Celsius), at
solution (pH 2.0) by pepsin to easily dissolve
which point it is removed from the kettle. By
both mineral and organic parts of fish bone.
now, almost all of the water has evaporated,
( Calcium from Fish Bone and Other Marine
leaving calcium sulfate.
Resources Won-Kyo Jung, Fereidoon Shahidi,
and Se-Kwon Kim)
The treated fish bones were milled for iii. Sifting, cleaning, and shipping
easy handling. The product of fish bone powder is the chalk
small particle size, white colour and without fish The particles of chalk or calcium sulfate
odour. The Ca : P ratio of fish bone extract are now conveyed to vibrating screens that sift
powder was close to 2:1 and its calcium content out the finer material. The ensuing fine chalk is
of three kinds of fish bone occurs between from then washed, dried, packed in bags, and shipped
21g and 24 g per 100g of fish bone extract to the manufacturer. Upon receiving chalk or
powder. (Luu, P. H.; Nguyen, M. H.) calcium sulfate, the chalk factory usually grinds
the materials again to render them smooth and
uniformly fine.

The process of making chalk from the Calcium of


tilapia fish bones:
iv. Making white classroom chalk
i. Pulverizing the chalk To make white classroom chalk, the
Pulverized to meet the demands of the manufacturer adds water to form a thick slurry
chalk industry. The first step is primary crushing. with the consistency of clay. The slurry is then
Various crushers exist, but the principle is the placed into and extruded from a die—an orifice
same: all compress the treated fish bones with of the desired long, thin shape. Cut into lengths
jaws or a cone, or shatter it through impact. of approximately 24.43 inches (62 centimeters),
Secondary crushing is accomplished by smaller the sticks are next placed on a sheet that contains
crushers that work at higher speeds, producing places for five such sticks. The sheet is then
pebbles which are then ground and pulverized. placed in an oven, where the chalk cures for four
days at 188 degrees Fahrenheit (85 degrees
The next phase, wet grinding, washes Celsius). After it has cured, the sticks are cut into
away impurities. It is used to make the fine grade 80 millimeters lengths.
v. Making colored classroom chalk determined using a tap density test apparatus
employing USP type I test in which the cylinder is
Pigments (dry, natural, colored raised by a height of 14+2 mm and then allowed to
drop under its own weight.
materials) are mixed in with the calcium
carbonate while both are dry (the procedure is
similar to sifting flour and baking powder
together before adding liquid, as in a cake recipe).
Water is then added to the mixture, which is then
baked in the same manner as white classroom
chalk.

(Boynton, Robert. Chemistry and


Technology of Lime and Limestone. John Wiley &
Sons, 1980.
Cobb, Vicki. The Secret Life of School
Supplies. J. B. Lippincott, 1981.
Institution of Civil Engineers Staff, eds.
Chalk. American Society of Civil Engineers,
1990.)

Proposed Method of Evaluation


The chalk will be evaluated by teachers,
professors and students. They will use the sample in
blackboards. The test panel was evaluated in terms of
[1] how clear the experimental chalk will be once
used in the blackboard. [2] It will also be evaluated in
in terms of found particle (dust) size measurement
during writing process. Large particle size favors
sedimentation in the air rather than staying in air for a
longer time. This makes good quality carbonate chalks
dustless. [3] Another is terms of breaking strength
based on breaking strength Instrument which gives
vertical compressive load value. Compressive strength
was measured to understand behavior of chalk particle
interaction. Tightly packed particle generate less dust
and give higher breaking strength whereas loosely
pack particle generate more dust and also having less
breaking strength. This Instrument gives maximum
load (KGF) applied on chalk. LabVIEW based serial
communication system is used to acquire data in to
computer and to observe real time chart. It is observed
that when chalk breaks it gives peak from high to low
load. The necessary features like to store data in excel
and store maximum peak value during experiment
was developed in the software. [4] And lastly is in
terms of measuring the poured bulk density of CaCO3
powder using tapped density apparatus, this powder
mainly used as a raw material in chalks. For the
measurement gently filling the powder sample in a
glass cylinder by keeping the cylinder in a slightly
inclined position and pouring the powder into it so as
to avoid the compaction of the powder during free
fall. The poured volume and mass of powder were
noted. The tap density of powder samples were

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