Fragmentary Nitration of Pineapple

Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology

Department of Chemical Engineering
Fragmentary Nitration of Pineapple

(AnanasComosus)Leaf Bracts for the
Production of Pyroxylin Lacquer
Submitted by:
Madrial, Andrea Coleen E.
Mendoza, Marian D.
Raguini, Jasmin Fatima D.
Saya, Diana Jane S.
Submitted to:
Engr. Milagros R. Cabangon
Date of Submission:
February 11, 2016
Fragmentary Nitration of Pineapple Bracts for the production of Pyroxylin Lacquer

TABLE OF CONTENTS
Introduction
Statement of the Problem
Objectives of the Study
Significance of the Study
Methods of Research
Review of Related Literature and Study
Experimental Method
26

INTRODUCTION
Developing for the past years is the utilization of agricultural residues and by-products as
a raw material for the production of a useful item for consumption. Though already being
employed in the textile industry in the country (Fitzgerald, B., 2015), pineapple leaf bracts are
still being burned for disposal by majority of the farmers here in the Philippines (Baconguis, S.
2014). This burning, in turn, produces environmental issues due to the emission of considerable
amounts of dioxins (Commission for Environmental Cooperation, 2014). Our country produces
2.4MT of pineapple for the year 2013 with which generates 200,000 to 300,00MT pineapple leaf
bracts (Food and Agriculture Organization of the United Nations Statistics Division). One
excellent way to dispose pineapple leaf bracts, which has a cellulose content of 66.2% (Zawawi,
D., et al. 2014), while avoiding the method of burning for disposal is to use them as a raw
material for the production of a coating material called lacquer.
Lacquer is a protective coating primarily based on nitrocellulose (cellulose nitrate) that
dries primarily by evaporation of solvent rather than oxidation of polymerization (Department of
Trade and Industry). Demand for this product increased by 16% from 2013 to 2014 and is
anticipated to have a continuous increase on the coming years (PAPM, 2014). However, the local
supply in the market could not satisfy the mere 11% of the total demand for 2014 and the rest of
these are satisfied by importation (PAPM, 2015).
To aid in dealing with the problems stated above, a study entitled Fragmentary Nitration
of Pineapple (AnanasComosus) Leaf Bracts for the Production of Pyroxylin Lacquer was
conducted.

STATEMENT OF THE PROBLEM

According to the Department of Agriculture, Philippines is one of the worlds largest
producer of pineapple, placing 2nd after Thailand. Philippines was able to generate 2.3 MT of
pineapple with an existing production area of 58,457 hectares in 2015. But by the second half of
the same year the performance of pineapple and such decreased due to hot weather conditions
that amounted to 200.4 billion with 3.05 percent decrease based on the Philippine Food Security
Information System. Still, Philippines is a major exporter with an annual average growth rate of
11.33 percent (Food and Fertilizer Technology Center,UP Los Banos).
About 70 percent of the pineapple produced worldwide is consumed as a fresh fruit in the
origin country (Loeillet, 1997). The other 30 percent is transformed into canned slices, chunks
and concentrates. Leaves, crowns, cores, bud ends and non-fruit parts are often considered
wastes (Devendra, 1985; Hepton et al., 2003;Sruamsiri, 2007). Most of thepineapple residues is
disposed and either serves as fertilizer, feedstock or is burnt in an open field, however these
methods are not only ineffective but also contribute to air pollution (Wan &Zainuddin, 2013).
Burning of the pineapple residues that includes the leaves produces considerable
amounts of dioxins (Commission for Environmental Cooperation, 2014). This substance is
known to be highly toxic and long exposure may lead to reproductive and developmental
problems, damage the immune system, interference with hormones and also cause cancer
(World Health Organization). However, these leaves are also the source of fiber to make
course textiles and threads in some Southeast Asian countries (Zakaria et. al., 2005). These
leaves contain 66.2% cellulose (Zawawi, D.et. al., 2014), which is important in producing
lacquer that can solve the growing demand for this product.
The demand for lacquer increased immensely by 16 percent from 2013 to 2014 and is
expected to increase in the following years (PAPM, 2014). However, local supplies cannot match
the growing demand that results to importation of the product.

With all these put into consideration, this paper addresses the utilization of handling
pineapple leaves and the growing demand for lacquer through the groups research entitled:
Fragmentary Nitration of Pineapple (AnanasComosus) Leaf Bracts for the Production of
Pyroxylin Lacquer.

OBJECTIVES OF THE STUDY

General:
To produce pyroxilin lacquer through fragmentary nitration of cellulose from pineapple
leaf bracts
Specific:
To assure optimum qualities of the product by comparing the physical and chemical
properties of the standardlacquer
Parameter
Standard
Viscosity
5 centistokes
Drying Time
15 minutes
Density
0.86 g/ml
Table 3.1 Standard Properties of Lacquer as per DTI, Philippine National Standard
To find out the best pre-conditioning parameters of the pineapple leaf bracts before
undergoing chemical reaction

To determine the best operating conditions like concentration of reagents and most
effective catalyst which will provide best yield

To identify the equivalent unit operation and equipment of every laboratory process and
apparatus

SIGNIFICANCE OF THE STUDY

To the Pineapple Plantation Proprietors of Lagusan Drive, Tagaytay City
The consumption of pineapple leaf bracts as the main raw material for varnish production
instead of disposing it by burning would provide the pineapple plantation proprietors an extra
income if it will be sold to the manufacturers.
To the Chemical Engineering Undergraduates
This study can be used as a reference for undergraduate subjectsby chemical engineering
students who will use pineapple leaf bracts or any other useful agricultural by-products as their
main raw material to manufacture products related to pyroxylin lacquer.
To the Public
Through this study, the public will benefit frompyroxylin lacquer with good quality and
more inexpensive price. In addition to that, local manufacturers who will initiate the production
of pyroxylin lacquer from pineapple leaf bracts will provide more job opportunities for the
people.
To the Environmentalists
Burning of agricultural wastes such as pineapple leaves produces 40% of carbon dioxide
(CO2), 32% of carbon monoxide (CO), 20% of particulate matter (PM), and 50% of polycyclic
aromatic hydrocarbons (PAHs) released into the environment around the globe.This type of
burning contributes to climate change, since among the compounds released are greenhouse
gases and short-lived climate-forcing pollutants like black carbon. Also, visibility in nearby areas
and highways is affected. In addition, these incomplete combustion processes produce dioxins,

which are highly toxic, carcinogenic pollutants. Through this study, pineapple leaf bracts are
reuse for more beneficial products such as pyroxylin lacquer.
METHODS OF RESEARCH
The experimenters conducted extensive research in order to have a comprehensive study and
analysis of the properties and characteristics of raw materials and product. The researchers used
different methods of research to obtain vital information and data for the study. The studies are
the following:
I.
Descriptive Method
The researchers collected data from books, periodicals and electronic resources for the
useful information of the raw material and processes involved.

A. Science Direct
Data were collected through books, articles and other experiments to aid the
researchers to come up with the idea of producing lacquer from pineapple leaves.
B. Electronic Resource
Local and international articles from different institutional and organizational
websites in relation to production and processing of lacquers from pineapple leaves were
collected by the researchers.
II.
Experimental Method
This method of research scientific undertaking was done through laboratory set-up for
experimentations. Various parameters were considered to come up the best quality of the product.
Imus, Cavite for the execution of experimental method, further observation and
improvement of the product.

REVIEW OF RELATED LITERATURE

1. Raw Materials
1.1 Pineapple
The pineapple is the leading edible member
of the family Bromeliaceae which embraces
about 2,000 species, mostly epiphytic and
many strikingly ornamental. Now known
botanically
(syns. A.
as AnanascomosusMerr.
sativus Schult.
f., Ananassa
sativa Lindl., Bromeliaananas L., B.

comosa L.), the fruit has acquired few
vernacular names. It is widely called pina by Spanish-speaking people, abacaxi in
the Portuguese tongue, ananas by the Dutch and French and the people of former
French and Dutch colonies; nanas in southern Asia and the East Indes. In China, it
is po-lo-mah; sometimes in Jamaica, sweet pine; in Guatemala often merely
"pine (Morton, J. 1987).
1.1.1
Classifications of Pineapple
a. 'Smooth Cayenne' or 'Cayenne', 'Cayena Lisa' in Spanish (often known in

India, Sri Lanka, Malaysia and Thailand as 'Sarawak' or 'Kew') was selected
and cultivated by Indians in Venezuela long ago and introduced from Cayenne
(French Guyana) in 1820. From there it reached the Royal Botanical Gardens,
Kew, England, where it was improved and distributed to Jamaica and
Queensland, Australia. Because of the plants near freedom from spines except
for the needle at the leaftip and the size-4 to 10 lbs (1.8 4.5 kg)-cylindrical
form, shallow eyes, orange rind, yellow flesh, low fiber, juiciness and rich
mildly acid flavor, it has become of greatest importance worldwide even
though it is subject to disease and does not ship well. Mainly, it is prized for

canning, having sufficient fiber for firm slices and cubes as well as excellent
flavor.
It was the introduction of this cultivar into the Philippines from Hawaii in
1912 that upgraded the Philippine industry from the casual growing of the
semi-wild type which was often seedy. There are several clones of 'Smooth
Cayenne' in Hawaii which have been selected for resistance to mealybug wilt.
It is the leading cultivar in Taiwan.
b. 'Queen' is the leading cultivar in South Africa, Queensland and the
Philippines. The plant is dwarf, compact, more cold-resistant and more
disease-resistant then 'Smooth Cayenne'. It matures its fruit early but suckers
freely and needs thinning, and the yield is low. The fruit is conical, deepyellow, with deep eyes; weighs 1 to 2 1/2 lbs (0.45-1.13 kg); is less fibrous
than 'Smooth Cayenne', but more fragrant; it is juicy, of fine flavor with a
small, tender core. It is sold fresh and keeps well. It is only fair for canning
because of its shape which makes for much waste.
c. 'Abacaxi' (also called 'White Abacaxi of Pernambuco', 'Pernambuco',
'Eleuthera', and 'English') is well known in Brazil, the Bahamas and Florida.
The plant is spiny and disease-resistant. Leaves are bluish-green with redpurple tinge in the bud. The numerous suckers need thinning out. The fruit
weighs 2.2 to lllbs (1-5 kg), is tall and straight-sided; sunburns even when
erect. It is very fragrant. The flesh is white or very pale yellowish, of rich,
sweet flavor, succulent and juicy with only a narrow vestige of a core. This is
rated by many as the most delicious pineapple. It is too tender for commercial
handling, and the yield is low. The fruit can be harvested without a knife;
breaks off easily for marketing fresh.
10

d. Red Spanish ,the fruit is more or less round, orange-red externally, with deep
eyes, and ranges from 3 to 6 lbs (1.36-2.7 kg). The flesh is pale-yellow,
fibrous, with a large core, aromatic and flavorful. The fruit is hard when
mature, breaks off easily and cleanly at the base in harvesting, and stands
handling and transport well. It is highly resistant to fruit rot though subject to
gummosis.
1.2 Pineapple Leaf
Pineapple leaves are waxy, strapshaped leaves 2 to 6 feet in length. They
usually have a sharp point on the tip of the
leaf and spines along the margins of the
leaves. The leaves may be green or variegated
in color.
1.2.1
Structure
Figure 6.1: Pineapple Parts and Fibre
1.2.2
Cellulose Content
CONSTITUENTS/COMPOSITION
PINEAPPLE
CORN
NAPIER
11

(w/w %)
LEAF
STALK
Ash Content
4.50
24.9
Cellulose Content
66.2
39.0
Holocellulose Content
85.7
82.1
Hemicellulose Content
19.5
42.0
1% NAOH Solubility
39.8
69.9
Lignin Content
4.28
7.30
Moisture content
81.6
7.32
Table 6.1 (Zawawi, D.et. al., 2014)
GRASS
14.6
12.4
80.4
68.2
52.0
10.8
11.7
1.3 Sodium Hydroxide

Sodium hydroxide is widely usedin the manufacture of soaps, paper,
rayon, cellophane, mercerized cotton,
aluminum, and many chemicals. It is also
used in petroleum refining, degreasing,
etching,zinc extraction, tin plating, oxide
coating, and food processing (for peeling
fruits and vegetables). In concentrated
form, it is used as a drain cleaner. Sodium
hydroxide has been used in the management of pleural effusions.
1.4 Sodium Sulfide
12

Sodium sulfide is a yellow, solid flake with a

sulfurous (rotten egg) smell. It is used in the
pulp and paper industry and in leather
processing to remove hair from hides.
Sodium sulfide may be used in the making of
colors and dyes. It can also be used in the
manufacture of other chemicals, metals or in
mining (ore processing) and in waste water, soil and process sludge treatment
1.5 Sulfuric Acid
Sulfuric acid (alternative spelling sulphuric acid) is a highly corrosive strong
mineral acid with the molecular formula
H2SO4 and molecular weight 98.079 g/mol.
It is a pungent-ethereal, colorless to slightly
yellow viscous liquid which is soluble in
water at all concentrations. Sometimes, it is
dyed dark brown during production to alert
people to its hazards. The historical name of
this acid is oil of vitriol.
Sulfuric acid is a diprotic acid and shows
different properties depending upon its
concentration. Its corrosiveness on other
materials, like metals, living tissues or even stones, can be mainly ascribed to its
strong acidic nature and, if concentrated, strong dehydrating and oxidizing
properties. Sulfuric acid at a high concentration can cause very serious damage
upon contact, since not only does it cause chemical burns via hydrolysis, but also
secondary thermal burns through dehydration. It can lead to permanent blindness
if splashed onto eyes and irreversible damage if swallowed. Accordingly, safety
precautions should be strictly observed when handling it. Moreover, it is
hygroscopic, readily absorbing water vapour from the air.
13

Sulfuric acid has a wide range of applications including domestic acidic drain
cleaner, electrolyte in lead-acid batteries and various cleaning agents. It is also a
central substance in the chemical industry. Principal uses include mineral
processing, fertilizer manufacturing, oil refining, wastewater processing, and
chemical synthesis. It is widely produced with different methods, such as contact
process, wet sulfuric acid process and some other methods.
("sulfuric acid". The Columbia Encyclopedia (6th ed.). 2009. Retrieved 2010-03-16.)
1.6 Hydrochloric acid
Hydrochloric acid is a clear, colorless, highly pungent solution of hydrogen
chloride (HCl) in water. It is a highly corrosive,
strong mineral acid with many industrial uses.
Hydrochloric acid is found naturally in gastric acid.
When it reacts with an organic base it forms a
hydrochloride salt.
It was historically called acidumsalis, muriatic
acid, and spirits of salt because it was produced
from rock salt and green vitriol (by Basilius
Valentinus in the 15th century) and later from the
chemically similar substances common salt and
sulfuric acid (by Johann Rudolph Glauber in the
17th century). Free hydrochloric acid was first formally described in the 16th century
by Libavius. Later, it was used by chemists such as Glauber, Priestley, and Davy in
their scientific research.
With major production starting in the Industrial Revolution, hydrochloric acid is
used in the chemical industry as a chemical reagent in the large-scale production of
vinyl chloride for PVC plastic, and MDI/TDI for polyurethane. It has numerous
smaller-scale applications, including household cleaning, production of gelatin and
other food additives, descaling, and leather processing. About 20 million tonnes of
hydrochloric acid are produced worldwide annually.
(William L. Jolly "Modern Inorganic Chemistry" (McGraw-Hill, 1984), p.177)
14

1.7 Nitric acid

Nitric acid (HNO3), also known as aqua fortis and spirit of niter, is a highly
corrosive mineral acid.
The pure compound is colorless, but older samples
tend to acquire a yellow cast due to decomposition into
oxides of nitrogen and water. Most commercially
available nitric acid has a concentration of 68% in
water. When the solution contains more than 86%
HNO3, it is referred to as fuming nitric acid. Depending
on the amount of nitrogen dioxide present, fuming nitric
acid is further characterized as white fuming nitric acid or red fuming nitric acid, at
concentrations above 95%.
Nitric acid is the primary reagent used for nitration the addition of a nitro group,
typically to an organic molecule. While some resulting nitro compounds are shockand thermally-sensitive explosives, a few are stable enough to be used in munitions
and demolition, while others are still more stable and used as pigments in inks and
dyes. Nitric acid is also commonly used as a strong oxidizing agent.
(Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A22.)
1.8 Ethanol
Ethanol is miscible with water and is a good general purpose solvent. It is found
in paints, tinctures, markers, and personal care products such as mouthwashes,
perfumes and deodorants. However, polysaccharides precipitate from aqueous
solution in the presence of alcohol, and ethanol precipitation is used for this reason in
the purification of DNA and RNA.
15

(Lide, David R., ed. (2008). CRC Handbook of Chemistry

and Physics (89 ed.). Boca Raton: CRC Press. pp. 955.)
1.9 Petroleum ether
Petroleum ether is the petroleum fraction consisting of C and
C hydrocarbons and boiling in the range 3560 ;
commonly used as a laboratory solvent. The term ether is
used only figuratively, signifying extreme lightness and
volatility.
(David R. Lide, ed. (2010), CRC Handbook of Chemistry
and Physics (90th ed.), CRC Press)
2. Process
2.1 Pulping Method
2.1.1 Kraft Pulping Process
The kraft process, which uses sodium hydroxide (NaOH) and sodium
sulfide (Na2S) to pulp wood, is the dominant pulping process in the pulp and
paper industry. About 130 million tons/year of kraft pulp are produced globally,
accounting for two-thirds of the worlds virgin pulp production and for over 90%
of chemical pulp. The high strength of kraft pulp, the ability of the process to
handle almost all species of softwood and hardwood, and the favorable economics
due to high chemical recovery efficiency (about 97%) give the kraft process an
advantage over other pulping processes.
In the kraft process, about half of the wood is dissolved and together with
the spent pulping chemicals, forms a liquid stream called weak black liquor
(Figure). The weak black liquor is separated from the pulp washing by washing,
and is sent to the kraft recovery system, where the inorganic pulping chemicals
are recovered for reuse, while dissolved organics are used as a fuel to make steam
and power.
16

Figure 6.2: Kraft Pulping Process

2.2 Nitration Process
Nitration is a general class of chemical process for the introduction of a nitro
group into an organic chemical compound. More loosely the term also is applied
incorrectly to the different process of forming nitrate esters between alcohols and
nitric acid, as occurs in the synthesis of nitroglycerin. The difference between the
resulting structure of nitro compounds and nitrates is that the nitrogen atom in nitro
compounds is directly bonded to a non-oxygen atom, typically carbon or another
nitrogen atom, whereas in nitrate esters, also called organic nitrates, the nitrogen is
bonded to an oxygen atom that in turn usually is bonded to a carbon atom
(Gerald Booth "Nitro Compounds, Aromatic" Ullmann's Encyclopedia of Industrial
Chemistry, 2005, Wiley-VCH, Weinheim.)
Typical nitration syntheses apply so-called "mixed acid", a mixture of
concentrated nitric acid and sulfuric acids.[2] This mixture produces the nitronium
ion (NO2+), which is the active species in aromatic nitration. This active ingredient,
which can be isolated in the case of nitroniumtetrafluoroborate,[3] also affects
nitration without the need for the mixed acid. In mixed-acid syntheses sulfuric acid is
not consumed and hence acts as a catalyst as well as an absorbent for water.
(John McMurry Organic Chemistry 2nd Ed.)
17

REVIEW OF RELATED STUDIES

ABANDONED BIOMASS RESOURCE STATISTICS IN THE PHILIPPINES
bySANTIAGO R. BACONGUIS
The Philippines is largely an agricultural country with the agricultural sector contributing
about one-third of GNP. The total area is about 30 million hectares and about half is
approximately A & D lands which is devoted to agricultural production and urban development.
The remaining areas are forests, shrublands and wetlands. Rice, corn and coconut are the most
abundant crops planted with a total area of about 9 million hectares. The major abandoned
biomass/wastes resources presented in this paper are: rice hull/husk, rice straw, sugarcane
bagasse, coconut wastes, forestry residues and urban waste. However, in some parts of the
country, there are some minorly abandoned fruit residues due to the lack of knowledge of the
processors regarding its possible uses: pomelo, watermelon, pineapple, and mango.
(http://www.nscb.gov.ph/ncs/10thNCS/papers/invited%20papers/ips-20/ips20-03.pdf)
BURNING AGRICULTURAL WASTE: A SOURCE OF DIOXINS

18

byCOMMISSION FOR ENVIRONMENTAL COOPERATION

It is estimated that burning biomass, such as wood, leaves, trees and grassesincluding
agricultural wasteproduces 40% of carbon dioxide (CO2), 32% of carbon monoxide (CO),
20% of particulate matter (PM), and 50% of polycyclic aromatic hydrocarbons (PAHs) released
into the environment around the globe. Although agricultural waste burning is not an
environmentally acceptable form of agricultural management, it is a frequent practice and is
worrisome
from
public
health
viewpoint
for
number
of
reasons:
(http://www3.cec.org/islandora/en/item/11405-la-quema-de-residuos-agr-colas-es-una-fuente-dedioxinas-en.pdf)
Smoke from agricultural burning is released at or near ground level in areas that are
generally populated, producing direct, intense exposure to pollutants for the nearby
populations.
This type of burning is generally carried out in stages, during specific times of the year,
and may lead to very high concentrations of pollutants.
Burning agricultural waste creates non-specific sources of pollutants for the atmosphere
and takes place over very large areas. It is therefore difficult to measure and to regulate
the resulting emissions.
Combustibles and combustion conditions vary, and pesticides may be present.
This type of burning contributes to climate change, since among the compounds
released are greenhouse gases and short-lived climate-forcing pollutants like black
carbon.
Visibility in nearby areas and highways is affected.
In addition, these incomplete combustion processes produce dioxins, which are highly
toxic, carcinogenic pollutants.
INDUSTRY PROFILE
19

by PAPM
The estimated total capacity of the lacquer manufacturers is approximately
equivalent to 250 million liter per annum.

Volume is forecast to expand a modest 8-9% annual rate.
A 16% annual rate growth is forecast for demand in architectural coatings as
building activity expands and the economy grows at a modest rate from 2013 to
2014.
NITRATION AND AROMATIC REACTIVITY

by J. G. HOGGETT, R. B. MOODIE, J. R. PENTON & K. SCHOFIELD
The means which have been used for effecting nitration are numerous, but not all of the
methods are in common use. Dilute nitric acid is useful for nitrating reactive substances such as
phenol, but the oxidising properties of more concentrated nitric acid can be disadvantageous.
Solutions of nitric acid or nitrates in sulphuric acid of various concentrations, or in oleum,
provide reagents of a wide range of vigour. They have the additional property, often useful, that
some organic compounds are appreciably soluble in them, and the disadvantage of being able to
sulphonate some aromatic compounds. The disadvantage is rarely serious, for nitration is
generally a more rapid process than sulphonation. Nitric acid in organic solvents also provides
reagents in which aromatic compounds are usefully soluble, but these solutions are milder
nitrating agents than those in mineral acids. In preparative nitration, acetic acid is probably the
most frequently used of organic solvents. Solutions of nitric acid in organic solvents are less
acidic than solutions in mineral acids, a virtue when compounds sensitive to acids are being
nitrated, and one which is shared by solutions of nitric acid in acetic anhydride (these reactants
react together fairly rapidly to give acetyl nitrate.
ORGANIC COATINGS
20

byDEPARTMENT OF TRADE AND INDUSTRY

Lacquer is defined as a coating that dries primarily by evaporation rather than by
oxidation or polymerization. Because the solvents or water used in lacquers are relatively volatile
and no chemical change is required for formation of the film, lacquers dry very rapidly.
(http://monographs.iarc.fr/ENG/Monographs/vol98/mono98-6.pdf)
PIA COUTURE: PINEAPPLE FIBER MAKES FABRIC IN THE PHILIPPINES

byBENJAMIN FITZGERALD
As couture bites into fruit as a source of natural fiber, the amount of pia used in textiles
is steadily growing across North America. Pia importer Ecossar, is just one textile firm working
directly with local artisans in The Philippines, to spread pia's reach. More designers need to
experience the luxury of this fruit-based thread, completely derived from pineapple leaves.
(http://www.lesouk.co/articles/material-inspiration/pina-couture-pineapple-fiber-makes-fabric-inthe-philippines)
PRODUCTION OF PINEAPPLES IN THE PHILIPPINES
By Food and Agriculture Organization of the United Nations Statistics Division
21

Figure 7.1 Production of the Pineapples in the Philippines
PYROXYLINUM, B.P. PYROXYLIN

fromHENRIETTES BOOK # 2
Pyroxylin, cellulose tetranitrate, or dinitro-cellulose, is prepared by immersing to of
cotton in a mixture of 50 of sulphuric acid and 50 of nitric acid, stirring it constantly for three
minutes, then removing the product, washing with water until free from acid, draining on filter
paper, and drying on a water-bath. The product is a white fibrous substance, resembling cotton in
appearance. Pyroxylin is also official in the U.S.P. When ignited it burns with great rapidity; it
should be carefully stored in a dry place, or immersed in methylated spirit. When pyroxylin is
made by immersing the cotton in the mixture of acids at a high temperature the product yields
with ether-alcohol a collodion known as "high-temperature collodion," which, on evaporation,
leaves a film of a friable character, and the collodion is unsuitable for many purposes. Made at a
low temperature, however, the resulting pyroxylin yields a collodion, the film of which is tough
22

and well adapted in every way for surgical use. The solubility of both varieties is the same.
Pyroxylin consists of cellulose tetranitrate, C12H16(ONO2)4O6, or dinitro-cellulose,
C6H8(NO2)2O5. and is distinguished from guncotton by its solubility in a mixture of equal
volumes of ether and alcohol. Unless it has been properly nitrated, collodions prepared with it
may be thicker than is desirable. Guncotton is cellulose hexanitrate, C12H14(ONO2)6O4, or
trinitro-cellulose, C6H7(NO2)3O5. it is insoluble in a mixture of alcohol and ether. Celloidin
consists of pyroxylin which has been purified by solution in alcohol and ether.
PYROXYLIN, ITS MANUFACTURE AND APPLICATIONS

byWALTER D. FIELD
By the term pyroxylin is understood the soluble nitric ethers of cellulose, namely the di,
tri, tetra, and penta-nitrates. From the date of the use of pyroxylin in photography by Scott
Archer in 1851, the number of its uses has increased until, at present time, tons of the lower
nitrates of cellulose are produced yearly.
In the form of celluloid it is before us constantly. As a varnish it is used on penholders,
pencils, silver and brass ware. Articles are bronzed with it as a medium. An artificial leather has
been produced with it. These applications are all made, with the exception of celluloid, by the
use of a solution of pyroxylin.
EXPLORING THE AGRO WASTE (PINEAPPLE LEAF, CORN STALK, AND

NAPIER GRASS) BY CHEMICAL COMPOSITION AND MORPHOLOGICAL STUDY
byZAWAWI, D., MOHD, Z.M.H., ANGZZAS, S.M.K., HALIZAH A.,
&ASHUVILA, M.A
Pineapple leaf fibers were found to have a lower ash content (4.5%) than corn stalk
(24.9%) and napier grass (14.6%). The function of the ash content is to show the absence or
presence of other materials such as various organice and inorganic matter. The low ash content
23

indicates high pulp yield from pulping process (Lopez et al. 2004). Pineapple leaf has a very
high moisture content (81.6%) compared to that of corn stalk (7.3%) and napier grass (11.7%).
This high moisture content will affect the mechanical and surface properties of the paper as less
dimensional stability of that paper. A quality paper product needs a good dimensional stability,
because the structure and the strength of the sheet are dependent on it (Cauldfield, 1998).
Cellulose fibers will swell up to 15 to 20% from dry conditions to saturation, which can cause
the changes in dimensions when the humidity changes. Such changes in dimension will make the
dimensional stability decrease and lead to undesirable cockling and curling in the dimensional
stability of the paper (Sridach, 2010). These results shows that corn stalk has a higher stability
compared to the pineapple leaf and napier grass. This stability will cause the paper produce from
it to be of higher quality (Khampan et al 2010).
CONSTITUENTS/COMPOSITION
PINEAPPLE
CORN
NAPIER
(w/w %)
LEAF
STALK
GRASS
Ash Content
4.50
24.9
14.6
Cellulose Content
66.2
39.0
12.4
Holocellulose Content
85.7
82.1
80.4
Hemicellulose Content
19.5
42.0
68.2
1% NAOH Solubility
39.8
69.9
52.0
Lignin Content
4.28
7.30
10.8
Moisture content
81.6
7.32
11.7
Table 7.1 Comparison between Pineapple Leaf, Corn Stalk, and Napier Grass
24

EXPERIMENTAL METHOD
The experimentation was done in a laboratory scale. In order to produce the desired product,
variation of parameters, like concentration, ratio of liquor to raw material, and time were
observed.
A. Collection and Preparation of Raw Material
This process involves the collecting, preparing and conditioning by washing, size
reducing and drying of raw material which is the pineapple leaf bracts.
The pineapple leaf bracts that are collected from Brgy. Francisco, Lagusan Drive,
Tagaytay City contain dirt such as soil which may hinder and interfere the completion of the
entire process, hence washing using tap water is employed.
A.1 Determination of the Optimum Amount of Water for Washing
a. Apparatus and Materials
Tap water
Pineapple leaf
Basin
Sprayer
bracts
Analytical balance
25

b. Objective
To determine the optimum amount of water used for washing the
pineapple leaves
c. Procedure
1. Prepare 1 kg of pineapple leaves.
2. Wash the pineapple leaf with 1 kg tap water using a sprayer.
3. Repeat steps 1-2 using 2 kg, and 3 kg tap water.
4. Weight and record the water after washing.
d. Data and Results
Weight of Water
Ratio of Water
Weight of
Weight of Dirt
Percent of
to Pineapple
Water with
1000 g
Leaves
1:1
Dirt
1050 g
50 g
4.7619 %
2000 g
1:2
2150 g
150 g
6.9767 %
3000 g
1:3
3228 g
228 g
7.0632 %
Removed Dirt
Calculations:
weight of water with dirt weight of water
x 100=Percent of Removed Dirt
weight of water with dirt
1:1 Ratio
10501000
x 100=4.7619
1050
1:2 Ratio
26

2 1502000
x 100=6.9767
2150
1:3 Ratio
32283000
x 100=7.0632
3228
e. Analysis
To find out the most efficient ratio of pineapple leaf to water that will remove dirt;
three sets of 1000 g of pineapple were washed with different ratio of water. The
researchers used 1:1, 1:2 and 1:3 ratio of leaf to water and the dirt removed resulted
to 50g, 150g and 228g respectively. 1:3 ratio yield the highest percentage of dirt
removed which is 7.0632% while 1:2 ratio have 6.9767%. The least dirt removed was
the 1:1 ratio with 4.7619%. The yielded removed dirt from ratios 1:3 and 1:2 have
small increment. 1:2 ratios would be the most efficient ratio of water to pineapple leaf
that will remove dirt.
f. Conclusion
Therefore, the optimum ratio of leaf to water that would remove dirt most
efficient is 1:2, using 1000g of leaf to2000 g of water, yielding to 6.9767% dirt
removed with a little difference with the highest dirt removed.
A.2 Size Reduction of Pineapple Leaves

Size reduction of the pineapple leaves is done in preparation for the next process which is
the drying. The raw material is size reduced into different lengths: 2.5 cm, 5 cm, and 7.5 cm.
This variation of sizes is to determine the highest moisture content removed from drying.
Scissors
Basin
27

Pineapple leaves
Ruler
b. Objective
To determine the optimum size of the washed pineapple leaves that will yield the
highest moisture content removed prior for drying process
c. Procedure
1. Weigh 1000g of pineapple leaves
2. Measure and cut the washed pineapple leaves into 2.5 cm length using the
ruler and scissors.
3. Collect and gather the cut pineapple leaves in a basin.
4. Repeat steps 1-2 using 5 cm, and 7.5 cm length.
d. Data and Results
Parameter
Size (cm)
Drying time (hours)
Mass of Dried Pineapple
Trial 1
2.5
4
800
Trial 2
5
4
855
Trial 3
7.5
4
905
Leaves (g)
Percent yield (%)
Percent Moisture Content
80
20
85.5
14.5
90.5
9.5
Removed (%)
28

Calculations:
Initial massdried mass
x 100=Percent of Moisture Content Removed
ini tial mass
2.5 cm leaf
1000800
x 100=20
1000
5 cm leaf
1000855
x 100=14.5
1000
7.5 cm leaf
1000905
x 10 0=9.5
1000
e. Analysis
The researchers cut 2.5 cm, 5 cm and 7.5 each of 1000 g of pineapple to
determine the most efficient size of the leaf to be dried. The time was kept constant. The
2.5 cm of leaf yielded 80% after drying having 20% moisture content removed. For the 5
cm, it yielded 85.5 % after drying having 14.5% moisture removed. On the other hand the
7.5 cm of leaf yielded 90.5% after drying having 9.5% moisture content removed. The
researchers consider the 2.5 cm of leaf because it has the most percent moisture content
removed.
f. Conclusion
Thus, the optimum size that would remove highest moisture content is 2.5 cm,
yielding to 20% moisture content removed. This parameter would be use in the
next process.
29

A.3 Determination of the Length of Time for Drying

Cut Pineapple Leaves
Basin
b. Objective
To determine the optimum time used for the drying process that will yield the
highest moisture content removed
c. Procedure
1. Weigh 1000 g of 2.5 cm pineapple leaves and flatten it on a basin for the
drying process.
2. Put the basin in direct sunlight.
3. Let the pineapple leaves be sundried for 9 hours, 12 hours, and 15 hours.
4. Weigh the pineapple leaves and record the observation.
d. Data and Results
Parameter
Size (cm)
Drying time (hours)
Mass of Dried Pineapple
Trial 1
2.5
9
607
Trial 2
2.5
12
453
Trial 3
2.5
15
235
Leaves (g)
Percent yield (%)
Percent Moisture Content
60.7
39.3
45.3
54.7
23.5
76.5
Removed (%)
Calculations:
Initial massdried mass
x 100=Percent of Moisture Content Removed
init ial mass
30

9 hours
1000607
x 100=39.3
1000
12 hours
1000453
x 100=54.7
1000
15 hours
1000235
x 100=76.5
1000
e. Analysis
The optimum size for the pineapple leaves is determine from the highest moisture
content that is removed. The data shows that 15 hours of sun drying yield to 76.5%
moisture content removed. Nine hours and twelve hours of sun drying yield to 39.3% and
54.7%, respectively which are lesser than the former. The longer time it took for the
pineapple leaves to be dried, the highest moisture content removed because of the
extended exposure of the pineapple leaves to sunlight.
f. Conclusion
The optimum time for drying of the pineapple leaves is 15 hours since it yield the
highest percentage of 76.5% close to the value found in a related study that pineapple leaf
has 81.
g. Equivalent equipment
Laboratory scale
Basin, tap water, sprayer
Basin
Industrial scale
Washing tanks, spray nozzles
Industrial oven
31

scissors
Rotary knife cutters
SUMMARY OF PARAMETERS
SUMMARY FOR COLLECTING AND PREPARING THE RAW MATERIALS
Amount of Water for Washing
2000g of water per 1000g pineapple leaves
Size of Pineapple Leaves
2.5 cm
Length of Time for Drying
15 hours
Amount of Initial Mass
1000
B. Kraft Process of Pineapple Leaf Bracts
Delignification refers to the chemical process of removing the pulp from wood by
eliminating the lignin. The removal of lignin from the wood has traditionally taken place
by a method called the Kraft process.
Reaction for Kraft Process:
Wood + NaOH + Na2S
C6H10O5 (Cellulose) + Na2SO4 + Na2CO3
In this experiment, the researchers varied the parameters to determine the best
possible condition concentration of solvents, ratio of solvents, drying time and
temperature.
In the variation of concentration of solvents in white liquor in a solution of
sodium hydroxide (NaOH) is varied to 7%, 9% and 11% and for sodium sulfide (Na2S),
32

the concentration is varied to 3% and 5%. The amount of solvents is varied to 1:2 and 2:1
ratio. For the variation of drying time, it is varied to 9, 12 and 15 hours.
The cellulose is recovered through filtration, in preparation for the nitration
process.
B.1 Determination of the Concentration of Sodium Hydroxide (NaOH)
Sodium Hydroxide
Sodium sulfide
Beakers
Thermometer
Vials
Stirring Rod
Analytical Balance
Pipette
Aspirator
Electric Stove
b. Objective
To determine the optimum concentration of sodium hydroxide that will yield the
highest percentage of lignin removed
c. Procedure
1. Prepare 100 g of 5% sodium sulfide by weight of solution.
2. Prepare 100 g of 7% sodium hydroxide by weight of solution.
3. Mix the two solutions in a 400mL beaker and stir. This will serve as the white
liquor.
4. Weigh 20 g of pineapple leaves and transfer it into the white liquor.
5. Heat the beaker until it reaches 100 . Cook the pineapple leaves for 50
minutes after boiling.
6. Filter the pulp after cooking and wash it in 300 g tap water.
7. Place the washed pulp in a foil and sundry until no traces of wetness can be
felt.
8. Weigh the dried pulp and record the observation.
33

9. Repeat the steps 1-8 using different concentration of sodium hydroxide: 9%,
11% (w/w).
d. Data and Results
Parameter
Mass of Pineapple Leaves (g)
Size (cm)
Concentration of NaOH (% w/w)
Concentration of NaxS (% w/w)
Amount of White Liquor (g)
Temperature ( )
Trial 1
20
2.5
7
5
200
100
Trial 2
20
2.5
9
5
200
100
Trial 3
20
2.5
11
5
200
100
Time (min)
Mass of Dried Pulp (g)
Percent Yield (%)
Percent Lignin Removed (%)
50
11
55
45
50
8
40
60
50
9
45
55
Calculations:
PERCENT YIELD:
recovered mass
x 100=Percent Yield
initial mass
7% NaOH
11
x 100=55
20
9% NaOH
8
x 100=40
20
11% NaOH
34

9
x 100=45
20
PERCENT LIGNIN REMOVED:

initial massrecovered mass
x 100= percent lignin removed
initial mass
7% NaOH
20.0011
x 100=45
20.00
9% NaOH
20.008
x 100=60
20.00
11% NaOH
20.009
x 100=55
20.00
e. Analysis
The optimum concentration of the sodium hydroxide is determined to be
9% sodium hydroxide by weight of solution. The data shows that 9% sodium
hydroxide by weight of solution yield to 60% lignin content removed, 7% w/w
yield to 45% and although the 11% w/w yield to 55% lignin content removed. The
researcher consider 9% sodium hydroxide because of the highest lignin removed.
f. Conclusion
The maximum percentage lignin content removed is accomplished through
9% concentration of sodium hydroxide.
35

B.2 Determination of the Concentration of Sodium Sulfide (Na2S)

Sodium Hydroxide
Sodium sulfide
Beakers
Thermometer
Vials
Stirring Rod
Analytical Balance
Pipette
Aspirator
Electric Stove
b. Objective
To determine the optimum concentration of sodium sulfide that will yield the
highest percentage of lignin removed
c. Procedure
1. Prepare 100 g of 9% sodium hydroxide by weight of solution.
liquor.
36

felt.
9. Repeat the steps 1-8 using different concentration of sodium sulfide: 5%, 7%
(w/w).
d. Data and Results
Parameter
Size (cm)
Concentration of Na2S (% w/w)
Temperature ( )
Trial 1
20
2.5
9
3
200
100
Trial 2
20
2.5
9
5
200
100
Trial 3
20
2.5
9
7
200
100
Time (min)
50
12
50
8
Percent Yield (%)

60
40
40
60
50
The white
liquor
evaporated
that burned
the pineapple
leaves
-
Calculations:
PERCENT YIELD:
recovered mass
x 100=Percent Yield
initial mass
37

3% Na2S
12.00
x 100=60
20.00
5% Na2S
8.00
x 100=40
20.00

initial mass
3% Na2S
20.0012.00
x 100=40
20.00
5% Na2S
20.008.00
x 100=60
20.00
e. Analysis
The optimum concentration of the sodium sulfide is determined to be 5% by
weight of solution. The data shows that 5% sodium sulfide by weight of solution
yield to 60% lignin content removed, 3% concentration only yields 40% lignin
removed and since the white liquor in trial 3 having 7% sodium sulfide concentration
evaporated quickly, the researchers considered 5% concentration of Na2S.
38

f. Conclusion
The maximum percentage lignin content removed is attained through 5%
concentration of sodium sulfide.
B.3 Determination of the Ratio of NaOH and Na2S
Sodium Hydroxide
Sodium sulfide
Beakers
Thermometer
Vials
Stirring Rod
Analytical Balance
Pipette
Aspirator
Electric Stove
b. Objective
To determine the optimum ration of NaOH and Na 2S that will yield to the highest
percentage of lignin removed.
c. Procedure
2. Prepare 67g of 9% sodium hydroxide by weight of solution.
liquor.
felt.
39

9. Repeat the steps 1-8 using different 2:1 ratio of sodium hydroxide and sodium
sulfide
d. Data and Results
Parameter
Size (cm)
Temperature ( )
1:1
20
2.5
9
5
200
100
Time (min)
Percent Yield (%)
50
8
40
60
Ratio of NaOH to Na2S

1:2
2:1
20
20
2.5
2.5
9
9
5
5
200
200
100
100
50
7
35
65
50
10
50
50
Calculations:
PERCENT YIELD:
recovered mass
x 100=Percent Yield
initial mass
1:1 Ratio
8.00
x 100=40
20.00
1:2 Ratio
7.00
x 100=35
20.00
1:2 Ratio
40

10.00
x 100=50
20.00

initial mass
1:1 Ratio
20.008.00
x 100=60
20.00
1:2 Ratio
20.007.00
x 100=65
20.00
1:2 Ratio
20.0010.00
x 100=50
20.00
e. Analysis
The ratio of sodium hydroxide to sodium sulfide is determined by the highest
percentage of lignin content removed. Based on the data presented, trial 1, which is in
equal ratio of NaOH to Na2S, gives 40% yield and trials 2 and 3, provide 65% and 50%
lignin removed, respectively. The higher the amount of NaOH, the higher the percent
yield but lesser percentage of lignin removed. The researchers determined 1:2 to be the
most efficient ratio.
41

f. Conclusion
Hence,1 part sodium hydroxide and 2 parts sodium sulfide which yields to 65% is
the chosen parameter that will yield the highest lignin content removed.
B.4 Determination of the Amount of White Liquor to Raw Material
Sodium Hydroxide
Sodium sulfide
Beakers
Thermometer
Vials
Stirring Rod
Analytical Balance
Pipette
Aspirator
Electric Stove
b. Objective
To determine the optimum amount of white liquor to raw material that will yield
to the highest percentage of lignin removed.
c. Procedure
2. Prepare 50g of 9% sodium hydroxide by weight of solution.
liquor.
felt.
42


9. Repeat the steps 1-8 using different 84 g of sodium hydroxide and 166 g of
sodium sulfide.
d. Data and Results
Parameter
Size (cm)
Temperature ( )
Time (min)
Percent Yield (%)
Amount of White Liquor

150 g
200 g
250 g
20
20
20
2.5
2.5
2.5
9
9
9
5
5
5
1:2
1:2
1:2
100
100
100
50
9
45
55
50
7
35
65
50
8
40
60
Calculations:
PERCENT YIELD:
recovered mass
x 100=Percent Yield
initial mass
150g
9.00
x 100=45
20.00
200g
43

7.00
x 100=35
20.00
250g
8.00
x 100=40
20.00

initial mass
150g
20.009.00
x 100=55
20.00
200g
20.007.00
x 100=65
20.00
250g
20.008.00
x 100=40
20.00
e. Analysis
The efficient amount of white liquor is determined to be 200g to remove high
lignin amount from 20g pineapple leaf. The data shows that 150 g of white liquor
only removes 55% of lignin while the 250 g removes 40% lignin. On the other hand,
44

65% of lignin is removed using 200g of white liquor which the researchers will
consider the best parameter for the next process.
f. Conclusion
Therefore, 200 g of white liquor is the best amount to be used, yielding 35% of
cellulose and removing 65% of the lignin. This will be the parameter used for the next
process.
Laboratory Scale
Beaker, Hot Plate
Filter Cloth
Basin
Industrial Scale
Batch Reactor
Filtration Tank
Rotary Dryer
g. Equivalent Equipment
SUMMARY OF PARAMETERS
SUMMARY FOR KRAFT PULPING
Amount of Initial Mass
20 g
Size of Pineapple Leaves
2.5 cm
Concentration of NaOH
9%
Concentration of Na2S
5%
1:2
Amount of White Liquor
200g
Temperature for Cooking
100
Time for Cooking
50 min
45

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