FYP Lignin Chemical Engg

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CHAPTER 1
1.0 INTRODUCTION
Lignin is a natural resource which exists in woody materials, agricultural residues, and other
plant materials (so-called lignocellulosic materials). Lignocellulosic materials consist of 10–30%
lignin by weight and 40% by energy. However, it has mainly been used as an energy source in
combustion processes, and less than 5% lignin has been used for other purposes nowadays .
Because of its high energy content and polymer structure, lignin is considered as a potential
renewable resource of chemicals and fuels especially in condition of escalating petroleum price
and renewable energy demand. Lignin depolymerization is very promising process which can
generate value added products from lignin raw materials. The primary purpose of lignin
depolymerization is to convert the complex lignin compound into small molecules for fuels and
basic chemicals or oligomers for further application.
Considerable amount of research has been done to convert lignin into renewable fuels and
chemicals using pyrolysis and gasification methods. Pyrolysis refers to the thermal treatment of
the biomass or lignin in the absence of oxygen, with or without any catalyst usually at the
temperature between 300 and 600°C. The cleavage of OH functional group linked to aliphatic
side chain, the breaking of alkyl side chain, aryl ether, and linkage between aromatic rings occur
when temperature increases, forming a mixture of phenol, guaiacol, syringol, and catechol’s.
Moreover, the aromatic ring cracking occurs at the temperature above 500°C. However, the
process is highly complex and is affected by several factors, including feedstock type, heating
rate, and reaction temperature.
[1]
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1.1 LIGNIN
Lignin is a complex polymer of aromatic alcohols known as monolignols. It is most commonly

derived from wood, and is an integral part of the secondary cell walls of plants and some algae.
Lignin was first mentioned in 1813 by the Swiss botanist A. P. de Candolle, who described it as
a fibrous, tasteless material, insoluble in water and alcohol but soluble in weak alkaline
solutions, and which can be precipitated from solution using acid. He named the substance
“lignine”, which is derived from the Latin word lignum, meaning wood. It is one of the most
abundant organic polymers on Earth, exceeded only by cellulose. Lignin constitutes 30% of non-
fossil organic carbon and a quarter to a third of the dry mass of wood.[citation needed]
The composition of lignin varies from species to species. An example of composition from an
aspen sample is 63.4% carbon, 5.9% hydrogen, 0.7% ash, and 30% oxygen (by difference),
corresponding approximately to the formula (C31H34O11)n. As a biopolymer, lignin is unusual
because of its heterogeneity and lack of a defined primary structure. Its most commonly noted
function is the support through strengthening of wood (xylem cells) Global production of lignin
is around 1.1 million metric tons per year and is used in a wide range of low volume, niche
applications where the form but not the quality is important.in trees.[1]
Lignin exists naturally in plants and trees and its complex chemical structure allows for use in a
wide range of applications. The major sources of lignin are cooking liquors generated in wood
pulping processes, e.g. black and red liquor. Black liquor is to date mainly used for energy
conversion at the producing plant, but with the Lignoboost technology – a new Swedish-patented
method – lignin can be isolated from the black liquor, resulting in both a raw material that can be
used to produce value added products, and the opportunity to overcome equipment bottle necks
when planning for capacity increases in the pulp mills. This opens up for development of the
potential of lignin as a raw material for different products - a raw material that is potentially
available in large amounts and that could provide large benefits for a range of actors in the
Nordic/Baltic region.
[2]
Structure of lignin
[3]
1.2 CELLULOSE:
Cellulose is an organic compound with the formula (C6H10O5)n, a polysaccharide consisting of

a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose
is an important structural component of the primary cell wall of green plants, many forms of
algae and the oomycetes. Some species of bacteria secrete it to form biofilms.[ Cellulose is the
most abundant organic polymer on Earth. The cellulose content of cotton fiber is 90%, that of
wood is 40–50% and that of dried hemp is approximately 45%.
Cellulose is mainly used to produce paperboard and paper. Smaller quantities are converted into
a wide variety of derivative products such as cellophane and rayon. Conversion of cellulose from
energy crops into biofuels such as cellulosic ethanol is under investigation as an alternative fuel
source. Cellulose for industrial use is mainly obtained from wood pulp and cotton.
[4]
The DP of cellulose can extend to a value of 17000, even though more commonly a number of
800-10000 units is encountered. For instance, cellulose from wood pulp has a DP between 300
and 1700. The nature of bond between the glucose molecules (β-1,4glucosidic) allows the
polymer to be arranged in long straight chains. The latter arrangement of the molecule, together
with the fact that the hydroxides are evenly distributed on both sides of the monomers, allows for
the formation of hydrogen bonds between the molecules of cellulose. The hydrogen bonds in
turn result in the formation of a compound that is comprised of several parallel chains attached to
each other.
Cellulose is a relatively hygroscopic material absorbing 8-14% water under normal atmospheric
conditions (20 ° C, 60% relative humidity). Nevertheless, it is insoluble in water, where it swells.
Cellulose is also insoluble in dilute acid solutions at low temperature. The solubility of the
polymer is strongly related to the degree of hydrolysis achieved. As a result, factors that affect
the hydrolysis rate of cellulose also affect its solubility that takes place, however, with the
molecule being in a different form than the native one. At higher temperatures it becomes
soluble, as the energy provided is enough to break the hydrogen bonds that hold the crystalline
structure of the molecule. Cellulose is also soluble in concentrated acids, but severe degradation
of the polymer by hydrolysis is caused. In alkaline solutions extensive swelling of cellulose takes
place as well as dissolution of the low molecular weight fractions of the polymer (DP < 200).
Solvents of cellulose that have been applied in industrial or laboratory practice include
uncommon and complex systems, such as cupriethylenediamine (cuen) hydroxide or the
cadmium complex Cad oxen. Additionally, aqueous saltsolutions, such as zinc chloride, dissolve
limited amounts of cellulose. Cellulose does not melt with temperature, but its decomposition
starts at 180o C).
[5]
1.3 HEMI CELLULOSE:
The term hemicellulose is a collective term. It is used to represent a family of polysaccharides

such as arabino-xylans, gluco-mannans, galactans, and others that are found in the plant cell wall
and have different composition and structure depending on their source and the extraction
method. The most common type of polymers that belongs to the hemicellulose family of
polysaccharides is xylan. The result is a branched polymer chain that is mainly composed of five
carbon sugar monomers, xylose, and to a lesser extent six carbon sugar monomers such as
glucose. Important aspects of the structure and composition of hemicellulose are the lack of
crystalline structure, mainly due to the highly branched structure, and the presence of acetyl
groups connected to the polymer chain.
Hemicellulose extracted from plants possesses a high degree of polydispersity, polydiversity and
polymolecularity (a broad range of size, shape and mass characteristics). However, the degree of
polymerization does not exceed the 200 units whereas the minimum limit can be around 150
monomers. Hemicellulose is insoluble in water at low temperature. However, its hydrolysis starts
at a temperature lower than that of cellulose, which renders it soluble at elevated temperatures.
The presence of acid highly improves the solubility of hemicellulose in water.
1.4 ALPHA CELLULOSE:
Alpha cellulose is the major component of wood and paper pulp. It may be separated from the
other components by soaking the pulp in a 17.5% solution of sodium hydroxide. The pure
white,alpha cellulose is insoluble and can be filtered from the solution and washed prior to use in
the production of paper or cellulosic polymers. A high percent of alpha cellulose in paper will
provides a stable, permanent material. Linen and cotton contain high proportions of alpha
cellulose.
[6]
1.5 MORINGA OLEIFERA
Moringa oleifera is the most widely cultivated species of the genus Moringa, which is the only
genus in the family Moringaceae. English common names include: Moringadrumstick tree (from
the appearance of the long, slender, triangular seed-pods), horseradish tree (from the taste of the
roots, which resembles horseradish), ben oil tree, or benzoil tree(from the oil which is derived
from the seeds). It is a fast-growing, drought-resistant tree, native to the southern foothills of the
Himalayas in northwestern India, and widely cultivated in tropical and subtropical areas where
its young seed pods and leaves are used as vegetables. It can also be used for water purification
and hand washing, and is sometimes used in herbal medicine.
[7]
Oil from Moringa seeds is used in foods, perfume, and hair care products, and as a machine
lubricant.
Moringa is an important food source in some parts of the world. Because it can be grown cheaply
and easily, and the leaves retain lots of vitamins and minerals when dried, moringa is used in
India and Africa in feeding programs to fight malnutrition. The immature green pods
(drumsticks) are prepared similarly to green beans, while the seeds are removed from more
mature pods and cooked like peas or roasted like nuts. The leaves are cooked and used like
spinach, and they are also dried and powdered for use as condiment.
1.6 FIBER
Fiber is a natural or syntheticstring or used as a component of composite materials, or, when

matted into sheets, used to make products such as paper, papyrus, or felt.[2] Fibers are often used
in the manufacture of other materials. The strongest engineering materials often incorporate
fibers, for example carbon fiber and ultra-high-molecular-weight polyethylene.
Synthetic fibers can often be produced very cheaply and in large amounts compared to natural
fibers, but for clothing natural fibers can give some benefits, such as comfort, over their synthetic
counterparts.
1.6.1 Synthetic fibers
Synthetic come entirely from synthetic materials such as petrochemicals, unlike those man-made
fibers derived from such natural substances as cellulose or protein.
Fiber classification in reinforced plastics falls into two classes: (i) short fibers, also known as
discontinuous fibers, with a general aspect ratio (defined as the ratio of fiber length to diameter)
between 20 to 60, and (ii) long fibers, also known as continuous fibers, the general aspect ratio is
between 200 to 500.
[8]
1.6.2 Metallic fibers
Metallic fibers can be drawn from ductile metals such as copper, gold or silver and extruded or
deposited from more brittle ones, such as nickel, aluminum or iron. See also Stainless steel
fibers.
1.6.3 Carbon fiber
Carbon fibers are often based on oxidized and via pyrolysis carbonized polymers like PAN, but
the end product is almost pure carbon.
Silicon carbide fiber
Silicon carbide fibers, where the basic polymers are not hydrocarbons but polymers, where about
50% of the carbon atoms are replaced by silicon atoms, so-called poly-carbo-silanes. The
pyrolysis yields an amorphous silicon carbide, including mostly other elements like oxygen,
titanium, or aluminum, but with mechanical properties very similar to those of carbon fibers.
1.6.4 Fiberglass
Fiberglass, made from specific glass, and optical fiber, made from purified natural quartz, are
also man-made fibers that come from natural raw materials, silica fiber, made from sodium
silicate (water glass) and basalt fiber made from melted basalt.
1.6.5 Mineral fibers
Mineral fibers can be particularly strong because they are formed with a low number of surface
defects, asbestos is a common one.
[9]
1.7.0 APPLICATION
1.7.1 Industrial Cellulose Fibers

Specific Applications:
Adhesives: Cellulose fibers provide rheological properties including viscosity, sag control, and
contribute to tensile strength. Common use level: 1-8%.
Asphalt Roof Coatings and Cements:Cellulose fibers are used for thickening and bodying, oil
absorption, and internal reinforcement. Common use level: 1-10%.
Asphalt Sealers for Pavement and Crackfillers: Cellulose fibers provide high oil absorption,
build viscosity, control rheology and flow, and reduce shrinkage and cracking. They behave like
asbestos fillers without the concern of asbestos. Common use level: <1-4%.
Concrete Castings: Cellulose fibers enhance mold release and add green strength. Common use
level: <1-3%.
Fireproof Coatings: Cellulose fibers are used for rheology control, to prevent slump, and add
green strength. Common use level: 1-5%.
General Coatings: Cellulose fibers provide viscosity and flow control, add texture for
appearance, and provide green strength improvements. Common use level: 1-15%.
Lost Circulation Materials and Drilling Fluids: Cellulose fibers are used as lost circulations
control materials to stop fluid loss within geological structures. Common use level: 2-10%.
Plaster Compounds: Cellulose fibers are used for texture, thickening, green strength, and
improved trowling. Common use level: 1-15%.
Refractory Coatings: Cellulose fibers provide thixotropy, sag control, and green strength.
Common use level: 1-5%.
Sealants: Cellulose fibers act as oil absorbers in asphalt/rubber sealants and minimize
component migration during storage and application. Common use level: 2-5%.
Stone Mastic Asphalt (SMA): Cellulose fibers are added to a mastic of bitumen and filler to
provide adequate stability of the bitumen and prevent drainage of the binder during transport.
Common use level: <1-2%.
[10]
1.7.2 APPLICATION OF LIGNIN
1.7.2.1 Lignin as a Binder
Lignosulfonates are a very effective and economical adhesive, acting as a binding agent or
“glue” in pellets or compressed materials. Lignosulfonates used on unpaved roads reduce
environmental concerns from airborne dust particles and stabilize the road surface. This binding
ability makes it a useful component of:
 Biodegradable Plastic
 Coal briquettes
 Plywood & particle board
 Ceramics
 Animal feed pellets
 Carbon black
 Fiberglass insulation
 Fertilizers and herbicides linoleum paste
 Dust suppressants
 Soil stabilizers
1.7.2.2 Lignin as a Dispersant
Lignosulfonate prevents the clumping and settling of undissolved particles in suspensions. By

attaching to the particle surface, it keeps the particle from being attracted to other particles and
reduces the amount of water needed to use the product effectively. The dispersing property
makes lignosulfonate useful in:
 Cement mixes
 Leather tanning
 Clay and ceramics
 Concrete admixtures
 Dyes and pigments
 Gypsum board
 Oil drilling muds
 Pesticides and insecticides
1.7.2.3 Lignin as an Emulsifier
Lignosulfonate stabilizes emulsions of immiscible liquids, such as oil and water, making them
highly resistant to breaking. Lignosulfonates are at work as emulsifiers in:
 Asphalt emulsions
 Pesticides
 Pigments and dyes
[11]
 Wax emulsions
1.7.2.4 Lignin as a Sequestrant
Lignosulfonates can tie up metal ions, preventing them from reacting with other compounds and
becoming insoluble. Metal ions sequestered with lignosulfonate stay dissolved in solution,
keeping them available to plants and preventing scaly deposits in water systems. As a result, they
are used in:
 Micro-nutrient systems
 Cleaning compounds
 Water treatments for boilers and cooling systems
1.7.2.5 Lignin Applications – Chemicals
Phenols prepared by taking lignin reacting with a H‐supplying solvent at elevated temperature or
pressure
Lignin depolymerization provides routes to:

 Cresols
 Catechol
 Resorcinol
 Quinones
 Vanillin
 Guaiacols
1.7.2.6 Lignin Applications – Grease
Ca lignin sulfonate, mol. wt. of ≥ 10,000 g/mole, has been used to thickened base grease to form
a lubricating grease
A grease with a wax/lignin had improved corrosion protection properties.
Wear resistance of the tools is increased by using a grease containing hydrolytic lignin
1.7.2.7 Lignin Applications – Dust Control
Lignin, glycerin in water applied upon the surfaces of dust‐yielding situations like coal mines,
coal transportation by rail car, and stock yards, etc.
Select Ca lignin sulfonate powders have been shown to stabilize widespread contamination
following a nuclear accident, field studies demonstrate a dependence on the weather conditions
and the benefits is a short‐term corrective action.
Dust movement can be controlled by spraying a road surface with an emulsion of asphalt,
lignosulfonic and water
[12]
CHAPTER 2
2.0 LITERATURE REVIEW
Cellulose, hemicellulose and lignin are the main organic compounds which make up the biomass
of trees and agricultural by-products (lignocellulosic materials - LM).
LM are the most important renewable resources of the terrestrial ecosystem and have been used
for many biological and industrial purposes. From the nutritional point of view, agricultural by-
products such as cereal straws can provide only a fraction of the daily requirement of energy by
ruminant animals. The main constraint for using LM as an animal food is its low nutritive value.
Cell wall barriers observed in such materials negatively affect the bio-degradation of both
cellulose and hemicellulose.
Amongst the treatments that have been studied over the years steam treatment has shown
promise method for upgrading LM bio-availability. The need for specific equipments and the
high cost of setting up the processing unit have been important constraints for its application on a
farm scale. Nevertheless, steam treatment has been widely used in sugar refineries in Brazil
(Wayman and Parekh) as a method to upgrade sugar cane bagasse for animal feed.
Moringa Oleifera
Drumstick tree, also known as horseradish tree and ben tree in English, is a small to medium-
sized, evergreen or deciduous tree native to northern India, Pakistan and Nepal. It is cultivated
and has become naturalized well beyond its native range, including throughout South Asia, and
in many countries of Southeast Asia, the Arabian Peninsula, tropical Africa, Central America,
the Caribbean and tropical South America. The tree usually grows to 10 or 12 m in height, with a
spreading, open crown of drooping, brittle branches, feathery foliage of tripinnate leaves, and
thick, corky, deeply fissured whitish bark. It is valued mainly for its edible fruits, leaves, flowers,
roots, and seed oil, and is used extensively in traditional medicine throughout its native and
introduced ranges.
[13]
Plant cell wall
Plant cell walls consist of primary and secondary cell walls. Primary walls are deposited at early
stages of growth while the cells are expanding.
The middle lamella which forms a common boundary layer between adjacent cells occupies the
site of the cell plate. Contiguous cells are bound together by deposition of lignin in the middle
lamella.
Secondary cell walls are formed at later stages either lignified or unlignified.
Unlignified walls have a high tensile strength and stiffness mainly due to the mechanical
properties of the cellulose microfibrils (Northcote). Lignification results in a rigid cell wall with
high compressive strength and low porosity. The highest concentration of lignin is observed in
the middle lamella and the primary wall. The secondary wall contains most of the cell lignin as it
forms the greatest volume of cell wall (Harris).
Lignin.
Lignin is the most abundant natural non-carbohydrate organic compound in fibrous materials.
The importance of lignin in plants should be considered from different aspects, i.e. its role in
plant development, contribution to mechanical strength and protection from degradation
[14]
(Walker). From the nutritional point of view, lignin has always been blamed as an important
barrier to polysaccharide utilization.
Lignin is a complex polymer of aromatic alcohols known as monolignols. It is most commonly
derived from wood, and is an integral part of the secondary cell walls of plants and
some algae. Lignin was first mentioned in 1813 by the Swiss botanist A. P. de Candolle, who
described it as a fibrous, tasteless material, insoluble in water and alcohol but soluble in weak
alkaline solutions, and which can be precipitated from solution using acid. He named the
substance “lignine”, which is derived from the Latin word lignum, meaning wood. It is one of
the most abundant organic polymers on Earth, exceeded only by cellulose. Lignin constitutes
30% of non-fossil organic carbon and a quarter to a third of the dry mass of wood.
Lignin Isolation from Pulp
Several different enzymatic, chemical and mechanical methods have been developed for the
isolation of lignin from wood and pulp. However, due to the heterogeneous nature of wood and
pulp fibers and the heterogeneity that exists between individual fibers, no method is currently
available for the quantitative isolation of native or residual lignin without the risk of structural
changes during the isolation. Even if the perfect isolation technique could be found, the product
would at best represent the average structure of native or residual lignin components. However,
the information gained about the chemical reactivity and structure of isolated lignin is valuable.
Lignin is made up of three primary precursors, ie. Trans-coniferyl, trans-sinapyl and trans-p-
coumaryl alcohols(Sarkanen and Ludwic). Lack of enzymic control during lignin polymerization
(formation) results in an almost random series of bonding and a very complex structure. The
existence of strong carbon-carbon (C-C) and ether (C-O-C) linkages in the lignin affects its
susceptibility to chemical disruption. Lignin are always associated with hemicellulose, not only
in intimate physical mixture, but also anchored to the latter by actual covalent bonds (Sarkanen
and Ludwic).
Most research on chemical structure, metabolic pathways and decomposition reactions of lignin
have been carried out on woody materials. Grass lignins are comparatively much less studied
than wood lignins.
Lignin structure has been discussed previously.In order to elucidate lignin structure and
reactivity several studies on lignin acidolysis have been completed.
Lignin disruption under acidolysis is essentially attributed to the cleavage of various ether bonds,
the most important being of the aryl glycerol-ß-aryl ether bond Chua and Wayman reported that
lignin-lignin and lignin-carbohydratebonds are more sensitive to temperature than acidity.
Therefore, under auto-hydrolysisconditions (t>160oC in absence of exogenous catalyst) one
could expect greater lignindepolymerization as compared to mild temperature acid hydrolysis
(100-140 oC) withexogenous acid).
[15]
Cellulose
Cellulose is the most abundant cell wall polysaccharide in nature and consists of long chains of
ß-1,4 linked glucose residues. The chains are held together by hydrogen bonds between oxygen
of alternating glycosidic bond in one glucan chain and the primary hydroxyl groups at position 6
of glycosyl residues in another chain to form thin, flattened, rod-like structures that are referred
to as microfibrils.
The cellulose microfibrils are bound to each other and to hemicellulose polymers by hydrogen
bonding but there is no evidence of covalent linkage between cellulose and other cell wall
constituents.
Cellulose microfibrils contains regions with highly oriented molecules or less oriented
microfibrils called crystalline and amorphous regions respectively. The crystallinity index of
cellulose, i.e. degree of microfibrils orientation, is highly variable and depends on the source and
age of the tissue. Because of its structure.
Pulp of high cellulose content, also known as dissolving pulp, is needed for many purposes,
including the production of cellulosic fibers and films. Paper-grade pulp, which is rich in
hemicellulose, could be a cheap source but must be refined. Hitherto, hemicellulose extraction
procedures suffered from a loss of cellulose and the non-recoverability of unaltered
hemicelluloses. Herein, an environmentally benign fractionation concept is presented, using
mixtures of a cosolvent (water, ethanol, or acetone) and the cellulose dissolving ionic liquid 1-
ethyl-3-methylimidazolium acetate (EMIM OAc). This cosolvent addition was monitored using
Kamlet–Taft parameters, and appropriate stirring conditions (3 h at 60 °C) were maintained. This
allowed the fractionation of a paper-grade kraft pulp into a separated cellulose and a regenerated
hemicellulose fraction. Both of these exhibited high levels of purity, without any yield losses or
depolymerization. Thus, this process represents an ecologically and economically efficient
alternative in producing dissolving pulp of highest purity.
Acid hydrolysis (saccharification) of cellulose produces a random cleavage of glucosidic

linkages containing hemiacetal and hydroxyl terminal groups (Harris).
Cellulose acid hydrolysis is dependent upon H+ concentration. A high cellulose hydrolysis rate is
observed even below 100oC when acid concentration is high. However, under less acidic
conditions higher temperature and/or longer reaction time are required for achieving similar
cellulose hydrolysis.
The crystallinity index (CrI) of native cellulose has been suggested as a limiting factor for
enzymic hydrolysis. Interestingly, cellulose CrI is increased during acid hydrolysis whilst greater
cellulose bio-availability is achieved (Dekker and Wallis). The reason for such an increase in
cellulose availability is the significant change observed in the chemical structure of lignin as well
as in the degree of polymerization of cellulose and accessible surface area (fibre swelling). The
degree of polymerization of cellulose can be significantly decreased during acid hydrolysis
(Knappert).
[16]
Alpha Cellulose
One of three classes of cellulose, alpha cellulose has the highest degree of polymerization and is
the most stable. The other two classes, known as hemicellulose, are beta cellulose and gamma
cellulose. Alpha cellulose is the major component of wood and paper pulp. It may be separated
from the other components by soaking the pulp in a 17.5% solution of sodium hydroxide. The
pure white, alpha cellulose is insoluble and can be filtered from the solution and washed prior to
use in the production of paper or cellulosic polymers. A high percent of alpha cellulose in paper
will provides a stable, permanent material. Linenand cotton contain high proportions of alpha
cellulose.
Hemicellulose.
The term hemicellulose is applied to cell wall polysaccharides which occur in close association
with cellulose, especially in lignified tissues. It is often restricted to substances extracted with
alkaline reagents (Aspinal). Hemicelluloses are built up of a relatively limited number of sugar
residues (100-200 sugar units), eg. D-xylose, D-mannose, D-glucose, D-galactose, L-arabinose,
4-Omethyl- D-glucuronic acid, D-galacturonic acid, D-glucuronic acid and to a lesser extent, L-
rhamnose, L-fucose and various O-methylated neutral sugars.
Xylans are quantitatively the most important hemicellulose of graminaceous cell walls. Xylan is
composed of chains of 1-4 linked ß-D-xylopyranose residues. Different plants may contain the
same basic xylan structure but different arrangements with other sugar residues, especially L-
arabinose, D-glucuronic acid and 4-methyl ether, may occur (Wilkie).
The composition of hemicellulose in softwoods and hardwoods is different from that in grasses.
Galactoglucomannans are the major constituents (20%) of softwood hemicelluloses. Hardwood
hemicellulose contains glucoxylan (15-30%) polymer backbone similar to that of the softwoods.
Hemicellulose is linked to lignin through D-galactose, L-arabinose and D-xylose by glycosidic
linkages. Isolation of lignin-carbohydrate complexes from rumen liquor of animals fed roughage
confirms the presence of bonds between lignin and carbohydrates. According to ester linkage by
the O-5 position of arabinose to core lignin seems to be a major bond between lignin and
hemicellulose in forages.
Proteins.
Proteins are a minor component of the plant cell wall which may be covalently cross-linked with
lignin and polysaccharides (Lamport). Extensins (hydroxyproline-rich glycoprotein) are the most
abundant protein in the plant cell wall. Primary cell walls of dicotyledons contain between 5 and
10% extensin which is rich (20%) in hydroxy-L-proline (Dey and Brinson).
[17]
CHAPTER 3
3.0 MATERIAL AND METHODS
3.1 Klason lignin
3.1.1 Scope:
This method describes a procedure which can be applied to the determination of acid-insoluble
lignin in wood and in all grades of unbleached pulps. In semi-bleached pulp the lignin content
should not be less than about 1% to provide a sufficient amount of lignin, about 20 mg, for an
accurate weighing. The method is not applicable to bleached pulps containing only small
amounts of lignin.
3.1.2 Test specimens:
Allow the sample to reach moisture equilibrium in the atmosphere near the balance, and weigh
out two test specimens to the nearest 0.1 mg as follows: for wood, 1.0 ± 0.1 g; for pulp, 2.0 ± 0.1
g, equivalent to oven-dry weight. Place the test specimens in 100-mL beakers.
3.1.3 Apparatus:
Filtration apparatus, consisting of a filtering flask, 2000 mL, a filtering crucible, about 30
mL,anadapter, and a siphon tube. Other types of filtration apparatus may also be used.
Dry the filtering crucibles in an oven at 105 ± 3°C for about 2 h, cool, and weigh before use.
Constant temperature bath, to maintain a temperature of 20 ± 1°C.
[18]
Flasks, Erlenmeyer, 1000 mL, with a mark added at 575 mL volume (for wood specimens; and
2000 mL, with a mark added at 1540 mL volume (for pulp specimens).
Reflux condenser (optional), to be attached to the flask. If used, flasks and condenser should be
equipped with ground glass connectors. If ground glass connectors are not available, a rubber
stopper may be used.
Drying oven, forced circulation type, maintained at 105 ± 3°C. Hot plate, electric. Wiley mill,
with a 10 or 20-mesh screen, or a Waring-type blender.
Other glassware: burette, 50 mL; beakers, 100 mL; glass stirring rods.
3.1.4 Reagents:
Sulfuric acid, 72% H2SO4 solution, 24 ± 0.1N, sp gr 1.6338 at 20°/4°C, prepared as follows:
Carefully pour 665 mL of concentrated H2SO4 (95.5 to 96.5%, sp gr 1.84) into 300 mL of water,
and after cooling, make up to 1000 mL. Adjust the strength to 24 ± 0.1N by titration with a
standard alkali, or by measuring specific gravity. A variation of 0.1% in the strength of acid at
this concentration causes a change of 0.0012 in specific gravity.
Cool the acid solution in a refrigerator or under tap water to 10 to 15°C before use.
Ethanol-benzene mixture. Mix one volume of approximately 95% ethanol and two volumes of
C.P.benzene.
3.1.5 Procedure:
Add to the beakers containing the test specimen’s cold (10 to 15°C) 72% sulfuric acid, 15.0 mL
for a wood and 40.0 mL for a pulp specimen. Add the acid gradually in small increments while
stirring and macerating the material with a glass rod. Keep the beaker in a bath at 2 ± 1°C during
dispersion of the material. After the specimen is dispersed, cover the beaker with a watch glass
and keep it in a bath at 20 ± 1°C for2 h. Stir the material frequently during this time to ensure
complete solution. Add about 300 to 400 mL of water to a flask (see 5.3) and transfer the
material from the beaker to the flask. Rinse and dilute with water to 3% concentration of sulfuric
acid, to a total volume of 575 mL for wood, and to 1540 mL for pulps. Boil the solution for 4 h,
[19]
maintaining constant volume either by using a reflux condenser or by frequent addition of hot
water. Allow the insoluble material (lignin) to settle, keeping the flask in an inclined position. If
the lignin is finely dispersed, it may require an “overnight” or a longer period to settle. Without
stirring up the precipitate, decant or siphon off the supernatant solution through a filtering
crucible (see Note 7). Then transfer the lignin quantitatively to the filter, using hot water and a
rod with rubber policeman. Wash the lignin free of acid with hot water. Dry the crucible with
lignin in an oven at 105 ± 3°C to constant weight. Cool in a desiccator and weigh. If a correction
for ash in lignin is desired, transfer the lignin to a small platinum or porcelain crucible and
proceed in accordance with TAPPI T 211 “Ash in Wood and Pulp.”
3.1.6 Calculation:
Klason lignin for wood sample

Lignin, % = A 100 / W
Where:
A = weight of lignin = 1.7 gm
W = oven-dry weight of test specimen =5 gm
Lignin % =1.7*100 / 5 = 34 %
Klason lignin for pulp sample
Lignin, % = 3.8 *100 /10 = 38 %
3.2 Batch pulping
3.2.1 Object:
To perform batch pulping of given raw material.
3.2.2 Apparatus:
Research laboratory digester,

Watch glass
Electric oven
[20]
Measuring cylinders
Beakers
3.2.3 Reagents:
Sodium hydroxide (NaOH)

Sodium sulfide (Na2S)
3.2.4 Procedure:
Calculate the moisture content of the given raw material. Fill the chips, liquor and chemical to
80% of the cooking vessel and close the vessel tightly .Warm liquor could be taken from the
separate vessel (reservoir vessel), ifrequired, through circulation pumps. Put on the running
water supplied to the pump glands.Close the liquor (reservoir vessel) supply, if used .Switch on
the motor and allow the circulation pumps. Switch on the supply to the heaters. Set the
temperature and heat rate on the control panel. Continue the operation unit the desired
temperature (170 C) and pressure (7 kg/cm2) in the cooking vessel are achieved .The condition
be maintained for the duration desired. Drain out the sample during the process to check the
quality of the pulp liquor .Before taking the sample, cooling water to the sample is put on. PH
value of the cooking vessel as observed through the ON-LINE pH indicator be noted for any
change to be affected in the liquor quality and chemical. PH condenser shall always be kept in
cooled condition by circulating water around it, so that the sensor takes the correct pH values.
When the cooking is complete etc. the heater be put off. Water supplied to the cooking vessel
.be put ON before draining off the spent liquor. Take out pulp for further processing. Put off the
heater and the water supplies.
3.2.5 Calculation:
Lignin, % = (Pulp produced * 100) / Material charged
= 49 * 100 /120 = 40.83 %
[21]
3.3ALPHA-, BETA- AND GAMMA-CELLULOSE IN PULP
3.3.1 Scope:
This method for determination of alpha-, beta- and gamma-cellulose can be applied to bleached
or delignified pulps only. Unbleached and semi-bleached pulps must be delignified before
testing.
3.3.2 Apparatus:
Pulp dispersion apparatus, consisting of a variable speed motor and a stainless steel stirrer with a
shell.
Constant temperature bath, to maintain a temperature of 25+0.2 °C.
Timer, stop watch or electric timer.
Filtering funnel or crucible, 50 or 100 mL, with a fritted glass disk of coarse porosity.
Other glassware: beakers, tall-form, 300-mL; pipets, 10, 25, 50, and 75 mL; burette 50-mL;
flasks, 250-and 300-mL; filtering flasks, 250-mL; graduated cylinders, 25-, 50-, and 100-mL;
glass stirring rods.
3.3.3 Reagents:
Sodium hydroxide solution, 17.5% NaOH by weight Potassium dichromate solution, 0.5N.
Dissolve 24.52 g of K2Cr2O7 in water and dilute to 1000 mL. Ferrous ammonium sulfate
solution, 0.1N. Dissolve 40.5 g of Fe (NH4)2 (SO4)2 6H2O in water, add 10 mL of concentrated
H2SO4, and dilute to 1000 mL. Phenanthroline - ferrous sulfate. Dissolve 1.5 g of 1, 10-
phenanthroline monohydrate and 0.7 g of FeSO4 7H2O in 100 mL of water. Sulfuric acid,
concentrated H2SO4, 96 to 98%, sp gr 1.84.Sulfuric acid, 3N. Add 83.5 mL of concentrated
H2SO4 to an excess of water and dilute to 1000 mL.
3.3.4 Procedure:
[22]
Place the test specimen in a 300-mL tall-form beaker and add 75.0 mL of 17.5% NaOH reagent,
adjusted previously to 25+0.2 °C. Note the time at which the reagent is added. Stir the pulp with
the apparatus until it is completely dispersed. Avoid drawing air into the pulp suspension during
stirring. When the pulp is dispersed, raise the stirrer and remove the adhered pulp fibers with a
pointed glass rod. Rinse the stirrer with 25.0 mL of 17.5% NaOH reagent, adding it to the
beaker, so that exactly 100.0 mL of the reagent have been added to the pulp. Stir the pulp
suspension with a rod and place in a bath at 25+0.2 °C. After a period of 30 min from the first
addition of the NaOH reagent, add 100.0 mL of distilled water at 25+0.2 °C to the pulp
suspension and stir thoroughly with a rod. Leave the beaker in the bath for another period of 30
min so that the total extraction time is 60 min. At the end of the 60-min period, stir the pulp
suspension with a rod and transfer to a filtering funnel. Discard the first 10 to 20 mL of the
filtrate, then collect about 100 mL of the filtrate in a clean and dry filtration flask.
3.3.4.1 Alpha-cellulose determination
Pipet 25.0 mL of the filtrate and 10.0 mL of 0.5N potassium dichromate solution into a 250-mL
flask. Add cautiously, while swirling the flask, 50 mL of concentrated H2SO4. Allow the
solution to remain hot for 15 min, then add 50 mL of water and cool to room temperature. Add 2
to 4 drops of Ferroin indicator and titrate with 0.1N ferrous ammonium sulfate solution to a
purple color Make a blank titration substituting the pulp filtrate with 12.5 mL of 17.5% NaOH
and 12.5 mL of water
3.3.4.2 Beta- and gamma-cellulose determination
Pipet 50.0 mL of the pulp filtrate into a 100-mL graduated cylinder having a ground glass
stopper. Add 50.0 mL of 3N H2SO4 and mix thoroughly by inverting. Heat the cylinder
submerged in a hot water bath at about 70-90°C for a few minutes to coagulate the Beta-
cellulose. Allow the precipitate to settle for several hours, preferably overnight, then decant or
filter, if necessary, to obtain a clear solution.Pipet 50.0 mL of the clear solution and 10.0 mL of
0.5N K2Cr2O7 into a 300-mL flask and add cautiously 90 mL of concentrated H2SO4. Allow
the solution to remain hot for 15 min, then proceed with titration as outlined in Make a blank
titration substituting the solution with 12.5 mL of 17.5% NaOH, 12.5 mL of water and 25 mL of
3N H2SO4.
[23]
3.3.5 Calculation:
3.3.5.1 Alpha-cellulose
Alpha-cellulose, % =100 - 6.85 * (V2-V1) *N*20
A*W
Where,
V1 = titration of the pulp filtrate =12 mL
V2 = blank titration = 32mL
N = exact normality of the ferrous ammonium sulfate Solution =0.1 N
A = volume of the pulp filtrate used in the oxidation = 25 mL
W = oven-dry weight of pulp specimen = 5 gm
Alpha-cellulose, % =100 - 6.85 * (32 - 12) *N*20
25*5
= 97.8%
3.3.5.2 Gamma cellulose
Gamma cellulose, % = [6.85 (V4 -V3) x N x 20] / [25 x W]

Where:
V3 = titration of the solution after precipitation of beta- cellulose = 12 mL
V4 = blank titration = 16 mL
Gamma cellulose, % = [6.85 (16 - 12) *0.1* 20] / [25 * 5]
= 0.43 %
3.3.5.3 Beta-cellulose
Beta-cellulose %=100 - (alpha-cellulose% + gamma cellulose %)
= 100 - (97.8 + 0.43) = 2.63 %
[24]
3.4 Hollocellulose
3.4.1 Scope:
The extracted wood sample in the form of 60 mesh is treated with sodium chloride solution in
the acidic medium to remove lignin from the sample with degrading cellulose
3.4.2 Apparatus:
Soxhlet apparatus, Water bath with thermo-staterlin merge flasks, Weighing bottle, Sintered
crucible, Beakers, Pipette, and Burette
3.4.3 Reagents:
Methanol, Benzene, Sodium chlorite, acetic acid, acetone, Ice.
3.4.4 Procedure:
20g of wood sample in the form of 60-mesh is extracted with a mixture of methanol benzene
(1.2) in the Soxhlet apparatus .the percentage of moisture is then determined in the extracted
material.5g of O.D. extracted wood sample is put in an Erlenmeyer flask (250ml) and 150 ml
solution containing 1.5g of sodium chloride and 10 drops of acetic acid at 70 °C is added to it
.the flask is loosely covered and as put in a thermo-staterlin regulated at 70°C .The contents of
the flask are shaken from time to time. After one hour, add another 10 drop of acetic acid and a
solution containing 1.5g of sodium chloride .this operation is repeated for three time every
hour .The contents of the flask are cooled in a ice bath and filtered immediately in a sintered
crucible .the residue in the crucible is washed with ice water (5*40ml) .it is finally washed with
50-ml acetone and acetone and dried under vacuum till the constant weight is obtained.
[25]
3.4.5 Calculation:
Hollocellulose % = (A*100) / B
Where A= Oven dried weight of holocellulose, gm
B = Oven dried weight of initial sample, gm
Table:
Sr.No. A (gm) B (gm) H%

1 3.04 4.5 67.50
2 3.11 4.5 69.11
3 2.95 4.5 65.56
Avg Hollocellulose= (67.5+69.11+65.56)/3 = 67.39 %
[26]
CHAPTER 4
4.1 ASH CONTENT
4.1.1 Scope:
The ash content of wood is defined as the percentage of residue remaining after dry oxidation
575+25°C for 3hr, or longer if necessary to burn off all the carbon. The ash content is an
approximate measure of the mineral content and other inorganic matter in wood.
4.1.2 Test Specimen:
The test specimen shall consist of approximately 2 g of wood that has been ground to pass a 40-
mesh screen. Care shall be taken to ensure that it is representative of the entire lot of material
being tested.
4.1.3 Apparatus:
Crucibles, with tightly fitting lids, having a capacity of 30 mL or more, shall be used. Platinum
crucibles are preferred, but silica or porcelain crucibles may be used.
Analytical Balance, Sensitive to 0.1 mg.
Electric muffle furnace adjusted to maintain a temperature of 575+25°C.
4.1.4 Procedure:
Carefully clean the empty crucible and ignite in a muffle furnace at 575 ± 25°C for 3hr. . After
ignition, cool slightly and then place in a desiccator, containing indicating-grade anhydrous
alumina. When cooled to room temperature, weigh the ignited crucible on the analytical balance
to the nearest 0.1 mg.
[27]
Place the crucible and contents, with the cover removed, in the muffle furnace and ignite until
all the carbon is eliminated. Heat slowly at the start to avoid flaming and protect the crucible
from strong drafts at all times to avoid mechanical loss of test specimen. The recommended
temperature of final ignition is575 ± 25 °C. Avoid heating above this maximum.
When the specimen is completely combusted as indicated by the absence of black particles,
remove the crucible from the furnace, replace the cover, and allow to cool somewhat; then place
in a desiccator containing indicating grade anhydrous alumina and cool to room temperature.
Weigh the crucible with ash to the nearest 0.1 mg. Repeat the ignition and weighing until the
weight of the ash is constant to ± 0.2 mg.
4.1.5 Calculation:
Ash Content, % = (C/ B) * 100

Where;C =weight of ash,gm
B=weight of oven-dried test specimen, gm
Table:
Sr.No. C (gm) B (gm) % ASH

1 0.08 5 1.6
2 0.07 5 1.4
3 0.09 5 1.8
4 0.10 5 2.0
5 0.08 5 1.6
Avg. ash content % = 1.68 %
[28]
4.2 MOISTURE CONTENT
4.2.1 Scope:
The amount of water contained in the wood, usually expressed as a percentage of moisture in a
sample by drying the sample to a constant weight. The water content is expressed as the
Percentage, by weight of the dry sample.
The test specimen shall consist of approximately 2 g of wood that has been ground to pass a 40-
mesh screen. Care shall be taken to ensure that it is representative of the entire lot of material
being tested.
4.2.3 Apparatus:
Oven—A forced-convection oven that can be maintained at a temperature of 103 ± 2°C

throughout the drying chamber.
Balance—The sensitivity shall be a minimum of 0.1 % of the nominal oven-dry mass of the
specimen.
Petri dish, in which sample is taken.
4.2.4 Theory:
In the paper industry, we most often define moisture content on a dry basis. This means that the
moisture content is defined as
Moisture content = (Weight of moisture/Total weight of sample) * 100
Ovens used for the test are usually electrically heated and sit on a counter top. The oven needs to
be able to attain and hold a temperature of 217°F (103°C). This is rather important for an
accurate test.
[29]
4.2.5 Procedure:
Take 2 gram of sample in a crucible and weight it, A.

Place the crucible + sample in an oven which is maintained at constant temperature of 103°C for
2 hours.
After 2 hr. remove it and again weight, of dry sample only, B
Write the observation in a table and repeat it for three times (if required accurate reading).
4.2.6Calculation:
Moisture Content, % = [(A - B) X 100]/A

Where:
A = mass of the as-received test specimen, gm
B = mass of the oven-dried specimen, gm
Table:
Sr. No. A(gm) B(gm) %Moisture

1 2 1.79 10.5
2 2 1.80 10
3 2 1.78 11
4 2 1.81 9.5
5 2 1.82 9.0
Avg. moisture content = 10 %
[30]
4.3 APPARENT DENSITY
4.3.1 Scope:
To determine the apparent density of wood sample at normal condition.
4.3.2 Apparatus:
Dimension measuring equipment

Weighing balance
4.3.3 Theory:
The density of a substance is its mass per unit volume. The symbol most often used for density
is ρ, although the Latin letter D can also be used. Mathematically, density is defined as mass
divided by volume.
Where ρ is the density, m is the mass, and V is the volume. In some cases (for instance, in the
United States oil and gas industry), density is loosely defined as its weight per unit volume.
4.3.4 Procedure:
We take a single wood piece of wood sample and measure its dimension like height, width, and
length, multiplication of all these three quantity gave us volume. Mass can be achieved by
weighting that wood piece. Using formula above, density can be measured easily.
4.3.5 Calculation:
LENGTH WIDTH HIGHT WEIGHT VOLUME DENSITY
Sr. No.
(cm) (cm) (cm) (gm) (cc) (gm/cc)
1 4.5 1.6 0.9 2.85 6.48 0.439
2 3.5 1.6 0.8 2.97 4.48 0.663
3 3.6 1.8 0.8 1.44 5.184 0.278
4 3.2 1.8 0.8 2.88 4.608 0.625
5 3.4 1.7 1.2 3.40 6.93 0.490
6 3.8 1.8 1.0 3.27 6.84 0.47
Avg. density = 0.439+0.663+0.278+0.625+0.490+0.470 = 0.431 gm/cc
[31]
4.4 BULK DENSITY OF WOOD SAMPLE
4.4.1 Scope:
To determine the bulk density of wood sample at normal condition.
4.4.2 Apparatus
Beaker
Weighing balance
4.4.3 Theory:
Bulk density is a property of powder, granules, and other "divided" solids, especially used in

reference to mineral components, chemical substances, (pharmaceutical) ingredients, foodstuff,
or any other masses of corpuscular or particulate matter. It is defined as the mass of
many particle of the material divided by the total volume they occupy. The total volume includes
particle volume, inter-particle void volume, and internal pore volume. Bulk density is not an
intrinsic property of a material; it can change depending on how the material is handled or filled.
4.4.4 Procedure:
For bulk density we take wood pieces in bulk in a measuring beaker filled up to 200 ml. doing
this gave us volume, then we weight those wood pieces together. Thus we found bulk density
and we take several reading.
4.4.5 Calculation:
Initial weight of beaker = 138.76 gm

Final weight of beaker = 180.7 gm
Weight of sample = 41.94 gm
Volume of sample in beaker = 200 ml
Bulk density = 41.94/200 = 0.2097 g/cc
[32]
4.5 COLD-WATER SOLUBILITY
4.5.1 Scope:
These test methods cover the determination of the water solubility of wood. This method
provides a measure of the tannins, gums, sugars, and coloring matter in the wood.
The test specimen shall consist of 2 g of air-dried sawdust that has been ground to pass a 425-μm
sieve and be retained on a 250-μm sieve.
4.5.3 Apparatus:
Filtering Crucibles—Alundum or fritted-glass crucibles of coarse porosity will be required.

Filtering Flask—Asuction filtering flask, equipped witha rubber flange for the crucible and
funnel, shall be provided.
4.5.4 Procedure:
Place a 2-g test specimen, the moisture content of which has been previously determined, in a
400-mL beaker, and cover with 300 mL of distilled water. Let this mixture digest at a
temperature of 23 6 2°C, with frequent stirring, for 48 h. Filter the material on an Alundum or
fritted-glass crucible, using suction, wash with cold distilled water, and dry to constant weight at
100 to 105°C. Drying usually requires approximately 4 h. Place the crucible in a loosely
stoppered weighing bottle, cool in a desiccator, and weigh.
4.5.5 Calculation:
Cold water solubility %= (W1 -W2)/W1 *100
Where:
W1 = weight of moisture-free specimen used.

W2 = weight of dried specimen after extraction with cold wate
[33]
Table:
Sr. No. W1 (gm) W2 (gm) SOLUBILITY %

1 2 1.93 3.2
2 2 1.84 5.5
3 2 1.90 5.0
4 2 1.94 3.0
5 2 1.95 2.5
Avg. solubility = 3.84 %
4.6 HOT-WATER SOLUBILITY
4.6.1 Scope:
These test methods cover the determination of the water solubility of wood. This method
provides a measure of the tannins, gums, sugars, coloring matter, and starches in the wood.
The test specimen shall consist of 2 g of air-dried sawdust that has been ground to pass a 425-μm
sieve and be retained on a 250-μm sieve.
4.6.3 Procedure:
Place a 2-g test specimen, the moisture content of which has been previously determined, and
100 mL of distilled water in the Erlenmeyer flask and attach the reflux condenser. Place the flask
in the boiling water bath, with the solution in the flask just below the level of the water in the
bath, and heat gently for 3 h. Filter the contents of the flask on a tared Alundum or fritted-glass
crucible, using suction, wash with hot water, and dry to constant weight at 100 to 105°C. Place
the crucible in a loosely stoppered weighing bottle, cool in a desiccator, and weigh.
4.6.4 Calculation:
[34]
Hot water solubility % = (W1- W2)/W1*100
Where:
W1 = weight of moisture-free specimen used in 9.1, and
W2 = weight of dried specimen after extraction with hot water.
Table:
Sr. No. W1 (gm) W2 (gm) SOLUBILITY %

1 2 1.866 6.7
2 2 1.851 7.45
3 2 1.89 5.5
4 2 1.88 6.0
5 2 1.83 8.5
Avg. solubility = 6.83 %
4.7 ONE PERCENT SODIUM HYDROXIDE SOLUBILITY OF WOOD
4.7.1 Scope:
This method for determination of 1% sodium hydroxide solubility can be applied to wood and to
unbleached and bleached pulp. Wood or pulp is extracted with hot 1% sodium hydroxide
solution for 1 h. The loss in weight is determined and calculated as percent solubility.

[35]
Allow the sample to come to moisture equilibrium in the atmosphere near the balance; then
weigh out two test specimens of 2.0 ± 0.1 g to the nearest 1.0 mg. Place the test specimens in
200-mL tall-form beakers.
4.7.3 Apparatus:
Pulp dispersion apparatus

Water bath, designed so that the temperature of the material during treatment is uniformly
maintained at 97° to 100°C.
Beakers, tall form, 200 mL.
Filtering crucibles, 30 mL, medium porosity (nominal maximum pore size 10-15μm). Dry before
use in an oven at 105° ± 3°C for 60 min, cool in a desiccator, and weigh.
Filtering flasks, 1000 mL.
Other equipment: graduated cylinder, 100 mL; watch glasses; stirring rods; thermometer.
4.7.4 Reagents:
Sodium hydroxide solution, 1.0% ± 0.1% NaOH (0.25N). Dissolve 10.0 g of solid NaOH in
water and dilute to 1000 mL.
Acetic acid, 10%. Dilute 100 mL of glacial CH3COOH with water to 1000 mL.
4.7.4 Procedure:
To the wood meal, add 100 ± 1 mL of 1% NaOH solution and stir with a glass rod. To the pulp
add 75 mL of 1% NaOH solution and stir with the pulp dispersion apparatus until the pulp is
dispersed. Raise the stirrer and remove the adhered pulp fibers with a glass rod. Rinse with 25
mL of the NaOH reagent, adding it to the beaker so that 100 ± 1 mL of the reagent are added to
the pulp. Cover the beaker with a watch glass and place in a water bath maintained at 97° to
100°C for a period of 60 min. Keep the water in the bath boiling and its level above that of the
alkali solution in the beaker. Stir the pulp with a rod for about 5 s at 10, 15, and 25 min after
placing in the bath. At the end of 60 min transfer the material to a tared filtering crucible and
wash with 100 mL of hot water. Then add 25 mL of 10% acetic acid and allow to soak for 1 min
before removal. Repeat this step with a second 25-mL portion of 10% acetic acid. Wash the
[36]
material finally with hot water until acid free. Dry the crucible and contents in an oven at 105° ±
3°C to a constant weight, cool in a desiccator, and weigh.
4.7.5 Calculation
S = [(A - B)/A] × 100

Where
S = % solubility
A = oven-dry weight of the test specimen before extraction, g
B = oven-dry weight of the test specimen after extraction, g
Table
Sr.No. A (gm) B (gm) %S
1 2 1.76 12
2 2 1.73 13.5
3 2 1.74 13
4 2 1.75 12.5
Avg. Solubility % = (12+13.5+13+12.5)/4 = 12.75 %
4.8 SOLVENT EXTRACTIVES OF WOOD AND PULP
4.8.1 Scope:
[37]
This method describes a procedure for determining the amount of solvent-soluble, non-volatile
material in wood and pulp. Dichloromethane extraction gives lower amounts of extractives.
Extraction with1/3 ethanol and 2/3 benzene gives reproducible results and includes some
additional compounds.

For wood:
In accordance with TAPPI T 257 “Sampling and Preparing Wood for Analysis,” obtain a sample
of air-dried Sawdust to pass a 0.40 mm (40 mesh) screen and determine its moisture content
according to TAPPI T 264 “Preparation of Wood for Chemical Analysis.” For each solvent used,
at least 4 g are required for determination in duplicate. From the air-dry sample, weigh to the
nearest 5 mg, in a tared extraction thimble, a specimen equivalent to 2 ± 0.1 g of moisture-free
wood.
4.8.3 Reagents:
Ethanol, approximately 95% C2H5OH by volume, or denatured with 5% methanol, having a

residue after evaporation of less than 0.005%.
Benzene, purified C6H6, having a residue after evaporation of less than 0.001%.
Dichloromethane, U.S.P. 98% CH2Cl2, having a residue after evaporation of less than 0.002%.
Ethanol-benzene mixture. Mix together 1 volume of ethanol and 2 volumes of benzene.
4.8.4 Procedure:
Clean, then dry the Soxhlet extraction flask. Place the extraction thimble and specimen in
position in the Soxhlet apparatus. Fill the extraction flask with 150 mL of the required solvent.
Connect the flask to the extraction apparatus, and start water flow to the condenser section.
Adjust the heaters to provide a boiling rate which will cycle the specimens for not less than 24
extractions over a 4-5-h period. If the extraction is left unattended, a provision should be made to
shut off the heat if the water and/or the electricity shuts off unexpectedly. Remove the flask from
the apparatus and partially evaporate the solvent in the extraction flask to a volume of 20-25 mL.
Transfer the extract to the tared weighing dish by washing with small amounts of fresh solvent.
Handle the weighing dish with forceps or tongs. If using benzene, evaporate the solvent to near
[38]
dryness while in the chemical fume hood. Dry the dish and contents in an oven for 1 h at 105 ±
3ºC, cool in a desiccator, and weigh to the nearest 0.1 mg. Run a blank determination with the
solvent used in the test. Evaporate 150 mL of the solvent to dryness, and weigh the residue to the
nearest 0.1 mg. Correct the weight of the dried extract by the weight of residue found.
4.8.5 Calculation:
Solubility % = [(We - Wb)/ Wp] x 100

Where
We = oven-dry weight of extract =1.95 gm
Wp = oven-dry weight of wood or pulp = 2 gm
Wb = oven-dry weight of blank residue = 1.81 gm
Solubility % = [(1.95 – 1.81)/ 2] x 100 = 7 %
4.9 SILICA
4.9.1 Scope:
This method describes a procedure for determining the acid-insoluble ash content of cellulose
samples. The sample is dry-ashed and the residue treated with hydrochloric acid. The insoluble
residue is filtered, washed, ignited, and weighed. This method measures all acid insoluble
material.
4.9.2 Test Specimens:
The size of the specimen, approximately 25 g, depends on the ash content and should be adjusted
so that the weight of the acid-insoluble ash will be at least 10 mg. Tear pulp Paper, and
paperboard samples into small pieces. For wood, use approximately 25 g of the ground and
screened material prepared in 5.1. Weigh duplicate specimens to the nearest 0.01g.
4.9.3 Apparatus:
Platinum crucible, or dish, 50 mL.

Muffle furnace, maintained at 525+ 25C.
[39]
Filter paper, ash-free, double acid-washed, higher retention, of a type recommended for use with
the finest precipitates.
4.9.4 Reagent:
Hydrochloric acid, 6M. Carefully add one volume concentrated HCl to one volume distilled
water. Use caution in making and handling of this reagent.
4.9.5 Procedure:
As directed in TAPPI T 211 “Ash in Wood and Pulp, Paper, and Paperboard: Combustion at
525C,” determine moisture level in the sample and ash the pulp in portions in a platinum dish,
previously ignited in the muffle furnace to a constant weight (to the nearest 0.1 mg).
Ignite the sample at 525C in the muffle furnace until the residue is free from black carbon
particles. Cool the dish to room temperature, add 5 mL 6MHCl, and evaporate carefully to
dryness on a steam bath. Add a second 5-mL portion of 6MHCl and again evaporate to dryness.
Add a third 5-mL portion of 6MHCl to the residue, heat on the steam bath, anddilute with 20 mL
of distilled water. Filter the solution through the ash-free filter paper, being careful to remove all
the residue from the dish by means of a rubber policeman, and wash the residue several times
with hot distilled water until the filtrate is free from chloride ions (check with silver nitrate
solution). Place the filter paper containing the insoluble residue in the platinum dish. Heat very
carefully until the water has evaporated, and then ignite the residue in the muffle furnace at
525ºC until free from carbon. Allow the dish to cool in a desiccator and weigh to the nearest 0.1
mg.
4.9.6 Calculation:
Silica % = A*100 / B
[40]
Where
A = weight of silica = 0.82 gm
B = weight of test specimen = 20 gm
Silica % = (0.82 * 100) / 20 =4.1 %
4.10 UV SPECTROPHOTOMETER FOR COMPOSITION ANALYSIS:
4.10.1 Basic Principles
A spectrophotometer is employed to measure the amount of light that a sample absorbs. The
instrument operates by passing a beam of light through a sample and measuring the intensity of
light reaching a detector.
The beam of light consists of a stream of photons, represented by the purple balls in the

simulation shown below. When a photon encounters an analyte molecule (the analyte is the
molecule being studied), there is a chance the analyte will absorb the photon. This absorption
reduces the number of photons in the beam of light, thereby reducing the intensity of the light
beam.
You can visualize this process by running the simulation shown below. Click on the Start button
to start the simulation and the Stop button to stop the simulation.
The light source is set to emit 10 photons per second. Watch the motion of the photons and
observe how some of the photons are absorbed (removed) as the beam of light passes through the
cell containing the sample solution. The intensity of the light reaching the detector is less than
the intensity emitted by the light source.
4.10.2 For white liquor

[41]
Absorbance = 2.681
Wavelength = 217nm
Concentration = 0.1N
0.1N conc of NaOH

3
2.5
2
absorbance
1.5
0.5
0
219 218 217 214 213 306 305 310 311
wavelength
We found the concentration of white liquor by the help of wavelength v/s absorbance at 217nm
and 2.681 is 0.1N.
Absorbance = 0.18
[42]
Wavelength = 506 nm
0.3N conc of NaOH

0.2
0.18
0.16
0.14
0.12
absorbance
0.1
0.08
0.06
0.04
0.02
0
499 506 509 511 512 514 532 533 535
wavelength
We found the concentration of white liquor by the help of wavelength v/s absorbance at 506nm
and 0.18 is 0.3N.
4.10.3 For black liquor:
[43]
Absorbance = 3.305
Wavelength = 615nm
0.3N Black liquor

3.5
2.5
Absorbance
1.5
0.5
0
499 596 599 602 603 607 609 611 613 615
Wavelength
absorbance
We found the concentration of black liquor by the help of wavelength v/s absorbance at 615nm
and 3.305 is 0.3N.
CHAPTER 5
[44]
5.1 DISCUSSION
From this project, the result achieved meet the expected values from calculation that be expected.
The values that have been declared fulfill the desired value. This project work teach us about the
cellulose, ligning and fiber and their applications and productions. Pulping process is very
important to learn because it has a wide range of application in our daily life. We could do better
in it if we would have some more time to work in this field. This was a team work so we also
learn how to work as a team.
5.2 RESULT
According to our experiments and project work, we found these results.
Klason lignin for wood sample = 38%
Lignin percentage from batch pulping = 40.83 %
Alpha-cellulose = 97.8 %
Beta-cellulose = 2.63 %
Gama-cellulose = 0.43 %
Hollo cellulose = 67.39 %
[45]
CHAPTER 6
6.1CONCLUSION
Lignin represents the second most abundant natural polymeric material on earth and is still
currently underutilized. Large amounts of lignin are expected to be produced in future bio-
refineries as a by-product of bio-fuel production which is stimulating new emerging applications,
principally as sustainable alternatives to nonrenewable products such as polyurethanes,
thermoplastic polymers, epoxy and phenolic resins, as well as corrosion inhibitors. However, all
the researches currently developed in these fields are carried out at the laboratory scale. Thus, the
ability of organosolvlignin’s to provoke significant impact as a substitute for polymeric materials
depends on its availability in industrial quantities.
6.2 FURTHER WORK:
The development of innovative biomass conversion technologies is of major importance in

realizing the European goal of 16% sustainable energy in 2020. These technologies allow the
sustainable use of all the valuable components in biomass. Lignin is a very interesting
component of lignocellulose biomass that can be converted into various valuable biobased
products using the proper conversion technologies.
Lignocellulosic biomass consists mainly of lignin and the polysaccharides cellulose and
hemicellulose. Compared with the production of ethanol from first-generation feedstock, the use
of Lignocellulosic biomass is more complicated because the polysaccharides are more stable and
the pentose sugars are not readily fermentable by Saccharomyces cerevisiae. In order to convert
lignocellulosic biomass to biofuels the polysaccharides must first be hydrolyzed, or broken
[46]
down, into simple sugars using either acid or enzymes. Several biotechnology-based approaches
are being used to overcome such problems, including the development of strains
of Saccharomyces cerevisiae that can ferment pentose sugars, the use of alternative yeast species
that naturally ferment pentose sugars, and the engineering of enzymes that are able to break
down cellulose and hemicellulose into simple sugars.
[47]

FYP Lignin Chemical Engg

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Lignin is a complex polymer of aromatic alcohols known as monolignols. It is most commonly

Cellulose is an organic compound with the formula (C6H10O5)n, a polysaccharide consisting of

1.3 HEMI CELLULOSE:

The term hemicellulose is a collective term. It is used to represent a family of polysaccharides

1.4 ALPHA CELLULOSE:

1.5 MORINGA OLEIFERA

Fiber is a natural or syntheticstring or used as a component of composite materials, or, when

1.6.1 Synthetic fibers

1.6.2 Metallic fibers

1.6.3 Carbon fiber

Silicon carbide fiber

1.6.5 Mineral fibers

1.7.1 Industrial Cellulose Fibers

1.7.2 APPLICATION OF LIGNIN

1.7.2.1 Lignin as a Binder

1.7.2.2 Lignin as a Dispersant

Lignosulfonate prevents the clumping and settling of undissolved particles in suspensions. By

1.7.2.3 Lignin as an Emulsifier

1.7.2.4 Lignin as a Sequestrant

1.7.2.5 Lignin Applications – Chemicals

Lignin depolymerization provides routes to:

1.7.2.6 Lignin Applications – Grease

1.7.2.7 Lignin Applications – Dust Control

2.0 LITERATURE REVIEW

Plant cell wall

Lignin Isolation from Pulp

Acid hydrolysis (saccharification) of cellulose produces a random cleavage of glucosidic

3.0 MATERIAL AND METHODS

3.1 Klason lignin

3.1.2 Test specimens:

Constant temperature bath, to maintain a temperature of 20 ± 1°C.

Klason lignin for wood sample

3.2 Batch pulping

To perform batch pulping of given raw material.

Research laboratory digester,

Sodium hydroxide (NaOH)

Lignin, % = (Pulp produced * 100) / Material charged

= 49 * 100 /120 = 40.83 %

3.3ALPHA-, BETA- AND GAMMA-CELLULOSE IN PULP

3.3.4.1 Alpha-cellulose determination

3.3.4.2 Beta- and gamma-cellulose determination

Alpha-cellulose, % =100 - 6.85 * (V2-V1) *N*20

Alpha-cellulose, % =100 - 6.85 * (32 - 12) *N*20

3.3.5.2 Gamma cellulose

Gamma cellulose, % = [6.85 (V4 -V3) x N x 20] / [25 x W]

Beta-cellulose %=100 - (alpha-cellulose% + gamma cellulose %)

= 100 - (97.8 + 0.43) = 2.63 %

Methanol, Benzene, Sodium chlorite, acetic acid, acetone, Ice.

Where A= Oven dried weight of holocellulose, gm

B = Oven dried weight of initial sample, gm

Sr.No. A (gm) B (gm) H%

Avg Hollocellulose= (67.5+69.11+65.56)/3 = 67.39 %

4.1.2 Test Specimen:

Ash Content, % = (C/ B) * 100

Sr.No. C (gm) B (gm) % ASH

Avg. ash content % = 1.68 %

4.2 MOISTURE CONTENT

4.2.2 Test Specimen:

Oven—A forced-convection oven that can be maintained at a temperature of 103 ± 2°C

Moisture content = (Weight of moisture/Total weight of sample) * 100

Take 2 gram of sample in a crucible and weight it, A.

Alpha-cellulose, % =100 - 6.85 * (V2-V1) N20

Alpha-cellulose, % =100 - 6.85 * (32 - 12) N20