new raw materials for paper pulp (the book)

II

ACKNOWLEDGEMENTS

First of all, our deepest thank for ALLAH who gave us the

help and patience to complete this work.

we would like also to acknowledge and thank our

supervisor Prof. Dr. Mamdouh M. Nassar, Professor of

Chemical Engineering, Chemical Engineering Department,

Minia University, Egypt, for his sincere guidance,

reviewing, commenting, supervision and support from the

preliminary to the concluding level enabled us to develop

an understanding of the subject.

We would like also to extend our grateful to Dr. Mervat

Hosny, for her supporting, commenting, and continuous

helping all through the carrying out of this work.

We would like also to extend our grateful to Eng. Kholood

Madih, for her supporting, and continuous helping during

our work in the laboratory in our department.

We would like also thank Eng. Ramadan, who helped us

to contact with Qena factory where we could complete this

study.

III

We would like to thank those individuals who contributed

information and research assistance for this research.

Mostafa Ahmad Muhammad

Gehad Osama

Aya Ashraf

Marwa Ragab

El-Minia – 2016

IV

ABSTRACT

Paper is usually made from pulp produced from trees

(woody pulp). However, in countries lake forest as Egypt

paper is made from agricultural residues materials (non-

woody pulp).

In Egypt paper pulp is produced by cooking bagasse. Due

to the high speed of modern machine, woody pulp about

15-20% is added to bagasse pulp.

Pulping of two new agricultural residues namely palm

fronds and banana leaves was carried out. Two kinds of

cooking methods were used one at atmospheric pressure

and the other one at high pressure (at about 9 atm). Also

hand-made decorative paper was produced. It was found

that strength results of the obtained pulp were comparable

to the bagasse pulp (commercial pulp produced at Qena

paper mills, using pandia continues digester).

It was found that the tensile index of new pulp was 33.65

N.m/g compared to 50.90 N.m/g for bagasse pulp, tear

index was 10.35 mN.m2/g compared to 5.74 mN.m2/g for

bagasse pulp, burst factor was 17.14 compared to 36.40 for

bagasse pulp.

The produced new pulp was semi-chemical due to lack of

ideal reactor (digester). The semi-chemical pulp is usually

produce weaker paper due to presence of high percentage

of lignin in the pulp, in spite that the produced semi-

chemical pulps from the new raw materials are comparable

to the strength properties of the bagasse.

This can lead to conclusion that if the new pulp is

optimized to chemical pulp, we can produce high strength

pulp which can substitute some of the imported wood pulp.

V

LIST OF FIGURES

Figure12: Results of tests in each sample of raw

materials 32

Figure 13: Bulk versus pulp yield for different pulps 35

Figure 14: Relationship between opacity and

percentage pulp. 36

Figure 15 Relationship between yellowness and

percentage pulp. 37

Figure 1: Micrographs of wood before pulping and the

flattened fibres after pulping. 1

Figure 2: Different types of woody and non woody

materials 11

Figure 3: Cell wall architecture 14

Figure 4: cellulose formula 15

Figure 5: Paper Making Processing Steps 16

Figure 6: batch digester 17

Figure 7: Pandia continuous pulping of Bagasse 18

Figure 8: Pulp cleaning flow diagram 21

Figure 9: (a) cutting to small pieces, (b) steal container 26

Figure 10: Beater 26

Figure 11: Comparison between the produced pulp

and bagasse in each step of production of

pulp

31

VI

Figure 16: Relationship between air permeance and

percentage pulp. 38

Figure 17: Relationship between tensile index and

percentage pulp. 39

Figure 18: Relationship between breaking length and

percentage pulp. 40

Figure 19: Relationship between burst strength and

percentage pulp. 41

Figure 20: Relationship between tear and percentage

pulp. 42

Figure 21: shows (a) the blender, (b) the pulp we get 43

Figure 22: Shows (a) mixture of bleaching, (b) three

samples before and after first and second

bleaching stages.

45

Figure 23: Hand sheets preparation 47

Figure 24: decorative paper sheet 47

VII

TABLE OF CONTENT

ІІ Acknowledgment

ІV Abstract

V List of figures

VII Table of content

1 1. CHAPTER (1): INTRODUCTION

3 2. CHAPTER (2): LITERATURE REVIEW

9 3. CHAPTER (3): BACKGROUND

9 3.1 Fiber raw materials

10 3.2 Influence of the raw materials

10 3.2.1 Effect of the length, diameter, wall thickness and

flexibility on the ultimate strength of paper.

11 3.2.2 General structure

11 3.2.3 Fine structure of the cell wall

13 3.3 Chemistry of wood and fiber

14 3.3.1 Cellulose

14 3.3.2 Hemicellulose

14 3.3.3 Lignin

15 3.4 Pulp and Paper Making

18 3.4.1 Description of batch process

18 3.4.2 Pandia continuous pulping of Bagasse

19 3.5 Yield in wood

21 3.6 Addition in the paper industry

24 4. CHAPTER (4): Experimental part І

24 4.1 Semi chemical pulp

26 4.2 Testing for physical, optical and mechanical

properties of pulp hand sheets

30 5. CHAPTER (5): RESULTS AND DISCUSSION

43 6. CHAPTER (6): Experimental part ІІ Hand-made paper

43 6.1 Pulp washing

43 6.2 Defibration

44 6.3 bleaching of fiber

44 6.3.1 Bleaching chemicals

VIII

44 6.3.2 Bleaching Steps

44 6.3.2.1 First stage

45 6.3.2.2 Second stage

45 6.4 Chemical additions in the paper industry

46 6.4.1 First add alum

46 6.4.2 Second: Add coloring materials and pigments

46 6.5 Hand sheets preparation

48 7. CHAPTER (7): CONCLUSION

49 REFERENCES

53 APPENDIX

1

CHAPTER 1

INTRODUCTION

If we look around, we can find different types of trees,

agricultural crops, grasses, … etc. All these materials, chemically

composed of cellulose, hemicellulose, and lignin with different

percentages, they are known as lignocellulosic materials.

The paper we produced from such materials without lignin (only

cellulose and hemicellulose after removing lignin) such stuff is

known as pulp.

The chemical composition mentioned above is not important

aspect without we consider also, physical properties of the

building material of the lignocellulosic material which is known

as fibres.

(a)

Fig. 1: Micrographs of (a) wood

before pulping showing its

structure of vertical fibers

bundles held together by lignin

and (b) the flattened fibres after

pulping.

(b)

2

The fibers are cylindrical tube, and therefor the high length and

the smaller diameter of fibers produce flexible fibers such

property together with the high percentage of cellulose are the

main criteria for choice the materials for paper manufacture.

Bagasse (which is the solid residue after extraction sugar juice)

is the main part for paper pulp. It is short fibered stuff therefor to

accommodate the high speed paper machine (900 m/min), it

blends with about 10 – 20 % wood fiber (long fibers).

The aim of this work is to produce a new type of pulp from

agricultural materials i.e. banana leafs and palm fronds to

substitute some of the imported wood fiber.

3

CHAPTER 2

LITERATURE REVIEW

Around the world, wood fiber supply is expected to tighten.

Even in the US. The wood fiber supply is expected to tighten

in the not so distant future. In India there already is a shortage

of wood fibers. Even the European Union suffers from

shortages of wood fibers and search is on for alternative fibers.

Japan is also investigating the use non-wood plant fibers for

pulp and paper manufacture.

Over the last several years, a number of plants have been tested

for their papermaking qualities.

Atchison, (1962) (1), A review of past and present uses of

bagasse is given. Included are purchase, collection, storage,

and preservation aspects. Additionally, the preparation for

pulping and the process and equipment necessary for pulping

are described.

4

Atchison, (1962) (2), The paper reviews the methods of

cleaning straw and depithing bagasse. A two-stage depithing

system has been suggested for bagasse, involving a partial pith

separation in a humid condition followed by wet depithing.

Flow diagrams are given.

Chapman, (1957) (3), The American practice of purchasing,

storing, and handling bagasse, and the layout and equipment

required are described in detail. Mechanization of harvesting

sugarcane may adversely affect its use in board manufacture

since mechanically harvested bagasse contains a larger

percentage of leaves and other debris than that harvested by

hand.

Cusi, and Jolley, (1968) (4), The Simon-Cusi multistep pulping

method is used at the world’s largest bagasse pulp mill. All

steps in the process, including storage of baled bagasse, and

both wet depithing and a cheaper alternative moist process are

described.

Gabir and Khristova, (1983) (5), High temperature shock

(HTS) cooking of cotton stalks and bagasse at 204.4°C to

260°C for 2 to 4 min gave pulps in 68 to 74 percent yield as

compared with 46 to 59 percent yield obtained in the soda

process. The alkali consumption of the HTS process was lower

than that of soda pulping, and strength properties of HTS pulps

were comparable to those of soda pulps.

5

Goswami, Dipul Kalita & Rao, (2008) (6), North East Institute

of Science and Technology (CSIR) investigated the production

of grease proof paper from banana pseudo stem.

The morphological characteristics of plant and fibre, chemical

constituents of the sheath, characteristic of pulp and physical

strength properties of hand sheet made from banana pulp alone

or in combination with bamboo pulp fibre are presented. And

also investigated imparting of grease proof properties by a

compound called pentosan (13.5%). The drainage time of

banana pulp increases with increase in beating time. The paper

made out of this banana pulp showed the characteristics of

grease proof paper. The physical strength of the paper can

further be improved by incorporating 20% bamboo pulp into

banana pulp. Production of pulp and paper on laboratory scale

is also presented.

Johansson (1952) (7), investigated the simplest procedure to

determination pentosan content present in various soft and hard

woods by using hydrochloric acid and furfural as main

involved chemicals.

Yuan-Shing Perng and Eugene I-Chen Wang (2012) (8),

studied the improvement of grease proof properties by addition

of certain chemicals (which acts as fillers, binders and refiners)

and by mechanical treatment. Certain calibration curves are

also generated for strength of papers for various concentrations

of binders, fillers and refiners.

Uraiwan Pitimaneeyakul, (2008) (9), King Mongkut’s

Institute of Technology Ladkrabang, Thailand investigated the

6

simplest procedure to extract banana fibre from the pseudo

stem without damaging the fibre. And also studied various

properties related to fibre strength like percentage elongation,

moisture regain and fineness. Composition of fibre is also

investigated and presented in this literature.

Sunday and Benjamin (2010) (10), Department of Mechanical

Engineering, Federal University of Technology, Nigeria

investigated the cellulose content in both hard woods and soft

woods and also described available methods to improve the

properties of the fibre like scouring etc.

Shrieves chemical process industries (1984) (11) and

Wikipedia (12) provided the information about various pulping

methods available today such as Mechanical, Thermo-

mechanical, Chemical, Chemo thermo-mechanical pulping and

briefly describing about them like types of Chemical pulping

and Chemicals required in both of the process.

Aung and Fleury, (1960) (13), Shredded bamboo has shown

distinct advantage over chipped bamboo in the production of

kraft pulp and hardboard. The shredder developed at the

institute in Rangoon tears the long fibers from the bamboo

culm along its natural axis and eliminates most of the

undesirable waste material and silica. For the production of

hardboard, no binder or chemicals are required.

Birdseye, (1959) (14), A method for storing shredded bamboo,

straw, bagasse, and other agricultural residues involves

impregnating the baled or piled material with NaOH and

effecting roughly 20 percent of digestion without decay. Prior

7

to storage, the material may be sterilized by heating it to at least

180°C. After 9 to 12 months, the material is treated with kraft

white liquor, subjected to a steam pressure of 1.0 MPa and a

temperature of 185°C for 5 min before being exploded through

a break valve.

Mohammad Izzuddin Bin Yakari, (2008) (15), The production

of paper and pulp from palm waste is the best way as a result

of environmental issues today. The used paper also can be

recycling to produce new paper for packaging, printing and

manufacturing.

Ilvessalo-Pfaffli, (1995) (16), Corn stalks are similar to

sugarcane in structural features with an average fiber length of

1.5 mm (0.5-2.9 mm) and average fiber width of 0.018 mm

(0.014-0.024 mm).

Typical fibers are fairly narrow, thick walled and have blunt or

pointed ends.

Ilvessalo-Pfaffli, (1995) (16), These studies have yielded good

results as to the possibility of using cotton stalk pulp in blend

with other pulps to produce good quality paper. Cotton stalk

fibers have an average fiber length of 0.6-0.8 mm and an

average fiber diameter of 0.02-0.03 mm.

Ilvessalo-Pfaffli, (1995) (16), Despite these drawbacks, it is a

favored fiber source in the wood short countries, due to its

ready availability. Average fiber length of the rice straw fiber

is 1.4 mm and average fiber width is 0.009 mm.

8

Wiedermann (1989) (17), reed is a tall perennial grass, which

grows generally in marshes. Reeds grow abundantly in

swamplands, river bottoms lands and delta areas of Russia,

Romania, Egypt, northern China, North Korea and Spain.

Depending on conditions, such as soil characteristics,

hydrologic condition, amount of nutrients, and pH, the

diameter will vary from 9 to 22 mm and the height from 2.5 to

5 meters.

Francis et al., (2005) (18), studied bleached hardwood pulps by

the soda anthraquinone and 2-methylanthraquinone processes,

black liquor gasification (BLG) as well as the recovery of

lignin and other organic compounds.

Abdullah et al., (2004) (19), studied cooking conditions for

Eucalyptus cammaldulensis and Populus euphratica with

anthraquinone. This study was undertaken to detect the effects

of anthraquinone on the yield and quality of Populus euphratica

oliv and Eucalyptus cammaldulensis in soda pulping.

Finell et al., (2004) (20), studied Kraft and soda-A0 pulping of

dry fractionated reed canary grass. The effect of dry

fractionation on pulping and pulp properties of reed canary

grass (Phalaris arundicaea) was studied for two alkaline

pulping processes.

Multivariate data analysis was used to evaluate the influence of

dry fractionation, alkali charge and cooking time on pulp yield,

screening reject, drainage, fiber length distribution, kappa no.

9

and residual alkali in black liquor for kraft and soda-

anthraquinone pulping of the grass. Of the factors included in

the design, dry fractionation had the greatest influence on all

the responses. Dry fractionation gave a pulp with higher yield,

lower screening reject, lower kappa no., and better drainage

and reduced fines for both pulping processes.

Springer et al., (2002) (21), studied Potential sulphur-tree

pulping methods.

10

CHAPTER 3

BACKGROUND

3.1 Fiber raw materials:(22)

Paper as we know it today is always made from a fibrous raw

material. The most important sources of fibers are forests of the

world.

More than 90% of the total world production of fibers come from

wood, (soft wood, hard wood). Fibers are cells of a tubular

structure where the walls are made up of more or less pure

cellulose. Fibers from different sources have different physical

properties, length, width, wall thickness and cavity diameter in

addition to varying chemical composition. The three main

constituents of wood: cellulose, hemicellulose and lignin.

Variation of properties like those mentioned will often decide the

usefulness of the raw material for various paper and board

products. Fiber length can for example vary from less than

0.5mm to more than 5mm, thus the most important wood fibers

being 0.5 to 5mm.

11

Fig. 2: Different types of woody and non woody materials

3.2 Influence of the raw materials:

3.2.1 Effect of the length, diameter, wall thickness and

flexibility on the ultimate strength of paper.

1- The longer the fibers, the stronger the paper since longer

fibers allow better interlocking at point of contact between the

fibers.

2- The smaller the diameter and thinner wall thickness, the more

flexibility is the fibers.

3- Flexible fibers give stronger paper, since they allow better and

more point of contact between fibers.

Wood is by far the most widely raw material for paper pulp, but

other non woody materials as bamboo, reed, bagasse, rice straw,

wheat straw, …. are the main raw materials in countries lake

wood forest.

12

To summaries up, the principal factors that determine whether a

plant shall or shall not be used in the manufacture of paper are

suitability of fiber (long or short, thin wall or thick, wide lumen

or narrow); dependability of supply, cost of collection,

transportation, and preparation, and tendency to deteriorate in

storage.

3.2.2 General structure:

Wood which is the most important materials for producing paper

pulp is classified as softwood or hardwood.

Fibers of softwood are composed of hollow tubular cells

(tracheid) with closed, more or less pointed ends with average

length of 3.5mm.

Fibers of hardwood are known as vessels and libriform.

Vessels are cells of relatively large cross section, they are usually

short, less than 1mm long, and they have wide open ends.

Libriform are cells as that of tracheid but are shorter. In both

softwood and hardwood fibers, they are about 100 times as long

as they are wide.

Bagasse, cells of bagasse are composed of libriform, vessels and

pith (pith is nonfibrous material).

3.2.3 Fine structure of the cell wall:

As shown in fig. 3 the cell-fiber is composed from outside to

inside (lumen) as:

Thin wall called primary wall (P), then a thin outer layer of the

secondary walls (S1), the substantial middle layer (S2), and the

very thin layer (S3) sometimes called tertiary layer.

13

In the P layer irregular helical arrangement of micro-fibrils

around the cell axis is existed.

In the S1 layer, the micro-fibrils groups are in helixes alternately

crossed.

In the middle layers S2, the micro-fibrils are oriented nearly

parallel to the cell axis.

In the internal layer S3, the direction is nearly perpendicular to

that in S2.

Between fibers is middle lamella (ML) and it surrounds each

fibers.

ML. is composed mainly of lignin, while primary and secondary

walls are composed mainly of cellulose. Hemicellulose are

present in fiber with different percentages and it decreased as we

go from outer layer of fiber toward lumine. In the cell wall,

cellulose molecules strongly linked in long chain with lateral

links that unite parallel chains into structure called micro-fibrils

are the smallest natural units of structure within the cell wall.

Each micro-fibril appears to be an aggregation of 100 or more

parallel chains of cellulose molecules united laterally by

chemical cross -linked over much of their length in a regular

alignment.

14

Fig. 3: Cell wall architecture. Middle lamella wall. S1 transition lamella, S2 main layer of

secondary wall, S3 tertiary wall, or tertiary lamella of secondary wall.

3.3 Chemistry of wood and fiber:

The principal chemical components of wood (soft and hard

woods), non-woody materials (bagasse and rice straw) and fibers

are classified as: cellulose, hemicellulose, lignin and solvent

soluble substances (extractives). The amount present are in the

range of 40% to 50% cellulose, 15% to 35% hemicellulose, 20%

to 35% lignin, and 3% to 10% extractives.

15

3.3.1 Cellulose:

It has an empirical of C6H12O6, cellulose is polymer comprise

of large number of repeated units of glucose (C6H12O6).

Fig. 4: cellulose formula.

3.3.2 Hemicellulose:

The term hemicelluloses refer to mixture of low molecular

weight polysaccharide polymers.

It is agreed generally that wood and non-wood plant contains no

saccharide repeating units other than D-glucose (cellulose). In

contrast hemicellulose polymers are composed of condensation

of the following major saccharide units:

D-Xylose, D-mannose, D-glucose, L-arabinose, D-galactose, D-

glucuronic acid, and D-galacturenic acid.

3.3.3 Lignin:

It is non-carbohydrate fraction of extractive free wood. It

comprises about 20% to 40% woody or non-woody materials by

weight.

Lignin is basically an aromatic polymer comprised of

heterogeneous, branched, and network with no evident simple

16

repeating unit. The system appears to be totally amorphous and

is possibly chemically bonded to hemicellulose.

3.4 Pulp and Paper Making (23)

The pulp and paper making process is carried out in following

way, Fig.5 Paper Making Processing Steps shows the Paper

making process.

Raw Material Collection:

Banana and palm waste, which is

thrown away by farmers after

harvesting of fruits, is obtained as raw

material.

Chopping:

The materials are chopped into small

pieces of 2-3 inch in size.

Digestion:

The material is soaked in 2-5% NaOH

for appropriate period. The alkali

loosens the ligno-cellulosic bonds,

thereby softening the material.

Washing:

The softened material is washed with water to remove the black

liquor of sodium lignite and unused alkali.

Beating:

The washed material is then subjected to beating. Beating is

required for a getting good quality pulp, depending upon the

quality of boards/paper to be produced.

Fig. 5: Paper Making Processing Steps

17

Storage:

After beating, the desired pulp is produced which is then stored

in storage tanks.

Paper making:

Paper is then making from the pulp of desired quality.

Drying:

The wet boards/papers are then allowed to dry.

Pulping is usually carried out in a reactor either batch or

continuous which is known as digester.

Fig. 6 shows the batch digester and fig. 7 shows Pandia

continuous pulping of Bagasse

Fig. 6: batch digester

18

Fig

. 7: P

andia co

ntin

uous p

ulp

ing o

f Bag

asse

19

3.4.1 Description of batch process:

The wood chips are steam-heated in a large steel pressure vessel,

the digester with a cooking liquor consisting of an aqueous

solution of sodium hydroxide (alkaline pulping) or sodium

hydroxide and sodium sulphide in approximate proportion of

5NaOH + 2Na2S (kraft pulping). In batch, or discontinuous

process, the heating or “pulping” is carried out according to

predetermined program in which the temperature is raised

gradually 60 to 90 min to constant value during one hour,

typically 170 C and held from two to three hours.

3.4.2 Pandia continuous pulping of Bagasse:

The pandia chemi-pupler and its associated processing system

has proved effective in handling bulky materials such as straw

and sugarcane bagasse.

The basic system consists of a screw feeder, an impregnation

chamber, a pair or more horizontal tubes joined by vertical

connecting necks, conveyor screw, a rotary discharged, and a

cyclone –type collector.

Provision must be made to overcome the spring; bulky

characteristics of materials such as straw or bagasse before the

material is introduced into the digester. Chopped and cleaned or

depithed raw material is metered onto conveyor by which it is

moved to a mixer –impregnator, where cook liquor is added.

This tends to lubricate and soften the material and thereby

overcome some of it springiness. From the mixer-impregnator

the material is delivered to the hopper of a screw feeder, where

the density of the mass is increased sufficiently to resist the

internal pressure of the digester. The compacted materials in the

20

screw feeder serves as a pulping to the digester. Once the fibrous

material enters the digester proper it is no longer constrained to

remain in a compacted mass. Additional liquor may be added in

the screw feeder or in the reaction chamber before the materials

drops into the first horizontal tube. Reaction time within the

horizontal tubes is controlled by the speed of the internal screw

conveyors. Intimate mixing of chemicals and steam with the

fibrous materials continuous during the travel through horizontal

tubes.

With our present knowledge of what really happens during the

pulping processes and with mechanical equipment (refiners) for

defibration of uncooked or little cooked chips, it possible to

produce a large variety of pulp between the two extremes:

mechanical pulp and chemical pulp. A decreasing amount of

mechanical defibration is required as the chemical treatment is

increased.

3.5 Yield in wood:

Mechanical pulp (refiner and stone ground wood) 95-100%

Chemi-mechanical pulp 85-95%

Semi-chemical pulp 70-85%

High yield chemical pulp 60-70%

Chemical paper pulp 45-55%

Dissolving pulp 35-40%

After pulping under high pressure about 10 atmosphere (≈

175°C) the pulp slurry is blown to anther tank known as blow

21

tank from which is washed over a rotary vacuum filter then

cleaned in three stages names:

Johnson screen (it is a flat vibration screen), then cowan screen

(it is rotary cylindrical screen), and finally the hydro-cyclone

stages as shown in figure 8.

Fig. 8: Pulp cleaning flow diagram

22

3.6 Addition in the paper industry:

Fillers:

Fillers are pigments that are added to stock opacity and

brightness improvements of printing paper are high brightness,

high index of refraction (to help scatter light and increase

opacity), small and uniform particle size fore smooth paper, low

water solubility, inertness, low cost, low abrasion, low specie

gravity, and high retention levels. About 50% of the filler is

retained in the sheet. Fillers are often ground or precipitated

calcium carbonate (with paper machines operating at PH of 7 or

higher), titanium oxide or clay.

Fillers are often ground or precipitated calcium carbonate (with

paper machines operating at PH of 7 or higher), titanium oxide

or clay. Filler is used at 10 – 30% to replace expensive fiber. At

the higher levels of addition, the paper becomes week since

fillers interfere with fiber-fiber bonding and do not impart

strength themselves. Fillers are not used in linerboard or other

papers where strength is the principal desired property. Fillers are

used in magazine and book paper. Clay is not as bright (80-92 %)

as calcium carbonate or titanium dioxide; it has an index of

refraction of 1.55, a specific gravity around 2.58 and is abrasive.

More clay is used than any other filler in paper traditionally,

accounting for 90% of all fillers and coating pigments clay

consists of hydrate SiO2 and Al2O3. Calcium carbonates (chalk

or limestone) is becoming an extremely filler to the industry.

Since calcium carbonate reacts with HCl to give CaCl2 and CO2

it must be used in alkaline papermaking systems pH 7.0 or

higher. The brightness is about 92-95% with an index of reaction

of 165, and specific gravity of 2.7 to 2.85.

23

Titanium Dioxide:

is expensive filler which costs slightly more than bleached pulp

and is very bright (98%). It has a high index of refraction (2.56-

2.70) that is contribute to high opacity and specific gravity of

3.90. it is used in airmail, and other printing papers, which are

lightweight, expensive, and require high opacity. It is also used

in most white paints as the pigments .

Talc:

hydrated magnesium silicate, refractive index of 1.57, brightness

of 90-95 %, and specific gravity of 2.7.

Dyes and brighteners:

Days are water soluble colours added to stock to important colour

to the final product. Days are absorbed on the fiber surface

important their colours to the paper fibers. They have structures

involving large conjugated double bond systems with metallic

azo and similar structure.

1. Basic days: are cationic organic dyes (containing amino-

groups) that are used with inorganic anions to fix them to

the surface of fibers. They have strong affinity for lignin

but not for bleached pulps.

2. Blue dye: is often added to pulp to offset the tendency for

pulp to be yellow. The blue dye does not make the pulp

brighter, it only makes the yellow colour look grey, and

grey has the perception of being brighter than yellow.

3. Fluorescent brightening: sometimes called optical

brighteners are used to brighten paper. Thy are colourless

(technical not ayes) and convert invisible UV light to lower

24

energy visible light especially blue light which make the

inherent yellowness of paper .

Internal sizing and surface sizing :

Internal sizing (Rosin) develops resistance to penetration of

aqueous liquids throughout the sheet. Internal sizing is

accomplished by adding materials to the stock, before the head

box to retard water penetration into the final paper. Water

penetration is retarded by the nonpolar portion of the size

molecule. A reaction portion of the size molecule anchors it to

the surface of the fiber. Rosin sizing with alum is used in printing

papers filled with calcium carbonate that must be used at PH of

7 or higher, because in acid condition it decomposes to carbon

dioxide gas that causes pitting of the sheet.

Surface sizing works by a different mechanism and occurs at the

size press where an application of starch (or oilier material) fills

the capillaries of paper, making water penetration much more

difficult. Starch is not hydrophobic as are internal sizing agent.

Paper may be hard-sized (high resistance liquid penetration. Such

as many printing and packing papers), slack-sized (low resistance

to liquid penetration, such as newsprint), or no-sized paper

(towelling and blotting).

25

CHAPTER 4

EXPERIMENTAL PART

Part І Two types of pulping produced are carried out:

1- atmospheric pressure (1 atm):

This type of pulp is semi chemical pulp. such pulps were carried

out at the lab in our department (chemical engineering

department, faculty of engineering, Minia university).

2- pulping under high pressure (9 atm):

Such pulp which is produced in Quena pulp factory.

4.1 Semi chemical pulp

Process:

The pulping process was carried out as follows:

1- raw material either Palm fronds or Banana Paper was dried

and cut to small pieces about 2-3 cm length as shown in

figure 9, (a).

2- pulping was carried out by adding 20 gm NaOH (10%).

3- water was added to keep solid : liquor ratio as 4:1.

4- the pulping was carried out in a steal container (2 lit) and is

heated up using Bunsen flam as shown in figure 9, (b).

26

Fig. 9: (a) cutting to small pieces, (b) steal container

5- heating up for 6 hrs. was taken to keep constant level by

adding water all the time

6- the produce pulp slurry was washed well and defiberated

using beater as shown in figure 10.

Fig. 10: Beater

27

This process is repeated 4 times with difference in concentration

of NaOH with palm fronds and banana leafs.

4.2 Testing for physical, optical and mechanical properties of

pulp hand sheets:

This procedure is applicable for laboratory sheets of pulp

samples, made for evaluation of pulp properties.

- Apparatus

The following apparatus were used: weighing scale, speed dryer,

thickness tester, tensile tester, bursting strength tester, air

permeance and colour touch tester.

- Procedure

Select a minimum of four sheets, free of visible defects, having

a grammage of 60 ± 3 gsm oven dry, dried in standard

conditioning and testing atmosphere.

- Grammage

Determine the mass of four sheets, by weighing together to

nearest 0.01 g.

Grammage (OD) =mass in gm / 0.0214 *4 x (100 – moisture)

- Caliper

Measure the thickness of pile of hand sheets consisting of four

specimens, with their topsides up.

Make measurements at five different places.

Calculate the mean thickness of single sheet in V. (viscosity)

28

- Bulk

Calculate the bulk in cc/g = caliper V / OD Grammag

- Optical properties

Measure the optical properties of the hand sheet using (colour

touch)

- Tensile index

Measure the tensile strength of the strips of ± 2 mm for four

pieces, one from each specimen. Maintain the distance between

the clamps at 100 ± 2 mm and time for the test piece to break at

10 ± 3 seconds.

- Breaking length m = Tensile index x 102

- Tear index

Determine the tearing resistance, using four test pieces one from

each of four sheets. Make at least four tests, and calculate the

mean.

Tear Index (mNm^2/g) = tear strength/ OD Grammage

Tear factor = Tear index x 10.2

- Burst index

Measure the bursting strength, Make one burst on each side of

the hand sheet, for four samples.

Burst index (kPa.m^2/g) = burst strength / OD Grammage

Burst factor = burst index x 10.2.

29

- Moisture

Determine the moisture of the samples after burst determination.

30

CHAPTER 5

DISCUSSION

The main purpose of pulping is to separate fibers by either

tearing from each other by mechanical means, as in

MECHANICAL PULPING, by dissolving the cemented

material (lignin) by chemical means as in CHEMICAL

PULPING or by combination of mild chemical and mechanical

means as in SEMI-CHEMICAL PULPING.

The yield of pulp in mechanical pulping is high (95%) but the

pulp suffers considerable fiber damage and they are stiff of low

strength but have high scattering coefficient and opacity.

Chemical pulping involved treatment of cellulose with selective

chemicals (NaOH or NaOH+Na2S) which dissolve the lignin

cementing materials and separate fibers. The pulp yield is low

(45%) but the fibers are strong but of low opacity.

31

New materials:

Fig.11 Comparison between the produced pulp and bagasse in each step of production of

pulp

Palm fronds Banana leaves

Bagasse

Raw material

Cutting the

materials

After pulping

After beating

After bleaching

32

Results of tests:

Fig.12: Results of tests in each sample of raw materials

Properties Palm

fronds Banana

leafs Bagasse

Yield (%) 47.5 % 36 % 42 %

Bulk (cm3/g) 1.38 2.28 1.49

Opacity (%) 89 % 89.9 % 76.9 %

Yellowness (%) 38.7 % 49.4 % 4.5 %

Air permeance (ml/min)

600 166 450

Burst index (kpa.m2/g)

1.68 1.74 3.56

Burst factor 17.14 17.7 36.40

Tensile index (N.m/g)

33.65 26.1 50.90

Breaking length (m)

3432 2750 5190

Tear index (mN.m2/g)

10.35 9.51 5.74

Tear factor 105.57 97.1 58.50

33

Results revile that Kappa No. is high for Banana tree leaves

and Palm Fronds because both are semi-chemical pulps with

high lignin content (Kappa No. is above 14) while the Kappa

No. for bagasse is low (Kappa No. is below 8)

Kappa No. is indication of residual lignin content.

Results in this table shows that bulk value is high for Banana

leafs and the lowest bulk value is for Palm fronds.

Bulk is a term used to indicate volume or thickness in relation

to weight.

The more bulk, the worse quality of paper.

Results in this table shows that opacity value is high for

Banana leafs and the lowest opacity value is for bagasse.

Opacity is related to the ability of light to pass through paper.

The more opacity, the better quality of paper.

Results in this table shows that yellowness value is high for

Banana leafs and the lowest yellowness value is for bagasse.

Results in this table shows that Air permeance value is high

for palm fronds and the lowest Air permeance value is for

banana leaves.

Air permeance: air flow rate through unit area under unit

pressure difference in unit time.

The more air permeance, the more weakness of paper.

Results in this table shows that burst index value is high for

bagasse and the lowest burst index value is for palm fronds.

34

And burst factor value is high for bagasse and the lowest value

for palm fronds.

Bursting strength tells how much pressure paper can tolerate

before rupture. (Depends on hydrogen bond).

The more bursting strength, the better quality of paper.

Results in this table shows that tensile index value is high for

bagasse and the lowest tensile index value is for banana

leaves.

Tensile strength is indicative of fiber strength, fiber bonding

and fiber length.

Results in this table shows that breaking length value is high

for bagasse and the lowest breaking length value is for banana

leaves.

Breaking length: the length of paper strip.

Results in this table shows that tear index value is high for

palm fronds and the lowest tear index value is for bagasse, and

the higher tear factor for palm fronds and the lowest value for

bagasse.

Tearing resistance: ability of paper to withstand any tearing

force. (Depends on cutting fibres)

The more tearing resistance, the better quality of paper.

Due to the abundance of Palm Fronds (There is 14 million palm tree in

Egypt, Palm produces annually (10-12) branches and ranges from age

(3-7 years), and the number of fronds is (30-150) in the single palm tree)

the experimental work is focused only on Palm Fronds. (24)

35

Fig.13 Bulk versus pulp yield for different pulps

Figure 13 demonstrate that bulk is decrease by increasing

percentage pulp yield. More yield means more lignin and lower

sheet compactness. Bulk is decreased from 1.42 to 1.38 as yield

is as yield increased from 47.5% to 45%.

The bulk of the three palm frond pulps are better than bagasse

pulp because bagasse is chemical pulp with lower lignin content

that’s mean more cellulose which creates more hydrogen bonds

that leads compact sheet with high bulk. It should be

remembering that palm fronds pulp is semi-chemical pulp which

means pulp with some lignin content.

When we added soft wood pulp to bagasse pulp it didn’t improve

the property, both pulps are chemical pulps.

In general, the more bulk, the worse quality of paper.

36

Fig.14 relationship between opacity and percentage pulp.

Figure 14 demonstrate that opacity is increase by increasing

percentage pulp yield.

The three palm fronds pulps are better than bagasse pulp from

opacity point of view, because bagasse is chemical pulp with

lower lignin content that’s mean more fiber with higher

percentage of hydroxyls groups which create higher percentage

and leads to strong paper due to hydrogen bond, consequently

more compact sheet with lower opacity. It should be

remembering that palm fronds pulp is semi chemical pulp which

means pulp with some lignin content with less compact sheet.


the sheet opacity because both pulps are chemical pulp.

In general, the more opacity, the better quality of paper.

37

Fig.15 Relationship between yellowness and percentage pulp.

Figure 15 demonstrate that yellowness is increase by increasing

percentage pulp yield in case of palm fronds pulp. As pulp yield

increased, lignin content increased, pulp yellowing increased

(lignin is brown).

The three palm fronds pulp are worse than bagasse pulp because

bagasse is chemical pulp with lower lignin content. It should be


means pulp with some lignin content and more yellowness.

When we added soft wood pulp to bagasse pulp it improved the

property of the sheet because wood pulp is more whitens.

In general, the more yellowness, the worse quality of paper.

38

Fig.16 Relationship between air permeance and percentage pulp.

Figure 16 demonstrate that air permeance is increase by

increasing percentage pulp yield. As yield increased more lignin

content and less paper bonding and more voids between fibers,

consequently more air permeance.


bagasse is chemical pulp with lower lignin content and more

hydrogen bond. It should be remembering that palm fronds pulp

is semi chemical pulp which means pulp with some lignin

content and more voidage in the paper sheet.


the property because wood pulp contains more long and flexible

fibers cause more compact sheet.

In general, the more air permeance, the more weakness of paper.

39

Fig.17 Relationship between tensile index and percentage pulp.

Figure 17 demonstrate that tensile index is increase by

decreasing percentage pulp yield. As yield decreased, more

cellulose with higher content of hydroxyl groups and more

hydrogen bonds and thus stronger paper.


bagasse is chemical pulp with lower lignin which leads to more

hydrogen bond in the paper and stronger sheet. It should be


means pulp with some lignin content. Lignin interfere with

hydrogen bonds and produce weaker paper.


property. As stated before more longer and flexible fiber wood

pulp cause stronger sheet.

In general, the more tensile index, the better quality of paper.

40

Fig.18 Relationship between breaking length and percentage pulp.

Figure 18 demonstrate that breaking length is increase by

decreasing percentage pulp yield, due to the same reasoning

stated in tensile.


bagasse is chemical pulp with lower lignin content and more

fibers lead to strong paper due to hydrogen bond. It should be


means pulp with some lignin content, which leads to weaker

paper.


property as stated before wood pulp contains longer and flexible

fibers.

In general, the more breaking length, the better quality of paper.

41

Fig.19 Relationship between burst strength and percentage pulp.

Figure 19 demonstrate that burst strength is increase by

decreasing percentage pulp yield, due to the same reasoning of

more cellulose.

The three palm fronds pulp are worse than bagasse pulp

because bagasse is chemical pulp with lower lignin content

that’s mean long fiber and strong paper due to hydrogen bond.

It should be remembering that palm fronds pulp is semi

chemical pulp which means pulp with some lignin content and

lower strength of paper.


property which improve strength as stated before.

In general, the more burst strength, the better quality of paper.

42

Fig.20 Relationship between tear and percentage pulp.

Figure 20 demonstrate that tear is decrease by decreasing

percentage pulp because some fibers may be cut down to shorter

fibers and thus number of long fibers is decreased.

The three palm fronds pulp are better than bagasse pulp because

bagasse is chemical pulp with lower lignin content and palm

fronds pulp is semi chemical pulp which means pulp with some

lignin content.


property due to larger numbers of long fibers.

In general, the more tear, the better quality of paper.

43

CHAPTER 6

EXPERIMENTAL PART (Part II)

HAND MADE PAPER

In this part, preparation of handmade sheet of paper is described

in details to make a decorative paper. The pulp used is semi-

chemical pulp from Palm Fronds prepared in previous section.

6.1 Pulp washing

The pulp is washed with hot water to wash out the cooking

chemicals and dissolved lignin from the fibers so that they will

not interfere with later process steps.

Good removal of chemicals (inorganic and organic) is necessary,

for successful the next steps.

The washed pulp is then defibrillated using Kitchen Blender.

6.2 Defibration

The washed Palm Fronds pulp is defibrillated in a blender until

we get the pulp as shown in Figure 21.

The pulp was diluted well till the blender is running smoothly.

(a) (b) Fig. 21: The following figures shows (a) the blender, (b) the pulp we get

44

6.3 bleaching of fiber

The purpose of bleaching the fiber is to attain the good properties

of the fibers in terms of the degree of whiteness, consistency,

cleanliness, and strength. Bleaching the fibered pulp is usually

carried out by multiple stages, namely hypochlorite and peroxide

stages.

6.3.1 Bleaching chemicals:

1-hypochlorite (NaOCL)

2-Hydrogen peroxide (H2O2)

6.3.2 Bleaching Steps:

6.3.2.1 First stage:

Hypochlorite(NaOCL)

1- Added of 5% of active Cl2.

2- Mixing fibered pulp with the prepared hypochlorite solution

and the pH is controlled until the mixture reach to pH=9.

3- Heat this mixture in a water bath at 40oC for 90 minutes.

4- Repeat the same steps at concentrations of 7% and 9% of

active Cl2.

Note:

We found that the best bleaching of fibers with good properties

and degree of whiteness at concentration of 7% active CL2.

45

6.3.2.2 Second stage:

peroxide(H2O2)

1- Added of 8% of (H2O2,35%).

Notes: (liquid : solid = 20 % ( 4:1)).

1- Mixing of fiber with H2O2 and control it until the mixture

reach to pH=11.5.

2- Heat this mixture in a water bath at a temperature of 70oC for

120 minutes.

(a) (b)

Fig.22: (a) mixture of bleaching, (b) Three samples before and after first and second

bleaching stages.

6.4 Chemical additions in the paper industry:

Addition of chemicals is carried out operate by special

arrangement to earn paper qualities required for the required

paper properties.

This addition operates in mixing basin and the important

materials that added to dough are:

46

alum

colored materials, a different types of coloring pigments and

dyes.

fillers such as talc powder

6.4.1 First add alum:

alum added to the dough after to give the paper immunity

against leakage of aqueous solution.

The alum is added to the dough by 2-6% of the dry weight of

the pulp.

6.4.2 Second: Add coloring materials and pigments:

1- Colors are added after dissolving the pigment in cold or hot

water depending on the type of coloring material and bleach

ability needed.

2- Filtering the colored solution to separate any granules did not

dissolve to prevent the occurrence of color spots in paper

produced.

3- After adding colors and mixing them with dough add resin to

fix the color.

4- Then add alum, which is also working on fixing the color to

cellulose in the paper fibers.

6.5 Hand sheets preparation

A dilute pulp slurry (bleached and colored) with very law

consistency about 0.6% is placed over screen as shown in Figure

23. The slurry was left to drain all the water. Then the wet sheet

over the screen is covered by a dry cotton cloth sheet and pressed

well to squeeze more water. Then transfer the wet sheet over a

47

clean smooth shiny stainless steel sheet and cover the wet pulp

sheet with new dry cotton cloth sheet. Dry using electric iron,

care was taken not to burn the paper sheet.

Fig. 23: Hand sheets preparation

By this way we have a good decorative paper sheet. A sample of

such decorative sheet is shown in Figure 24.

Fig. 24: decorative paper sheet

48

CHAPTER 7

CONCLUSION

1- In this study, semi-chemical pulps from palm fronds and

banana leaves were produced.

2- The strength properties of the produced semi-chemical pulp

are comparable to the chemical bagasse pulp.

3- It was found that the tensile index of new pulp was 33.65

N.m/g compared to 50.90 N.m/g for bagasse pulp, tear index

was 10.35 mN.m2/g compared to 5.74 mN.m2/g for bagasse

pulp, burst factor was 17.14 compared to 36.40 for bagasse

pulp.

4- Optimizing pulp of palm fronds and banana leaves can

produce better pulp with high strength then can substitute part

of the imported wood pulp.

49

REFERENCES 1. Atchison, J.E. (1962), Bagasse becoming a major raw

material for manufacture of pulp and Paper-Background,

present status, and future possibilities, Proc. ISSCT Conf.,

1185-1211

2. Atchison, J.E. (1962), Pulp and paper prospects in Asia and

the Far East, Bangkok, Thailand: Food and Agriculture

Organization of the United Nations (FAO), Vol. 2, 431-443.

3. Chapman, A.W. (1957), Purchasing, handling and storing of

bagasse, Food and Agriculture Organization of the United

Nations Document (FAO), Paper 4.12.

4. Cusi, D.S.; Jolley, P.W.R. (1968), How bagasse is pulped by

method used in Mexico, Pulp and Paper International, 10(6),

56-59.

5. Gabir, S.; Khristova, P., (1983), Fibrous semi-products from

raw materials resources for paper and board production in

Sudan. Agricultural residues: bagasse and cotton stalks, 8(1),

9-15.

6. Goswami T, Dipul Kalita* & P G Rao, (2008) Greaseproof

paper from Banana (Musa paradisica L.) pulp fibre, North East

Institute of Science and Technology (CSIR), Indian journal of

chemical technology vol. 15, 457-461.

7. Johansson, A., (1952), "The Determination of Pentosan,"

Svensk Papperstid, 55(21): 820.

8. Yuan-Shing Perng and Eugene I-Chen Wang, (2012)

optimization of hand sheet greaseproof properties: the effects

50

of furnish, refining, fillers, and binders, Da-Yeh University,

Department of Environmental Engineering, 7(3), 3895-3909.

9. Uraiwan Pitimaneeyakul, (2008) Banana Fiber:

Environmental Friendly Fabric (research), King Mongkut’s

Institute of Technology Ladkrabang, Thailand.

10. Sunday Albert Lawal and Benjamin Iyenagbe

Ugheoke, (2010), Investigation of Alpha-Cellulose Content of

Agro-Waste Products as Alternatives for Paper Production,

Department of Mechanical Engineering, Federal University of

Technology Minna, Nigeria, 13(4): 258-260.

11. Austin, G.T., (1984), Shreve's Chemical Process Industries,

5th ed; McGraw-Hill Book Co.: New York, 1984. TP145.S5.

12. en.wikipedia.org.

13. Aung, U.M.; Fleury, J.E. (1960), Breakthrough in bamboo

pulping, Pulp and Paper International. 2(5): 21-23.

14. Birdseye, C. 1959. Process for storing and digesting of fibrous

agricultural residues. Patent, P.N.: US 2889350, I.D.: 590811.

15. Mohammad Izzuddin Bin Yakari, (2008), Oil palm

frond (OPF) as an alternative source of pulp & paper

production material, 1-4.

16. Ilvessalo-Pfäffli, (1995), Fiber Atlas. Identification of

Papermaking Fibers, Springer-Verlag Berlin, Heidelberg, 400

pages,

51

17. Wiedermann, Alfred; (1989), Reeds, In Pulp and Paper

Manufacture Volume 3 – Secondary Fibers and Nonwood

Pulping, Ed. M. J. Kocurek, TAPPI press, Atlanta, 94-105.

18. Francis, R. C.; Bose, S. K.; Shin, N. H.; Omori, S.;

Brown, A. F., (2005), bleached hardwood pulps by

soda/AQ and MAQ processes, TAPPI engineering, pulping

and environmental conference, 26-31.

19. Abdullah, Ahmed S.; Al Abbase, Mohammed H.,

(2004), cooking conditions for Eucalyptuse

cammaldulensis and poplus euphratica with anthraquinone,

TAPPI engineering, pulping and environmental

conference, Atlanta, GA, United states, 31(3), 34-36.

20. Finell, Michael; Nilsson, Calle, (2004), "Kraft and soda-

AQ pulping of dry fractionated reed canary grass," 19(2),

155-165.

21. Springer, Edward L.; Attalla, Rajai H.; Reiner,

Richard S, (2002), Potential sulfur-tree pulping methods.

TAPPI Fall Technical Conference and Trade, 624-628,

22. Mamdouh M. Nassar, (2003) Pulp from agricultural residues,

chemical engineering department, Minia University, Egypt,

20421.

23. Jaya Bharat Reddy Marella, Sairam Madireddy, Anudeep

Naidu Maripi, (2014), Production of Pulp from Banana Pseudo

stem for Grease Proof Paper, International Journal of

Engineering Research and General Science Volume 2, 36-40.

52

24. medinadates.blogspot.com.eg

www.aljazeera.net

53

APPENDIX

Hand sheets preparation

A volume of well disintegrated pulp slurry equivalent to give a

60gsm sheet in the standard sheet making unit is stirred well in

the sheet making unit after making up the volume of water to the

mark. the drain lock is opened so that a sheet is formed on the

grid plate. The sheet is couched by a blotting sheet and

transferred to the sheet press. A number of similar sheets and

piled over one over the other and pressed to squeeze out water.

The sheets were removed from the press and air dried in drying

rings with couch plates on.

• Take 30 g oven dry pulp and dilute to 2 litres and the

disintegrate to 10000 revolutions in the disintegrator. if the

pulp initial consistency is above 20%, the pulp is disintegrated

to 30000 revolutions and make up to 10 litres in a bucket.

• With sheet former open, turn on the water and clean the surface

of the wire then close the machine and fill with water to the

mark.

• Pour 400 ml of the diluted pulp into the sheet former and insert

perforated stirrer and stir rapidly down and up five times,

keeping the perforated disc beneath the level of water.

• Remove stirrer from the sheet former and after a pause of

about 5 secs, fully open the drain valve by a rapid movement

to let all water drain under suction.

54

• Place a blotter centrally and a couch plate over it and roll the

couch roll over the plate to and fro, 4 times and remove couch

and blotter along with the wet sheet.

• Press the sheet and dry in a rapid dryer and find the weight of

the sheet and then correct the volume of slurry to be taken to

get a sheet weight of 1.28gms OD, corresponding to 60gsm

OD, and make a sheet as above.

• Open the sheet former and lay a blotter centrally on the sheet

formed and place the couch plate centrally on the blotter and

couch roll on the middle.

• Without applying extra pressure move the couch roll back and

forth four times to within 5 mm of plate edge and finally to

middle and remove the couch and pulp sheet along with

blotter.

• Place the couch blotter, hand sheet side up on a fresh blotter

and cover the hand sheet with a polished plate, polished side

down.

• Follow this with two fresh blotters and backwash the wire

mesh in the sheet machine.

• Repeat the sheet making process to make 6 sheets and place

the sheets in a standard sheet press centrally with the help of

template.

• Press to give 0.27mpa pressure for 5 min and release pressure,

remove cover of the press.

• Remove the blotters from hand sheets and replace wet blotters

with dry ones by reversing the order of formed sheet along

with plates.

55

• Place the sheets in the press and apply 0.27mpa pressure for 2

min and remove the sheets from the press.

• Dry them under the standard conditioning and testing

atmosphere for paper in drying rings.