EFFECT OF HARVESTING TIME ON THE PWSICAL, CHEMICAL AND PULPING PROPERTIES OF HEMP

(CANNABIS SATIVA L.)

Jaymini Kamat

A thesis submitted in conformity with the requirements for the degree of Master of Science in Forestry

Faculty of Forestry University of Toronto

@Copyright by Jaymini Kamat 2000

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Abstract

Jaymini Kamat

Master of Science in Forestry 2000

Faculty of Forestry

University of Toronto

Effect Of Harvesting Time O n The Physical, Chernical And Pulping Properties Of Hemp (Cannabis sativa L.)

Excessive overuse of forests has led to environmental degradation. which deserves urgent

attention. by switching to non-Forest fiber resources where possible. Hemp, a non-woody plant.

has long been considered as a potential fiber source substitute for the pulp and paper industry.

The prlln- aim of ihis study is to assess the physicd. chemicd and pulping properties of hemp

with respect to the harvesting t h e . in order ro determine the optimal growth point for hanresting.

Hemp stems were harvested in the field at the end of 30 days. 60 days. 90 days and 120 days. and

analysis conducted using standard TAPPI procedures to measure their properties. The hemp

fibers were seen to exhibit similar properties as woody fibers. The optimum t h e to harvest the

crop was found to be benveen 60-90 days. in order to achieve low lignin concentration and hi&

pulp yield. resuitîng in optimal mechanical properties of the paper produced.

Acknowledgement

1 sincerely espress my deep gratitude and thanks to my supervisor. Dr. D. N. Roy, for his support

and guidance in each step of this thesis work.

1 wouid also Iike to express my gratitude to Dr, K. Goel of Domtar Inc. for worthy feedback and

support in the Iast hvo years.

A sincere thanks to the Pulp and Paper Center of the University of Toronto and Donohue Inc. for

making their laboratories available to me for my research work.

I am thankful to the Faculty of Forestry. for giving me the oppolhinity to be a part of this pro--

in M.Sc.F.

I am diankflll to my schooImates. h u i t Bhuie. Fatima Comeia and Warren Maybee for their

assistcuice and suggestions during the Iaboratory work.

I am thankful to my husband. Santosh for his nippon and encouragement throughout the study

period and to my parents for their love.

Table of Contents

Cover page

Abstract

Acknowledgment

Table of Contents

List of Tables

List of Figures

Glossary of Tenns

Chapter 1 Introduction

Chapter 2 Literature Review

2.1 Global scenario

2.2 Non-woody fibers in the pulp and paper indu=

2.2.1 Background

2.2.2 Cornparison of non-woody with woody fibers

2.3 Pulping of non-woody fibers

2.1 Age effect on plant anatomy and pulping

2.5 Hemp as a potential source of non-woody fiber

2.6 Rational. objectives and significance of this research

Chnpter 3 Materials and Methods

3.1 Raw materiai for the study

3.2 Outline of the experiments

3.3 Physical analysis of the fibers

3.3.1 Macro-analysis of the fiber

3 -3.2 Micro-fiber analysis

3.3 2.1 Maceration

3.4 Chemicd analytis

3 . 4 1 Freparation of the raw matends

3 -4.2 Extractives

3 A.3 Holocellulose

1

. . I l

- -. 111

iv

vi

vii

viii

3.4.4 a-cellulose

3.4.5 Lignin

3.4.6 Ash and s i h a

3.5 milping

3.5.1 Mcro-scale puiping

3-32 Pilot-scale pulping

3.6 Disintegration and Screening

3.7 S!edGrig

3.8 Hand sheet making and testing

Chapter 4 Results and Discussion

4.1 Morphological study

4.1.1 Height and diameter of field hemp plant

4.1.2 Bio-mas produced by hemp stems

4.2 Physical characterization of hemp stem

-I.I.l Study of cross sections of field hemp stems

4.2.2 Dimensions of hemp fibers

4.3 Chemical analysis of hemp stems groown in field and greenhouse

4.4 Micro-scale pulping

4.4.1 Pulping selectivity in hemp stems

4.42 De-lignification kinetics in hemp stem pulping

4.4.2.1 initial and buk de-lignification in hernp

4.4.3 Activation energy for de-lignification in hemp

4.5 Pilot-scale pulping of hemp harvested at different times

4.5.1 Physical properties of the paper made 6om hemp

Chapter 5 Conclusions and Recommendatiois

5.1 Conclusions

5.2 Recomrnendations

References

Appendices

List of Tables

Table 2A

Table 2B

Table 2C

Tabk 2D

Table ZE

Table ZF

TableZG

Table 2H

Table 21

Table 3A

Table SB

Table 4C

Table 3D

World production of paper and paperboard

Use of non-woods in pulp and paper production

Comparison of average annual yield of woody and non-woody plants

Comparison of the fiber morphology benveeli woody and non-woody plants

Cornparison of the chernical composition behveen woody and non-woody plants

Comparison of physical properties of woody and non-woody pulps (bleached)

Differences of juvenile and mature wood properties of IobloUy pine and cottonwood

MorphoIogical characteristics of hemp bast and core fibers

Chernical characteristics of hemp bast and core fibers

k e a s occupied by bast. core and pith in stems harvested at different times

Bast and core fiber dimensions in hemp harvested at different times

Yields at different stages of kraft pulping and blraching

Physical properties of hand-sheets made from 60-day and 90day field hemp pulp

List of Figures

Figure 2.1

Figure 3.1

Figure 4.1

Figure 4.2

Figure 4.3

Fikure 4.4

Figure 4.5

Figure 4.6

Fikure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.1 1

Figure -1.12

Fi-me 4.13

FiCg.ue 4.14

Figure 4.15A

Figure 4.15B

Figure 4.16

Figure 4.1 7

World's five main producers of pulp and paperboard

Sampling design in the field

Height of hemp plants in five plots (field)

Width of hemp plants in five plots (field)

Bio-mass produced by hemp plants in five plots (field)

Cbemical analysis of hemp stem grown in field harvested at different times

Chernical analysis of hemp stem g r o w in greenhouse harvested rit different times

Estractive analysis of field hemp

Estractive anaIysis of greenhouse hemp

Percentage lignin retained afier pulping in different cooking conditions

hlping selectivity in hemp stems harvested at different times

Delignification kinetics of field hemp plants harvested at 30 days

Deli_pification kinetics of field hemp plants harvested at 60 days

Delignification kinetics of field hemp plants hawested at 90 days

Delignification kinetics of field hemp plants harvested at 120 days

initial and bulk de-iignification in field hemp stems

Arrhenius p p h of soda pulping of hemp stem harvested at 30 and 60 days

Arrhenius --ph of soda pulping of hemp stem harvested at 90 and 120 days

Activation energy for delignification in hemp harvested at different times

Cornparison of soda and kraft puiping for 60 and 90 day field samples

Glossary of Terms

Sym bo t Explanation

Analysis of variance

Hemp harvested at 30 days fiom the fie

Hemp harvested at 60 days fiom the field

Hemp harvested at 90 days fiom the field

Hemp harvested at 120 days kom the field

Hemp harvested at 30 days fiorn the greenhouse

Hemp harvested at 60 days frorn the greenhouse

Hernp harvested at 90 days fiom the greenhouse

Hemp hrulrested at 120 days from the greenhouse

Unbleached

Bleached

viii

Chapter 1

Introduction

Forests have historically been hamested for many uses like timber. for increasing agiculturai

land and for wood. which is used as a raw material for various Forest-based industries. Forests

defuritely play an important role in econornic. social and environmental aspects of different

nations around the globe. Though the forests can be renewed and regenerated. there is an upper

bound on the degree to which the forest resources codd be used rvithout harmful consequences to

the environment. Especially in the last half-century. forests have been harvested in a non-

sustainable way above their potential and now it is upon us to give hem some time to re-generate.

Behveen the years of 1980 to 1995. 200 million hectares of forests. including some plantations

were lost for some of the applications mentioned above. Evrn thou&. during the sarne penod.

about 30% increase in the forests was recorded in the developed counûies. it is too little to

compensate the loss during that penod in developing countries. resulting in a net loss of around

200 million hectares of the forests. ~~Iobally ' (FAO. State of the world's forests 1999).

One of the major industries depending on forests is the pulp and paper industry. which uses the

woody fiben obtained tiom forest. Presently. woody fibers extracted fiom the forests are the

dominant raw material in the pulp and paper indusûy. But obtaining the continuous supply of

such woody fibers fiom the h g i l e forest ecosystem in the hiture will become more and more

dificult. The reasons for this potential short supply of wood are: (1) pressure fiom the

environment, (2) over-harvesting, (3) sustainable forest management which allows less cuts per

year. though it aims to supply fibers for many more years. and (4) dernands from social corners

like recreational facilities etc. As a result, industries like the pulp and paper industry. which

currently depend heavily on forests for their raw material supply. should be looking either toward

inventing changes in the technology to improve the efficiency of the use of harvested wood or

research for some alternative raw materials.

As for the route of inves t iga~g the potential alternative raw materials in the pdp and paper

indusûy. there is enough historicd evidence that ic fact, the burden on the forests could be

somewvhat aileviated by substituthg non-woody raw materials like hemp and kenaf. in fact, f?om

16" cenhuy to 18" century, much of the pulp produced was Eom non-woody fiben, especially

fiom hemp and flax '. But due to the developing new technologies at that tirne, use of forest wood

was much cheaper than using non-woody fibers for pulp and paper production, which resulted in

the declùie of hemp and flau in pulp preparation. In 1937. because of the association of hemp

with marijuana, its cultivation was banned. But its importance has now been understood and

growth of hemp is now Iegal in Canada. The f m e r s are eocounged to grow more hemp (with

license), which is becoming comrnercially saleable, with an atternpt to replace the harmful

tobacco plantations by industrial hemp.

The re-advent of hemp can help to provide sustainable fiber resource for pulp production. Use of

agicultural crops like hemp can decrease the pressure on harvested forests and the environment.

Also less e n e r a is required for using hemp in pulp production ihan for using wood '. Secondly.

li-nin content in hemp is Iess than that of wood, which means less use of chlorine for pdp

bleaching and potential increased use of alternative methods of non-chlorine bleaching (pulp

prepared from hemp is comparatively white in color). Also. hemp cdtivation needs moderate use

of pesticides and fertiiizers '.

This thesis work investigated the physical, rnorphological and chernical properties of hemp fibers

as a fùnction of the harvesting t h e and other operating parameters. in order to relate those

operating parameters and fiber properties to the quality of pulp and paper produced. The results of

this study can potentially be used to further evaiuate the candidacy of hemp as a substinite raw

materiai for pulp and paper production.

The thesis is divided into five chapters. After this fm chapter, introduction. thc second chapter,

Lirerature Review surveys the existing knowledge and the r e d t s of the work done by daerent

researchen in the field. The thhd chapter, Materials and Methods. descnbes the materials and the

methodoloq used to conduct the experiments for this study. The fourth chapter, Results and

Discussion, presents and discusses the renilts of the analysis on the raw data obtained from the

experiments. The concluding fifth chapter nunmanzes the r e d t s of the study in relation ro the

previous work of other resemchers and also, gives recornmendations for future work in the area.

Chapter 2

Literature Review

2.1 Global scenario:

in the developing countries. with increasing literacy and irnproving economic conditions. the pulp

and paper industry \vil1 need an increase of at least 4.3 % in pulp production per year to meet the

intensifying demand. The demand Eom developed countries will need an extra 1.2 % of pulp per

year '. Table ZA lists the chronologica1 production of paper and paperboard behveen the

developed and developing countries, whereas Figure 2.1. depicts the proportionate share of tbe

world's five major producers of pulp and paperboard. To meet such an escalating demand. based

on the conventionai methods of paper production. more and more forests d l have to be

harvested. Demand 6.om other Forest-based industries will also uicrease with the developing

economies. It is estimated that by the year 20 1 O. about 50- 100 million hectares of forests \vilL

have to be harvested to meet the global demand 6. And if that is the case. the esisting forests will

no longer be able to satisfy such demand.

Table ZA: World production of paper and paperboard

Paper and paperboard

World

Developed countries

To address the above problems. the pulp and paper i n d m shouid strive to: (1) Unprove their

technology to make the best use of available fibers. (2) use other Bber resources Like non-woods.

(3) promote more recycling of paper, (1) use fast-growing species like poplar, and (5) make best

use of the available residues of round wood fiom other industries for pdp-making.

1990 (%) 1970 (%)

Developing countries

At present, the bea use of non-woody Bers is made in China and India. Whereas the major pulp

producing counûies like the USA (Figure 2.1) mostly use woody fibers for their pulp and paper

1994 (%)

1 O0

93

Source: FA0 -State of the world's forests 1997

7

100

83

100

79

17 1

21

production. Lf such major pulp producing countries do start looking bto substituting even a

portion of their raw materials by non-woody fibers, the deteriorating state of the forests wodd

definitely be restored to a certain extent.

- - - -

Source: FA0 yearbook of forest products 1994

Fig. 2.1 World's five main producers of pulp and paperboard

2.2 Non-woody fibers in the pulp and paper industry:

The first paper ever made was produced from non-woody fibers 6. However. with the growing

popularity of paper. the search for new raw materials began in order to increase the supply of

paper to satisS the growing demand (as straw and other non-woody fibers were not enough to

nipply the demand for raw materials). Woody fiben. which were readily available at that tirne.

became popular especially with the improvement in the technolog, which focused m a d y on the

use of woody fibers 6.

Countries with hadequate forest resources still use non-woody fibers for their pulp production. In

1970, about 6 million tonnes of non-woody fiber pulp was produced, which accounted for 4% of

world's total pulp production. By 1994. non-woody pulp production increased to 21 million

tomes representing 8% of the total world production 7. Table 1B shows the chronological use of

non-woods in the pulp and papa production on a giobal bais fiom 1985 to 1998. As seen fiom

the table. the use of non-woody fiben, as a percentage of the raw materials in the total pulp

production is gradually increasing with tirne.

Source: What about non-wvoods: TAPPI Global Fiber Supply Symposium 1995

Table 28: Use of non-woods and wood pulp in paper production

2.2.1 Background:

I Type of raw material

Non-woody pulp

(,O00 metric tonnes)

Woody puip

(.O00 rurtric tonnes)

Non-woody as % of

total pulp .

Non-woody fibers. sornetirnes called as alternative fiben. refer to fibers capable of producing

paper and obtained fkom non-woody cellulosic plants. Such non-woody plants c m be classifird

in three different groups: (1) cultivated plants like abaca and flau. Born which very specialized

paper can be obtained. (3 ) indigenou plants like bmboo. esparto. gras and reed, which grow

naturally in sorne countries. (3) in the third group there are tsvo categories. one as agicultural

residues Like straw. bagasse and Cotton (linters and staks). while the second category includes

crop fibers like kenaf. hemp. jute and sisal. which are grown exclusively to yield Bber '.

The most important non-woody fibers in use for puip making are wheat stmv (46 %), bagasse

(14%). and bamboo (6 %) 6. The reniainine 33% of the non-wvoody fibers used corne Born other

plants like conon, hemp, sisal and kenaf ! Some of the specialty paper is obtained from the non-

woody fibers. which have special properties not found in woody pulps '! Half of the global non-

woody pulp is produced in China and whereas another 30% is produced in india. in China. the

non-woody pulp accounts for 86.9% of its totd pulp production, while in india, it accounts for

55.5 % (1988).

1985

13,352

15 t ,000

8.1

Notwithstauding the various benefits of using the non-woody fibers in pdp and paper production.

as is discussed at length in this thesis, the use of non-woody raw materid for puip production has

some disadvantages, which need to be mentioned here. Some of the problems encountered in the

use non-woody fibers for pulp production are: (1) theu seasonality makes it more difficult for the

1990

15,562

168,600

8.5

1993

20,736

174.000

1998

(estimated)

23,46 1

1 85 .O00

I 10.6 11.2

year round availability of the raw materiai, (2) these Iess dense materials need to be stored for

year round supply of the raw material: hence large storage area is needed, (3) proper care has to

be taken durhg storage, as otherwise degradation of the fibers wodd lead to the loss of raw

matenal (4) growing non-woody fibers requires hi& input and is therefore costiier compared to

sorne other sources of fibers such as the residues available as a bye product fiom various wood-

based industries. and (5) hi& silica in the raw material makes recovery of the chernicals in

chemicai puiping dificult '.

2.2.2 Comparison of non-woody with woody fibers:

Any non-woody fiber has to compete with the comrnercially used woody species. Yield.

morpholog of fibers. chemical composition of stems. properties of the pulp and paper produced.

as well as the economical factors are important parameters in determining the potential of a raw

matenal for the pulp and paper industry. Tables ZC. ZD and ZE highlight the comparative

properties of the non-woody plants with those of the woody variety.

Table X: Cornparison of average annual yield ofwoody and non-woody plants

Plant Fiber yield Puip yield (chernical) tomedveadha tonnedvearha

Fast growing sohvood 8.6 4 Scandinavian softwood 1.5 0.7 Fast growing hardwood 15 7.4 Temperate hardwood 3.4 1.7 wheat straw 4 I .9 Bagasse 9 4.2 Kenaf 15 6.5 Hemp 15 6.7 Source: Pierce ( 199 1)

Table 2C shows that the yield of the non-woody fibers is comparable with that of woody fibers.

in fact, in sorne of the non-woody fibers. pulp yield is higher than that of the woody tibers. Yield

of non-woods can be highly affected by the climatic condition of the particuiar year as they

complete their life cycle ~vithin a short t h e (4 months to one year). Being seasonal crops. year

round availability of non-woody fibers is problematic and storage of such Iess dense matenai

needs lots of space and care to avoid loss due to degradation. Harvesting and collection of non-

woody 6bers c m be dinicuit and could be economically costly due to high labor prices.

Table 2D: Comparison of the fiber morphology behveen woody and non-woody pIants

Plant Average length Average width (mm) (PI

Temperate zone coniferous woods 2.7-4.6 3243 Temperate zone hardwoods 0.7- 1.6 20-40 Mived tropical hardwoods 0.7-3.0 2040 Wheat stratv 1.5 15 Bagasse 1.0-1.5 20 Kenaf (bat ) 2.6 20 Hemp (bast) 20 22

Source: J. H. Atchison (1 993)

Table 2D hi_dights the cornparison of the fiber morphologies of the woody and the non-tvoody

plants. As seen fiom the table. the fiber rnorphology of non-woods is similar to that of hardwood

and sohvood. Short non-woody fibers possess qualities similar to that of hardwood whereas long

non-woody fibers have similar properties as sofnvood. Some of the fiber-yielding plants like

hemp and kenaf have two morphologically different types of fibers. which are classified as bast

and core fibers. Ln such cases. separation of the hvo fibers can give better r e d t s in pulp

production. but that process incurs additional cos. Pulping such fibers together results in either

overcooking of one type of the fiber or undercooking of the other. Too long fibers. as in the case

of hemp. c m create problems in the stages like screening and spinning, resulting in h o t

formation '.

Table 2E: Comparison of the chemical composition between woody and non-woody plants

Plant CeUulose L ignin Ash Silica (% of total) (% of total) (% of total) (% of totd)

-

Coni ferous (woody ) 4045 26-34 cl - Deciduous (woody) 38-49 23-30 <l - Wheat straw 29-5 1 16-2 1 4.5-9 3-7 Bagasse 32-48 19-34 1.5-5 0.7-3.5 Kenaf (bast) 44-57 15-19 II 3, j - Hemp (bast) 57-77 9- 13 - -

Source: Han and RoweIl( 1997)

Table 2E supports the findings, documented in different journds, that the non-woody fibers are

rich in cellulose and have low lignin. Both these characteristics of non-woody fibers are good for

the pdping process. Hi& cellulose Ieads to hi& yield of ceiiulose fibers during pulping. Low

iignin means lesser chernicals are required for pdpiog, less time is needed for cooking and there

is effective removal of lignin at Iow temperatmes. Mso, as we see fkom Table 2E. non-woody

materials, with the exception of hemp, are hi& in ash content. Most of this ash is in the form of

silica, which is not very welcomed by the pdping process. Hi& silica results in: (1) loss of

sharpness of cutting or chopping blade, and (2) more difficult recovery of the chemicais used in

chemical pdping '.

2.3 Puipiog of' non-woody fibers:

Non-woody fibers. like woody fibers, can be pulped in different ways: by kraft, soda. neutrd

sulfite. alkaline sulfite. or by soda dfk. Many of such processes are not in use now as the

presently used soda and kraft processes dominate them. giving high quality bleached and non-

bleached pulps 'O. Use of chemical or semi-chemical processes to obtain good bleached and un-

bleached pulp is common. Like the woody fibers. the best results in the non-woody fibers are

obtained by soda pdping or kraft pulping.

The sulfite process leads to a higher yield of pulp from non-woods. The simple process and the

easy recovery of the chemicals have led to the popularity of the technique. One important feahue

of the sulfite process is that it acts well for both woody and non-woody materials. Also. bvo types

of fibers c m be blended together in thîs process to get a rnixed pulp 'O.

Some special processes like organosolv pdping and extrusion pdping have been tried on many

non-woody fibers. Such processes. in small scde. give better resuhs in ternis of use of less

chemicals and hi& yield. Many non-woody materials like kenaf and hemp give good results with

the soda-anthraquinone (soda-AQ) and organosolv processes "- I L ".

Less dense materials ofien give good results with mechanical pulping. in fict. the mechanical

p d p of bagasse is used for the production of newsprint and writing/printing paper. Use of

mechanicd pulping in the case of other non-woody fibers stiii rernains to be investigated in detail.

14 Today, about 80% of the non-woody pulp is produced by the kraft pdping technique . Celidosic materials are cooked in white Liquor made fiom sodium hydroxide and sodium dfide.

The hvo important driving parameters for the reaction are active alkali concentration and

temperature. Within a temperature range of 155 c - 175 O C, an increase in temperature by ten

degrees results in almost doubhg the reaction rate. Deligrilfication in kraft pulping occurs in

three stages, initial removai of l i a foIIowed by bulk removd of lignin and at the end, removai

of residual lignin. which is a slow process. Along with delignification, some hemi-cellulose and

alpha-ceiidose are dso lost in h f t puiping. With the rernovd of 20% iignin, approximately

40% hemi-cellulose is lost '". Loss of alphasellulose and hemi-cellulose occurs by the peeling

reaction. which entails removal of end-group ketoses 6om polymers of hemi-cellulose and alpha-

cellulose by P-akoxy elimination. resulting in dissolution and degradation of the polymers ''.

Brightness can be achieved in two ways. either by discoloration of chromophoric groups without

removing Iic.enin (as in mechanical pulping) or by the removal of residuai Litgin (as in chemical

pdphg). The first rnethod resdts in about 70-80 % brightness. but such brightness is not

permanent. ln the case of bleached paper obtained by the former method. exposure of the paper

to light or oxygen from the atmosphere resuits in discoloration of the paper. due to lignin '". High

quaiity paper is obtained by the latter process (chemical pulping). in th is process. delignification

of residual lignin is followed by the removal of color by using oxidizing agents. This method

involves a combination of various stages including chlorinating (C), alkaline extraction (E).

hypochlorite (H). chlorine dioside (D). peroside (P), oxygen (O), and admixture of chlorine and

chlorine dioxide (DC or CD). For best resdts. combinations of five to six stages (CEDED 1

CEHDED / OCEDED) are used.

Pdp properties depend on fiber morpholog. li@n content and percentage of the retained alpha-

cellulose. Li@ binds the cellulose fibers together. thus making their surfaces less hydrophilic.

This in nim decreases the ability of the cellulose fibers to form bonds amongst thernselves.

Therefore, increase in the pulp Iignin content results in decrease in strength properties. Breaking

and bursting strength are maximum at a yield of around 45-55 % and M e r increases in the yield

decrease the strength. Tearing strength also decreases with increase in the yield beyond 50 % - 60 %. Al1 the above properties are also influenced by the type of pulping process. the active

alkali content and the degree of beating of the pulp 16.

Table 2F: Cornparison of physical properties of woody and non-woody pulps (bleached)

Plant Freeness Breaking height Burst Tear Fold Bulk

(m) TAPPI TAPPI (cc/!$ - -

Sohvood (spruce) 28 SR 11000 90 110 1900 1.70

Hardwood(birch) JSSR 7600 50 82 350 1.40

'&'&ai J ~ X K 50 SR 5500 -12 25 70 1.38

Bagasse 25 SR 6800 42 70 210 1.54

Kenaf (bas) 40 SR 10300 56 72 570 1.60

Hemp (not specified) 28 SR 7000 53 180 460 1.85

Source: A. LM. Hurter ( 1 988)

Table ZF shows the relative properties of woody and non-woody bleached pulps. -4s seen in the

table. physicai properties of the non-woody pulps (escept for wheat strawv and bagasse) are in

between those of sofhvood and hardwood. Hemp in particuiar has hi& tear and bulk values

compared to other marends in Table ZF. By studying these pdp properties in relation to the used

raw matenal. effective matenal selection of the non-woody fiber could be done to give the

desired properties to the paper depending on its end use. As aiready mentioned before. even

today. some of the fine and specialized papers are produced 6om the non-woody fibers because

of the specific desired properties they bring about in the final product.

2.4 Age effect on plant anatomy and pulping:

Woociy fiber-yielding plants have different qualities of wood Wte juvenile. mature and top wood.

each of which exhibit distinguishing characteristics. Juveuile wood. for example, is responsible

to aiter the properties of end products like sotid wood. paper and composition board ". Due to

the hi& pressure on forests for woody fiben. use of generically improved fast growing species of

wood is becoming more common. Such f a t growing species are rich in jwenile wood. Juvenile

wood. compared to mature wood. has lower specific +gravity, shorter fiber length and has diEerent

chemical ratios ". Bendrsen and Se& in 1986, reported that mechanical properties of juveoile

wood of lobloily pine and cononwood differ fiom their mature wood 19. They found mechanical

strength of juvenile pine was about 47 % - 63 % of that of mature pine wood, whereas the

mechanical strength of juvenile cottonwood was 62 % - 79 % of that of mature cottonwood. This

difference in mechanical strength is due to the increases in specific gmvity and fiber length, and

also improved fibril angle in the case of mature wood as against the juverde variety. Table 2G

shows the relative differences in the properties of juvenile and mature woods of loblolly pine and

cottonwood. Pulp fkom the young trees (7-8 years), wîth juvenile wood. has hi& burst and

breakuig strength but low tear snength compared to pulp &om mature eees 19. Top wood results

in low yield, which is due to the breaking down of the cellulose during the pulping process. Low

degee of po!perization of cellulme at the top results in its e q degradation in the pulping it

process -.

TableZG: Differences ofjuvenile and mature wood properties of loblolly pine and cononwood

LOBLOLLY PINE

Juvenile 6.850 Mature 1 1.500

Juvenile 4.070 O .4 70 1.730 0.344 1 .O2 18.4 Mature 5,170 0.76 1 2,360 0.375 1.17 14.2

Source: Bendtsen and Senfi ( 1986)

In non-woody fibers. nich major anatomical differences wiih the age of plant are not commoniy

observed because the non-woods complete their life cycle within a year or less. Watson et al

(1976) snidied the kenaf stem with respect to the age of the plant and concluded that

anatornically. kenaf stem is the same Erom top to bottom. except for an increase in the width of

the stem at the bottom of the plant. Length of the fiber &om top to bottom remains the same =O.

However. in non-woody plants. there is a positive co-relation between the plant height and width

with the age of the plants. These extenial morphologicd factors are iduenced by the available

moishue and sun 9. A h , the length and the width of fibers do change with respect to the age of

the plant For example, in the case of mesta (Hibiscus sabdariffa), specimens hnrvested at 120

days have longer fibers than at 150 days. Fiber length in Kenaf shows W a r trends, with

highest fiber length in 90 days old stems and thereafter shows decrease in the length dong with

the age of the plant 43. The crystaUinity of the cellulose increases with the age of the plant, which

in turn gives more strength to the paper, possibiy because of less degradation of the cellulose.

Also, iignin in older plants (150 days old plant, for example) is found to be higher, and as a result

the initiai de-lignification of older plants becomes easier with the same pulping pmcess ". Clark

and Wolff (1967) found increase in the chernical components Like pentosans, lignin and a-

ceilulose in kenaf plant as a b c t i o n of growth. At the same tirne. it is found that there is a

decrease in the amounts of extractives. ash and protein with increasing age of the plant 9. There is

somc mbiguity rcgxduig the incrcrrse the 5ber !mgth with age. Hanes et al (WJ) foond

increase in the fiber length in bast and core fibers of kenaf. with increasing age.

2.5 Hemp os a potential source of non-woody fiber:

Ts'Lun fus made paper by using old rags and textile waste, which were produced at that tirne

f5om hemp and china grass fiben 6. Thus the fust paper ever made was produced from hemp.

Until the early 1800's. hemp remained as one of the important fiber-producing crops. Around

1940. amendrnents to the dmg laws of many corntries (regarding ban on hemp cultivation) came

into existence due to the distant relative of the industrial hemp plant cdled marijuana. which is

considered a narcotic drug. Farmers then unwülingly shifted towards cultivation of other crops.

Most of the indushial variety of hemp has iow (0.3%-1.77% as compared to 10-1 5% in

marijuana) tetra-hydro cannabinol (THC). a psychoactive substance found in the marijuana

variety Thus. the use of hemp in industries is sometimes determined by the political issues.

rather than its botanical or agricdtural potential.

Hemp is known for its long, saong and durable soA fibers. Along with the pulp and paper

industry, it Gnds uses in many other industries. Examples are the textile industry. the fiber

composites industry, the nutrition and beauty products industry and the bio-mass hel industry.

USDA (United States Department of Agriculture) investigated different fiber-producing plants for

their potential in the use in the pulp and paper industry =. Hemp and kenaf came with promising

results, because of their beneficial properties, &ch give desired characteristics to the renùtant

pdp and paper.

Hemp, botanically known as Cannabis sativa L., is the only genus in the family cannabinaceae.

Hemp is an annual shrub growing about 4-5 m in height with yield as high as 12-14 tons of dry

matterhectare ". ft completes its life cycle within 90-120 days. Width of the mature plant varies

between 1.5 mm-7.5 mm, depending on the growing conditions "'. Hemp, though it originated in

central Asia, c m be grown in a wide varïety of climatic conditions and can be successfidly gowu

in most parts of North America. Leaves of hemp are opposite at top, altemate M e r down,

deccasate and stipdated with auuiiiruy bud. Leaves have long petioies, and are palmetely

compound \vit. six lobes (three in first few produced leaves). Leaves are pubescent, and each

leafIet is lanceolate with serrate margin. has acute apex and reticuiate venation. Flowers are

borne in clusters at the apex of the stem. Hemp is dioecious and depends on the wind for

pollination. Male flowers have 5 transparent sepals and 5 yeilowish green petals. Five stamens

-A$& +h filment tur;t 5ght pcllow dwhg mabty. Fernale inflorescence i s dense, with

inconspicuous flowers. which have one leaf-like calyu nirrounding the ovary with one ovule

(therefore have one seed / flower) '. Ln Netherlands. hemp is üied as a new crop. especially as it

is considered as an environmentally safe crop. It can do welf in poor soil conditions. and does not

require high fertilization in the fonn of pesticides or herbicides. and the yield is high '.

in Canada. the new Controlled Substance and Abuse Act of 1996. which came into pnctice on

March 12. 1998. pemitted famers to obtain licenses for the commercial production of hernp. In

Canada. the Tua hemp crop after the ban was produced in October 1998. Table 2C lists the

comparative average yields of hemp and wood. The table shows that the hemp yield per hectare

is much more than that of temperate hardwoods and comparable to that of fast growing

hardwoods. The average annual yield of hemp in Canada is reported to be around 9 tons / hectare

I year '".

Anatomicdy. hemp has two types of fibers known as phloem fibers and xylem fibers. Xylem

fibers. called as core fibers, are short, thick walled and have more lignin than that of phIoem

fibers. Phloem fibers, h o w n as bast fibers. are present on the outer side of the stem. and are long

with very littie lignin compared to s o h o o d and hardwood. Indumies prefer to separate the two

types of fibers. as pulping them together results either in overcooking of one type or under-

cooking of the other. thus losing some of the important characteristics ". Separation of the nvo

types of fiben is accomplished by a rening process. In retting, h g i decompose the pectin and

gummy soft layen between the xylem and phloern fibers, which enhances the separation of the

wo types of fiben. In field retting, harvested crops are lefi in the field for 2-6 weeks ". Field

retting c m be advantageous, as all the released components of the plants are recycled back to the

soil. Leaves dry out and are shed in the field. Also. since the field is covered with the hemp

stalks, there is reduction in soil erosion to some extent, Water retting or snow retting is practiced

in some areas. After retting, separated fibers 6nd use in production of different b d s of paper.

Core fibers are used in buk production of printing, writing or copying paper, and bast fibers are

used in high value grades of paper like cigarette paper and tea bags

h a mica l stem of hemp, about 35 % of the solid area is occupied by the bast fibers while 65 %

is occupied by the core fiben ". ". A mal1 amount of pith surrouods the hollow part of the stem.

Bast fibers are 5 - 55 mm Iong and have widths ranging From 16-50 p. whereas the core fibers

are 0.5 - 0.6 mm Iong with widths kom 15-25 p. Tables 2H and 21 show the detailed

morphoiogiçai and clamicd iharactixktiss af hcmp bast and core fibers. Hemp basr ha. high

cellulose content and low lim content compared to the hardwood and sohvood species used in

the puiping process ".

Table ZH: iMorphologica1 chc t ens t i c s of hemp bast and core fibers

Morpholog Hemp bast Hemp core

Average length (mm) Maximum length (mm) Minimal length (mm) Average width (pm) Ma.xhal width ( p) Minimal width (p) Length 1 width Wall thickness (p) Average bundle length (mm)

* n. d. = not detennined Source: DeJong. E.: Van Roekel. G. J.: Snijder M. H. B.. and Zhang, Y. (1999)

Table 21: Chemical characteristics of hemp bast and core fibers

Chemical composition Hemp bast Hemp core

Cellulose Crystallinity DP (* 10-3) Hemi-cellulose Li& Pectin Extractives Ash Silica * n. d. = not detennined Source: DeJong, E.; Van Roekel, G. J.; Snijder M. H. B., and Zhang, Y. (1999) "

Different methods of puiping hemp have been studied by many scientists. Organosolv pulping

and aikaline pulping are commorily tried For pulping hemp fibers. Mi'ring of antiraquinone with

the soda during the cooking of hemp core, gives higher yield and strength properties are improved

". in generai. core liber pulp is comparable to hardwood fiber pulp, with lower tear strength as

compared to that of hardwood pulp, and the burst and tensile strengths being comparable to that

of hardwood pulp. Hemp core pulp can be useful in producing printing. witing and copying

papes " '). The hast fiher pulp ~ n e r a l l y has hi@ yieid and tear strength. whereas it has low

b u - strength and tensile mength. The hemp pulp has interesting physical properties. which

could possibly be enhanced by blending the hemp pulp wvith hardwood or sohvood. depending on

the application of the end product.

2.6 Rational, objectives and significance of this research:

Cellulose is the main component useful ta the paper industry. which is presently obtained mostly

Grom complex heterogeneous wood. Many sources of cellulose are known. but ody few are

actually used in the pulp and paper industry. Some species of hardwood and sofhvood are

preferred by the pulp and paper indusûy. But due to the decline in the available forests for

harvening and the Uisuficient wood coming fiom the new plantations. supply of such hardwood

and softwood species is becoming more and more difficuit. M p and paper indu= is now

looking into some other alternative sources of cellulose. One of such important under-esploited

source of cellulose is the non-woody plant. Countries with poor forest resources, like China and

India. produce 75-80 % of their domestic pulp fiom non-woody fibers. It is time for other

countries to look into use of non-woody fiber as a source of cellulose.

Any potential candidate for a raw material in the pulp and paper industry, inciuding hemp, has to

compete with the desirable characteristics of hardwoods and sofcwoods. Hemp grown in Canada

is found to have al1 the good properties. like high cellulose, low lignin and high yield during pilot

scale pulping. tt is necessary to determine pmper harvesting time for the hemp crop. to achieve

optimal chemical and pulping properties in order to make its bea use in the pulp and paper

industry.

This research work attempts to invescigate the physical, morphological and chemical properties of

hemp fibers as a function of the harvesting time and other operating parameters, in order to relate

those aperating parameters and fiber properties to the quality of pulp and paper produced, To

achieve the above-mentioned purpose of this thesis study, the research needed to be carried out is

categorized into the following objectives:

(1) Physical and chemical analysis of the hemp stems and fibers respectively

(2) Correlation between age of the plant and chemical properties of the hemp stem, if any

(3) Characterization of fiber anatomy with the age of the plmt

(4) Measuring the hio-mass produced by the hem? plmt with the aoe

The results of this study can potentidy be used to fùrther evaluate the candidacy of hemp as a

substitute raw matenai and as a source of celluIose in the pulp and paper production. Once the

correlation behveen the various parameters and properties is understood, the f m e r s will be able

to harvest the hemp crop grotvn for h e industry at an optimal harvesting tirne. This may allow

harveshng of hvo crops pet year. thus increasing the availability of non-woody fibers as a nw

material for the pulp and paper industry. The increasing substitution of non-woody plants.

iduding hemp. in the pulp and paper industry will result in releasing some pressure on the

demand for the depleting forest resources.

Chapter 3

Materials and Methods

3.1 Raw material for the study:

The euperirnental work for the thesis research was divided into hvo studies. the field studv and

the greenhouse study. For the field study, the hemp plants were harvested fiom the field

belonging to Hempline. and Iocated at Delware near London. Ontario. The seeds of hemp are

sowed at an average of 65-70 pounds per acre. Rows of hemp plants were about 7 - 7 1/2 inches

apart and ?4 -1 inch deep, with !h-2 inch distance between the pIants in each row. Prior to

seeding. the field soi1 was fertilized by 120-90-90 NPK lbs/acre. Cultivation started on the 19th

day of May 1999. Samples of the crop were harvested at the end of 30 days. 60 days. 90 days and

120 days. Five plots. each of 7 m' area. were selected at random near the outer edge of field (as

the interior portion of the field could not be accessed rasily without damaging the hemp plants).

Fi-we 3.1 shows an example of the random sample of the tive plots. From each of these plots. I

m' (sub-plots) area was harvested at each tirne interval.

Figure 3.1: Sampling design in the field

For the greenhouse study, plants were goum in the greenhouse in the Faculty of Foresûy ai the

University of Toronto. In case of green house experiments, 12 pots of dimensions 2 1 " x 15.5 x

17.5 " were used. Seeds were sown in five rows. PImting was started fiom about 1 Yi inch Eom

the edge of the pots. Each row was separated bom the adjacent rows by 4% inches. in each row.

plants were about one inch apart. Plants of the edge rows of the pots were not taken during

coiIection for the study. Plants were colîected at the end of the 30 days. 60 days. 90 days and 120

days. Although greenhouse samples were intended to be used to conduct a11 the experimental

tests to compare with the fieId sample test results, many experiments could not be practicaily

conducted on the greenhouse samples because of the iasufficient test material generated by the

greenhouse plants.

FoiIowing harvesting, leaves and roots of the plants were removed and the morphological

p m e t e r s (height and widthj of the plant were measured. Al1 the plants in a sub-plot were used

to measure the dimensions. Harvested plants were then airiliied at room temperature for 15

days. On the 15' day. the bio-mass produced was measured and recorded. AAer bat. the stems

were chopped and used for hture analysis.

3.2 Outline of the experiments:

The study had three dimensions. the physicd characteristics of the bast and core fibers. the

chernical andysis of the whole stems. and the pulping of whole stems. To study the physical

properties. plants harvened at different times were observed and measured for different

characteristics. To maintain consistency. stem sections were taken bom about 5 cm away from

the bottom. Later. chernical andysis was conducted by grinding the stems. For rnicro-scale

puiping, ground extractive-fiee fibers were used, while for pilot scale pulping. stem pieces were

used.

3.3 Physical analysis of the fibers:

Physicai analysis of the fibers was done on each of the 30 days. 60 days, 90 days and 120 days

field study samples.

3.3.1 Macro-analysis of the fiber:

Stems were cut into small pieces at the k t inter-node region and pictues of the transverse side

were obtained. From the photograph, area occupied by each of the bast fibers, core fibers, and

pith was measured. This helps in determination of the percentage of each type of fibers in the

stem.

3.3.2 Micro-fiber analysis:

In order to study the fiber rnorphology, it is necessary to separate the fibers. Maceration is a

commonly used technique to separate the fibers f?om the stem.

3.3.2.1 Maceration:

Bast and core fibers w r e separated Eom the stem pieces in different test tubes and aspirated by

boiling them in water. Water was then replaced by macerating solution. which was prepared by

adding equal quantities of acetic acid and 30% hydrogen peroxide. This solution should be

prepared fresh; othenvise. it loses its effectiveness. Fibers. dong with the maceraihg solution.

wcre then kept in the boiling water bath in the fume hood until they were snow-white. This

ensures that the de-ligaification process is completed and mild shaking makes the fibers to

separate Erom each other. After becoming snow white. the macerating solution was washed away

with water. Complete washing can be confmed by smelling the test tube. No smell of acetic

acid Unplies that the washing off of the macerating solution is completed. Fiben were then

preserved in 50 % alcohol For M e r use.

Slides were prepared by taking a few drops of fiber suspension on a slide by a hollow tube. 50 %

alcohol solution \vas used as a mounting medium. Slides were dned on a slide wrmer. taking

care to keep the fibers separated. by using a forceps and pin. Drying of the slide helps to stick the

fibers to the slide. Such fibers were then observed under projection microscope and the fiber

dimensions measured using a stage micrometer.

3.4 Chemical analysis:

Chemical analysis of the stem was done on all of the 30 days. 60 days, 90 days and 120 da. field

study and the greenhouse study samples. Air dried samples kom the five plots were mked

together and Standard TAPPI procedures were used to conduct the chemical analysis and

detennine the amounts of extractives, holo-cellulose, a-cellulose, fi- ash and silica contents.

3.4.1 Preparation of the raw materials:

Standard TAPPI procedure T257 om-83 \vas used to prepare the raw material for testing. Air-

dried samples were ground in a Wiley mill. using 40 size mesh screen. Ground materiai was

coilected and preserved for M e r use. For each experiment. moisture content was detemiined

by the standard oven-drying TJ 12 0111-83 method.

3.42 Extractives:

TAPPI standards T264 om-82 and T204 os-76 were used to measure the amount of extractives.

Small tea bags were prepared of the ground matenal with not more than 2-2.5 gnms per bag.

Such bags were then arranged in the Soxldet apparatus. The bag matenal was extracted thrice:

rit tvith the solution of toluene and ethanol with 2 1 ratio: second time with pure ethanol and

lastly with water. Fim extraction was carried out for 6 hours with four siphons pet hou.. Bags

were then \vashed with ethanol and dned ovemight and ethanol extraction was then done for 4

hours. The Final extraction \vas done with water for S hours. After w te r extraction. washed tea

bags were air dried for one week and then again weighed to get loss in wei&t due to loss of

extractives. Moisture content kvas also determined. Extractives from each step were saved and

then evaporated on the buchi rotary evaporator to obtain each fnction of extractives.

Extractive-free fiber matenal obtained fiom the above step was used to detemiine the amount of

holo-cellulose. The method used here was pioneered by Zobel et al (1966). Appmxhately 0.7

grams of material was taken in a 250 ml conical flask, to which 10 ml of solution A (1 liter of

solution obtained by adclhg 60 ml of glacial acetic acid and 20 p m s of NaOH in distiiled water)

was added. Promptly one ml of solution B (made by 200 grams of NaC1O2 I liter) was added to

the Bask. The nask was then covered and shaken vigorously to make sure chat al1 the fiber

material is in contact with the soIutions added. Flasks were then kept in tvater bath maintained at

a temperature of 70 O C. After every half an hour. the flasks were swirled. Stock solution B was

added d e r 45 minutes, 90 minutes. 150 minutes and 2 10 minutes of the experiment. Digestions

ran for four hours, after which holocellulose was filtered through the coarse crucibles and washed

with 100 ml of 1 % acetic acid. Final washing was done with 10 ml of acetone and the crucibles

with holocellulose were left in conditioner chambers for four days. On the fourdi day,

holocellulose \vas m e m e d and calculated in percentage form based on oven-dried weight.

3.4.4 a-cellulose:

After weighing for the hoIoceliulose, a-cellulose \vas determined Erom the holoceilulose. 3 ml of

17.5 % NaOH solution \vas added to each crucible with holocellulose. M e r 5 minutes. another

addition of 3 mi of NaôH was Jone. Afier 35 minures from the second addition, i 5 d of water

was added to the cmcibles to stop the reaction and then fiItered with 60 ml of water followed by 5

ml of îcetic acid and again with 60 ml of water. Two additions of acetone were made at the end

and the cmcibles now Mth acellulose were kept in oven at IO5 OC overnight and weighed on the

next day aAer allowing tu cool in the desiccator. a-cellulose was determined based on oven-dried

weight.

3.4.5 Lignin:

The acid-insoluble and acid-soluble Iignin contents were deterrnined by using the T U P I standard

T223 om-83 and TAPPI Usefid Method UM250 respectively.

In the sulfuric acid solution. the carbohydrates fiiom the fiber materials are hydrolyzed into

soluble forms. Though some iignin is aiso soluble in the acid. it can be determined by using an

ultra violet /visible spectrophotometer. The sum of soluble and in-soluble lignin amounts gives

the total Li-grin content.

One gram of ground, extractive-free fiber material (some of the extractives like resins are not acid

soluble and therefore will add to the lignin content if not removed before) was dispersed in 15 ml

of 72 Oh sulfuric acid. Dispersed solution was kept in the water bath at 20 O C For 2 hours. while

stirring the material in between to ensure thorough rniuing. AAer 2 hours. in a conical flask the

mkture of fiber and sulfuric acid was diluted to 3 % by making the total volume up to 575 ml

with distilied water, This diluted mkture was then boiled for 4 hours with fkequent additions of

hot water to keep the volume to 575 ml and dilution of 3 %. After 4 hours of boiliog, the mixture

was nItered through previously weighed medium cmcibles. The filtrate was coilected to measure

soluble Lignin. The in-soluble Iignin collected in the crucible was washed with hot distilled water

to make it acid fiee and then kept ovemight in an oven a< 105 C and weighed the next day d e r

cooling in a desiccator. Percentage of in-soluble rignin \vas found based on oven-diied weight.

Filtrate coliected by the above method kvas then used to detennine the acid-soluble lignin.

Filtrate kvas diluted and the absorbame \vas measured at 205 nm on spectrophotometer. Using

the given formula in the TAPPI Usehi Evlethod UM250. soluble lignin &vas determined by oven-

dried weight bais.

3.4.6 Ash and silica:

For ash determination, the standard TAPPI T211 om-93 method was used. Woody and non-

woody fibers have inorganic components in srnaIl amounts. which are nothing but various types

of sdts like carbonates. silicates, onlates and phosphates deposited in the ce11 wall and lumen.

The most cornmon salts are of calcium (Ca). sodium (Na), potassium (K) and magnesiun (Mg).

Few salts of other matenah like iron (Fe) and manganese (Mn) occur at about 100 ppm

concentration, while various others are below I O ppm.

A clean porcelain crucible was filled with ground fiber material and ienited in a muffle h a c e at

525 C. The crucible was then cooled and weighed. Percentage of the ash content was

determined based on oven dry weight.

To fmd the s i k a content from the ash. the T244 om-93 method was used. Non-woody fibers. in

pxtïcular. have lot of silica accumulated in epithelial cells. Amount of silica varies depending on

the growing conditions.

Ash obtained from the above method was digested with 5 ml of 6 M HCI and evaporated on a

s t e m bath to dryness. After evaporation, another 5 ml of HCI was added and evaporated. Thea

addition of another 5 d of K I to the residue was followed by heating, and then the solution was

diluted wih 20 ml of distilled water. Hot distilled water was used to wash the residue on the ash

free filter paper. Afier sufficient washing to removs chloride. filter paper dong with residue was

placed in the crucible and ignited at 525 O C. M e r cooling down, the amount of silica was

measured and adjusted for rnoist~rre content.

3.5 Pulping:

The chemical anaiyses were done on aU the greenhouse and field study samples (30 days, 60

days. 90 days, 120 days). Whereas, pulping could be done only on field study samples. as the

matenal generated fiom the plants grown in the greenhouse was not ninicient to produce pulp.

3.5.1 Micro-scale pulping:

Micro-scale pulping \vas done in 35 ml staidess steel reactors tvith 2-2.5 grams of ground

extractive-&ee fiber material. Ground material was used to ensure the proper mixing of the

materiai with the liquor as in this setting, circulation of liquor is not possible. The big vesse1 with

silicon oil acted as heat transfer agent. Liquor with 32 grams per Iiter of NaOH was used with

active aikali charge of 15 Oh Na20. Liquor was added to the wcighed material in the reactor in a

ratio of 1:6 (fiber:liquor). The reactors were closed with screw caps. Material was soaked for

half an hour and, then suspended in the heated silicon bath of set temperature. which was

maintained by a thermostatic device. Five reactors were used for each time and temperature

setting. -4Fter the desired time of cooking, pulp from each reactor was collected separately on the

filter paper and washed to get rid of black liquor. Washed pdp fiom the hvo reactors were used

to determine the yield and were kept ovemight in the oven set at 105 O C for weighmg the next

day. The pulps obtriined bom the remaining three reactors were air-dried for seven days to

determine Li@. holo-cellulose and a-cellulose content of the puip.

3.5.2 Pilot-scale pulping:

Pilot-scale pulping was done on two groups only of the 6eld study samples: 60 days field and 90

days field. There was not enough material in the case of 30 days field. Since plants are small at

30 days, large numben of plants may be needed to have lots of dry material, which seemed

impossible to collect fiom a commercial field, as it can redi in a heavy loss to farmers. Also as

Licensed farmers cannot keep their crops of hemp afier it starts f l o w e ~ g , it was not possible to

get enough material at 120 days due to the fact that by that time almoa ai l the plants of hemp go

hto the flowering stage.

The MK Digester vas used for pilot-scale pdping. Whole stem pieces of about 4-7 cms were

packed in the screen basket and were covered with a Lid having holes in it. The basket with stem

pieces was loaded in the reactor chamber and then the liquor with active alkali of 15 % Na20 (as

NaOH and Na$) and suifidity of 20 % was poured in it to achieve a ratio of fiber to liquor of

1 : 12. The MK Digester has a pump, which helps in circulation of the liquor from top to bottom

of the reactor chamber. Afier the iiquor was poured, impregnation was allowed to occur for 30

minutes with the circulation of liquor with the help of the pump. At the end of impregnation. the

chamber was closed tightly by using butterfly clips and the desired temperature ( 170 O C) and time

(150 minutes) \vas set on the cornputer monitor. It took around one hour to reach the desired

;zmperat.xc aficr i~tiich the of the coolcing stmed. III ~ b e MEC Digester. cc?obg r&es

place under pressure and was carried out at 170 O c for 150 minutes. Afier cooking, the pulp from

the basket was collected and washed to remove the black liquor and weighed. Yield was

determined based on the oven dry weight. htlp wvs stored in a refrigerator for its further use.

3.6 Disintegration and Screening:

Screening is important to remove the oversized or uncooked fibers fkom the pulp. The pulp

obtained fiom the pilot-scale puiping process was screened using the vibrating screening machine

with vertical dots. Rejects were collected koom the top of the screener and accepts goi

accumulated on the big bucket with very thin mesh and srnall pore size. Water was drained out

nom the bucket afier which accepts were gathered. Moisture contents of both accepts and rejects

were measured and percentages of each were determined based on the oven dry weight.

3.7 Bleac hing:

Both the 60-day-field and 90-day-field groups of the screened pulp obtained fiom the pilot-scale

pulping process were bleached. 50 grams of screened pulp. based on oven dry weight. were used

for bleaching. Four-stage bleaching procedure (DEpAP), with Chlorine dioxide (D), extraction

(Ep), acid (A) and peroxide (P) stages in the given sequence, was used. In the f b t step, the puip

afier obtaùllng consistency of 3.5 % was acidified with dilute sulfuric acid. Kappa number of the

pulp was obtained by standard TAPPI procedure (TAPPI standard T236 cm-85). Sodium chlorite

solution \vas added in proportion to the kappa number of pulp [Sodium Chlorite = (kappa

number) * 0.11. The treated pulp was then kept in the water bath at a temperature of 50 OC for 60

minutes. Pulp was then washed carefully and used for the extraction stage. In the extraction

stage, consistency of 10 % was applied and NaOH (2 % of the O.D. basis) and peroxide (1 % of

the O.D. basis) were used for extraction. This stage ws retained for 90 minutes at a temperature

of 80 OC of water bath. M e r completion of desired time, pulp was washed with cold distiiied

water and used for the next step, the acid stage. In the acid stage, a consistency of 3 % \vas

maintained. Pulp was acidified with the 1 % acid (O.D. basis) and retained for half an hour at a

temperature of 50 OC. At the end of 30 minutes, pulp was washed with distilled water, and the

last stage of peroxide was then camied out. Pulp consistency of 10 O h was maintained and the

chemicals added in this stage induded magnesium sulfate (0.25 %). DTPA (0.25 %), NaOH (2%)

and perolcide (3 %). Puip was then mixed wel1 and retained in water bath at temperature of 80 OC

Cor four I m m . At the c d , pdp ;vas wCvashcd nith distilled w t e r to remove the cherriicds used

and then collected and weighed. Moisture content \vas measured to determine the yield of the

bleached pulp.

3.8 Hand sheet makiog and testing:

Hand sheets were made trom both the bleached and unbleached pulps (obtained From pilot-scale

pulping process) of both the 60-day-field and 90-day-field sarnples. r e s u i ~ g in a total of four

groups of hand sheets. Fifieen sheets were prepared in each gooup. British hand sheet former

was used for making hand sheets. Each sheet of 200 cm' had about 60 g/m2 consistency. Wet

sheets were dried by using nvo-stage drying process and then kept on the rings in a room with

temperature of around 23 OC with relative humidity of 50 %. Hand sheets were then peeled off

fiom the steel plate and collected for hrther physical testing. The hand sheets were tested in the

research laboratory of Donohue hc.

Chapter 4

Results and Discussion

4.1 Morp hological study:

D-e recdtc ln the rneawements nf morphological dimensions (heioht and diameterl of the hem?

plants. and the bio-mass produced by the stems of the field samples are documented below.

41.1 Height and diameter of hemp plant in the field:

Hemp is a fast growing tall. annual plant and completes its life cycle within four to four and half

months. To achieve high height. plants have to grow very fast. Based on the results ofheight and

diameter measurements. Figure 4.1 clearly shows that the maximum increase in the height is seen

in the i k t half of the life cycle (60 days). in the later half of the life cycle. the plant prepares

itself for the reproduction: so at the end of the life cycle. enough seeds are produced. which have

the potential of continuhg the propagation of the hemp species. Not much increase in the height

can be espected after 90 days. as at the end of 90 days. plants were already flowvenng. which

indicates that the vegetative growth is completed. As a result. hei@t and diameter data is not

available for the 120 days old stem.

h

m m - :::jig .- -

3 50.

O 1

Figure 4.1 : Height of hemp plants in five plots (field)

The same growth rate is obsenred for the diameter of the plant. A large amount of the increase is

seen in the £ k t half of the Life cycle (as shown in Figure 4.2), which represents the vegetative

growth period. in the second haif of the life cycle. which is dominated by reproductive growth

stage, however there is hardly any increase in diameter. (See Appencii.. 1, for details)

Figure 4.2: Diameter of hemp plants in five plots (field)

4.1.2 Bio-mass produced by hemp stems:

It is important to correlate changes in bio-mass to the changes in the height and diameter (age), so

as to fmd out whether the increase in bio-mass is due to the increase in density or due to increase

in dimensions (height and diameter). Figure 4.3 shows the bio-mass produced in each of the five

field plots (in grams per area of the plot) after 30days. 60 days and 90 days.

Plot fi -- - -. - - -. - -- - -

Figure 4.3 : Bio-mass produced by hemp plants in five plots (field)

With the maximum increase in the height and diameter in the nrst hdf of the life cycle, increase

in the bio-mass is also concentrated in the first half of the Life cycle. A very smaii increase in the

bio-mass is observed in the 60-90 days tirne period, except in plot # 3. This may be due to two

exceptional factors: (1) Plot # 3 was located near the puddle, due to which water was avaiIabIe

Iate in the growing season. and/or (2) dui-ing the first half of the Life cycle, roots were stagnant in

the water. and as hemp Iikes well drained soi1 to grow, vegetative growth in the ûrst half cycie

was reduced. Overall. the hemp field is seen to have higher annual yield (bio-mass per unit area)

as compared to other woody plants, used in the pulp and paper industry ". (See Appendix II)

4.2 Physical characterization of hemp stem:

in physical characterization of hemp stem, areas occupied by the different fibers (ba t and core)

and pith in a cross-section of the stem were measured. Also. the dimensions of the ftbers were

determined.

4.2.1 Study of cross sections of field hemp stems harvested at different tirnes:

Photos 4.14.4 show the transverse section of the field stems harvested at 30 days, 60 days. 90

days and 120 days respectively.

Photo 4. i : 30-day stem ( l6X) Photo 4.2: 6O-day stem ( lOX)

-- -

Photo 4.3: 90-day stem (10X) Photo 4.4: 120-day stem ( 1 0 ~ ) -

Photos 4.1-4.4: Transverse sections of hemp stems harvested at 30,60,90 and 120 days

As we c m see in the above photos, there is not much variation in the transverse sections of the

four hemp groups. But diameter in case of 30day stem is different fiom the rest of the group.

Areas (percentages) occupied by bast and core fiben. and pith in the cross sections of hemp stems

(five replications) were measured and are iisted in Table 4A.

Table JA: Areas occupied by ban, core and pith in stems harvested at ciiffixent rimes

30 days 76.82 + 4-44 19.8 1 + 3.86 3.37 C_ 1.18

1 60 days 1 77.65 + 2.55 1 19.29 f 1.93 1 3.06 + 1.37 / 90 days

The botmical fact that the plants produce more sylem (core) fibers than phloem (bast) fibers is

corroborated for the hemp plants by the resuits in Table 4A. As seen the area occupied by the

bast fibers is less compared to chat occupied by the core fibers. As plants grow, there is not much

difference in the respective areas occupied by bast and con fibers of ench group. This is to some

extent also seen in the Photos 4 . 1 4 4 On doing statisticai analysis. it is observed that there is no

statistically significant difference between the areas occupied by each of the bast and core fiben

in the different groups (30 DF. 60 DF. 90 DF and 120 DF) at the 5 % significance level (p-value

= 0.9845). (See Appendk KT)

I 120 days ( 77.3 1 f 4.00

4.2.2 Dimensions of hemp fibers harvested at dûrerent times:

79.02 k 5.85

As aiready mentioned. hemp has two rnorphologicalIy different fiben, the bast fiben and the core

fiben. Due to the similarity of their fiber anatomy. core fibers are ofien compared with hardwood

fibers and bast fibers with those of softwoods. Table 48 swnmarizes the measurements done on

the core and bast fiben of hemp. As seen from the table. there is a clear difference in dimensions

b e ~ e e n the core and bast fibers of hemp. It is interesting to note that both the core and bast

fibers appear to eshibit slight ~duction in their length and a slight increase in their diameter. as

they gow. The same type of redts were observed by P. K. Ray et al in 1988 in mesta (Hibiscus

sabdariffa) plants and in jute by Das (1979) ". This reduction in fiber length is due to reduction

in ceii height, because of increased interwoven ügnification and decreased turgal pressure, as the

plants grow. The statistical analysis on the fiber lengths shows that there is statistical variation in

20.34 2 3.1 5

18.88 I 5 . 7 4

2.35 i 1.01

2.10 f 0.13

the core fiber leagths harvested at four different penods (30,60,90, 120 days), with p4.00 1 139.

rvhile the bast tibers do not show signincant statistical difference in lengths in the four groups (p

= 0.6829). (See Appendk N)

Table 4B: Bast and core fiber dimensions in hemp harvested at different times

1 Type of fibea 1 Days

The numbers in Table 4B are the average of the dimension readings on a number of sarnples (50

fibers) of each days' group of fiben. Large variations in the iength of bast fiben were seen within

each group. Quite a few had lengths in the range of 5-12 mm. This variation is due to the

presence of prirnary and secondary bast fibers. Secoodary bast fibers are comparatively shorter

than the primary ones and resemble more to the conifer fiben, while primary fiben are very long

as seen fiom the average numbers in the above table " (measurements were done only on long

primary fibers).

Core

in bast and core sections of the hemp stem. dong with the fiber cells. other types of ceUs were

also seen. Bast fibers were accompanied by sieve tubes and parenchyma cells, while core fibers

were seen with vessels and parenchyma cells. In the following photos, no visual difference is

observed.

Length Diameter

30 I

0.719 + 0.09 1 0.0367 4 0.009

Photo 4.5: 30 DF Core (4OX) Photo 4.6: 60 DF Core (40X)

Photo 4.7: 90 DF Core (40X) Photo 4.8: 120 DF Core (40X)

Photos 45-13 show core fibers fiom stems harvested at 30.60.90 and 120 days resp., whiIe

Photos 4.9-4.12 show bast fibers from stems hmested at 30,60,90 and 120 days respectively.

Photo 4.9: 30 DF bast (40X)

Photo 4.1 1 90 DF bast (40X)

Photo 4.10: 60DF bast (40X)

Photo 4.12: 120 DF bast (40X)

4.3 Chernical anaIysis of hemp stems grown in field and greenhouse:

As \vas mentioned in Section 3.4 of Materials and Methods chapter, the chernical analysis of the

stem was done on al1 of the 30 days, 60 days. 90 days and 120 days field study and the

greenbouse study samples. The chernical analysis of hemp helps in explaining why hemp had

been traditionaily used for paper production in some countries. It shodd dso help in assessing

the potential of hemp to substitute on a large scale the woody raw materials used in pulp and

papa prductiuu. The detcrminatiün d'lignin. icllulosc. ;ish and s ika contevts :vue dcne cc the

extractive-free stem fiber and Figure 4.4 sunimarizes the results on the measurement of these

constinients of hemp stem gram in the field. ui Figure 4.4, the percentage of extractive is the

fiaction of extractive in the total stem fiber, whereas the percentages of holocellulose. alpha-

cellulose. lignui. ash and silica are expressed in terms of fractions with respect to the extractive-

free stem fiber. Holocellulose is made up of hemi-cellulose (not s h o w in the figure) and alpha-

ceIlulose. and silica is a part of the ash.

-

80 - a 30 days

60 days 60 -

O 90 days

% 40 . - . - -13 120 days

20 -k- I Hardwood*

Softwood* 'Lt,- __- - ---- O - -

Alpha- mractive Holoceiiul tignin

celluIose (%)

Ash (%) SElica (%) s (%) ose (%)

(%)

-- P -- ---------p.- - - - - -- - - - -

*Rowell1984 (average values)

Figure 4.4: Chemical analysis of hemp stem grown in field hanrested at diffe~nt t h e s

Extraciives in hemp stem show si@cant reduction fiom 3O-day old plants to 120-day old

plants. The possible reason for this abrupt reduction could be that in young stems. large amounts

of proteins and chlmophyll are dso extracted by the solvents. Also, it is to be noted here that al1

the stems used in the a d y s i s were air dried just for 15 days. May be a Little more dtying, as is

usuaily practiced. or good retting practice, would have helped in the reduction of extractives

content in younger plants. Reduction in the extractive content with age has been reported in cases

of bamboo and kenaf"'.

Holo-cellulose analysis results show mixed variation as a function of growth. in the first haIf of

the life cycle. there is an increase in holo-cellulose content but it decreases, during the time period

of 60-90 days. before increasing again slightly at the end of 120 days. Though there is much

variation in holo-cellulose, variation obsewed in alpha-cellulose contents is less. With respect to

both the cellulose contents, there is still some benefit of hemp compared to sohvood or hard

wood species. as cellulose is beneficial in pulp and paper production. Lignin content decreases

with age of plant. though the change is insignificant. The actual KIason Iicgnin values may be

siightly different due to the presence of the proteins and it can be useful to note rhat the total

protein values do decrease ~ 5 t h plant age '.

Ash has been considered as one of the problems in using the non-woody fibers for pdp

production. However, there is significant decrease in the ash and siiica contents with plant

erowth. Decrease in the ash content with plant age is recorded in jute. bamboo and kenaf job". -

Similar to Figure 4.4, the Figure 4.5 Nmrnarizes the results on the measurement of hemp stem

constituents in the plants gro~vn in the greenhouse. Results are comparable to the previous

published data '*.

- - - -

100 - m30 days

80 - 60 àays

60 - 0 9 0 ~ s

2s 120 days 40 -

I SoR-wood* 20 .

Hard-wood*

O - E-ract ives HoloceiIuIose AIp ha-

Lignia (?&) Ash ( 9 6 ) Siliu ( O 6 ) ( O h ) (%) celiulose (%)

- . - m3Odays 1 S 82 36 12 - . . . - -- - - - - . - - - - -- 4.44

- - - - - - - - - - - - - 0.1 1

1.60chys 9 68 3 6 11 1.83 - - - - - + - - A - - - - . - - -

0.19

'0 90 &YS 7 75 45 11 2.68 - - - - -- -- - -

O. I O , - - - - - 1 O 120 days 5 80 U 11 2.82 - -- - - - . - . - - -

0.0 1 - - .

Soft-wood* 7 66 43 27 - - - - - - . - .

0.30

Hard-wood* 6 75 45 19 0.30 - - - -

- - - -

* Rowe111984 (average values)

Figure 4.5: Chernical analysis of hemp stem grown in greenhouse hamested at different times

Looking at the results of chernical analyses. one cm easily note that there is little variation in

tems of Iignin and ceiIulose contents as a bc t ion of growth. There is decrease in the

percentages of extractives. lignin. ash and silica with gro\vth. Using statisticai techniqua of

ANOVA and t- test. it is seen that there is a significant difference in the four groups harvested at

different times. in terms of Lignin and holo-cellulose contents, However, it is observed that there

is no significant statistical difference in alpha-cellulose content between the 90 DF and 130 DF

plants at the 5 % significance level (See Appendices V. VI and VU, for details). Wirh good post-

harvea care, Wte retting for removing extractives, these beneficial changes wvith more aging of

plant wvould not be significant, beyond a particular point in the growth of the hemp plants. In that

case it can be hypothesized that one can harvest hemp crop in behveen the 60-90 days period.

achieving optimutn level of chernicd constituents, as needed by the puip and paper ind-.

As seen from Figure 1.4 and Figure 4.5, it couid be observed that in general. the chernical

analyses on the extractive-fiee stem fibers of both the field-grovm and greenhouse-goum hemp

plants gave similar redts. The major diffkrence between the two types of samples was observed

in the amount of extractives in the stem. To sh~dy the composition of these extractives in both

Fig. 2.6: Estmcûvc anaiysis of fidd hcnp Fig. 4.7: Extracti~c m*)>sis of gert.lhouse hemp

the field and greenhouse samples and possibly explain the reason for the difference in the amount

of extractives in the IWO samples, fkactional analyses kvas performed on the extractives. Figure

4.6 and Figure 4.7 summarîze the results of these analyses. It c m be seen that the fnctional

analyses of the extractives give simiIar proportionate results in both the cases of hemp grown in

field and greenhouse.

4.4 Micro-scale pulping:

Extractive-tiee fibers korn the field hemp plants harvested at different times (30 days. 60 days.

90 days and 120 days) were used for micro-scale soda pulping. In each set. three different

cookcing timings ( 120 min.. 150 min. and 180 min.) and three different temperatures ( 1 JO OC.

1 % ' ~ and 170 OC) were used. During pdping, de-Iignification as well as degradation of

carbohydrates occurs. In the de-lignification process, insoluble polymers of tignin molecules are

broken do~vn chemicaliy so that they become soluble and are then removed by the liquor.

Carbohydrate retention with the de-lignification is important and is called "de-lignification

selectivity" '! Figure 4.8 shows percentage of ügnin in extractive-kee fiber, retained &er

pulping the four field samples (30D. 60D, 90D and 1ZOD) in different cooking conditions (tirne

and temperature). For each of the three graphs correspondhg to different cooking temperatures.

the X-suis in the figure classifies four different sets of three observations each. The four sets

relate to the four harvested times and the three obsentations in each set relate to the three cooking

times, in ascending order.

Figure -1.8: Percentage tignin retained d e r pulping in different cooking conditions

As seen Crom Figure 4.8, it is evident that the higher cooking temperature and higher cooking

tirne to some extent worked better for the de-lignification process. resulting in less retained lignin.

Also. the figure shows that for each cooking condition, the % li-gin retained is not much different

in the 60DF, 90DF and EODF samples.

ANOVA vcrifies the significant differences in 1 ip .h contents for the different cooking conditions

(See Appendlx XI). To fuid out whether this actuai variation lies in dl the groups or in a specific

group. Duncan's test was perforrned. Duncan's test shows li-pin in the pulp cooked at various

conditions at 90 DF is significantly different than that of the others in the group. Duncan's test

confirms the significant differences in the lignin content in the pulp cooked at different times and

temperanires. proving that cooking tune and temperature are important parameters for the pulping

process.

As to the content of holo-cellulose in the extractive-kee fiber after pulping, the statistical tests

show that 90 DF and 120 DF groups are similar and differ &orn the groups of 30 DF and 60 DF,

which in hini are similar to each other (See Appendix XXI). in case of dpha-cellulose. variation

Lies between ail the four groups (no group is similar to that of othen). Variation in the alpha

celluiose may be due to the increase in the crystallinity with growth of pIant (See Appendix ,XII).

4.4.1 Pulping selectivity in hemp stems:

The degree of carbohydrate (cellulose) retention during the de-lignification process is called as

pulping (de-Lignification) seIectivity. Figure 4.9 shows below the plot of the pdp yield v/s the

totai lignin. in pulping, as the cost of raw material (woodylnon-woody fiber) is the major part of

total production cost, yield becomes very important in terms of the economics of paper mil1

(Kleppe 1970) 16. Karim et ai (1994) noted that the degree of polymerization of pulp cellulose in

heemp m d wheat itmcasts v.ith higkr cocbg teqerîtures and decteases ~ 4 t h more cookine

times ". ". Thus. the optimum cooking time and temperature parameters are very important in

achieving both the desired yield and the 1igni.n content. in this research. increase in the yield with

temperature is observed. which may be due to the increase in the polymerkation.

- .- - - -- - - -

30 DF: y = 1 . 8 8 5 5 ~ + 25.18 L (R2 = 0.7843) 60 3F:y = 1.1441~ + 46.478 (R2 = 0.9383) 90 DF:y = 1.4763~ + 43.826 (R2 = 0.9633)

3.5 5.5 7.5 9.5 11.5 13.5 Total lignin (% on fiber)

Figure 4.9: Pulping selectivity in hemp stems hawested at different times

T. F. Clark et al (1967), in their study on kenaf. note that the time of harvest has no direct effect

on pulp yield. However. the variation in the yield in crops harvested at different times, as seen in

Figure 4.9. may be due to various other growhg factors ". It is very clear that in the 30 days old

stem, dong with de-lignification. more carbohydrate degradation takes place. Bea results of pulp

yield are seen in 120 days old plants. There are not much differences in the yield of 60 day and

90 day old stems. A possible explmation for the increasing pulp yield in plants with increasing

harvesthg Urnes is that the alpha-cellulose and crystailinity increase dong with plant age as is

also obsewed in Hibiscus sabdariffa (mesta) 'O. So with the increase in crystallinity, it becomes

more difficult for the peeling reaction of the carbohydrates. thus resulting in higher pulp yieid in

plants with longer harvest times. In woody plants, yields in mature parts are higher than that of

juvenile mes because of high hemi-cellulose present in juvenile wood, which is more susceptible

to degradation as compared to alpha-cellulose ".

4.4.2 De-lignification kinetics in hemp stem pulping:

De-lignifrcation follows three distinct stages. First, there is fast extraction of lignin in the initial

de-lignification stage. followed by bulk de-lignification. where most of the li@n is dissolved. In

the thkd strge. v:hich is cd!ed residria! de-!ignXca!im. the dissolution o f lignin i q ciirtailed. ln

the fust and third stages, there is rapid decrease in the carbohydrate yield while in the second

stage it is very slow.

Relation between lignin content and cookuig temperature has been rxtensively studied '". "- 38. 39 . Relation of pulp yield and lignin content is also very essential for process control and for

evaluation of the alternative processes ". Delignification is a tùTt order reaction. çiven by

equation.

In (Lo / L) = Ko * t In (L) = - Ko * t + In (Lo)

Where. L = instantaneous residual lignin content

La = effective initial lignin content

t = pulping time

Ko = constant which depends on the liquor concentration and cooking temperature

By plotting ln (L) against pulphg tirne. t. a Iinear relation with siope of - Ko and intercept of

In(Lo) is obtained.

At the same concentration of the soda liquor, Ko depends only on cooking temperature. Thus Ks

(Ko for soda pulping) cm then be related to the cooking temperature by the Arrhenius equation.

Ks = Ae' E l R T z h(Ks) = In(A) - (E/RT) ln(Ks) = -(E/R) ( i/T) + h(A)

where. A = the Arrhenius constant

E = activation energy (cal / g-mole)

R = gas constant ( 1.987 cal I %.g-mole)

T= absolute temperature (k)

As seen Born the above equation, a plot of ln (Ks) against (ln) gives a h e a r relation with dope

equal to (-ER) and intercept of Ln (A). From the dope, activation enerw, E, can be calculated.

Figures 4.10-4.13 represent the de-lignificatioa kinetics of field hemp plants harvested at different

cimes. The plot of ln (L) against pulping tirne, t, shows linear relationship with intercept In(Lo)

which corresponds to the effective initial Li& content. and dope (Xo), where Ko is the rate

constant for the de-lignification process. Ln (Lo) obtained is not necessarily the logarithm of the

actual initial lignin prejent in th2 fiber. but is jbtaiiisd h i n tic cxtmpo!ation of t i c !ilcri; plot

pn(L) v/s t] for digestion t h e of t = 0.

Figure 4.10: Delignification kinetics of field hemp plants harvested at 30 days

F i p 4.1 1: Delignification kinetics of field hemp plants harvested at 60 days

Figure 4.12: Delignification h e t i c s of field hemp plants harvested at 90 days

Figure 413: Delignification kinetics of field hemp plants harvested at 120 days

in al1 the four cases. logarithm of lignin content against pulping t h e shows a linear relationship.

Theoretically. within each DF group, Lo should be the same for experiments with different

cooking temperatures, as Lo is the effective initial Iignin content, which should be same for plants

harvested at the same rime. However, fiom the results in Figures 4.10-4.13, it is seen that there is

variation in Lo within each DF group. This variation may be due to either meanirement errors or

changes in the pulping conditions, especially in terrns of the temperature during the initiai stage

of the pulping process or some variation in the specific gravity or size of the milled fibers.

Theodor N. Kleuien (1966) aiso found variations in tenns of intercept and he reiated it to the fact

that the amount of tignin following different types of de-lignification kinetics is dependent on the

cooking temperature ''- 37. For example, decrease in the temperature results in an increase of the

residud (transition of the bulk to residud de-lignification) Lignlli. suggesting that the

transformation depends more on the cooking condition and aot to that extent on the percentage of

soluble lignin present in the raw material.

4.4.2.1 Initial and bulk de-iignification in hemp stems:

The dfierence between the actual initial Lignin content in the fiber and Lo represents the rapidly

removed iignin in the initial stage of the puiping process. Figure 4.14 shows the relative amounts

of delignification that occurred during the initial and bulk delignification stages.

30DF 60DF 90DF 120DF - - - . - - . -

a Bulk defignification Itnitial lignification - - - - - - -

- - -. . - -. --

Figure -1.14: Initial and bulk de-lignification in field hemp stems

It is seen from Figure 4.14 that the majority of lignin sets removed during the b d k de-

lignification stage, especidly in the puip of hemp plants harvested later.

4.4.3 Activation energy for de-lignifrcation in hemp stem:

Activation energy was calculated by using the equation. Ko = ~ e ' ~ ' RT , as explained in Section

44.2. and as shown in Figure 4.15. To compare the results benveen the plants harvested at

different thes. statistical t-tests were conducted on the intercept and dope of the regression line.

Results indicate that there is a significant difference between the activation energies of hemp

plants harvested at different times at the 5 % significance level. As shown in Figure 4.16, the

activation energy is lowest in the 30 days old plants and highest in die 120 days old plants. This

is expected from the two equations in Section 4.4.2. because the initial lignin content in hemp

plants harvested at later tirnes is lower compared to the plants harvested earlier. thus makiog the

reaction constant. Ko in those plants lower. (See Appendix XIV, for details)

The differences in the activation energy in the four groups may aIso be partiaUy due to the fact

that the iignin structure modifies itself with the age of the plants. This variation in l i a

structure is studied on some hardwoods by different researchers. For exampie, juvede wood is

made up of more guaiacyl Iignin structure with low methoxy groups, as compared to mahue

wood ". Aiso, in the Salk species of hardwood, lignin content and structure varies within the

species and with age ". in the Populus species of hardwood, it is noted that the Iignin content in

the fist growth penod is higher. which subsequently decreases in the next eight years before

again showing an hcreasing trend in later years. Any such variation in the Li- structure is not

yet studied in hemp.

Figure 4. l5.A: Arrhenius graph of soda puiping of hemp stem harvested at 30 and 60 days

Figure 4. 15.8: .Arrhenius graph of soda pulping of hemp stem harvested at 90 and 120 days

Figure 4.16: Activation energy for deiigdication in hemp harvested at different times

4.5 Pilot-scale puiping of hemp harvested at different times:

Field hemp plants harvested at 60 days and 90 days were used for kraft pulping, bleaching as well

as hand-sheet making. Whole stem pieces of about 4-7 cms were used for the pilot-scale pulping.

The optimum conditions of the micro-pulping process (170 OC, 150 min.) were used. Table JC

summarizes the various parameters employed and the yield results obtained in the kraft pulping

and bleaching process.

Table JC: Yields at different stages of kafi pulping and bleaching

Kraft (Pitot Scale) pulping (MK digester) results Plant age [ Temp. , Time ,AA/nilf L:F Pulp Accepts Long fibers Yield

-idity yield (not gone afier h o u & the bleacbg

( days ) (OC) (min) l (%) (%) (%) (%) ,

60 DF 170 180 15/21 ' 7:l 53.6 , 70.8 29.24 9 1 .2J

Chemical analysis of lignin. holoceIlulose and alpha-cellulose were done on the pilot-scale (kraft)

puip and Figure 4.17 shows the cornparison of the renilu of kraft (pilot-scale) and soda (micro-

scale) pulping under the same conditions ( 170 OC. 150 min.). There is not much ciifference seen

in the amounts of lignin. hoIocellulose and alpha-celhlose in the nvo cases. Also. ANOVA

shows no significant difference at 95 % confidence level. (See Appendix XVI)

-- -- -- - - - - - -- - ----

Chernical analysis in b M pulp --- 860 DF (K) H 90 DF (K)

120 - 0 6 0 DF (S)

L ignin Holocellulose Aipha-cellulose -. -- -.--A- -

Figure 4.17: Cornparison of I c d ? and soda puiping (170 OC, 150 min.) for 60DF and 90DF

4.5.1 Physical properties of the paper made from hemp:

The bleached and unbleached pulp obtained fiom kraft pulping (pilot-scale) \vas used to prepare

hand-sheets, which were then tested for various properties and the resuits are s h o w in Table 4D

below.

Table 4D: Physical properties of hand-sheets made fkom 60DF and 90DF fieId hemp pulp I 1

I Pro pertiea I 6ODF- i 6oDF- ' I 90DF- ' I 90DF-

Unbleached

Brightness (% ISO)

(glossy side)

Burst index ( ~ ~ a . m ' / ~ )

The paper made tiom the hemp whole stem shows chmcteristics comparable to paper made

commercially using hardwood or s o h o o d fibers. P. K. Ray et al observed h@er tensile and

burst factors in 130 days plants (as compared to plants harvested earlier) in Hibiscus sabdariffa.

which is possibly due to the higher crystallinity of the pulp in l2O-day plants ? However. no

significant variations in the teosile men& are seen h the rcsults in hemp studies on 60DF and

90DF samples. as seen in Table 4D. even though there is slight variation in burst index behveen

paper made fiom the bleached and unbleached pulp, especially in the 90DF sample.

Bleached

Tear index (mN.m2/~)

Tensile strength ( W g )

18

49

Unbleac hed

137

59

Bleached

73

53

189

60

19

16

76

58

168

56

156

59

Chapter 5

Conclusions and Recommendations

5.1 Conclusions:

Hemp, a non-woody plant, has long heen considered. and in fact used in some places. as a

potential fiber source for the pulp and paper industry. This thesis study assessed the physicai.

chernical and pulplig properties of hemp with respect to the age of the plant. in order to

determine the optimal growth point for harvesting.

There is a hi& increase in hemp bio-mass at the age between 30 days and 60 days. afier which

bio-mass content does not change appreciably. Fiber morpholow of the hemp stem shows that

bast fibers are comparable to the softwood fibers and core fibers are comparable to the hardwood

fibers. The physical andysis of the stem fben shows that the percent area occupied by the bast

ftbers decreases with age and that of core fibers increases with age. There is some variation in

the fiber length and wvidth with the age of the plants. But such variation is found io br so small

that it wodd hardly make any significant difference in paper quality.

Chemical analysis of the stem shows a slight decrease in the percentage of extractives and lignin.

and increase of alphaseLlulose with the age of the plants. Such variation in lignh and alpha-

cellulose contents can influence the kinetics of the pulping reaction and the quaIity of the paper.

Chemical analysis of hemp plant and pulp at any stage studied in this project is comparable to

that of hardwood or softwood fibers.

The puiping of the hemp stem harvested at different iimes shows different results. In d l cases,

with the increase in the cooking temperature and cooking time there is a decrease in the lignin

content, accompanied by degradation of cellulose and hence decrease in yield. Plants harvested

at 30 days show poor redts with respect to yield (selectivity), while plants harvested at 120 days

give the best results. as far as yield is concemed There is not much difference observed in

selectivity between the 60-day old and 90-day old stems.

The de-lignification reaction takes place as per the first order reaction kinetics equation, which is

confirmed from the results of the experiments. It was seen that the activation energy needed for

the reaction in plants harvested older, was higher than that compared to the plants harvested

younger. which may be due to the lower amounts of initiai lignin contents in older plants.

Finally, the mechanical properties of the paper produced &om pulp obtained from pilot-scale

pulping of field hemp plants harvested at 60 days and 90 days are found to be comparable to the

propzrties of papa obtaiaed f r o ~ sofkmod or h ~ & ~ v o o d .

In conclusion. it was seen that the hemp plants do undergo change in their physical, chemical and

pulping properties with their age. However, the changes occurring in the plants do not affect the

pulping properties to a significant degree in the plants aged betsveen 60-90 days. So. it wodd be

optimal for the farmers to harvest the hemp crop between the penod of 60-90 days. They would

then be able to grow one more crop of hemp during the remainder of the favorable cultivation

season. This d e f ~ t e l y will depend on the pied of growing season available within the region.

One of the problems in the use of the non-woody pIants for paper production. at present. is the

cost factor. If the f m e r s c m take two crops per season, then the availability of the hemp plants

will increase and this \vil1 help to bring d o m the higher prices of commercial hemp seen at

present. Also it wiII give more incentive to the puip and paper indusûy to use hemp or non-

woody plants. in general. as their raw materials. This in tum would help in alleviating the

pressure on forest resources and the environment.

5.2: Recommendations:

Composition and structure of lignin changes with growth. Therefore, studies should be carried

out to 6nd detnils on the lignin structure as a function of growth. Such study would then possibly

exp lain the qualitative as well as quantitative differences in the deügni fication activation energy

observed for hemp harvested at different tirnes.

It is also important to know the differences in Li@ content and structure between the bast and

core regions. in kenaf, the different activation energies obtained for bast and core fibers, indicate

bat the structure of lignin may be different in the two fibers. The same c m aiso be mie for the

bast and core fibers of the hemp plants. So, studying the structure of lignin in bast and core fibers

separately as a function of growth will throw more light on the Lignin behavior and the

delignification process. As paper quality. to some extent, does depend on ceii composition other

than the fibers, ratio aodysis of the different types of the ceiis (fibers, parenchyma, vessels and

sieve tubes) should be conducted to study the effect of plant age on ceIl composition.

in Canada. where the pulp and paper industries are abundant. the supply of commercial hemp. on

a large scaie. as a raw material could be very difficult because hemp is a seasonal crop and the

growing season in Canada is shon. A possible solution to this problem could be blending the

hcmp. whcn a~aihblc. witi ~ ! i c hx&.~ccd or sc~.vccd, SC th3t the consirmption of woody fibers

will be reduced as compared to the case when only the woody fibers alone are used. More

research will be needed to study the pulping properties of such blended fibers and the quality of

paper produced.

As found in this study. it is possible to have two crops of hemp per year. with 60-90 days of

hmvesting t h e . But the growing season in Canada is short. As an alternative route to investigate

the possibility of increasing hemp production and substitution in the pulp and paper indusûy. it

wiil be worthwhile to probe into some varieties of hemp, which would probably be more tolerant

to slightly severe clirnatic conditions. -4s hemp is ubiquitous. with different varieties. finding

such a variety and trying it in the Canadian fields may not be difficult.

References

FAO, State of the world's forests. United Nations - Food and Agriculture Organization,

Rome. M y , 1997 and 1999.

Bocsa, 1; K m , M; The cuitivation of hemp: Botany. Varieties, Cdtivation and Harvesting.

1998. HEMPTECH.

Van, R: Gerrit J.; L, Steef J. J.; Richard G. M.; op den kamp and Gijs. Baron; Extrusion

pulping of tme hemp bast fibre (cannabis sativa L.), TAPPI proceedings, 477-485. ( 1995).

Van. Der. Werf, H. M. G.; Mathijssen. E. W. J. M. and Haverkort A. J.: The potential of

hemp (Cannabis sativa L.) for sustûiriable fibre production: a crop physiological appraisal.

Arm. Appl. Biol., 129. 109-233 (1996).

Matussek. H: Lockie. M and Kenny, I: More paper. but thinner marguis mar the results. pulp

and paper intemationaI.40 (7), 16-88. ( 1998).

Atchison. J. E. and McGovem. J. N.; Pulp and paper manufacture: Volume 3 Secondary

fibers and non-wood pulping, published by the joint textbook committee of the paper industry

kfcCloskey. J. T.: what about non-woods; 1993 TAPPI global fiber supply symposium.

proceedings. 95- 102, ( 1995).

Pande. H.: Non-wood fiber and global fiber supply: Unasylva 193. vol. 49.44-50. ( 1998).

Rowell. R M.; Young, R A.; Rowell. Judith. K.: Paper and composites Erom agro-based

resources, 1997, CRC Press, Inc.

Hurter. A., M.: Utilization of annual plants and agriculturai residues for the production of

pulp and paper. TAPPI proceedings. 1 39- 160. ( 1988).

Kaldor. A, F.: Reparation of kenaf bast and core fibers for pulping by the Ankal method.

TAPPI, 137-140. ((September 1989).

12 Zorners, F, H. A.; Gosselink, R, J. A. and Tjeerdsrna. B, F.; Organosolv pulping and test

paper characterization of fiber hemp, 1993 pulping conference. book 2.475-1 55, ( 1993).

13 Zomers, F. H. A.; Gosselink, R I., A.: van Dam, Jan, E.. G. and Tjeerdsma. B. F.:

Organosolv pulping and test paper characterization of fiber hemp, TAPPI Vol. 78. No. 5.

149-155 (May 1995).

14 Smook, G., A.; Handbook for pulp and paper technologists, second edition. Angus wiide

publications.

15 Sjostrom, Eero; Wood chemistry. Fmdarnentals and applications, second edition, Academic

press, inc.

16 Kleppe, P, J.; Kraft pulping, TAPPI, Vol. 53, No. 1,3 5-47 (January 1970).

1 7 Gadir-Abdel, Yassin, A. and Krahmer, R, L.; Estimating the age of demarcation of juvenile

and mature wood in Douglas-fi, wood and fiber science, 25 (3). 242-249 (July 1993)

18 Packman, D., F.; Laidlaw, R., A.; Pulping of British- grown sofbuoods. Part N; A study of

juveniie, mature and top wood in a large sitka spruce tree, Hoizforschung, 21(2), 38-35.

( 1967).

19 Bendtsen. B. A.: Senft, I: Mechanical and anatomical properties in individual growth of

p!mtation-gown e s t e n i co~onwood !ob!olly pine, weod and fiber science, 1 8( 1 ). 23-38.

( 1986).

20 Watson. A. J.: Davies, G.. W. and Gartside, G.; Pulping and papemaking properties of kenaf,

Appita Vol. 30, No. 9. 129-134. (September 1976).

21 Ray, P. K.; Das. B. K.: Day. A.. and Banerjee. S. K.; Physicai characteristics of pdps

obtained fiom mesta (Hibiscm sabdmiffn) plants of different ages. TAPPI. 67-69. (Febni;.

1988).

22 Johnson. P; industrial hemp: A critical review of clairned potentials for Cannabis sativa.

TAPPI, Vol. 82. No. 7, 1 13- 123. (July 1999).

23 Wonp, A and Chen. C; Pulping and bleaching of hemp (Cannabis sativa). Pdping conference.

TAPPI proceedings. 47 1-476 ( 1995).

14 Correia. F: Roy. D. N.; and Goel, K.: Pulping of Canadian industrial hemp (Cannabis sativa

L.) Puip and paper Canada. 99:9.394 1. ( 1998).

25 DeJong. E.: Van Roekel. G. J.: Snijder M. H. B.. and Zhang, Y.: T owards industriai

applications of bast fibre pulps, Puip and paper Canada, 100:9. 19-22. (1999).

26 Groot. B. de: van, Dam. Jan, E., G.; van, der, nva'n, fick, P.; and Riet. Klaas van?:

Simpli fied kinetic modeling of alkaline delignification of Hemp woody core, Holdorsc hung,

Vol. 48, NO. 3,207-214, (1994).

27 Kovacs. A.: Rab. R and S.. Annus; Hemp (Cannabis sativa) as a possible raw materid for the

paper industry, cellulose chem. Technolog, 26,627435. (1992).

28 Krotov, V., S.; Use of AAS pulping for flau and hemp shives. Journal of hemp association

3(1): 16-18 (1995).

29 de. Meijer. E.. P.. M.: Hemp variation as pulp source researched in the Netherlands. Pulp and

paper. 4 1-43 ( July 1993).

30 Clark, T., F.; Uhr, S., C.; Wolff, L, A.; A search for new fiber crops, X., Effect of plant

maturity and location of growth on kenaf composition and pulping characteristics, TMPI.

Vol. 50, No. 1,52 A-56 A, (Nov 1967).

31 Groot, B. De; Van, Der, K o k Johannes, C.; Van Dam, Jan, E.. G.; Riet, Kiaas, Van't:

Papemaking characteristics of alkaline hemp- woody-core pulps TAPPI, Vol. 82, No. 7. 107-

1 12. (July 1999).

32 Laith A. A: Attila. Rab: Eva P and istvan. Rusznak; Optimization of process variabies for

production of dissolving pulps fkom wheat straw and hemp, TAPPI, Vol. 77, No. 6, 141-150

( 1994).

33 Deka, G. C.; Barry, M.. Wong and D., N., Roy; Suitabiiity of hybrid willow as a source of

pdp. J O L À ~ ! of xood chenistry and techdog;, ! 2 (3, ! 97-2 ! ! ( ! 092).

34 Daleski. E, J.; The effect of elevated temperatures on the alkaline pulping processes. TAPPI.

Vol. 48. No. 6.325-330 (June 1965).

35 Dorland. R., M.: Leask EL, A. and J.. W., McKinney; Pulp production with sodium bisulphite

1. The cooking of spruce. Annual meeting of the technical section. Canadian pulp and paper

association. in Montreal. Que., January 29.30.3 1 (1958).

36 Kleinert. T. N.: iMechanisms of alkaline delignification 1. The overall reaction pattern. TAPPI

Vol. 49. No. 2. 53-57 (Febniary 1966).

37 Kleinert. T. N.: Mechanisms of alkaline delignification 11 Free radical reactions. TAPPI. Vol.

49. No. 3. 126-1 30 (March 1966).

38 Pande. H. and Roy. D.. N.: Delignification kinetics of soda pulping of kenaf. Journal of wood

chemistry and technology. l6(3), 3 I 1-325 ( 1996).

39 Wong, B.. M.: Deka. G.. C.; Roy D.. N.: Bulk delignification kinetics at selected vertical

heights within jack pine plus trees Wood science and technology, 19. 1 1-18. (1995).

40 Groot. B. de: Aikaline hernp woody core pulping, impregnation characteristics. b e t i c

modelhg and papemaking qualities, Ph., D., thesis, (9' October 1998).

41 Deka. G. C.: Physical, Chernical and Pulping Characteristics of hybrid Salis clones. Ph.D.

thesis, University of Toronto. ( 1987).

42 Pierce. B.. Recycled how many times? Timber Producer. April, 18-2 1, ( 199 1).

43 Karakus. S.. Physical, chernical, soda pulping and paper making properties of Kenaf as a

function of growth. M. Sc. thesis, Universiiy of T oronto, (1998).

Appendices

Appendix 1

Plant height and diameter harvested at different times (field study)

30 DF Plot # 1 Plot #2 Plot # 3 Plot # 4 Plot # 5 height width ha*ght width height width hcight width

Mean 51.414 3295 42771 3.259 30.563 1.547 24387 1.298 43390 SD 12.06 1.73 653 0.80 7.52 0.7 1 5.15 0.58 11.01

Plot # 1 Plot $2 Plot # 3 Plot # 4 Plot # 5 height width hcight width height width height width

Mean 119.522 4.841 133160 4.680 126.634 4.601 130.986 5.083 113.415 SD 42.78 2.27 51.40 2.77 5123 L 17 4339 2.17 47.59

Plot # 1 Plot #2 Plot # 3 Plot # 4 Plot # 5 height width bcight width height width hcight width

Mean 118.966 4.146 153-644 4.913 162910 4.851 145.159 4.983 143.813 SD 39.70 1.66 68.82 221 6- 3 1 8 47.44 204 60.15

Appendir II Bio-mass in the field

30 Dl? Plot # Contauier(kg) b O / m 2 0.D- k i s (Kg/m2)

1 0.83 091 0.08 0.07 18 2 0.83 0.9 1 0.08 0-07 1 8 3 0.83 0.88 0.05 0.0449 4 0.84 0.88 0.04 0.0359 5 0.83 0.89 0.05 0.0449

Average 0.06 0.0538 Moisturc contcnt=I 0.27%

60 DF Plot # Conîaïntt (kg) Con-fiber (kg) Fiber o / m 2 O.D. basis (Kg/m2)

1 0.85 1.54 0.69 0.6252 2 0.84 1-57 0.73 0.66 15 3 0.86 1.51 0.65 05890 4 0.86 1.38 0.52 0.47 12 5 0.83 128 0.45 0.4077

Avt~agc 0.608 05509 Moi- contcnt+.39?!%

90 DF Plot # c-üntfb) Concainer+fi'ber(kg) O.D. bas& (Kg/m2)

1 1.88 3-64 0.8 0.7294 2 1.86 3.68 0.82 0.7477 3 1.86 4.34 1.12 1.02 12 4 1.88 3.64 0.8 0.7294 5 1.88 332 0.7 0.6383

Average 0.848 0.7732 Moisturc conttrit=û,82%

Bicr-auss in the greenhouse 30 M;:

Plot # Fiber @am)/pot O.D. b-ypOt 1 10.198 8.7774 2 7.078 6.0920 3 10387 8 M 1

Average 9 2 1 79365

60DC Plot # ma ( P w ~ o t O.D. ba&&ms)/pot

1 36.208 3 1.7472 2 39.1 08 34.2899 3 39.892 34.9773

Average 3 BAI266661 33.6715

90 DG Plot # Fibcr(srams)Epot O.D. bask@m)/pot

1 56.702 5 1.6272 2 35.209 320578 3 5029 45.7890

Average 47.40033333 43.1580 Moisture mtaii=4.95%

120 DG Plot # Fiber (W-Ypot O.D. basiigramsypot

1 54.45 48.4877 2 76,142 67.8045 3 46.693 41.5801

59.095 5î.6241 Moisturc amtcn~10.95%

Appendix III

Percent area ocuupied by bast, core and pith (field study)

Core Basî Pith 2 2 0.6 O. 1 2.3 0.4 O. 1 2.5 0.6 O. 1 1.4 OS O. 1 2 3 0.6 0.05 2-14 054 0.09

60 DF (aru occupied)

Corc Bast Pi th 3 0.9 0.2

3.8 0.8 0 2 4.1 1 0.1 3 -4 0.8 O. 1 3.9 1 o. 1

120 DF ( a m occupiad) Corn Bast Pith 5 3 12 O. 1 3.8 0.8 0, 1 4 5 1.1 0. 1 3.5 1.2 0 2 3-3 1 O. 1

Total ana

34 28 3.2 2

295 277 S.D.

Totai a m

4.1 4.8 5.2 43 5

S.D.

TOM ara

4.8 4.9 5

4 3 4.85

S.D.

Total rrea

6.6 4.7 5.7 4.9 4.4

SD*

Bast 20.69 t 429 18-75 25.00 2034 19.8 1 3.86

60 DF (% ares occupied)

Bast 2 1.95 16.67 1923 18.60 20.00 1929 1.93

90 DF (9% arcs occu pied)

120 DF (% areri a u pied) Cac Bast Pi th 8030 18.18 152 80.85 17.02 2-13 78-95 19.30 1.75 7 1 -43 24.49 4.08 75.00 22.73 227 7731 2034 2.35 4-00 3.15 1.01

Statistical analysis for percent area ocupied by bast and core (Appendk III - coat'd) Anova: TwbFactor Wth Repliatïon

SUMMARY 30 DF 60 DF 90 DF 120 DF Total COrY

Cotmt 5 5 5 5 20 Sum 384.096 388.2533 395.0822 38653 1553.962

Avaage 76.8 192 1 77.65066 79.0 1645 7'7.30 1 77.69808 VaRane 1 9.69485 6.483286 3420 1 18 16.02639 16-787 12

Sum 99.06435 96.4533 1 94.406 17 10 1.7 184 39 1.6422 Avaage 19.81287 1929066 18.88 123 203368 19 582 1 l Van*ancc 14.90775 3.735319 3292122 9.919184 1326215

S m 483.1 604 484,7066 489.4884 488.2484 Avaage 483 1604 48.47066 48.94884 48.82484 Variance 9 180796 950.622 1 1034.344 9 12.8387

Appendix IV Fiber study (fmm the field hemp)

Con faes- kngh and d t h 30 DF 60 DF

Leiigth Diameter LeWa Diameter 0.90 0.030 O55 0.030 O55 0.020 0.65 0.020 O55 0.030 0.45 0.020 0.65 0.040 0.75 0.020 0.65 0.050 0.60 0.020 0.70 0.040 0.75 0.040 0.65 0.040 0.64 0.040 0.85 0.040 0.75 0.030 0.65 0.030 0.55 0.030 0.75 0.020 0.80 0.020 0.70 0.030 0.70 0.020 0.75 0.020 0.75 0.030 0.70 0.030 0.85 0.040 0.65 0.040 0.65 0.030 0.65 0.020 0.45 0.040 0.60 0.020 0.85 0.030 0.70 0.030 0.70 0.030 0.85 0,020 0.90 0.030 0.70 0,030 0.85 0.040 0.80 0,040 0.65 0.040 0.80 0.050 0.75 0.040 0.70 0.040 0.65 0.040 0-90 0.030 0.76 0.030 0.65 0.030 0.80 0.040 0.75 0.035 0.70 0.040 0.80 0.020 0.75 0.020 0.80 0.030 0.60 0.040 0.65 0.0 1 5 0.75 0.040 0.75 0.030 0.84 0.030 0.65 0.025 0.45 0.050 0.60 0.030 055 0.050 0.75 0.020 0.75 0.030 0.72 0.0 15 OS5 0.040 0.70 0.020 0.55 0.040 0.60 0.025 0.85 0.040 0.75 0.020 0.65 0.040 0.85 0,030 0.70 0.030 0.95 0.0 15 O50 0.040 0.75 0,030 0.70 0.030 0.70 0-0 10 0.80 0,030 0.60 0,015 0.65 0,040 0.75 0.030 0.75 0.040 055 0,020 0.90 0.020 0.73 0,025 0.50 0.030 0.80 0.020 0.65 0.030

Appenàü IV (cont'd) Fiber stildy (fmm the tield hemp)

0.70 0.75 0.75 0.80 0.70 0.72 0.09

Length 035 0.70 0.45 0.70 0.50 0.75 0.50 0.70 0.65 O30 0.45 0.75 055 0.75 0.75 0.85 O 5 5 055 0.85 0.70 0.85 0.80 0.70 0.75 0.60 0.75 0.65 0.64 O S 052 0.40 0.80 0.85 0.65 0.65 0.65

Core tikc- kngth uid width 0.0 10 0.50 0.0 15 0.75 0.0 15 0.80 0.020 0.80 0.025 0.60 0.027 0.69 0.0 IO 0.12

Core ûbes- length rad width 90 DF

Oiameter 0.050 0.040 0,040 0.030 0,050 0,040 0.040 0.050 0.040 0,030 0,030 0.035 0.040 0,030 0.030 0,050 0*040 0.040 0.040 0,040 0.020 0.035 0.030 0.040 0.050 0.030 0.030 0.030 0.030 0,040 0,050 0.040 0.040 0.040 0.030 0.030

Length 0.60 0.75 050 055 0.70 0.60 0.70 0.50 0.65 0.75 0.80 0.80 0.65 0.75 0.70 0.80 0.65 0.70 0.65 0.75 0.80 0.70 0.75 055 0.75 0.70 0.60 0.75 0.75 050 0.80 0.55 0.55 0.65 0-75 0.45

120 DF Oiameter 0.040 0.050 0.040 0.040 0.030 0.030 0,040 0,030 0,030 0.040 0.030 0.030 0.030 0.030 0.030 0.030 0.030 0,030 0,040 0,040 0.030 0.040 0.040 0.040 0.030 0.040 0,030 0.040 0.040 0.040 0.040 0.040 0.030 0.030 0,030 0.930

37 38 39 40 41 42 43 44 45 46 47 48 49 50

Mean S.D.

Appendix N (cont'd) Eiber stady ( h m the field hemp)

Corc liber- lemgth and widtb 0.030 050 0.040 0.60 0.040 0.60 0.040 055 0.040 0.65 0.030 055 0.035 0.60 0.030 0.55 0.040 0.45 0.030 0.50 0.030 0.45 0.020 0.50 0.040 O55 0.030 0.75 0.037 0.64 0.007 0.1 1

Fiber study (€rom the field hemp)

3 7 -4

3 26 27 2s =O 30 3 1 32 33 34 35 36 37 3s 39 40 4 1 42 43 44 45 46 47 48 49 50

Mcan S.D.

Bast Ilba- kngth and wldth

13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50

Mean S.D.

Appendix IV (cont'd) Fiber study (from the field hemp)

Bast fibcs- leagth and width 0.020 22.50 0.020 20.00 0.030 19-10 0.0 15 20.00 0.020 11.90 0,015 19.08 0.020 27.80 0.0 15 24-40 0.0 15 2 1.90 0.0 10 22.40 0.020 28.00 0.0 15 23.90 0,020 3 1.00 0.020 23.10 0.0 15 33-10 0.020 Z40 0.0 15 20.65 0.015 16.50 0.0 15 25.90 0.020 18.10 0.020 28.40 0.0 10 14.60 0.020 33 -40 0.0 15 2420 0,030 3050 0.0 10 15.80 0.0 15 2620 0.0 1 O 15.60 0.0 10 19.90 0.0 15 26-90 0.010 3200 0.020 24.70 0.030 19.40 0.0 10 15.40 0.020 14.70 0.015 19.10 0.0 10 20.80 0.0 10 25.70 0.0 17 2 1.98 0.005 5.62

Statistical anaiysis of length and dinateter hemp fibers (Md study) (Appendix IV - coot'd) h o m Two-Factor WLfi Rcpbtion

SUMMARY 30 DF 60 DF 90 DF 120 DF Total

Sum 1157.9 1140.42 110012 109923 4497.75 Average 23.158 228084 22.004 219846 234ûûX Variance 36 5 5 147 41.80245 28.64804 3 1.56545 3438072

Diameter -

Count 50 50 50 50 200 Sum 0.8 0.8 15 0.84 0.837 3.292

Average 0.0 16 0.0 163 0.0 148 0.01 674 0.0 1646 VarianCC 204E-05 5.49E-05 2.73E-05 289E-05 3î5E4S

Tata Count 100 100 100 100 Sum i 158.7 1l41.235 1 101.04 1100.067

Average 11587 1 1,41235 11.0104 11,00061 Variance 1533316 151.8719 136.2594 137.4881

ANOVA Source of Varialkm SS df MS F P-YBIUB Fcrit

Sample 505ûû.38 1 5050038 2915.568 ME-183 3.8652% Columns 25.94n 3 8.649 1 0.499343 0.68î944 2.627672

intaadon 26.0138 3 8.671265 0500623 0.582061 2627612 Within 6789,809 392 17.32094

Appendix V (cont'd) Lignin (from field study)

NO Wt, Of fiber Wt.of crucible Wt. Of the crucible and lignin (a ftcr ovtn dry)

(grms.1 (grms.) m.) 1 0.5075 3 1,574 3 1.6442 2 0.5057 30.2654 30.334 1 3 ososa 30.4203 30.4892 4 0.5 174 30.2545 30.3268 5 0.5 183 30.400 1 30.4678

Lignin (0.0. basis)

('w 12.38 12.16 12.19 12.50 1 1.69

Absorbance (of filtratc)

(nm) 0.384 0.374 0.3 7 0.382 0.386

Dilution Soluble lignin Total lignin

Moisturc content- 10.52%

NO Wt. Of fiber Wt.of cruciblç Wt. Of the crucible and lignin (aftcr oven dry)

120 DF Lignin

(O.D, b i s ) (W

11.17 1 1.55 12.13 1 1 .O8 l f J 8

A bsorbanc t (of filtrate)

(nm)

0.4 0.365 0.396 0.34 1 0.35

Dilution Soluble lignin Total lignin

I:IO 0.0 197 11.19 1:IO 0.0 192 11.57 1:lO 0.0 194 12.15 1:lO 0.0 176 11.10 1: 10 0.0181 1 1.40

Average 1 1.48 Moisturc content- 5.24%

Staostlcal analysis for ligaia / m2 (Fidd stady) (Appendû V - cont'd) Anova: Siagk Factor

SUNMARY - - --

Gmups Count Sum Average Variance 30 Days 5 37.89004 7578009 0.078842 60 Days 5 348.0394 69.60787 6.762432 90 D ~ Y S 5 471.8221 9436443 5.78484 120 Days 5 443.8015 88.76029 1037141

Statisücal and@ for lignin I m2 (Fldd study) (Appeadir V - conttd)

H y p 0 t h d M e a . n Dinérrnct O df 8

t Stat -15.63 186 P(Tc=t) one-taii 1RE-07 t Critical o d 1 1.859548 P(T+t) two-Éarl Z8E-07 t Cntid t s v d 2306006

No.

i 2 3 4 5 6

Appendix VI

Holocellulose (Prom &id study)

Appendix VI (conttd)

No.

No. Wt Offiber (grms)

1 0.7273 2 0.7 176 3 0.771 1 4 0.7434 5 0.7288 6 0.776 1

Moisturt content = 10.52?4

Wt. of c~ct'ble + hcilocefl, (gnns)

3 1.9474 3 1572 3 1.8565 31.2718 25.8329 25.4009 Average

No. Wt Of fibtr (grms)

1 0.7605 2 0.75 17 3 0.7272 4 0.7888 5 0.7399 6 0,7555

No.

Appendix VI (cont'd)

HoloceIlulose (From greenhow study)

W t of cniciblc + boiacell- -1 326 164 320045 3 i -9809 3 1.7575 24,4222 243813 Average

Moimm content = 1 I 22%

Wt of cruaile Wt. ofc~uct'ble + holoctll (grms)

23,474 1 23.966 1 23,6695 24.1365 23 574 1 24.0358 23.8797 24.34 24.0207 24.5034 222837 îî.7633

Moisnut contait 43%

No. Wt Of fiber -1

1 0.71 11 7 - 0.7383 3 0.7477 4 0.7397 5 0.748 6 0,7289

No. WL Of fiber

1 0.7474 2 0.8387 3 0.8226 4 0.723 5 0.707 1 6 0.7275

Appendil VI (cont'd)

HoIoalluIose (Fmm greenhouse study)

Stntistical aiinlysis for Iioloccllulose I ni2 (Field Study) end en dix VI - coiit'd) Anova: Single Factor

SUMMARY - -

Groups Count Sum Average Vadance 30 Deys 6 232.7044 38.78407 0.440912 60 Dnys 90 Dtiys 120 Davs

ANOVA - - - Source of Vadation SS df MS F P-value F cn'l

Betwccn Groups 14O4300 3 468 100.1 84 16.168 3.578-3 1 3.098393

t-Test: Two-Sample Assuming Equal Variances

30 Days 60 Deys Mcan 38,78407 458,943

Variance 0.4409 12 65.98 145 Observations 6 6

Pooled Variance 33.21 1 18 Hypothcsized Mean Diffcrcnce O

d f 1 O t Stat - 126.2793

P(T<=t) one-tail 1.19E-17 t Critical one-tail 1.8 12462 P(T+t) WO-tail 2,388- 3 7 t Critical hvo-tail 2.228 139

Statistical analysis for IioloeeIlulosc / rn2 (Field Study) ( ~ ~ ~ e a d i x V I - cont'd) t-Test: Two-Sample Assuming Equal Variances

Variance Observations

Pooled Variance Hypothesized Mean Differcnce

d f t Stat

P(T<==t) one-tail t Critical one-tail P(T<=t) two-tail

t-Test: Two-Sample Assuming Equal Variances 90 &YS f20 0 8 ~ ~

Moan 607,6498 65 1.2 1 89 Variance

Observations Pooled Variance

Hypothesized Mean Di ffercnce d f

t Stat P(T<=t) one-tail t Critical one-tail P(T<=t) two-tail t Critical two-tail

Appendix VI1 Alpha-cellulose (From field study)

Alpha-cell. content Alpha-cell, content based on O.D,(%)

34.29998 153

No. Wt. of crucible (grma

24.0 19 1 23.7264 23.5763 23.7528 23.706 23.4728

Wt. of cnicible + hoIoceIl. (gms)

24.5634 24.3052 24.1344 24.3076 24.2622 24.0374

Wt. Of cmcible+alpha-cell. Wt. Of fibet (snns) t w s ) 24.306 0.7037

0.7 134 23.9147 0.7038 24,0593 0.70 17

0.7 126 23,7736 0,7055

Al pha-cell, content No, Wt, of cnicible (gnns)

Wt, of cruciblo + holocell, (grma)

Wt. Of cnicible+alpha-ccll. Wt. Of fibcr

( g m )

29,5984 0,7554 M.C. 0.7 147

24.0 194 0.7654 MC. 0.7736

24.3886 0,70 1 8 24.2574 0.71 19

AVERAOE

No, Wt, of cruciblc 1 (P4 2 3 1.2724 3 3 1.8965 4 3 1,7778 5 3 1,2363 6 30.8509

3 1.628 1

No. Wt. of cnicible 1 (VI 2 3 1,3327 3 30.97 1 4 31.1972 5 30.630 1 6 25,2292

24.7555

Wt, of cruciblc + holoccll. (&!mis) 3 1.9354 32,488 1 32.3962 3 1.8304 3 1.4529 32.2457

Wt. of cruciblc + holoccll, (Jima 3 1.9474 3 1,572 3 1.8365 3 1,2718 25.8329 25,4009

Appcndix VI1 (cont'd) Alpha-celIuIose (From field study)

Wt. Of crucible+alpha-ccll. Wt. Of fiber Alphaîell. content

(srms) (grmg) 0.7768

32.3 166 0.703 54.08084449 32,1566 0.7209 53,88335704

0.709 3 1.2376 0.7 157 54.54 16079 32,0059 0.7407 52,78748079

53,82332255

Moisture content=16.7 1 %

Alpha-cell. content based on O.Da(%)

Wt, Of cnicibletalpha-cell, Wt. Of fibcr Alpha-cell. content rn) (emrs)

3 1,8756 0,7273 3 1,3371 0.7 176 5 1 .O 1 727982 3 1,6042 0.771 1 52.78 174037 31,1964 0.7434 25,5749 0.7288 47,434 1383 1 25,1436 0,776 1 50.00644247

50.30990024

Alpha-cell, content based on O.D,(%)

No, Wt. of crucible (grms)

1 3 1.8921 2 3 1.2866 3 3 1.284 4 30,9959 5 23,7298 6 23,6724

No, Wt. of cniciblc (ema

Wt. of crucible + holocell. (sms)

32.6 164 3 1.944s 31.9019 3 1,6275 24,3722 24.34 13

Appendix VI1 (conttd) Alpha-cellulose (from greenhouse study)

Wt. of crucible + holocell, (gms)

Wt, Of cniciblc+alphn-cell. WC. Of fiber ( m s ) MC, 0.7605

3 1.6379 0.75 17 31,6178 0.7272 3 1,364 0.7888 MC. 0.7399

24,0229 0,7555 AVERAGE

Alpha-cell. content Alpha-cek content based on O,D.(%)

Wt. Of crucible+alpha-ccll. Wt, Of fiber Alpha-cell. content Alpha-ccll. content (srms) (srms) bas4 on O.D.(%)

No, Wt. of crucible 1 2 23.688 3 23,7603 4 23,647 1 5 23.8809 6 23.8778

24.0057

No. Wt, of cniciblc 1 2

(gnns) 3 1,8733

3 3 1,6539 4 3 1.8653 5 30.802 6 3 1.865

30.825

Wt, of crucible + holocell. (gms)

24.2484 24.3 104 24,1997 24,426

24.4528 24.5868

Appendix VI1 (cont'd) Alpha-cellulose (from green house study)

Wt. of cniciblc + holocell, ( e m ) 32,4934 32,354 1 32,5636 3 1.39

32.425 1 31.4145

Wt. Of crucibletalpha-cell, (Ems)

24.1856 24.0729 24.1419 24.2 1 O5 24.2243 24.3387

Wt. Of fiber (ms) 0.71 1 f 0.7383 0.7477 0.7397 0.748 0.7289

Moisturc content.. 10.83%

Wt. Of crucible+alpha-ceII, (grmg)

32,2352 32.2642 32,2828 31.1569 32,2058 3 1 .M62

Wt, Of fibcr (grnu) 0,7474 0.8387 0,8226 0.723 0.707 1 0.7275

Alpha-celle content

Alpha-cell. content

5 1,097 13674

50.75370776 49.087 13693 48.19686042

Alpha-cell. content based on O,D,(%)

Alpha-cell. content basai on O.D.(%)

44,858 17634

Statisticnl anolysis for alpha -cellulose I ni2 ( field study) end en dix VI1 - cont'd) t-Tcst: Two-Sample Assuming Equal Variances

60 days 90 days Mean 247.2502 346.6 1 04

Variance 20.07 17 22.95069 Observations 4 4

Pooled Variance 21.51 119 Hypothesized Mean Diffcrence O

d f 6 t Stat -30.2967

P(T<Pt) one-tail 4.298-08 t Critical one-tail 1.943181 P(T<=t) two-tail 8S8E-08 t Critical two-tail 2.4469 14

t-Test: Two-Sample Assuming Equal Variances

90 days 120 days Mean 346.6 104 343 X 6 3

Variance Observations

Pooted Variance Hypoihesizcd Mean Di ffercncc

df t Stat

P(T<=t) one-tail t Criiical one-tail P(T<=t) two-tail

Ash (?Cl cm-

- - * 1 3 1

726

728 0.04

4 3 1 424

4 2 8 0-05

142 244

243 0.02

2 17

2.21

2 19 0.03

Appendix MI (cont'd)

Ash and siüca (From greenhouse study)

28.909 1 28.6658 263093 26.0639 21.5332 6.32

Average SD

Ash (%) O.D.

4.27 4.60

4-44 023

2.84 2.8 1

2.83 0.02

272 2.63

268 0.06

286 278

282 0.06

Silica (%) O.D.

0.1 1 O. 12

0.1 1 0.0 1

0.2 1 0.17

0.19 0.03

0.10 o. 10

0.10 0.00

O. 14 o. 12

O, 13 0.0 1

S t a W c a I aaalysis for Ash I m'(in the field) (Appendlx MII - roattd) Anova: Siagie Factor

SUMMARY Gmups Count Sum Average Van'ance 30 Days 2 7.842743 3921371 0,00039

ANOVA Soum of Variation SS df MS F P-value Fcrit

Bctwaen Groups 423.0148 3 141 ,0049 4669.626 1.53E-07 6.59 1392 Within Groups 0.120785 4 0,030196

Total 423,1356 7

t-Test Two-Sample Assuming Equal Variances

30Days M&yS Mean 3.92137 1 2335852

variance 0,00039 0.065304 Observations 2 2

Pooied Variance 0,032847 Hypothesued Mean Diffmcc O

df 2 t Stat -1083504

P('R=t) one-tail 426E-05 t Critical me-tail W 19987 P ( T q ) two-taiI 8.SZE05 t Critical two-tail 4.302656

Stntistid analysis for Ash I m2(h the field) (Appendix VIII - cont'd) t-Test: Tw-k Assrrmmg EQual V w

variancc 0-

Pooled Variance Hypothesized Meau D i f f m a

df t Stat

P(T<=t) aac-tail t C r i t i c d h i P(T-t) two-taa t Cntical two-ail

t-Test- Twa-Sample Assuming EQual Variances

Statistical anaIysis for Silica / m2(im the field) (Appeadir - cont'd) Anmm Siagk Factor

Gmups Count Sum Amrage Vanhœ 30 Days 2 0,043837 0.021918 6.OSE-07 a0& 2 0257954 0.128977 6.46E-05 90 Days 2 0.019236 0.009618 5.08E-06 120 Days 2 0.01 1215 0.005608 1.OSE-06

ANOVA - - . - - - - Source of Vanation SS df MS F P-value F cht

Behvœn Groups 0.02068 1 3 0.006894 386.536 2.2 1 E-05 6.59 1392

Total 0.020752 7

VariaMx Observations

Poolcd varianct Hypothesizcd Mean Difiraaict

d f t Stat

P(T<T~) ont-tail t Ctitical one-tail P p = t ) two-tail t Criticai two-taii

Statistiicai anaiysis for Silica / m2 (in the field) (Appendix VIII - cont'd) t-Test Two-Sample Assuming Equal Variances

Mean 0.128977 0.0096 S 8 Variance 6 , 4 0 5 S.OSE-06

Observations 2 2 Pmted Variance 3.48E-05

Hypothesiztd Mean Di ffcmce O d f 2

t Stat 2022094 Pfl<=t) onetail 0.001218 t Critical onetail 29 19987 P(T<=t) twtHail 0.002437 t Critical two-cail 4302656

t-Test Two-Samplc Assuming Equal Variances

90aays 120 Days Mean 0,0096 18 0.005608

Variance Stû8E-û6 1.OSEc06 obscnsatioas 2 2

Poolcd varianct 3.06E-06 Hypotfishd Mean Difierence O

df 2 t Stat 2.291195

P(T<=t) one-tail 0.074523 t Critical one-tail 2 9 19987 P(T<=t) m i l O. 149047 t Critical iwo-tail 4302656

Bag #.

1 2 3 4 5 6 7 8

Bag #.

1 2 3 4 5 6 7 8

Kimwipe mass K (grms)

0.49 0.48 0,47 0.47 0.46 0,47 0.49 0.48

Kirnwipe mass K ( m e )

0,4736 0.4727 0.4839 0,4655 0,4649 0,4783 0,4783 0,4725

Appendix 1X EXTMCTIVES (From field study)

30 DF

K+Un-Fiber Air dried mass Air dned O.D. mass

Moisture content of un-extracteci wood = 10.27% Moisture content of extractcd wood = 7S6%

K+Un-Fiber Air dricd m a s Air dried O,Db mass

O.D.Un-fiber UF (grnid

0.83 0.94 1 *39 1.3 1 1.49 1-76 1.80 1.67

Average

0.D.Un-fiber UF (gnns )

2,625 2.754 2.303 2.450 2.727 3.014 2.4 18 2.868

Average

Extractive content 0.D. Basis

Extractive content

(%)

Moisture content o f un-extractcd wood = 9,39% Moisbre content of extrscted wood = 1 1.36%

Bag #,

1 2 3 4 5 6 7 8

Bag #.

1 2 3 4 5 6 7 8

Kimwipe mass K (grms)

0,4764 0.477 0,4642 0.47 18 0.47 18 0.48 1 1 0.4749 0,4694

Kimwipe mass K (grms)

0,455 0,4598 0,45 1 1 0.4658 0.45 12 0.4569 0.4588 0,4493

Appendix IX (cont'd) EXTRACTIVES (From field study)

90 DF

Moisturc contcnt of un-extractcd wood = 8.82% Moisturc contcnt of cxtractcd wood - 1 O,S2%

0.D.Un-fiber UF (gms)

1.84 1 S6 1.92 1.78 1.73 1.78 1.77 1.69

Average

O,D,Un-fiber UF (grms)

1.92 1.57 2.19 1.90 2.19 1.85 1 S2 1,93

Average

Extractive content (%)

Extractive content (%)

Moisture content of un-extracted wood = 9.62% Moisturc content of extmcted wood a 1 1 +85%

Bag #.

1 2 3 4 5 6 7 8

Bsg #.

1 2 3 4 5 6 7 8

Appendix IX (cont'd) EXTIUCTIVES (Froiii field study)

3ODG K+lJri-Fiber Air dried mass Air dricd O.D. mass

( gniis)

1.584 1.4344 1.2514 1.35 15 1.4597 1.205

1,5836 1.8524

Moistwe content of un-exîracted wood = 13.93% Moisture content of extractcd wood = 1 1.22%

0.D.Un-fiber lJF (gms)

0.94 O, 82 0.67 0.73 0.83 0.63 0.94 1.18

Average

O.D,Un-fiber LJF (gnns)

3 6 7 3.07 3.47 3.3 1 3.18 3,27 3.53 4.08

Average

Extractive contcnt (%)

Extractive content (W

Moisture content of un-extracted wood = 13.93%

Moisture content of extractcd wood = 9.3%

Bag #.

1 2 3 4 5 6 7 8

Bag #,

1 2 3 4 5 6 7 8

Kimwipe mass K (grms)

0,4764 0.4748 0.4629 0,4528 9,4569 0.4576 0.4672 0.4699

Kimwipe mass K (gnns)

0.46 16 0.476 0.468 1 0.480 1 0.4774 0.4672 0.468 0.4792

Appendix XX (con t'd) EXTRACTIVES (Fronr grccnhousc study)

Moisture content of un-cxtracted wood 8.95% Moisture contcnt of extracted wood 9.92%

0.D.Un-fiber UF (gnns)

2.22 1 ,59 1.33 1.86 1 A8 1.63 1.50 1,60

Average

O,D,Un-fiber UF (grms)

2.18 1.93 1.41 I,46 1.54 1.86 1.27 1.51

Average

Extractive content (%)

Extractive content (W

Moisture content of un-extractcd wood = 6.85% Moisture content of cxtracted wood = 10.62%

Field : Fractioa of extractives

% Of extractives

Solvent 30DF 60 DF 90 DF 120 DF Ethanol : Toluene 1338 11.6 7.82 3 -04

Ethanol 13.43 73 6.49 1.85 Water 11.7 1.97 1.16 0.82

Greenhouse : Fraction of extractives

Solvcnt 30 DF 60 DF 90 DF 120 DF Ethanol : Tolucne 3.05 3.49 298 252

Ethimol 3.94 429 261 0.446 Water f .92 1-15 0.63 201

Statist id analysis for extractives / m2 (field study) (Appendix M - cont'd) A n o m Single Factor

SUMMARY Grrwps Count Sum Average Vanànce 30 üays 8 304.6784 38.0848 7.881882 60 Days 8 161-4275 20,17844 1 .O83758 90 hr~ 8 123.7969 15.4746 1 0.636949 120 Days 8 41.7154 5214425 0360139

ANOVA Source of Variation SS df MS F P-value F cnt

Betwcen Groups 4527.278 3 1509.093 605.8954 1.47E-25 2,946685 Within Groups 69.73909 28 2490682

t-Test Two-Samplt Assuming Equai Variances 30Days 60-

Mean 38.0848 20.17844

df t Stat

Pv<==t) one-taii t Criticsir one-tail

Statistid andysis for extractives 1 m2 (field study) (Appendix M - cont'd)

Obscrvatioos 8 8 Pookd VsriaMx 0.860353

Hypothesi#d Meaa M i O df 14

t Stat 1 O, 14245 P(TU) ont-oiil 3.92E-08

t-Test T w o - S q k A s a m h g Variances 90Days 120Days

Mean 15.4746 1 5 2 14425

Appendix X Puip yidd (fidd stndy)

30 days field; Temp l55 ûqTime 120 min Fiber m a s Filtcr piper OD. mas % Yiid

25 149 12449 2.4729 4883 2.5411 13095 2.5 13 4736

43.10

30 days fieid;Temp 1% Oc$ïiiiie 150 min Fiber mas Filter papa O.D. mass % Yicld

2-5 14 1 1243 1 2.1 087 34-43 251 16 12396 2474 49.15

41.79

30 days fie1d;Ternp LS5 Oc;Time 180 min Fibu m a s Filter papa O.D. mass $6 Yield

2.520 1 1.295 1 24802 47.03 2.5 12 1207 1 2.0848 34%

40.98

30 days fie1d;Temp 170 Oc;Time 120 min Fiber m a s Filter papa OB. mass % W d

2.5099 1399 2,3775 4453 25052 1.3005 2.4 166 4455

4454

30 days fie1d;Tenip 170 RTime 150 min Fibcr mas Filter papcr OD. mass % Ydd

250 14 1.3099 24058 43.8 1 25047 12483 2.3634 4452

44.1 7

30 days fie1d;Temp 170 Oc;TïÜnc 180 min Fiber mas Filter paper O.D. mass % Yicld

2.5042 12425 23457 44.05 2.5046 1.2334 2.0873 34.09

39.07

30 days fie1d;Temp 140 Oc;Time 120 min F i k mass Filter papcr O.D. mass % YieM 3087 1.2327 2665 57.09 2.5037 12468 2.684 57.40

57.25

30 days fie1d;Temp 14û Oc;Tiune 150 min Fiber mass Filtu paper 0.D. m a s % Yield

2.497 1 1 x 9 2.665 57.1 1 2.4957 13 024 2,684 5536

56.23

Appendix X (cont'd) Puip yield (field study)

30 days fieid;Temp 140 @Tirne 180 min Fiber mass Filter paper O.D. m a s % Yicld

2.4978 1219 2.6229 562 1 2.4903 12964 2.69 55.96

56.08

60 days field; Temp 155 Oc,Ttme 120 min F t k r mass Filter paper O.D. mass % Yield

2.508 1.3005 2,6952 59.55 2.50 18 12295 2.6 132 59.05

5930

60 days fie1d;Temp 155 Oc;Tie 150 min Fiber m a s Film paper O.D. mas % Yield

2.50 f 9 1.2294 2.5498 5635 2.5038 1 .2729 2.6822 60.10

58.22

60 days fie1d;Temp 155 0c;Time 180 min Fiber m a s Filter paper O.D. mas % Yicld

2.5 185 13068 2.6521 57.03 2.5064 1.2802 2.598 56.!4

56.58

60 days field;Temp 170 OqTIme 120 min Fiber mass Fil& paper O.D. maçs % Ykld

25008 13642 2.4938 54.1 1 2.4937 1.258 2.458 1 5296

53.53

60 days fie1d;Temp 170 Oc,Time 150 min

Fiber mas Filter papa O.D. mass % Yicld 23982 12726 2.4074 52.07 2.3959 1.3138 2.5233 55.55

53.8 1

60 days fieid;Temp 170 0c;TIme 180 min Fiber m a s Filter paper O.D. mass % Tield

2.5055 1.2575 3 0 15 54.64 2.5038 1.2334 2.3674 49.84

5224

60 days fie1d;Temp 140 Oc;Time 120 min FI% rnass Filter paper 0.D- m a s % Yield

2.5087 1.2327 2.665 62.62 2.5037 1.2468 2,684 62.96

62-79

Appendix X (contvd) PuIp field (field study)

60 days Zield;Ternp 140 Oc;TLme 1SO min F i k mass Filter papa OD. mass % Yicld

2497 I 1-319 2.933 1 61.64 2.4957 13024 2.92 13 58.93

6028

60 days fieid;Temp 140 W T i 180 min F3.m nass Filter papcr 0.0. m a s % Y ield

2.4978 1219 2.61 19 61-16 2.4903 1.2964 259 56.97

59.06

90 days iield;Temp 155 ûqTi 120 min Fibet mass Fitcrpapcr OS). mus % Yidd

2003 12455 23414 59.68 2.0055 1.2094 2.2714 Sï.76

58.72

90 days fie&Temp 155 ûçTïme 19 min F i k rnass Filter paper O.D. mass % Yield 2009 12248 22985 58.29 2.023 1,2539 23 151 5722

Sî.76

90 days fld;Temp 155 Oc;Tlmc 180 mi^ Fibermass Fdta papa OD. mass %Yuld

2.0034 13555 23202 57.97 20106 1303 23032 55.49

56.73

90 days ûeid;Temp 170 Oc;Tïe 120 d a Ft'bétrnass F i t e papcr O.D. mass % Yield 2.0033 1231 2.22î6 54.13 20013 1.2344 2.1873 5207

53.10

90 days fieid;Temp 170 Oc;'Iïme 150 min Fibetmass Filtapaper O.D. mass % Yidd

2.0246 12145 2 18% S2.67 2.0022 1.273 1 21942 503 1

5 1 -49 90 days iield;Temp 170 Oc;TIme 180 min

Fi'bermass Filter paper OD. mas % Yield 2.0061 12694 2 1924 5032 20076 1271 2.1826 49.66

49.99

AppenaUr X (cont'd) Puip yidd (Md study)

90 &ys tKtd;Temp 146 ~ T i i m e 120 min Fibermass Filtapapcr OD. masi %&Id

20029 1.2581 2.4249 6350 2.0137 12242 2.3652 61.76

62.63

90 àays Geid;Temp 140 %Tirne 150 min Fiber mass Filter *papa OD. mass % Yidd

2.0 19 1 1263 2.6362 6239 2029 5 1237 23994 6158

61.99

90 &ys Md;Temp 1(8 ûqTCnie 180 min Fibermass Filtcrpapcr OD. mass % W d

20104 1 2 6 4 23686 6133 2.0 127 12021 23215 60.62

61 î û

120 days ficld;Tcrap 155 OçTlmt 120 min F1kmass Fdtcr papa OS. mass HYieid 2.0083 12128 239î7 63.06 2.0059 12132 2.3556 61.13

Q IO

120 d q s fidd;Trmp 155 ûqTimc 150 min F I ~ K M S S Fdterpaper OS. m a s % Yiid

2.0047 12021 23465 613% 2.0004 1.2132 234û3 60.48

60.8%

120 days fieid;Temp 155 Oc;Time 180 min F M mass Filter papa OD. m a s % YiId

2.0052 1.1709 22939 40.12 20089 12088 22995 5 8 3

59.20

120 d q s ficld;Tcmp 170 k$ïimc 120 min Fiber m a s Frit# paptr OS, mass % Yicld

2.0078 1.1699 22455 57.0 1 ZOO8 1,1987 22821 57.42

5721

Appendïx X (cont'd) Puip yieid (fieid study)

120 &ys fi4d;Temp 170 ûqTime 150 min Filter papa O.D. mas % Yi&

12002 22579 56.1 1 1.1768 22373 5632

5622

120 days fie1d;Temp 170 0C;Tlme 180 min Filter paper O.D. m a s % Yield

12124 2.2526 5524 1 .224 226 13 55.08

55.16

120 days 6eld;Temp 140 ûqTime 120 Filter paper OD. mas % Ykid

1.1655 24028 65.76 1.224 2445 643 1

65.34

120 days fitld;Temp 140 ~ T i m t 150 min Filtct Paper O.D. mass 9é Yidd

1.2459 23866 65.04 12036 23341 65.03

65.04

120 diys field;Temp 140 Oc;Time 180 min Filterpapa o n mass % Yteld

1203 1 2.4237 64.75 1.2879 2497 64.17

64.46

Source DF -*TernP 6 T i 2 Days*T;-.m 5 Temp'Time 4 Days8TempTîe 12

Statistial aiulysis for puip yieid (field study) (Appendix X- cont'd) The ANOVA Proaiare

Levcis Valucs 4 1 2 3 4 3 1 2 3 3 123

AnovaSS McanSquart F Value 20558159û 34263598 4.25

95.03 1968 475 15984 5.90 13.6301 64 227 1694 0.28 12835933 3208983 0.40

3 1.780666 26483 89 033

Duncan's Mdtip fe Range Test for Yidd

Duncan Gmupiq Mean N A 60.6222 18 4

- ~ u n ~ a n ~ r o ~ p ù i g MC- N r i

A 57.0504 24 1 ,

A 55.6561 24 2

Appendix XI (contvd) Lignin frorn pulp (field sludy)

30 days fleld;Tcmp 170 0c;Timc 120 min

NO Wt. Of fibcr Wt.of cruciblc Wt. Of the cruciblc and lignin Lignin Absorbancc Dilution Soluble lignin Total lignin (aller ovcn dry) (O.D. basis) (of filtrate)

(gnnd (srms*) (m.) (%) (ml (W (%) 1 0,503 30.9191 30.9696 9.09 0.285 1 :O5 0.007962 104 9.10 2 0.51 16 30,4099 30.4633 9,45 0,285 1 :O5 0.00782826 1 9.46 3 OS08 30.9204 30.972 1 9.22 0.274 1:05 0.007579452 9.23

Moisture contcnt-9,43% Avcraga 9.26

30 days fie1d;Tcmp 170 0c;Tlme 150 rnln

NO Wt. Of fiber Wt.of cnidbte Wt. Of the crucible and l i g h Lignin Abrorbsncc Dilution Soluble llgnin Total lignin (a ftw oven dry) (O,D, buis) (of filtrate)

(ermi*) (emis*) (enns*) (%) (MI) (W (W 1 0,5112 3 1.6247 3 1.67W 8.42 0.289 1 :O5 0.007643076 8.42 2 0.503 1 30.4 164 30,4603 8.2 1 0.3 1 :O5 0,008061727 0.22 3 0.501 1 30.3 169 30.36 1 8.28 0.266 1 :O5 0.007 176594 8.29

Moisturc content=5.86% Average 8.3 1

30 dayi field;Tcmp 170 0c;Ttme 180 mln

NO Wt. Of fibct Wtof cniciblc Wt. Of tho cmcibto and lignin Llgnin Absorbame Dilution Soluble lignin Total lignin (aAcr ovcn dry) (O.D. k i r ) (of filûatc)

(smw*) (smis*) (snns*) (%) (W (%)

1 0.5072 30.932 30.9754 8.10 0.339 1 :O5 0.008989323 8.1 1 2 0.5089 30.1346 30,1778 8.03 0.277 1:OS 0. 1289359 16 8.16 3 OS015 30,7042 30,747 1 8.09 0.267 1:OS 0.1261 1505 8.22

Moisture content-5.37% Average 8.16

Appendix X I (cont'd) Lignln from pulp (field study)

NO Wt. Of fiber Wt.of crucible

NO Wt. Of fibcr Wt,of cniciblc

30 days Ile1d;Temp 140 0c;Tlme 120 min

Wt. Of the crucible and lignin LlgnIn Absohanct Dilution Soluble lignin Total lignin (aftcr oven dry) (O.D. basis) (of filtrate)

(w-1 (%) (m) (W ("/O) 30.6939 1 1.48 0.425 1 :O5 0.01 1 1 10332 1 1.49 30.8 132 1 1.20 0.393 1:OS 0.010229584 11.21 3 1.2764 1 1.49 0.392 1:05 0.010171724 1 1.50

Moisturc contcnt=4.37% Average 1 t A0

30 dayr fie1d;Temp 140 0c;Tlmc 150 mlo

Wt. Of the crucible and lignin Lignin Absorbancc Dilution Soluble lignin Total iignin (anor oven &y) (O.D. basfa) (of filtrate)

(eirns*) (W (nm) (W (%) 30,6025 10.80 0.355 1:OS 0.009273345 10.81 30.092 1 10.53 0,378 1 :O5 O.OO992 1201 10S4 30.63 17 10.80 0,388 1 O O.OO99893 14 10.8 1

Moisturc content-3.73% Average 10,72

30 daya ficld;Temp 140 0c;Timc 180 mln

Wt, Of the cmciblc and lignin Lignin Absohance Dilution Soluble IignIn Total lignin ( a h oven dry) 0 b a s ) (of filtrate)

(m.) (W (m) (%) (W 28.5802 10.69 0.384 1 :O5 0,009706353 10.70 29.2612 10.06 0.38 t :OS 0.00979220 10.07 3 1.0384 10.70 0.34 !:O5 0.009070953 10.7 1

Moisturc conlcnW,80% Average 10.49

Appendix XI (conttd) Lignin from pulp (field study)

NO Wt. Offiber

NO Wt. Of fibet

60 days field; Teiiip 155 0c;Tinic 120 min

Wt, Of the cnicible and lignin Lignin Absorbancc (after ovtn dry) (0.D. b a h ) (of filtrate)

(m.) (%) (ml

60 days field;Tcmp 155 0c;Tlme 130 mln

Wt. Of the crucibla and lignin Lignin Absorbance (aftet oven dry) (O.D. buis) (of filtmte)

m.1 (%) (nm) 3 1,0024 11.06 0.4 16 30,9835 8,87 0,332 30,2645 11,Ol 0.396

Moisturc contcnt4.9 1 %

60 days field;Temp 155 0c;Tlme 180 mln

Wt. Of the crucible and lignin Lignin Absorbance (afùr oven dry) (O.D. buis) (of filüaîe)

WB*) W) (nm) 31.143 10.42 0.382 30,6755 7.25 0.318 3 1.764 10.70 0.383

Moisturc conttnt4,94%

Dilution

1 :O5 1 :O5 1 :O5

Dilution

1 :OS 1 :os 1 :O5

Dilution

1 :OS 1 :os 1 :O5

Soluble lignin

(%)

0.01 1171276 0.009846327 0.009864052

Soluble tignin

(%) 0.0 1 tO27789 O.ûû873O 132 0.01028 175

Soluble lignin

(W 0.0101 17652 0.008434228 0.0 1 O074385

Total lignin

(%)

1 1,73 9.53 1 1.44 1 0.90

Total lignin

(%) 1 1 ,O7 8.88 1 1 *O2 10,32

Total lignin

(W 10.43 7.26 10.7 1 9.47

Appendix XI (cont'd) Lignin from pulp (field study)

Wt. Of fiber

(gms.)

0.5065 0,5035 0,5076

Wt. Of fibcr

(ms4 0,5066 0.5046 OS056

Wt, Of fiber

(m.) 0,5004 0.5027 0.5008

60 dayr lic1d;Temp 170 0c;Tlme 120 min

Wt, Of the cmcibie and lignin Lfgnin Absuhance (aftcr ovcn dry) (0.D. basis) (of filbntc)

(msJ (%)

60 days fle1d;Tcmp 170 0c;Tlme 150 mln

Wt. Of the c~c ible and lignin Lignin Aboorbancc (after ovcn dq) (O.D. basis) (of filtrate) m.) (%) (W 30,8809 6.74 0,302 28,5862 5.12 0.253 3 1,7547 5.98 0.286

Moisturc contenM,94%

60 diys fleld;Tcmp 170 0c;Tlme 180 min

Wt. Of the cmciblc and lignin Lignin Abmrbancc (aRcr ovcn &y) (0.D. basis) (of filtrate)

(srma*) (nm) 31.1321 6.7 1 0.302 30.6812 3 .70 0.247 31.1756 4.30 0.308

Moisture content-5.2%

Dilution

Dilution

Dilution

Soluble lignin Total lignin

Soluble lignin Total lignin

Solublc lignin Total lignin

Appendix XI (cont'd) Lignin from pulp (field study)

60 dayi lield;Temp 140 0c;Time 120 mln

Wt, Of fibcr Wt.of c~cibll: Wt. Of the crucible and lignin Lignin Absorbancc (aflcr oven dry) (O.D. buis) (of filtrate)

(m.) (W (m) 30,5377 13.23 0,499 3 1.7945 12.71 0.429 30.7245 12.57 0.474

Moisture content-5,13%

Dilution Solublc lignin Total lignin

60 dayr field;Temp 140 0c;Tlmc 150 mln

Wt. Of the crucible and lignin Lignin Absotbance (sfter ovwi dry) (0.D. basis) (of filtrate)

(gnns.1 (W (nm) 30,3 122 12A2 0.406 3 1 A387 1 1.67 0.478 30.3256 12.96 0.44 1

Dilution Soluble Iignin Total lignin Wt, Of fiber Wt.of cruciblc

60 dry# flcld;Tcmp 140 0c;Tlme 180 mln

Wt, Of fiber Wt.of crucible Wt. Of the cruciblc and lignin LIgnin Absohancc (a ficr ovcn dry) (O.D. buis) (of filtmtc)

(gms.) (W (W 31.1579 12.20 0.4 1 2&62 1 12.14 0.4 15 31.2 1 1.66 0.469

Moishire content-5.23%

Diludon Soluble lignin Total lignin

Appcndix XI (cont'd) Lignin from pulp (field study)

90 dnys fleld;Temp 155 0c;Tlme 120 min

Wt. Of the cniciblt end lignin Lignln Absorbante (aftcr ovcn dry) (O.Da b i s ) (of filtrete)

(F*) (W (nm) 30.2589 10.72 0.424 30.8401 1 1.82 0.437 30.9932 1 0,70 0.466

Moisturc contcnt-4.3 1 %

Dilution Soluble lignin Total lignin NO Wt, Of fibcr

90 dayi field;Temp 155 0c;Tlme 150 min

Dilution Soluble lignin Tolal lignin NO Wt, Of fibcr Wt. Of the cruciblc and lignin Ljgnh Absorbancc (aftcr ovtn dry) (0.D. buis) (of filtrate)

W*) (W (nm) 29,2778 9.46 0.46 32.1629 10.07 0.357

90 dayi fie1d;Temp 155 0c;Tlme 180 mln

Wt. Of the crucible and lignin Lignin Absorôance ( a h oven &y) (O.D. barla) (of flllrito)

W.) (W 30,9293 7.15 0.4 17 3 1,7324 7.27 0.346 30.705 7.35 0,392

Moistura contcnt-4.74%

Dilution Soluble lignin Total Hgnh NO Wt. Offiber

P P P

Llec

zoo m u -

Appendix XI (cont'd) Lignin from pulp (fleld study)

90 dayr field;Temp 140 0c;Tlme 120 min

Wt. Of the crucible and lignin Lignin Absorbance (afttr oven dry) (0.D. b i s ) (of filtrate)

(gmiir.1 (W (nm) 32.1712 12.29 0.493 31.1622 1 1.80 0.436 29.29 1 1 12.14 0.478

Moisturc conttnP3.83%

Dilution Sotublc lignin Totsl lignin NO Wt. Offiber

90 days Sleld;Temp 140 0c;Tlmc 150 mln

Wt. Of the crucible and lignin LIgnin Absorbancc (afler aven &y) (0,D.basis) (offiltmtc)

Cgrmi*) (W (nm) 30.84 12 11.84 0,406 30.95 1 12.04 0.478 30.2636 1 2,03 0.44 1

Moisturc contcnt=4.88%

Dilution Soluble lignin Toial lignin NO Wt, Of fiber

90 daya fleld;Tcmp 140 0c;Tlrne 180 min

Soluble lignin Total lignin Wt, Of ihc crucibla and lignin Llgnin Absorbance (after oven dry) (O.D. buis) (of filtrate)

(smw (W (nm) 3 1 .y438 1 1 ,O7 0.4 1 3 1 .O0118 12.0 1 0.415 30,7233 1 1 .O3 0.469

Dilution

W

f CI, w U

Appendix XI (cont'd) Llgnin from pulp (field study)

Wt. Of fibcr

(sm.)

0.5266 0.5088 OS28 1

WC. o m c t

(w*) 0.5042 0,5021 0.505

Wt. Of fiber

m*) 0.5076 0,5171 0.508

120 days fle1d;Tenip 170 0c;Tlme 120 min

Wt. Of the crucible and lignin Lignin Absorbancc (anet oven dry) (0.0, basfs) (of filtrate)

(grms.) (%) (nm)

32.124 6.35 0.268 30.671 1 6.14 0.25 30,7883 5.86 0,28

Moisture content-4.46%

120 days field;Temp 170 0c;Tlme 150 min

Wt.OfthccniciblcaridlignIn Lignln AbJorbance (aftcr ovcn ~IY) (0.D.ba.d~) (offiltntc)

(etmr.1 (W (nm) 30,5925 6.46 0.302 3 1,6874 6.35 0,253 29,8335 6.30 0.286

Moisturc contcnM,47%

120 days fle1d;Temp 170 0c;TImo 180 mln

Wt. Of the cnicibla snd lignin LIgnIn Absorbancc (after ovcn dry) (O.D. b i s ) (of filtrata)

(W (nm) 29,8723 4,83 0,302 30.0642 4.04 0.247 30.2054 3.83 0.308

Dilution Solublc lignin Total lignin

(%) o/o)

1:05 0,0067796 6.36 1:OS 0.006545503 6.15 1 :O5 0.007063045 587

6.12

Dilution Soluble lignin Total lignin

Dilution Solublc lignin Total lignin

(W (W 1 :OS 0.007935627 4.84 1:OS 0.00637 t t 58 4.05 1 :OS 0,0080869 16 3,M

Moisture content-4.S8% 4,24

Appendix XI (corit'd) Ligniii from pulp (field study)

120 days lleld;Tenip 140 0c;TIme 120 min

Solublc lignin Toial lignin Wt.of cruciblc Wt. Of the crucible and lignin Lignin Absorbancc (after oven dry) (0.D. basis) (of filtrate)

(snns.1 (%) (nm) 32,1896 12.54 0.493 30.7354 12.48 0.436 30.825 1 12.78 0.478

Moistura content4.49W

Dilution Wt. Of fiber

120 days fleld;Temp 140 0c;Tlme 150 min

Wt. Of thc cruciblc and lignin Lignln Absorbarice ( a h ovcn dq) (O.D. bah) (of filtraie)

(W.) (W 30.6344 12.26 0.406 31.7516 12.87 0.478 29,8977 12.54 0.44 1

Moisturc contcnt4.39%

Dilution Soluble lignin Total lignin Wt. Of fibar

120 days fie1d;Temp 140 0c;Tlmc 180 mln

Soluble lignin Total lignin Wt,of cruciblc Wt. Of thc crucible and lignin Lignin Absorbancc (afùr ovcn dry) (O.D. basis) (of filtnb)

(W.) (W (nm) 29,9449 1 1.77 0.4 1 30.1413 12.30 0.4 15 30.3384 1 1 .79 0.469

Moistwe contcnt-4,94%

Dilution

Statistical amiysis for pulp lignin (Appendir M - cont'd) MOVA l./. Lfgnin' = Dtysl "ïunp.'l 'Ilmc

Factor Type Ltvtis Values Days fixcd 4 3 0 6 0 9 0 1 2 0 Tanp. 6aed 3 140 155 170 ri faed 3 120 1% 180

Anai* of Variance for % Lignin

Source DF SS MS F P D ~ Y S 3 12972 4324 9.85 0.000

Tmrp, 2 583.754 291,877 665.03 0.000 Timt 2 43.171 21585 49-18 0.000 ~ Y S ~ C ~ P - 6 75.149 12525 2854 0.000 D a y s T i 6 4300 0.717 1.630.151 T e m p . T i 4 7.758 1339 4.42 0.003 Days*Tcmp.Tûne 12 6.1 16 0510 1.16 0327 ~rror n 31.600 0-439

Total 107 764.821

1 Durtesnls Multipk Range Test fw lignin 1

No.

No.

No.

No.

No.

Appendix XII ~o~oceiiu~ose from the pulp (fidd a d y )

30 days field cook temp 155 Oc cook tirne 120 min

Wt. Of fiber Wt. of ~(11~1ilc Wt. of aucible + holocclL Hobotlluiosc -1 -1 (gmrs) b a d 011 On(%) 0.6087 3 1.64% 3 2 1746 89.00 0.649 1 3 14594 324155 88.4 1 0.728 1 3 1.2546 3 1 A762 88.10

MC437h Xvmgc 33.50

30 days field cook temp 155 O c cook üme 150 min

W t Of f i k W t of cniciblc Wt. of cniciblc + holoccclL Hobcdiulosc (gmrs) (grms) (gnns) b a d Orl O.D.(%) 0.646 23.4593 24.01 1 1 88.74 0.705 2 19276 225349 89.49 0.652 1 223048 228676 8934

M.C=3.73% Average 89.19

30 days field cook temp 1 SS Oc cook thna 180 mln

Wt. Of fiber WL of cmciile W t of clllc~'blc + boloctll. Holocdlulo~e (lm'@ (grnu) -1 basml al O.Il.(%) 0.6003 21J102 220392 9053 0.6633 23,7644 243477 90.34 0.6637 a 7 8 2 1 23368 1 90.70

UC4.800h Average 9052

30 days field wok temp 170 Oc cook t&w 120 min

Wt. Of fik Wt. of aucible Wt. of czucit'bk + holocclt. Hdo#Uuloac (grms) (grmj) -1 00 O,D.(%) 0.709 23.8î83 243228 90.77 0.7004 24.0209 24,657 W.@ 0.6455 TZ 1 294 22.71% 9130

UC.4.43% Avctage 90.92

3û days field cook temp t70 Oc cook tirrn 150 min

Wt. Of fiber Wt of aucible WL of aucible + tiofocdL Hobedliiirwr? @=) 6!P=) -1 b 0 d al On(%) 0.669 I %.as95 3 1.484s 92.30 0,6733 312787 3 1.m% 92.63 0.5784 3 1 .n14 322957 93.0 1

Average 92.65 MC.3.86%

No.

t

No.

No.

No.

Appendix XII (cont'd) HoloceiïuIose fmm the pdp (field rtiidy)

30 days field cook temp 170 Oc cook time 180 min

Wt. of auctibtc Wt. of crucible + holoctu. Holddose Cgrms) &?d bascd Oa On(%)

3 1.8937 324757 94.10 3 1.2898 3 1 A482 93.1 1 3 1.6224 32.1904 92-96

Average 93.39 M.C.=5.37%

30 dam field cook t m p 140 Oc cook time 120 min

30 days field cmk temp 140 Oc cook time 150 min

30 days field codt temp 140 Oc cook t h e 180 min Wt of auci'ble W t of awbie + holoccli. HoIOCCUulose

-1 -1 hllcrA al O.D.(%) 313106 3 1.9051 85.53 23.4394 24.0444 8628 22.1308 227364 85.98

A w r g ~ 8523 MC- t 0.02%

No.

1

No.

No,

No.

Appendir W (cont'd) Holocddose from the putp (field study)

60 days field cook temp 155 Oc cook time 1s min

60 days field caok temp 155 Oc cook time 180 min

60 days field cook temp 170 Oc cook d m tZû min

Wt of crudile Wt. of crucible + hoIoceIl, Hoiocdiulose (srms) (grms) bascd on O.D.(O/o) 23,4773 24,1547 9726 23.059'7 243184 9î58 23.7059 243254 9216

Avmge 95.67 M.C=52%

6û days field cook temp 170 Oc cook tlme 150 min

Wt of c~ciitc W t of aucible + holoceii. EiokcMost

(grms) -1 basal œ l O.D.("!) 23.7509 243924 9792 22.2567 22.9073 97.12 22.M5 22.7423 96-47

Average 9'7.17 UC.4*94%

No.

No.

No.

No.

Wt. Of fibcr

Wt. Of fibcr (gnns) 0.705

0.7062 0.7 1

Appendix W (cont'd) Holoceiialosc h m the pub (field stady)

6û days field cook temp 170 Oc c w k time 180 min

60 days field cook temp 140 Oc cook time 120 min

Wt. of aucl'ble W t of ~uctblc + holoctIi, HoIoctllulosc (grms) (gnw) bascd oa OB.(%)

23.4724 24,1351 89.43 23.6555 243181 88.34 î3.7034 243037 8924

Average 89-00 UC=423%

60 days M d cook demp 140 Oc cook ffme 150 min

6û days field cook t m p 140 Oc cook tirne 180 min

No.

No.

No.

wt Of- (@=) 0,7435 0,748 1 0-71 84

90 days fieCd c m k temp t7O Oc oook îüne 12û mfn

90 days fieid codt temp t 70 ûc cook time 15û min

No.

1

No.

No.

No.

Wt. Of fiber b?ms) 0.6528 0.663 0.5852

Appenàix XII (cont'd) Holoailalose h m the pulp (Wd study)

90 days field codc temp 170 Oc cook tkne 180 min

90 days field umk temp 140 Oc cook a m f 50 min

W t of cnict'ble WL ofaucibk + holoctlf, H o I o c d I ~ (Pm (gr=) bisad on OD.(%) 23.6824 243379 89.96 3 1.7528 32.378 88.86 3 1.7169 3233 89.83

A W C 8956 MC4.8Wo

90 âays field cook bsmp 14 Oc cook thne 180 min

W t of clllc~ilc Wt. of auci'ble + boloctll, Holdldose -1 (grms) basd 011 O.D.(?h)

23.7721 24.432 90.69 23.7963 24.4294 9053 23x93 24,4426 89.63

Avaagc 9028 UC494%

No.

No.

1

No.

No.

No,

Wt. Of fiber

Appendir XII (cont'd) Holocellulose fmm the puip (field study)

120 days field cook temp 155 Oc cook tfme 120 min

Wt of cmciile WL of auciMt + hoIoctlL HoloctlIuiost -1 rn) )raarA on O.D*(%)

3û.7985 3 1.4309 90.79 3 1.870 1 32- 89-18 3 1.653 32.2886 90.82

Average 9026 S2.C-3 .O%

120 days field cook temp 155 Oc cook time 150 min

12û days field cook temp 155 Oc cook time 180 min

120 days field cook temp 170 Oc cook tlme 120 min

120 days field cook temp 170 Oc cook tim 150 min

Wt of auciile Wt of cnicile + holocciL H-dose (grms) bitsai OQ OD.(O/O) 24342 255972 9439 23.46 24.123 95.90

25.0742 25.7339 9329 Average 94.73

UC=447%

No,

1

No.

No.

No.

Appendix W (confd) Xoluceiialose from the pdp (field study)

120 days field & temp 170 Oc cook a'me t 80 min

t 20 days field cook temp 140 Oc cook t h e 120 min

fZO days fieM cook temp 140 Oc ~ook time 150 min

120 days field cook temp 140 Oc cook time 180 min

Staüstical analysis for pdp holocelldose (field study) (AppendixW - cont'd) ANOVA 'Y* Holw' = Daysl Temp'l Tirne.

Factor Type Leveis Valws Days fixed 4 30 60 90 120 Tcmp. k e d 3 140 155 170 Tirne fixeci 3 120 150 180

Analysis of Variance for % Holw

Source DF SS MS F P D% 3 263.109 87.703 104.16 0,000 Temp. 2 1078.199 539,100 64027 0.000 Time 2 218.81 0 109.405 129.94 0.000 DaysTemp. 6 814.750 135.792 161.28 0.000 DaysTie 6 135.481 3-380 26.82 0.000 Temp. *Tirne 4 93.767 23.442 27.84 0.000 Days*Temp.YTime 12 304212 25351 30.1 1 0.000 Enor 72 60.623 0.842 Total 107 2968951

No.

No,

No.

Wt. of cmcible

23.4593 2 1,9276 22.3068

WL of cnicible (grma)

21,5102 23.7644 22,782 1

Appendix XII1 t

Alpha-cellulose from the pulp (fleld study)

30 days field cook temp 155 Oc cook tlme 120 min

Wt. of cmcible + holocell, Wt. Of cnicible+alpha-ccll. Wt. Of fibcr Afpha-cd. content (Ems)

32.1746 3 1,9741 0.6087 53.3 1 32.4 155 32.2 1 O5 0.649 1 54.09 3 1,8162 3 1.7435 0.728 1

M .C.=18,97% Average

30 days field cook temp 155 Oc cook tlme 150 mln

Wt. of crucible + holocell. Wt. Of crucibled-alpha-cell. Wt. Of fiber Alpha-cell. content (grms) (gnns) ( P d 24.01 1 1 23.8384 0,646 58.68 22.5349 22.34 17 0,705 58.74 22.8676 23.467 0,652 1

hK,=8,08% Average

30 days fleld cook temp 155 Oc cook tfme 480 mfn

Wt. of crucible + holocell. Wt. Of cnicibWalpha-ccll. Wt. Of fiber Alpha-cell. content (srma) (gnns) (ml

22,0392 2 1.8747 0.6003 60.72 24.3477 24,1705 0.6633 61.22 23.368 1 23,467 0.6637

M.C.4,99% Average

Alpha-cell. content b w d on O.De(%)

43.20 43.83

Alpha-ccll. content bascd on O.DO(%)

53.94 53699

Alpha-cell. content bascd on O,D.(%)

56.48 56.94

No.

No.

No*

1

Wt. of crucible (grms)

23,8783 24.0209 22,1294

Wt. of crucibie (grms)

30,8895 3 1.2787 3 1.7774

Wt. of crucible (gnns)

3 1,8937 3 1,2898 3 1,6224

Appendix XII1 (Cont'd) Alpha-ccllulosc from the pulp (field study)

30 days field cook temp 170 Oc cook tlme 120 min

Wt. of crucible + holoccll, Wt. Of crucible+aIpha-cell. Wt. Of fibcr Alpha-cell. content

30 days field cook temp 170 Oc cook t h e 150 mln

Wt. of cnicible + holocell, Wt, Of cruciblc+alpha-dl. Wt. Of fiber Alpha-cell. content ( g m ) ( w s ) (ml

3 1,4845 3 1 J947 0.669 1 3 1.8796 3 1.6923 0.6733 6 1.43 32.2957 32,1319 0.5784 6 1.29

MC-10.58% Average

30 days M d cook temp 170 Oc cook tlme 180 mln

Wt. of crucible + holocell. Wt, Of cmcibld-alpha-cell, Wt. Of fiber Alpha-cell, content bm) ( g m ) 32.3898 0.6453 3 1.6892 0.6257 63.83 32.0292 0,6375 6331

Average

Alpha-cell. content based on OoD.(%)

Alpha-cell, content bascd on O.D.(%)

Alpha-cell. content basd on O,D.(%)

No.

1 2 3

No*

1 2 3

No.

1 2 3

Wt. Of fiber (snns) 0.3425 0.3666 0.4 166

Wt. Of fiber (l!m9) 0.4 17

0.4293 0.475

Wt. Of fiber (gms) 0.467

0.527 1 0.4694

Appeiidix XII1 (cont'd) Alplia-cellulose Crom the pulp (field study)

60 days field cook temp 155 Oc cook tirne 120 min

Wt. of crucible Wt, of crucible + alphaccll. alpha cell Holo-ceIl Actual Fiber (srms) (Wns) (grms) O.D. basis (grms)

23.8847 24.1508 0.266 t 90.55 0,3 8 24.6529 24.9386 0,2857 90,55 0,40 3 1.2073 31,5381 0,3308 90.55 0,46

M.C,4,79%

60 days field cook temp 155 Oc cook tlme 150 min

Wt. of crucible Wt. of crucible + alphacell. alpha ce11 Holoccll Actuel Fiber ( t V s ) ( ~ s ) (grms) O.D. baais (gnns)

24,1353 24.4597 0,3244 91.96 0.45 23,7183 24.0605 0.3422 91.96 0.47 23,762 24.1 165 0.3545 91.96 0.52

M.C,4,7%

60 days field cook temp 1 5 5 ' ~ cook tlme 180 min

Wt. of ctucible Wt. of crucible + alphacell, alpha cell Holo-cell Actual Fiber (gms) ( ~ 4 (grms) O.D, basis (gnns) 23.692 24.0528 0,3608 92.3 0.5 1 23.6505 24,065 1 0,4146 92.3 0.57 3 1.0248 3 1,3936 0.3688 92.3 0.5 1

Alpha cell (%)

70.35 70.57 7 1 .!JO

Average

Alpha ccll (%)

7 1.54 73.30 68.63

Avemgc

Alpha ceil (W

71.31 72.60 72S2

M,C,=5,32% Average

Alpha cet1 O.D. basis

66.28 66.48

66.38

Alpha cell O,D, basis

67.46 69,12

68.29

Alpha cell O.Db basis

68,74 68,66 68.70

No.

No.

No.

Appendix XII1 (cont'd) *

Alpha-cellulose from the pulp (field study)

60 days fleld cook temp 170 Oc cook tlme 120 min

Wt. Of fiber Wt. of crucible Wt. of cruciblc + alphncell. alpha ccll Holo-cell Actual Fiber (grmg) (WS) (grms) (gnns) O.D. basis (grms) 0.4 133 31.0301 3 1.3553 0,3252 96.65 0.43 0.4324 3 1.8284 32.1662 0.3378 96.65 0.45 0.4 30.8226 31,1368 0.3142 96.65 0.4 1

MC-5.97%

60 days field cook temp 170 Oc cook tlme 150 min

Wt. Of fiber Wt. of cruciblc Wt. of crucible + alphacell. alpha cell Holu-ccll Actual Fiber ( ~ 8 ) (gmis) (8nns) (grms) O.D. basis (gnns) 0.407 1 24.4 1 07 24,7335 0,3228 97.16 0.42 0.4 155 2 1,9296 22.2593 0,3297 97,16 0.43 0.4833 22.1817 22.5594 0.3777 97.16 O. 50

M.C.-5.86%

80 days fleld cook temp 170 Oc cook tlme 180 mln

Wt. Of fiber Wt. of cruciblc Wt. of cmcible + alphaccll. alpha ce11 Holo-ceIl Actual Flber (ml (&!!mis) (srms) (grnio) O.D. b a h (gnns) 0,433 24,6475 24.9855 0,338 97.98 0.44 0.4783 24,8239 25. i 947 0.3708 97.98 0,49 0,4308 24.6039 24.95 16 0.3477 97.98 0.44

M,C,m5.9 1%

Alpha cell (%) O.D. bais 76.05 71.51 75.5 1 75.92 71.39

Average 7 1.45

Alpha cell (%) 0,D. bais 77.04 72.53 77.10 72.58 75.93

Average 72.55

Atpha cell (%) 0#D* basis 76.48 7 1,96 75*96 7 1,47 79.08

Average 7 1.72

No.

No.

No*

Wt. Of fiber (VI 0.44 15 0.429 1 0,4539

Wt, Of fiber (srms) 0.4 147 0.4096 0.458 1

Wt, Of fiber (-1 0.43

0.47 16 0.4 13

Appendix XII1 (cont'd) Alplia-cellulose [rom the pulp (field study)

60 days field cook temp 140 Oc cook time 120 mln

Wt. of crucible Wt. of crucibfe + alphacell. alpha celf Holocelt Actual Fiber (grms) (grms) 0.D. basis ( g m )

3 1.2586 3 1 S995 0.3409 89 OS0 3 1.0903 3 1.4224 0.332 1 89 0.48 25,1713 25.52 19 0.3506 89 0.52

M.C.4+85%

60 days field cook temp 140 Oc cook tlme 160 rnln

Wt. of crucible Wt. of crucible + alphacell. alpha ceIl Holo-call Actual Fiber (WS) ( F S ) (grms) O.D. basis ( g m )

23.9088 24.2266 0.3178 89.33 0.46 23.7673 24,085 0.3177 89.33 0.46 23.6246 23.9787 0.354 1 89.33 O S 1

M.C,=S.SS%

60 days field cook temp 140°c cook tlme 180 min

Wt. of crucible Wt. of crucible + alphacell. alpha cell Holo-ce11 Actual Fiber (8rms) (-1 (gnns) 0.D.basis (grms)

23.7262 24,0589 0,3327 90.03 0.48 24,1447 24,5059 0,3612 90.03 OS2 24.6973 25.0207 0.3234 90.03 0.46

M.C.=5.76%

(%) 68,72 68.88 68,ûû

Average

('w 68,46 69,29 69.05

Average

Alpha cell 0.D. basis

64.70 64.85

Alpha cc11 OeD. basis

Alpha cell O.D. basis

65.65

No.

No.

No.

Appeiidix XII1 (cont'd) *

Alpha-cellulose from the pulp (field study)

90 days field cook temp 155 Oc cook t h e 120 mln

Wt. Of fiber Wt. of crucible Wt. of crucible + alphacell. alpha ceIl Holo-cell Actual Fiber Alpha ce11 Alpha ceil (grms) kms) (grma (grms) 0.D.basis (gms) (%) 0.D. basis 0.3045 3 1,2594 3 1,4993 0,2399 90.73 0.34 7 1 A8 0.5226 3 1,6095 32.0237 0.4142 90.73 0.58 71,91 65.68 0,4575 32 32.363 1 0,363 1 90.73 0.50 72,Ol 65.77

M.C.=8,66% Avctage 65.73

90 days field cook temp 155 Oc cook tlme 150 min

Wt. Of fiber Wt. of crucible Wt. of cmcible + olphacell. alpha ceIl Holo-cc11 Actual Fiber Alpha ce11 Alpha cell (WS) (grms) ( ~ 3 ) (grms) O.D,basis (grms) (%) O.D. basis 0.45 16 3 1 .7647 32.1 1811 0.354 1 91.14 0.50 7 1 A6 67.25 0.5536 3 1.4386 3 1.8776 0,439 91.14 0.6 1 72.27 0.424 3 1.0652 3 t ,399 0.3338 91.14 0.47 7 1.75 67S3

M.C,=S , 89% Avt rage 67.39

90 days field cook temp 155 Oc cook tlme q80 mln

Wt. Of fiber Wt. of crucible Wt. of crucible + alphacell. alpha ce11 Holotell Actual Fiber Alpha cell Alpha cal1 -8) (snns) (gnns) (grms) 0,D. basla (grms) - (%) 0,D. basis 0.4068 30.9772 3 1,2975 0,3203 92,27 0.44 72.65 67.96 0.43 16 30.89 1 31.2314 0.3404 92.27 0,47 72.77 68.08 O ,4924 30.6062 30.99 3 0.3848 92.27 0.53 72.1 1

M.Ce-6.45% Avcraga 68,02

No*

No*

No,

Wt, Of fiber ( w s ) 0.43 19 0.539 1 0,4825

Wt. Of fiber ( s m 0.4229 0.4402 0,4706

Appendix XII1 (cont'd) Alpha-cellulose Crom the pulp (field study)

90 days field cook temp 170 Oc cook tlme 120 min

Wt. of crucible Wt. of cmcible + alphecell. alpha ce11 Holo-ce11 Actuel Fiber ( î P 3 ) (grms) ( p s ) O.Da basis (grms) 3 1.879 32.2 198 0.3408 93.37 0.46

24,562U 24.98 15 0.4187 93.37 0.58 3 1 .O689 3 1.4504 0,3815 93.37 0.52

M.C.d*18%

90 days field cook temp 170 Oc cook t h e 150 min

Wt. of crucible Wt. of crucible + alphaccll. alpha cal1 Holo-cell Actual Fiber (8mg) (srma) @ms) 0.D.basii (gms)

24,9473 25,2764 0.3291 94.89 0.44 22.19 16 22.57 16 0.38 94.89 0.5 1 23.0463 23.45 13 0.405 94.89 0.54

M.C.16.17%

90 days field cook temp 170 Oc cook tlme 180 min

Wt. of crucible Wt, of crucible + alphaceIl. alpha ceIl Holo-ceIl Actual ).'h (grms) ( s n n ~ ) (gms) O.D. basis (gmis)

24,3578 24,6858 0.328 96.06 0.44 31.1391 31,4818 0.3427 96.06 0.46 25.0926 25.46 16 0.369 96.06 0.49

M,C.=5,91%

Alpha cell (%)

73.68 72.52 73.83

Average

Alpha cell (W

74.62 74.72 74.61

Average

Alpha cell (W

74.50 74.78 75.32

Average

Alpha ccll O.D. basis

69.12

Alpha cell O.D. basis

70,02

Alpha ceil 0.D. basis

No.

1 2 3

No.

1 2 3

No.

1 2 3

Wt. Of fiber (gms) 0.4656 0,4697 0.5 193

Wt. Of fibcr (l3 mis) 0,4689 0.6239 0.5009

Wt. Of fibcr (ml 0.4097 0.5935 0.589

Appendix XII1 (cont'd) Alpha-cellulose from the pulp (field study)

90 days field cook temp 140 Oc cook time 120 mln

Wt. of cruciblc Wt. of crucible + alphacell. alpha ccll Holo-cell Actual Fibcr ( 8 w (gms) (gms) 0.D.basis (grms) 23.8773 24,2 136 0.3363 88.17 0.53 24.0022 24.34 14 0.3392 88.17 0.53 30.8 136 31.1877 0.374 1 88,17 0.59

M.C.=l2,87%

90 days field cook temp 140 Oc cook tfme 150 mln

Wt. of crucible Wt. of crucible + alphacell. alpha cell Hoto-ccll Actual Pibcr (PS) (Pm (gnns) O.D. basis (grrns)

23,6494 23,991 1 0.3417 89.56 OS2 23.76 13 24.2 145 0.4532 89.56 0.70 31.8212 32,1797 0.3585 89.56 0.56

M.C+=8,95%

90 days field cook temp 140 Oc cook tlme 180 rnln

Wt. of crucible Wt. of crucible + alphaceIl, alpha cc11 Holo-cell Actual Fiber (F) (gnns) (grms) O.D. buis (grms)

23,5933 23,8854 0.292 1 90.28 0.45 23,8706 24.293 0.4224 90.28 0.66 23,6903 24.1 202 0.4299 90.28 0.65

Alpha ce11

("/O) 63.68 63.67 63S2

Average

Alpha cell (%)

65.26 65 .O6 64.10

Average

Alpha ce11 (W

6437 64.25 65.89

M.C.=S.76% Average

Alpha cell O.D. basis

55.49 55.48

55.48

Alpha ceIl 0.D. basis

59.23 58,36 58.80

Alpha ceIl 0.D. bais

60.66 60.55

60.6 1

No,

Wt. of cmcible (gms)

23.7393 23,7665 2 1.9358

Wt. of crucible (ems) 24,942 23.46

25.0742

Wt. of cruciblc (grma

24.480 1 23.6758 21,5148

Appeiidix XI11 (cont'd) Alpha-cellulose from the pulp (field study)

120 days field cook temp 170 Oc cook tlme 120 mln

Wt. of crucible + holocell. Wt. of crucibletalpha-cell. Wt, Of fiber Alpha-cell. content (sms) ( l V 5 )

24,4063 24.2829 0.7243 75.05 24.4489 24.3 1 06 0,7191 75.66 22,5874 22.5522 0,7114

M.C.=5.40% Average

120 days field cook temp 170 Oc cook time 150 min

Wt. of crucible + holocell, Wt. Of cmcibl&alpha-cell. Wt, Of fibcr Alpha-ccll. content (grmg) (w) (gmis)

25.5972 25,4784 0.70 12 76.50 24,123 24.0006 0,7028 76.92

25.7339 25,6989 0.7 189 M.C.=5,3 1 % Average

120 days fIeld cook temp 170 Oc cook tlme 180 mln

Wt. of crucible + holocell. Wt. Of cmciblstalpha-cell. Wt. Of fiber Alpha-cell. content (-1 (srms)

25.1489 25,0388 0.7 166 77.97 24,3458 24.2229 0,708 1 77.26 22,1827 22,1468 0,7 173

M.C.=5.38% Average

Alpha-cell, content based on O.D,(%)

7 1 .O0 7 1 ,S8

Alpha-cell, content bascd on O.D.(%)

72,44 72,84

Alpha-cell. content bascd on O.D.(%)

73.77 73,ll

No.

No.

No,

Wt. of crucible ( s m î3,74 1 23.7698 2 1,9556

Wt. of crucible

Wt. of crucibla (grma)

24,4823 23.6833 2 1.5402

Appendix XII1 (cont'd) Alplia-cellulose Crom the pulp (field study)

120 days field cook ternp 140 Oc cook tirne 120 min

Wt, of crucible + holocell. Wt. Of crucibk+alpha-celf. Wt. Of fiber Alpha-cell, content ( g W (gms) ( v s ) 24.3937 24,2505 0.7497 67.96 24.42 14 24,2743 0.74 1 1 68.07 22.5681 22,s 195 0.7034

M.C.=10,85% Average

120 days field cook temp 140 Oc cook tlme 150 min

Wt. of crucible + holocell. Wt. Of cruciblc-talpha-cc11. Wt. Of fibcr Alpha-ccll. content (sms) (grms) (srms) 25.5709 25.4228 0.7063 67.80 24,0698 23.9472 0.7036 68.85 25.6873 25.6534 0,7053

MIC.=40.03% Average

120 days field cook temp 140 Oc cook t h e 180 min

Wt. of cruciblo + holoccll. W t Of cruciblo+alphe-ctl1. Wt. Of fiber Alpha-cell. content (gnns) (m) 25.009 0.7552 69.74 24. f 658 0,7026 68.67 22.1409 0.74 17

M.C,-9,96% Average

Alpha-cell, content based on O.il.(%)

60.59 60.69

Alpha-cell. content bascd on O.D.(%)

6 1 ,O0 6 1.94

Alpha-cell, content based on O.DO(%)

62.80 6 1.83

Statistical anaiysb for AlphaeUdose (field study) (Appendix Xm - cont'd) MTB > ANOVA '74 Aiphr-' a Dipl 'T-q Thne.

Facbf Type Levcis values Days fixed 4 30 60 90 120 Temp. f d 3 140 135 170 Time fixai 3 120 150 180

Analysk of Variance for % Alpha-

Source D W Temp. Time Days*Temp. Days*Time Temp. T i e Days%mp.*Tiie

Emr To ta1

Duncan's Mdtipte Range Test for alpha Duncan Gmriping Mean N Days

Duncaa Gnwping Mean N Temp A 66.6235 24 3

Duncan Grouping Mean N r i e A 64956 24 3

Appendix XN Activation energy

Days Tcmp. CC) Caok aime (min) Yield (%) Total fignin (%) La (total lignin)

Appendu XIV (cont'd)

Appendix XV YieId MK digester (pilot sale-Krrift pulping) (field study)

Type of fiber Wt of fiber taken W t On O, D. basis Fi'ber wt(afttrpu1ping) Wt. On O. D. basis yicld (grams) - (grams) (grams) (grams) (W

60 DF 290.72 27249 88998 140.1 1 53.62 Moistwt content of thefiber before puIping = 6 2 7 ?

Moisîure content of the puip a f k = 84205%

Type of fiber Wt of fiber taken Wt. On O. D. basis Fi'ber ~ ( a f t e r pulphg) Wt On O. D. bais yield (grams) (grams) (grams) (%)

90 DF 300.84 28 1 .72 80436 149.97 53.23 Moisturc content of the fiber before pulping = 635%

Moisturt content of the pulp after = 8 1.37%

Me Id after screening Type of fiber Wt of pufp takm Wt. On O. D. basis fulp wt(after d g ) Wt On O. D. basis yield

(grams) (grams) (granis) (gramSI (%) 90 DF Accepts 80456 149.97 T70.84 99.13 66.10 90 DF Rcgccrs 804.56 149.97 225.15 50.84 33.90

Moisture content of the puip beforc s a e d q = 8 137% Moistuh content of the pulp accqts -87.14% Moisturc content of the pulp regccts =7ï.42%

Type of fiber Wt of pulp takcci Wt. ûn O, D. basis Pulp wt(afta d g ) W t On O. D. basis yield (grarns) (grams) (graras) (grams) (Oh)

60 DF Acccpts 889.98 140.1 1 1 170 57 99.1 5 70.76 60 DF Rtgtcts 889.98 140.1 t 183% 40.96 29.24

Mois- coatent ofthc pdp beforc scrœnkg = 84205% Moisturt content of the puip acçcpts 19133% Moisiurc content of tbc pulp ttgtcts "77.61%

Weld after bleaching Type of fiber Wt of puip taken W t On O. D. basis Pulp wt(afticr blcaching) Wt. On O. D. basis yicld

(grams) (grams) (grams) (grsms) (W 60 DF 59032 50.00 249.73 45.62 9124 90 DF 388.80 50.00 223.62 4636 92.72

Moisarrit content of tht pulp More bleachmg for 60 DF = 91 33% MO* c0n-t ofthc bkached p ~ l p fat HI DF = 81.nm

Moïsûm content of the pulp beforc bleaching for 90 DF = 87.14% Moisture content o f the blcachcd puip fat 90 DF = 7927?!

Appendix XVI Lignin MK digester (pilot scale-Kraft pulping) (field study)

60 days field cook temp 170 % cook time 180 min

NO Wt. Of fiber Wt.of crucible Wt. Of the crucible and lignin Lignin Absorbance Dilution Soluble lignin Total lignin (aner oven dry) (0.D. basis) (of filtrate)

(snns.) (sms.) (grma*) (%) (nm) (%) (%)

Moisture contenti4.225%

90 dayi field cook temp 170 Oc cook tlme 180 mln

NO Wt. Of fibcr Wt.of cmcible Wt. Of the cmciblc and lignin Lignin Absorbance Dilution Soluble lignin Total lignin (ancr oven dry) (0.D. basis) (of filtrate)

(smsJ (gms. (gms*) (%) (nm) (%) (%)

Moisture content4.34%

No. Wt. Of fiber Wt. of crucible (wms, (gr@

1 0.6 137 30.92 18 2 0.4027 3 1.858 3 0.602 1 22.1704 4 0.6033 2 1,9223 5 0.6 197 21,501 1 6 0,607 1 3 1.062 1

No. Wt. Of fiber Wt. of cruci ble (md

1 0.6 141 23.7643 0.6062 24,5494 0.6039 23.46 12 0.6 172 25,2199 0.64 12 24.9408 0.6099 31.6501

Appendix XVI (cont'd) Iiolocellulose MK digester ( pilot scale-Kraft pulping) (field study)

60 days field cook temp 170 Oc cook time 180 min

Wt. of crucible + holocell. (gms)

3 1.4778 32.41 56 22.7 18 1 22.47

22,0622 31,6161

Holocellulose based on O.D.(%)

92.34 94.29 YZ.7 1 92.53 92.28 93 .O 1 92.96

90 days field cook temp 170 Oc cook tlme 180 mln

Wt, of cruciblc + holocell. (srms)

24.3277 25.108 24.0 168 25.7837 25.5298 32.2 1 O6

Holoccllulosc bascd on O.f?.(%)

93.39 93,8 1 93.66 92.99 93.5 1 93.55 93.50

Appendix XVI (cont'd) Alpha-cellulose MK digester (pilot scale-Kraft pulping) (field study)

60 days field cook temp 170 Oc cook tirne 180 min

No. Wt. of crucible of cnicible + holc Wt. Of crucible+alpha-ccli. Wt. Of fiber Alpha-cell* content Alpha-cell. content ( 8 m (grnid (~md based on O,D.(%)

1 30.92 1 8 3 1.4778 3 1.363 0.6 137 7 1.89 67.20 2 3 1.858 32.4 1 56 32.2923 0.6027 72.06 67.36 3 22,1704 22,7183 22.68 19 0.602 1 M.C. 4 2 1.9223 22.47 22.3479 0,6033 70.55 65.95 5 21.501 1 22.0622 22.026 1 0.6 197 M.C. 6 3 1.062 1 31.6161 3 1.4969 0.607 1 7 1.62 66.95

66.87 Moisturc contentP6,52%

90 days field cook temp 170 Oc cook tlme 180 min

NO. Wt. of cruciblc of crucible + holc Wt. Of cniciblutalpha-cd. Wt. Of fibcr Alpha-cell. content Alpha-celt. content

(grmg) ( F a (gmd based on O.Da(%) 1 23.7643 24,3277 24.206 1 0,6141 7 1.94 67.37 2 24.5494 25.108 24.9899 0.6062 72.67 6 8 ,O4 3 23.46 12 24.0 f 68 23.8983 0.6039 72.38 67.78 4 25.2 199 25.7837 25.7475 0.6 172 M.C. 5 24.9408 25.5298 25.4927 0.64 12 MC. 6 31.6501 32.2 1 06 32.09 12 0,6099 72.32 67.72

67.73 Moisture content=6.36

Statistical analysis (Appendi XVI - cont'd) cornparison behveen kraft and so& pulp d b

Anow: Two-Factor Witbout Repüatioti

60 DF (S) WDFCK) 90 DF (S)

ANOVA Soum of Vanatim SS df MS F P-value

Rows 25.23557 3 8,411895 3.058461 0.113236 C~~~IIUIS 1701278 2 8506389 3092832 9.1E-IO

Errer 16.502 13 6 1750356

60 DF-B Sh=t#l Shect#2 Shuîü3 ShuW Sheeî#5 SheeM

90 DF-UN Shect#l Shtet#2 S h e d 3 SheeM Sheet#5 Shed6

90 DF-B SheeH1 SheeH2 Shect#3 Sht~t#4 S heeM SheeîM

Appendix XVII Hand-sheet properties

Brigh tnesr (% ISO) (glosry ride) Bulk (cm31g) Bunt index (Kpi.m2/g) Tear index (rnN.rnUg)