Chemical composition of jute (Corchorus capsularis) fibers used for paper pulp manufacturing

J.C. del Río1,, G. Marques1, J. Rencoret1 J. Jiménez-Barbero2,Á.T. Martínez2, A. Gutiérrez1

1IRNAS-CSIC, Seville, 2CIB-CSIC, Madrid, Spain

Wood

The main rawmaterial for paperpulp manufacturingin developedcountries

Conifers

Hardwoods

(pine, spruce, etc.)

(eucalypt, birch, aspen, etc.)

Eucalypt plantation

In developedcountries are usedfor manufacturingspecialty papers

Herbaceousplants

The main rawmaterials for paperpulp manufacturingin developingcountries

Flax crop

(wheat straw, bagasse, etc.)

Raw materials for papermaking

Papers for electronic circuits

Tea bags

Cigarette papers

Filter papers

Decorative papers

Vacuum bags

Aplications of nonwood fibers

Specialty papers include tea bags, filter papers, decorative papers, cigarettepapers, bank notes, securitypapers…

Nonwood fibers from herbaceous plants

Flax (Linum usitatissimum)

Hemp (Cannabis sativa)

Kenaf (Hibiscus cannabinus)

Jute (Corchorus capsularis)

Sisal (Agave sisalana)

Abaca (Musa textilis)

IndiaIndia

BangladeshBangladesh

Jute plantationJute plantation

Green jute stem

Retted jute stem

stemsstems

Jute (Corchorus capsularis)Jute (Corchorus capsularis)

Jute fibersJute fibers

Jute sticksJute sticks

carpets

ropes

bags

yarns

coasters

Applications of jute fibers

carpets

ropes

bags

yarns

coasters

Applications of jute fibers

Paper products

Due to its porosity, this material can be used for applications like special filters for tea bags or high porosity cigarette papers

Tea bags

cigarette papers

Specialty papersApplications of jute fibers

The aim of this work is the chemical characterization of jute

(Corchorus capsularis) fibers used for manufacturing of

high quality paper pulp, in order to improve the industrial

processes in which they are used as raw materials…

Composition of lignocellulosic materials

Celullose

(lateral view)

Hemicelluloses

(lateral view)

Lignin

(axial/lateral view)

Lipids

withwith specialspecial emphasisemphasis in...in...

... the LIPIDS (responsiblefor pitch deposition) ...

... and LIGNIN (influencesdelignification and pulp yield) ...

Very low ash content, in contrast to other herbaceousfibers such as rice straw(18.2%) or wheat straw (6.9%)

According the general chemicalcomposition, a priori, jute fibers seemsuitable for paper pulp manufacturing

High content on polysaccharidesand low lignin and extractivescontent

General composition of jute bast fibers

Component (%)

Holocellulose 81.6

α-cellulose 61.0

Hydrosolubles 1.0

Klason lignin 13.3

Acid-soluble lignin 2.8

Lipophilic Extractives 0.4

Ash 1.0

Component (%)

Holocellulose 81.6

α-cellulose 61.0

Hydrosolubles 1.0

Klason lignin 13.3

Acid-soluble lignin 2.8

Lipophilic Extractives 0.4

Ash 1.0

Lignin structure

Composition of lipids

W42

W46

W48W50

W52 W56W54

W58W44

Ah34

Ah32

Ah30

Ah28

Ah22 Al29Fa16

Fa18:1+

Fa18:2Fa18

Fa22

O

O

OH

O

OH

O

OHOH

OHO

OH

O

OH

Jute (Corchorus capsularis) fibers

Lipid composition

5 10 15 20 25 30Retention time (min)

GC/MS

W42

W46

W48W50

W52 W56W54

W58W44

Ah34

Ah32

Ah30

Ah28

Ah22 Al29Fa16

Fa18:1+

Fa18:2Fa18

Fa22

5 10 15 20 25 30

epoxydammarane

Retention time (min)

O

Isomultiflorenone

O

Bauerenone Epoxydammarane

O

OH

HOR

R

campesterol

HO

Campesterol

sitosterol

SitosterolHO

stigmasterol

StigmasterolHO

Jute (Corchorus capsularis) fibers

Lipid composition

GC/MS

Waxes

C atom number

Rel

ativ

eab

unda

nce

100%

42 44 46 48 50 52 54 56 58C atom number

25 27 29 31 33 35

n-Alkanes

Rel

ativ

eab

unda

nce

100%

Free n-Fatty acids

C atom number

Rel

ativ

eab

unda

nce

100%

14

18:2

18:1 1816 20 22 24 26 28 30 32 34 16 18 20 22 24 26 28 30 32 34 36 38 40

Free n-Fatty alcohols

C atom number

Rel

ativ

eab

unda

nce

100%

Distribution of the main aliphatic series identified in the extracts of jute fibers

Predominance of high molecular weight ester waxes !Predominance of fatty acids, including α- and ω-hydroyfatty acids !Low content of free and conjugated sterols !

13.5Diglycerides

7.5Monoglycerides

181.2Ester waxes

8.4Steryl glycosides

25.1Steroid/triterpenoid ketones

3.1Tocopherols

64.8Epoxydammarane-type triterpenoids

43.4Sterols

16.1Steroid hydrocarbons

127.0n-Fatty alcohols

34.5ω-Hydroxyfatty acids

102.8α-Hydroxyfatty acids

130.2n-Fatty acids

48.5n-Alkanes

Abundance(mg/Kg)

Series of Compounds

Composition and abundance of the lipophilics in the extracts of jute fibers

The low amounts of neutrals in jute fibers, particularly the low abundances of free and conjugated sterols, which have a high propensity to form pitch deposits,

would point to a low pitch deposition tendency of the lipophilics from jute

Neutrals

dissolved(fatty acid soaps)

hydrolyzed during alkaline cooking

survive cooking(pitch deposition)

13.5Diglycerides

7.5Monoglycerides

181.2Ester waxes

8.4Steryl glycosides

25.1Steroid/triterpenoid ketones

3.1Tocopherols

64.8Epoxydammarane-type triterpenoids

43.4Sterols

16.1Steroid hydrocarbons

127.0n-Fatty alcohols

34.5ω-Hydroxyfatty acids

102.8α-Hydroxyfatty acids

130.2n-Fatty acids

48.5n-Alkanes

Abundance(mg/Kg)

Series of Compounds

Behaviour of the lipophilic compounds of jute fibers during alkaline pulping

Fatty acids

Klason lignin content: 13.3%

2D-NMR (inter-unit linkages, H:G:S)Thioacidolysis (linkages, units involved)

Jute (Corchorus capsularis) fibers

Lignin composition

Py-GC/MS (H:G:S)

Ball-milled fiber

Dioxane/water extraction

MWL lignin

Björkman protocol

% H 2% G 32% S 66

S/G 2.1

Retention time (minutes)5 10 15 20 25 30 35

Py-GC/MS

OH

O

OMeMeOS

OHOMeMeO

S

OHOMeMeO

S

OHOMeMeO

S

OHOMeMeO

O

S

OHOMeMeO

S

OH

OH

OMeMeOSOH

OH

OMeG

OHOMe

G

OHOMe

G

OHOMe

G

OHOMe

O

G

carbohydrates

levoglucosane

Jute (Corchorus capsularis) fibers

Lignin composition

jute ligninsimilar to a

hardwood lignin!

(b)100

105

110

115

120

125

130

7.5 7.0 6.5 6.0

δC

δH

-OMe(a)

5.5 5.0 4.5 4.0 5.5 3.0

55

60

65

70

75

80

85

90

δC

δH

Aβ(S)

Aγ

Aβ(G)

Aα

A

O

O

HO

HO

H3CO

165

43

2

2'

6'5'4'

3'

1'

αβ

γ

OCH3

H3CO OCH3

Bβ

Bγ

Bα

B

O

O

O

O

α'

β'

γ'α

β

γOCH3

OCH3

H3CO

OCH3

5'

3'2'1'

6'

4'

65

43

21

Cβ

Cα

C

α

βγ

OHO

O

OCH3

OCH3

H3CO

3'

1'6'5'

4'

2'

65

4 3

21

Fγ

F

O

OH

165

43

2

αβ

γ

H3CO OCH3

Dβ

Dα

Dα'

DO

OCH3

Oα

β

γ OAr

OHHO

O

1'6'

5'4'

3'

2'

α β'

γ'

165

4 32

OCH3

H3CO

H3CO

'

A'γ

A'

O

O

O

HO

H3CO

αβ

γ

OCH3

H3CO OCH3

O

165

43

2

2'

6'5'4'

3'

1'

(b)100

105

110

115

120

125

130

7.5 7.0 6.5 6.0

δC

δH

(a)

5.5 5.0 4.5 4.0 5.5 3.0

55

60

65

70

75

80

85

90

-OMe

δC

δH

Aβ(S)

Aγ

Aβ(G)

Aα

Bβ

Bγ

Bα

Cβ

Cα

Fγ Dβ

Dα

Dα'

A'γ

S'2,6

S''2,6

S'

OH

Oα

OCH3CH3O

165

4 3

2

S''

O

Oα

HO

OCH3CH3O

165

4 3

2

S2,6 S

CH3O

O

OCH3

OH

165

4 3

2

α

G2

G6

G5

O

OCH3

OH

165

4 3

2

α

G

Linkage relative abundance (% of side-chains involved) β-O-4' linked units (A/A') 72 Resinols (B) 16 Phenylcoumarans (C) 4 Spirodienones (D) 4 p-Hydroxycinnamyl alcohols (F) 4 Erythro/threo ratio 3.5 Percentage of γ-acetylation 4 S/G ratio 2.0

Structural characteristics from integration of signals in the HSQC spectra of the MWL from jute (C. capsularis) fibers

Jute lignin very similar to that in eucalypt wood !!!

•High content of β-O-4´aryl ether linkages

•High S/G ratio

Advantageous for delignification

DimersMonomers

5 10 15 20 25

6 7

8

910 11 12

13

14

15+16

17+18

20

21+22

23

24+25

26+27 30

IS

29

Retention time (minutes)

R1 R2

OH

R3

H

G

S

CH3O

R3

CH3O

OH

HO R2

R1

β-β´

β-1´

CH3O

CH3OOH

OHR2

R1

R3

OCH3

OH

OHR1

R2

CH3O

β-5´

4-O-5´

OOCH3

OCH3

OH

R

Isochroman

OR1

HO

OH

OCH3

OCH3

R2

5-5´

OCH3CH3O

OH

OH

R1

R2

Thioacidolysis (followed by Raney Ni desulphurization)

5-5' 4-O-5' β-1' β-5' β-β' β-1’/α-O-α'

GG GG SG GG SG SS GG SG SG SS GG SG SS

10 4 8 2 4 9 7 17 4 31 1 1 2

Relative molar percentages of the different dimer types released after thioacidolysis and Raney-nickel desulphuration of jute MWL

Resinol structures are made almost exclusively of syringaresinol, pinoresinol being completely absent !

(similar results found in eucalypt lignin, Rencoret et al. 2008 Holzforschung, 62:514)

7.5 10.0 12.5 15.0 17.5 minutes

Tetralin dimers

21

23

26a

b

c

Tetralin trimers

TMSiO

CH3O

CH3O

CH3O

OCH3

OTMSi

TMSiO

TMSiO

CH3O

CH3O

CH3O

O

OCH3

OCH3

S-β-β'-S'-4'-O-5''-G'' linkages

Lignin trimers identified among the thioacidolysis products (after Raney Ni desulphurization)

Reconstructed Ion Chromatogram (sum of ions at m/z 532 and m/z 696, from tetralin dimers and trimers)

Jute (Corchorus capsularis) fibers

- High content of hollocellulose (andα-cellulose) and low content of ash,appropriate raw material for pulp andpapermaking!

- Low lipid content, low content of neutrals,in particular free and conjugated sterols,low pitch deposition tendency!

- Low lignin content, with high S/G ratio, ahigh abundance of β-O-4 linkages and alow content of condensed structures,easily delignifiable!

Main Conclusions

Jute fiber is an excellent raw material for pulp and papermaking !

CONCLUDING REMARKSCONCLUDING REMARKS

The chemical characterization of these fibers offers valuable information for improving the cooking and bleaching processes. This knowledge will contribute to a better

sustainable industrial utilization of this interesting lignocellulosic material of important socioeconomic interest

The chemical characterizationchemical characterization of these fibers offers valuable information for improving the cooking and bleaching processes. This knowledge will contribute to a better

sustainable industrial utilizationsustainable industrial utilization of this interesting lignocellulosic material of important socioeconomic interestsocioeconomic interest

Gisela MarquesGisela Marques

Jorge RencoretJorge RencoretSete MolinaSete Molina Ana GutiérrezAna Gutiérrez

Göran GellerstedtGöran GellerstedtAngel T. MartínezAngel T. Martínez

PostDoc Position available

Contacts:José C. del Río or Ana Gutiérrez

IRNAS, Seville, Spain

ACKNOWLEDGEMENTSACKNOWLEDGEMENTS

Jiebing LiJiebing Li