chemical composition of jute (corchorus capsularis fibers used … conferences/2009-delrio-j… ·...
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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