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Removing Pectin and Lignin During Chemical Processing of Hemp for Textile Applications
H.M. Wang, R. Postle, R.W. Kessler and W. Kessler
Textile Research Journal 2003 73: 664
DOI: 10.1177/004051750307300802

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664

Removing Pectin and Lignin During Chemical Processing of Hemp

for Textile Applications
H. M. WANG AND R. 1
POSTLE
Faculty of Science, University of New South Wales, Sydney 2052, Australia

R. W. KESSLER AND W. KESSLER

Institut für Angewandte Forschung, University of Applied Science, Reutlingen 72762, Germany
ABSTRACT
Pectin and lignin are both very important noncellulosic substances occurring in hemp
fibers. The main task in preparing hemp fibers for textile applications is to remove these
noncellulosic substances without damage to the fiber cellulose. Pectin and lignin in hemp
before and after chemical processing are characterized by infrared spectroscopy. The
influence of chemical processes, fiber regions, and alkaline boiling parameters on lignin
and pectin removal are investigated in this paper. The results indicate that the alkaline
boiling process is effective for removing pectin and lignin. There is no residual pectin in
the fibers after the alkaline treatment, but there is a residual level of lignin. The
concentration levels of both sodium hydroxide and sodium sulphite have significant
effects on lignin removal, and there are variations in lignin properties and accessibility
from the lower to the upper regions of the hemp stem.

Bast fiber plants tend to be ideal candidates for non-
food organic production [20). The impetus for renewed
interest in bast fibers arises mainly from ecological con-
terns, environmental safety, future resource balance, po-
tential growth of bast fiber production, and future de-
mand for clothing and food [15J.
With this renewed interest in bast fibers, hemp has
recently been undergoing a revival worldwide as a fast
growing natural source of fibers [ 18]. The predominant
task in preparing these fibers is to remove noncellulosic
substances in the bast without damage to the fiber cellu-
lose.
. The chemical composition of the bast layer of these
plants has been analyzed by numerous researchers using
a variety of test methods. In raw hemp bast, there is about
67.0%-78.3% cellulose, S.5%-16.1 % hemicellulose,
0.8%-2.5% pectin, 2.9%-3.3% lignin, and some fats and
waxes in the fibers [2]. Differences in the chemical
composition data may be caused by the species and the
test methods used.
Cellulose is the principal constituent of fiber ultimates
that constitute the framework of the cell wall structure.
Pectin is considered to be the main binder and is rich in
the primary wall and middle lamella [7]. Pectin com-
1
Corresponding author, Room 525, Heffron Building, phone: 0061-
2-93854474, fax: 0061-2-93855953.
prises pectic acids and pectic salts in such forms as
calcium, magnesium, and iron salts [ 16].
Lignin is the encrusting substance gluing the fiber
cells together and providing rigidity to the cell wall 1171.
It can be found in the middle lamella and the secondary
layer of the fibrils. The nature of lignin has not yet been
revealed clearly. The presence of both lignin and pectin
in hemp fibers is highly related to fiber properties after
fiber preparation. Therefore, pectin and lignin removal
has usually been investigated for fiber processing.
Traditionally, bast fibers are retted by dew or warm
water and mechanically prepared for a particular bast
fiber textile processing system, such as the wet spinning
system for flax. There are some obstacles to retting bast
fibers. Considering fiber value added by a better price/
performance ratio, this processing system is not encour-
aged in industry today [ 10].
Enzyme retting was developed for flax in the 1980s [ 1,
5, 6]. Although several commercial enzyme products
have been introduced for retting bast fibers and fabric
treatment [3, 19], no reported commercial enzyme retting
process exists on a large scale for industrial operations.
In addition, lignin removal is difficult during enzyme
retting.
Chemical and mechanical processing of bast fibers is
effective for removing noncellulosic substances and can
also balance the quality fluctuations of raw materials.

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 665
i
The introduction of the steam explosion process for flax representing the
particular hemp variety grown in Aus-
and hemp facilitates the direct use of degummed fibers tralia [ 15], employed for the experiments. From the
was
for standard textile processing systems, such as the cot- experience of bast fiber processing, it is not necessary to
ton or wool spinning systems [8, 10]. In this paper, we use peroxide bleaching for raw
hemp, in which case the
investigate the effects of other chemical processes on fibers coated with noncellulosic substances. There-
are
pectin and lignin removal based on a series of experi- fore, incomplete randomized block design was used
an
mental studies. here for the experiments [ 13]. There are four blocks with
two treatments in block 1 and block 3 and three treat-

Experimental ments in block 2 and block 4 (as shown in Table II).

I
RAW MATERIALS AND CHARACTERIZATION
/
I
We selected two nonretted hemp varieties for the TABLE 11. Design of the chemical processing scheme.’
experiments. One variety, called Kompolt (AH 1 ), is a
novel, semi-tropical variety created by crossing Euro-
pean females with Indian and Chinese male plants. It was
grown at Quirindi, on the black self-mulching loam of
the Liverpool Plains in northern New South Wales, Aus-
tralia. This hemp variety was planted in November and ’
Note: S represents acid scouring, B alkali boiling process, and W
harvested by machine in early April the following year at
hydrogen peroxide bleaching.
the time of male flower maturity. The other hemp variety
is Qingshuima (CH), planted in Qingshui County of
Gansu, China. The sowing date was at the end of April,
/) jI
Sulphuric acid, which is a relatively cheap and safe
and it was harvested by hand pulling at the end of August
reagent, was used for acid scouring at a normal indoor
of the same year, at which time the male plants began
temperature (20°C). The H2SO4 concentration was about
flowering. Hemp fiber maturity is specified by the image 1.5 g/L and treatment time was 30 minutes. Sodium
analysis system in terms of the ratio of the cell wall area hydroxide and some surfactants were mainly used for the
to the fiber section area. The number of fibers observed
boiling process. The NaOH concentration was 1.8%,
was over 800 for each sample. The results are listed in
sodium silicate (water glass) ’ concentration was 4.5%,
Table I, showing the maturity of the two hemp varieties and sodium lauryl sulphate was 0.08%. The temperature
as very similar.
was 120°C at 0.2Mpa pressure and the
boiling time was
50 minutes. Hydrogen peroxide (30%) was used for the

TABLE I.
bleaching treatment at a concentration of 6mVL. 2gAL
Maturity of the raw hemp varieties selected.a
sodium hydroxide, 2m1/L sodium silicate, and 0.08 so-
dium lauryl sulphate. The temperature was 95°C and the
bleaching time was 45 minuteg.

a
Variation of Lignin Along the Bast Stem
Note: r =
raw hemp, M =
Maturity.
Considering the height of the hemp stems, we inves-
tigated variations of lignin content along the stems for
The pectin and lignin contents of the hemp fibers the alkaline boiling process. Three sections, top, middle,
before and after processing were specified by IR-spec- and bottom, each constituting a third of the stem, were
troscopy, and the relative spectroscopic units as &dquo;pectin&dquo; sampled from the Chinese hemp variety CH for these
and &dquo;lignin&dquo; are defined for the measurements [8, 9]. experiments (because it is easy to identify the fiber
Milled samples were used, with five observations for regions after harvesting).
each sample. A unique alkaline boiling scheme was designed:
NaOH solution concentration was 1.8°~, the sodium sil-
EXPERIMENTAL DESIGN icate solution (water glass) was 4.5%, and sodium lauryl
Chemical Processes
sulphate was 0.08%. The temperature was 120°C under
0.2Mpa pressure and the boiling time was 50 minutes.
Different chemical processes including acidic scour- The samples were denoted CHtB for the top region,
ing,alkaline boiling, and peroxide bleaching were in- CHmB for the middle region, and CHbB for the bottom
volved in this design. The Australian hemp variety AH1, region of the bast.
i
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 666
Alkaline Boiling Process for Australian
Hemp
Variety AHI
In order to investigate the effects of alkaline boiling on
pectin and lignin removal from hemp, the central com-
posite design (CCD), representing the most frequently
used response surface methodology, was introduced for
twenty-eight experiments, of which there were three
groups of design points. These three groups were a
two-level factorial design, axial (star) points, and center
points [ 14].
For the alkaline boiling process, there were four vari-
able parameters involved in the design, that is, sodium
hydroxide, sodium carbonate, sodium sulphite, and treat-
ment time. The design scheme is shown in Table III.
TABLE III. Design points of the factors for the alkali boiling
The order of the experiments was randomized by the
program. Surfactants in all experiments were 4.5% so-
dium silicate and 0.08% sodium lauryl sulphate. The
treatment temperature was maintained at 120°C at
0.2Mpa pressure. The Australian grown hemp variety
AH 1 was used for all experiments, and samples were
denoted from AH 1 B 1 to AH 1 B28.
Results and Discussion
INFLUENCE OF CHEMICAL PROCESSES ON PECTIN
LIGNIN CONTENT
&dquo;
~
Both pectin and lignin in hemp bast are targeted for
removal during the extraction of hemp fibers. The quan-
tity of lignin and pectin removed with processing de-
pends on the application or end use. From the viewpoint
of pectin and lignin chemistry, it is much easier to
remove pectin than to remove lignin with chemical meth-
ods when considering prevention of chemical damage to
cellulose.
The pectin in hemp bast can be totally removed when
the alkaline boiling process is integrated into the chem-
ical procedure (as shown in Table IV). However, acid
scouring does not help to remove any pectin, but tends to
form a cross linkage between the pectin molecular chains
so that more residual pectin is evident in the sample after
acid scouring.
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TABLE IV. Average and standard deviation pectin and lignin content
levels of hemp samples after chemical treatments.
’
Unlike pectin, the lignin in the hemp bast is very
difficult to remove. Table IV shows that there is residual
lignin in all samples, even though all the treatments can
degrade lignin to some extent. It is evident that there are
some strong carbon-carbon linkages and other chemical
process. groups such as aromatic groups, which are very resistant
to chemical attack, so that degradation or fragmentation
of lignin is very limited.
Table IV also shows that alkaline boiling is more
efficient at removing lignin than is acid scouring. Hy-
drogen peroxide bleaching after alkaline boiling removes
more residual lignin from hemp fibers. However, acid
scouring appears to provide assistance to alkaline boiling
or hydrogen peroxide bleaching in order to remove or
degrade lignin when it is integrated into the procedure
before boiling or bleaching. Examples include sample
AH 1 SB in contrast to sample AH 1 B, and AH 1 SB W in
contrast to AH 1 BSW. The explanation for this effect of
acid scouring may be that the acid reagent slightly swells
the cellulose in the amorphous regions of the fiber to
increase the accessibility of the alkaline or peroxide
reagents into the secondary layer of cellulose.
AND
VARIATION OF LIGNIN ALONG THE STEM
The pectin content in the fibers is reduced to zero after
alkaline boiling for hemp fibers obtained from all three
regions of the stem. Unlike pectin, the lignin content
levels for the three regions of the stem are all reduced to
a certain residual level after alkaline boiling. As shown
in Table V, there is a level of residual lignin in the fibers
obtained from the top similar to that from the middle of
the stem, but there is more residual lignin in the fibers
from the bottom region.
The lignin content in the raw hemp is lowest in the
middle region of the stem. Much more lignin is removed
from the top part of the stem than from the middle or the
bottom regions: about 41 % from the top region, 11 %
from the middle, and 23% from the bottom of the stem.
Apparently, the removal levels of lignin for fibers from
the three regions of the stem are quite different.
 667

TABLE V. Average and standard deviation pectin and lignin content

ofhemp fibers in different regions of the stem.’

’’
Note: r represents nonretted hemp bast. B after the boiling process,
t the top fiber region, m the middle fiber region, and b the bottom fiber
region.

The results indicate that there exist some differences

in the constitution and structure of the lignin from the
three regions of. the hemp stem, which may result from
hemp growth or bast storage. Furthermore, the results
show that in terms of chemical degradation in hemp bark,
there is also variability or heterogeneity of lignin in
terms of both morphological and chemical characteristics
[ 12].
FIGURE 1. Diagnostic plot of the normal probability of Studentized
INFLUENCE OF ALKALINE BOILING PARAMETERS residuals for the response model of lignin removal

We introduced response surface analysis to analyze !

the results of the experiments designed by the cco.
According to these results, there exists a quadratic re-
sponse model to calculate residual lignin (as shown in
Table VI).
Post-ANOVA results indicate that residual lignin is
dominated by alkaline processing variables involved in
the design scheme. There are strong interactions of so-
dium hydroxide with sodium sulphite and of sodium
sulphite with treatment time for residual lignin (as shown
in Table VI).
The diagnostic analysis of the studentized residuals
has proved that the chosen model is satisfactory for the
data (as shown in Figure 1 ). The significant effects of the
variables on the residual lignin according to the calcula-
tions of the model are exhibited in Figures 2-4.
The interaction of sodium hydroxide with sodium
sulphite indicates that at increasing concentration levels,
both chemicals can remove lignin effectively. A suffi-
cient amount of sodium
sulphite is necessary to assist
sodium hydroxide to remove lignin (as shown in Figure 2).
As an assistant, sodium sulphite is also able to shorten
the boiling time to remove lignin from hemp fibers. The
interaction of these two boiling variables shows that
when a high-level concentration of sodium sulphite is
used, a long boiling time is unnecessary for removing
lignin (as shown in Figure 3). A long boiling time can
also reduce lignin, but this resuh is no more significant
than the effect of sodium hydroxide (as shown in Figure 4).
Once again, we have shown that pectin is totally
removed after the alkali boiliing process, even at the
lowest sodium hydroxide concentration. However, the
results also show that lignin cannot be totally removed
by the alkali process within the design range in this work
for textile applications of hemp.
There is an evident tendency for the residual lignin
level to be reduced by increasing the severity of the alkali

TABLE VI. Response model equations and significant variables

a
I
Note: A represents the concentration level of sodium hydroxide in the solution. B sodium carbonate, C sodium sulphite. and D treatment time.
Prob. > It! represents the probability of seeing the absolute value of the observed t-value if the null hypothesis is true. The associated p-values
(&dquo;Prob. > III&dquo;) indicate significant coefficients in the model. Small values of p with the variables indicate significant model terms. The significant
level is set at 5% in this work.

i ’

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668

FIGURE 2. Interaction of sodium hydroxide and sodium sulphite for

residual lignin (sodium carbonate concentration and treatment time are
maintained at the middle levels of their respective ranges). FIGURE 4. Effects of sodium hydroxide and boiling time on residual
lignin (sodium carbonate and sodium sulphite concentrations are main-
tained at the middle levels of their respective ranges).

boiling process. Accordingly, the lignin residual level in

the fibers decreases by increasing the concentrations of
sodium hydroxide and sodium sulphite or by maintaining
a long treatment time. (Although this procedure may not
be appropriate for other fiber properties such as length
and mechanical properties, processing could be further penetration energy.
optimized in relation to these fiber properties.)
Sodium hydroxide plays the critical role of removing
lignin due to alkaline cleavage of ether linkages in the
lignin, which may be accompanied by condensation re- with increasing sodium hydroxide concentration.
actions [ 12]. According to Klemm et al. [ 11 ], for rela-
tively low concentrations of sodium hydroxide, so-called ing chemical
monomolecular water is formed in the solution system.
This water paves the way for penetration of the ion
dipoles of sodium hydroxide, which increase with alka-
line concentration. The depth of this penetration expands
at high concentrations of sodium hydroxide. Meanwhile,
the high temperature can provide the ions with high
In this way, sodium hydroxide can
attack both pectin and lignin due to the contact between
them. As a result, pectin is completely attacked without
any residue being left in the hemp fibers after alkaline
boiling. Residual lignin and other impurities decrease
Sodium sulphite may facilitate alkaline cleavage dur-
processing (as shown in Figure 2)~, and it
can also shorten the treatment time in terms of lignin
removal (as shown in Figure 3). These effects are caused
by the sulphite group SO;-, which is introduced into the
lignin side chains for sulphonation, so lignin quickly
dissolves in the alkaline solution [4].
A certain residual lignin level in the milled hemp fiber
samples indicates that some lignin in the fibers could not
be accessed or degraded by the chemicals during alkali
boiling. The lignin in the middle lamella may be ac-
cessed and degraded, and as a result the fibers are prop-
erly separated. Lignin in the cell secondary layers, how-
ever, may not be accessed because of the restriction of
primary cell layers or the swelling limit of cellulose.

FIGURE 3. Interaction of sodium sulphite and boiling time for residual
lignin (sodium hydroxide and sodium carbonate concentrations are
maintained at the middle levels of their respective ranges).
Conclusions
Chemical processing is an effective method for re-
moving pectin and lignin from hemp fibers. The alkaline
boiling process is very important in preparing hemp
fibers for textile applications from the viewpoint of pec-
tin and lignin removal. Acid scouring does not appear
satisfactory to remove pectin and lignin. Peroxide

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bleaching may remove lignin and also increase fiber
whiteness.
There exist differences in the quantity, constitution,
and structure of lignin in the top, middle, and bottom
regions of the CH (Chinese grown) hemp stem. Lignin in
the top of the hemp stem is more easily removed by
alkaline boiling than lignin in the middle region. Resid-
ual lignin in the bottom region of the stem is the most
difficult to remove with alkaline boiling of the three
regions of the bast stem.
Pectin can be totally removed without any residue in
the fibers through alkaline boiling, but lignin cannot be
totally removed. There is always a certain residual
amount of lignin left in hemp fibers, even when acid
scouring and peroxide bleaching are integrated in the
chemical process or when high concentrations of sodium
hydroxide and sodium sulphite are used in alkaline boil-
ing. For alkaline boiling, sodium hydroxide concentra-
tion is the dominant variable for removing pectin and
lignin. Sodium sulphite can assist sodium hydroxide to
remove further lignin from hemp and shorten the treat-
ment time.
ACKNOWLEDGMENTS
We thank the Australian government for offering the
International Postgraduate Research Scholarship to
Huimin Wang to undertake this project at The University
of New South Wales. We greatly appreciate the support
of Dr. A. Katelaris for providing the Australian hemp
samples grown in New South Wales. Also, many thanks
are due to Dr. K. Hegerhost and Mrs. Barac of the
University of Applied Science, Reutlingen, Germany, for
their assistance with the pectin and lignin measurements.
Literature Cited
1. Akin, D.E., Dodd, R. B., Perkins, W., Henriksson, G., and
Eriksson, K. E., Spray Enzymatic Retting: A New Method
for Processing Flax Fibers, Textile Res. J. 70
(6), 486-494
(2000).
2. Batra, S. K., "Other Long Vegetable Fibres, Handbook of
Fibre Chemistry," Menachem Lewin and Eli M. Pearce.
Eds., Marcel Dekker, NY, 1998, p. 530.
3. Buschle-Diller, G., Zeronian, S. H., Pan, N., and Yoon,
M. Y., Enzymatic Hydrolysis of Cotton, Linen. Ramie, and
Viscose Rayon Fabrics, Textile Res. J. 64(5), 270-279
( 1994).
4. Gellerstedt, G., Pulping Chemistry, in "Wood and Cellu-
losic Chemistry," 2nd ed., D. N. S. Hon and S. Nobus,
Eds., Marcel Dekker, NY, 2001, pp. 859-905.
5. Henriksson, G., Akin, D. E., Rigsby, L. L., Patel, N., and
Eriksson, K. E. L., Influence of Chelating Agents and
Mechanical Pretreatment on Enzymatic Retting of Flax,
Textile Res. J. 67
(11), 829-836 (1997).
Downloaded from trj.sagepub.com at UNIV OF CHICAGO LIBRARY on May 15, 2014
669
6. Henriksson. G., Akin, D. E., Slomczynski, D.. and Eriks-
son, K. L., Production of Highly Efficient
Enzymes for
Flax Retting by Rhizomucor Pusillus, J. Bioterhnol. 68,
115-123 (1999).
7. Ishii, T., and Shimizu, K., Chemistry of Cell Wall
Poly-
saccharides, in "Wood and Cellulose Chemistry," D. N. S.
Hon and S. Nobus, Eds., Marcel Dekker. NY, 2001, pp.
175-212.
8. Kessler, R. W., and Kohler, R., New Strategies for Ex-
ploiting Flax and Hemp, Chemtech (12), 34-42 (1996).
9. Kessler, R. W., Nebel, K., and Werner. H., Adaptive
Chemical Processing for Tailor Made Traditional Linen, in
"Proc. 1 st Nordic Conference on Flax and Hemp Process-
ing," Tempere, Finland. August 10-12, 1998.
10. Kessler. R. W., Kohler, R., Mayer, G., and Tubach. M..
New Economical Chances for Flax and Hemp by Fibre
Upgrading. in "Proc. 3 rd International Symposium on
Bioresource Hemp and Other Fibre Crops," Wolfsburg.
Germany, September 2000, pp. 13-16.
11. Klemm, D., Philipp, B., Heinze, T., Heinze, U., and
Wagenknecht. W., "Comprehensive Cellulose Chemistry,
Vol. 1, Fundamental and Analytical Methods," Wiley-
VCH, Weinheim, Germany, 1998, pp. 56-58.
12. Lai, Y. Z., Chemical Degradation, in "Wood and Cellulo-
sic Chemistry," 2nd ed., D. N. S. Hon and S. Nobus, Eds.,
Marcel Dekker, NY. 2001, pp. 443-501.
13. Mendenhall, W., and Sincich, T., "Statistics for Engineer-
ing and the Sciences," Prentice Hall. NJ. 1995. pp. 80-84.
14. Montgomery, D. C., Runger, G. C., and Hubele, N. F.,
"Engineering Statistics," John Wiley & Sons, NY. 1998, p.
35.
15. Postle, R., and Wang. H. M.. The Quality and Mechanical
Properties of Hemp after Chemical Processing, in "Proc.
Conference of Bast Fibrous Plants on the Turn of Second
and Third Millennium," Shengyang, China. September
18-22, 2001.
16. Rihouey, C., Jauneau, A., Cabin-Flaman, A., Demarty, M.,
Lefebvre, F., and Morvan, C.. Calcium and Acidic Pectin
Distribution in Flax Cell Walls: Evidence for Different
Kinds of Linkages in the Cell Junction and Middle Lamella
of the Cortical Parenchyma of Flax Hypocotyl, Plant
Physiol. Biochem. 33,497-508 (1995).
17. Saka, S., Chemical Composition and Distribution, in
"Wood and Cellulose Chemistry," 2nd ed., D. N.-S. Hon
and S. Nobus, Eds., Marcel Dekker, NY. 2001, pp. 51-79.
18. Struik, P. C., Amaducci, S., Bullard. M. J.. Stutterheim.
N. C., Venturi, G., and Cromack, H. T. H., Agronomy of
Fibre Hemp ( Cannabis sativa L.) in Europe. Ind. Crops
Prod. 11, 107-118 (2000).
19. Van Sumere, C. F., Retting of Flax with Special Reference
to Enzyme-retting, in "The Biology and Processing of
Flax," S. H. H. Sharma and C. F. Van Sumere, Eds., M
Publications, Belfast, Northern Ireland, 1992, pp. 157-198.
20. Waayer, N., Hemp and Organic Textile Production. J. Int.
Hemp Assoc. 2(1). 23 (1995).
Manuscript recen~ed August 7. 2002; ac(,epted Novtmber 22. 2002.