Industrial Crops and Products 34 (2011) 865872

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Industrial Crops and Products
j our nal home page: www. el sevi er . com/ l ocat e/ i ndcr op
Upgrading of hemp core for papermaking purposes by means of
organosolv process
L. Barber
a
, M.A. Plach
a,
, I. Prez
b
, J. Puig
a
, P. Mutj
a
a
Grupo LEPAMAP, Departamento de Ingeniera Qumica, Agraria y Tecnologa Agroalimentaria, Universitat de Girona, Campus Montilivi, Edici P-I, 17071 Girona, Spain
b
Departamento de Ciencias Experimentales, Universidad Pablo Olavide, Carretera de Utrera km2, Sevilla, Spain
a r t i c l e i n f o
Article history:
Received 5 November 2010
Received in revised form4 February 2011
Accepted 9 February 2011
Available online 9 March 2011
Keywords:
Non-wood resources
Hemp core
Organosolv cooking
Pulp characterisation
Papermaking ability
a b s t r a c t
Non-wood raw materials for paper production have been maintained constant during last decade. In
Europe, bres from non-wood resources proceed mainly from ax and hemp crops. Hemp core is con-
sidered a by-product of the process, mainly used in equestrian sector. The application of these bres for
papermaking process gives a signicant added value to the sector.
New technologies in cooking processes like organosolv pulping gives advantages compared with tra-
ditional Kraft cooking. Hemp bres obtained by means of organosolv process have been compared with
eucalyptus Kraft pulp to determine if physical and mechanical properties of nal pulps are similar.
Efciency of the organosolv cooking experiments was evaluated by means of yield, percentage of
uncooked sample, kappa number and viscosity.
To analyze the suitability of pulp samples for papermaking applications, different evaluation of mechan-
ical properties as morphological characterization were done. Controlling cooking conditions of hemp core,
similar properties of eucalyptus Kraft bres are obtained.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The use of non-wood raw materials has been maintained con-
stant around 5% of the total pulp for paper production worldwide
during last decade. But since 2001, there has been an increase of
28% in the total amount of non-wood pulp for paper production
achieving during 2007 the value of 18.36 million tonnes. At Euro-
pean level, the percentage of contribution of non-wood bres for
pulp production has been lower (1.3%) due to the higher uses of
recoveredpaper andlower surface of agricultural elds (FAO, 2009;
CEPI, 2010).
Production of pulp fromnon-wood resources has many advan-
tages such as easiest pulpability, excellent bres for speciality
papers and higher quality bleached pulp. It can be used as an effec-
tivesubstitutetoavoiddecreasingforest woodresources. Countries
like China and India, with a shortage of wood for their increasing
demands of cellulosic bres, haveinnon-woodpulps andrecovered
paper its rawmaterial for paper industry. Therefore, the utilization
of these pulps may help to solve the bre shortage anticipated to
arise in the future and also help to diminish the rural depopulation
giving an added value to elds (Navaee-Ardeh et al., 2004; Rousu
et al., 2002).

Corresponding author. Tel.: +34 972418455; fax: +34 972418399.

E-mail address: angels.pelach@udg.edu (M.A. Plach).
In Europe, bres from non-wood resources proceed mainly
from ax and hemp crops. The European Union takes a relatively
important share of world ax and hemp production with about
500,000ha and 15,000ha, respectively, representing a share of
20% for ax production and 29% from hemp production world-
wide, according to FAO. In a published report fromthe Commission
of the European Parliament about the ax and hemp sector (EU
Report, 2008) it is detailed than one ha of hemp produces in aver-
age 5.8tonnes of hemp straw. This industrial hemp strawrefers to
the stalk of the plant. This stalk can be separated, or decorticated,
into two main components: bres and hurds or core bres, as Fig. 1
shows. Fibre refers mainly to the long strands of material that come
fromthe outer rings of hempstrawpresentinglengths between200
and 600m and a diameter in the order of 1030m. Core bres
or hurds refer to the inner material of the straw. The yield in total
bres of one hectare of hemp crop is not too high, around 2628%
whereas the yield in hemp core is 3.2tonne per ha, i.e. a 55% versus
total hemp (EU, 2008; Vallejos et al., 2006).
Applications have beendiscoveredfor using hempineverything
from food products to textiles to structural materials. Conse-
quently, the viability of industrial hemp as an agricultural crop
is strongly linked to these markets and products for which hemp
can feasibly be used to produce. Valued added quality papers like
teabags and coffee lters (Dutt et al., 2007), wax match paper (Dutt
et al., 2002), cigarette papers (Jeyasingam, 1994), electrical insu-
lation papers (Dutt et al., 2003), glassine and grease proof papers,
0926-6690/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2011.02.005
866 L. Barber et al. / Industrial Crops and Products 34 (2011) 865872
Fig. 1. Hemp strawprocessing to obtain hemp strands or bres, and hemp core or hurds.
condenser papers (Dutt et al., 2004), are one of the mainmarkets for
industrial hemp bre (75%) with additional outlets for composite
materials (20%) and insulation material (5%).
High level of wet strength and shorter bres fromabaca make it
most effective in teabags (Thompson et al., 1998). Industrial hemp
bre is closest in strength and bre length to ax bre (Werf et al.,
1994). This is fortunate since ax bre is the largest component of
the specialty bre market.
Hemp core is considered a by-product of the process and is
mainly used for the equestrian sector (83%) and also for small ani-
mals (10%) and poultry breeds (2%) providing additional incomes.
Building sector also uses a percentage of hemp core (5%) as insu-
lation material for the preparation of panels or as an additive for
bricks. The use of this hemp core to obtain bres with added value
could help hemp sector to stabilise in the long run. However, a
lack of suitable technology and logistic constraints are the main
restrictions to the extended use of these nonwood materials like
hemp cores. The use of conventional technology has resulted in
overwhelming environmental problems. The most common pulp-
ing technology for wood pulps (alkaline route) causes problems
during the delignication process. The silicon present in the raw
material dissolves into the cooking liquor, which lets to difculties
in the recovery of cooking chemicals. So far, the costs of alkali and
silicon recovery are high (Rousu et al., 2002).
New technologies in pulping facilities like tornado pulper or
chemical pulping processes have to be improved to produce indus-
trial hemp pulp at competitive prices. Tornado like pulpers are
used to debre hemp and other non-wood raw materials (cotton,
hemp, ax, leather and synthetic bres) without pre-treatment or
chemicals. Organosolv process to replace standard alkaline pulping
has also been under study. The use of organosolv process compared
to kraft one has different advantages (Jimnez et al., 2004, 2008;
Rodrguez et al., 2008):
- Reduction of small- and mid-scale production costs.
- Facilitate the efcient recovery of solvents and by-products.
- Use less water, energy and chemicals.
- Less polluting and the bleaching efuents are easier to treat.
- Useful for all types of wood and non-wood plants.
- Similar pulp properties, higher yields and lower lignin contents.
- Organosolv pulp is brighter and easier to bleach and rene.
The greatest disadvantages of organosolv processes is that they
usually require high pressures (solvents of low boiling point, i.e.
ethanol), which require special equipments and raises operating
costs. This makes the use of solvents with a high boiling point
like ethanolamine, a potentially interesting alternative: however,
it supposes a more expensive solvent recuperation because the
distillation occurs at higher temperature. The separation of the sol-
vent fromthe degradation products is an essential part of recovery
(Jimnez et al., 2007; Rodrguez et al., 2008).
Theobjectives of studies intendedtopromotesustainabledevel-
opment in the use of hemp bres and hemp core as raw material
for paper industry have to be centred in:
- Efcient utilization of nonwood materials (hemp core represent
around 55% of hemp straw).
- Efuent-, sulphur- and chlorine-free operation.
- High quality pulp.
- Protable in small scale because mills have remained relatively
small due to logistic constraints.
Achieving these objectives, hempbres couldcompete withvir-
gin and recycled bres for the production of ofce papers (Rousu
et al., 2002).
The present study aims to optimise pulping conditions for
hemp core of Cannabis sativa by means of organosolv pulping pro-
cess using ethanolamine that could be considered environmentally
kind.
L. Barber et al. / Industrial Crops and Products 34 (2011) 865872 867
2. Materials and methods
2.1. Raw material
Hemp core of Cannabis sativa was provided by Agrobra, S.L.
from Puigreig (Barcelona, Spain) as chopped pieces of 10mm or
less long. The hemp core was disintegrated into powder (TAPPI T
264cm-97 Preparation of wood for chemical analysis) and the
fraction passed through a sieve of 40 mesh and retained in a sieve
of 60 mesh was used for -cellulose and hemicellulose (TAPPI
T 203cm-99 Alpha-, Beta-, and Gamma-Cellulose in Pulp), acid
insoluble lignin (TAPPI T 222 om-02 Acid-insoluble lignin in wood
and pulp) and ash content (TAPPI T 211 om-02 Ash in wood, pulp,
paper, and paperboard: combustion at 525

C) determinations.
2.2. Pulping conditions
Organosolv experiments were performed in a 25-L stainless
steel rotator digester with a heat exchanger system and pres-
sure control. Pulping conditions of industrial hemp core were
varied over the following ranges: 3090min, 155185

C, 4060%
ethanolamine. Pulping conditions that were maintained constants
were: liquor to wood ratio: 6:1 and digester pressure at T
max
:
57bar.
These conditions were previously tested by other authors
(Jimnez et al., 2007) in vine shoots pulping using ethanolamine.
After completion of cooking, the cooked hemp core pulps were
debred ina hydrapulper and screened througha Somerville vibra-
tory at screen with 0.15mmslot size, and the screened pulp was
washed, pressed, crumbled and stored at 4

C. The pulps were eval-

uated for kappa number (TAPPI T 236 om-06 Kappa number of
pulp), pulp yield, screening rejects, and viscosity (TAPPIT 230 om-
08 Viscosity of pulp: capillary viscometer method).
Morphological characteristics of hemp core pulp like bre
length, width and nes percentage were determined with a MorFi
compact device analyzer (Techpap). The pulp was disintegrated
in a standard disintegrator and laboratory handsheets of 60g/m
2
were prepared using a sheet former, pressed and air-dried under
atmospheric conditions (TAPPI T205 sp-06 Forming handsheets
for physical tests of pulp). Laboratory handsheets were precondi-
tioned at 231

C at a relative humidity of 502% and evaluated

for Scott index (TAPPI T 569 pm-00 Internal bond strength: Scott
type), tensile breaking properties (TAPPI T 494 om-01 Tensile
properties of paper and paperboard: Using constant rate of elonga-
tion apparatus), tearing resistance (TAPPI T 414 om-04 Internal
tearing resistance of paper: Elmendorf-Type Method), bursting
strength (TAPPI T 403 om-02 Bursting strength of paper) and air
resistance by means of Gurley method (TAPPI T 460 om-02 Air
resistance of paper: Gurley Method). These results were compared
with a typical Eucalyptus Kraft pulp.
2.3. Experimental design
To be able to relate the dependent and independent variables
with the minimum possible number of experiments, a 2n cen-
tral composite factor design was used. This design enabled the
construction of rst and second-order interaction terms of a poly-
nomial designandthe identicationof statistical signicance of the
variables used. The total number of experiments required (N) was
found fromthe equation:
N = 2
k
+2 k +1 (1)
where k denotes the number of independent variables.
Solving this equation for k =3, a total of 16 experiments were
planned. Independent variables were normalized using the follow-
Table 1
Results fromchemical characterization of rawmaterial and comparison with other
referenced values.
Analysis Hemp core Kenaf core
a
Hardwood
a
Published
hemp core
a
-Cellulose (%) 42.5 34 3849 3949
Hemicellulose (%) 22.2 19.3 (1824) 1926 1623
Lignin (%) 24.8 17.5 (1521) 2330 1623
Ash (%) 3.3 2.5 (24) 1 34.5
Holocellulose 70.6 79.580.5
a
Hurter (2006).
ing equation
x
n
= 2
x x
(x
max
x
min
)
(2)
where x is the absolute value of the independent variable con-
cerned, x is the average value of the variable and x
max
and x
min
are its maximumand minimumvalues respectively. In the present
study normalized variables were:
1 0 1
Time (Xt, min) 30 60 90
Temperature (XT,

C) 155 170 185

Ethanolamine (E, %) 40 50 60
Experimental results were tted to the following second-order
polynomial:
Z = a
0
+
k

i=1
b
i
X
ni
+
k

i=1
c
i
X
2
m
+
k

i=1
d
ij
X
ni
X
nj
(i <j) (3)
where Z denotes the response variables, X
ni
the normalized values
of the independent variables (time, temperature and ethanolamine
concentration), and a, b, c and d are constants.
Normalization of independent variables provides better esti-
mates for the regression coefcients by reducing correlation
between linear and quadratic interaction terms.
3. Results
Results fromchemical characterization of the rawmaterial used
in the study, i.e., hemp core, are presented in Table 1 and com-
pared with referenced values of kenaf core, hardwood bres and
published hemp core values (Hurter, 2006).
Results presented show that, hemp core material selected has
similar chemical composition than hardwood bres. Hemp core
ability to deliver chemical cellulose, dened as -cellulose, to nal
brous suspensions is higher than kenaf and really good compared
to hardwood. As it was conrmed previously by de Groot (De Groot
et al., 1999), hemp woody core is chemically related to hardwood.
When analysing hemicelluloses values, there are no real differ-
ences between them. Hemicelluloses are important for the paper
industry because they are needed for nal good pulp quality. Its
presence aids swelling of the pulp, bonding between bres, burst-
ing strength, tensile strength, tear resistance, folding endurance,
opacity and specic surface of the pulp sheet. Experimental values
of lignin fromhemp core samples are also within the range of hard-
wood pulp. Chemical characterization allowed continuing with the
objective of upgrading these bres for papermaking uses.
Organosolv cooking of hemp core samples using ethanolamine
were conducted according to experimental design described in
methodology. Table 2 shows the relation of experiments with the
corresponding normalized values for the independent variables
and characteristic results of cooked samples (yield, rejects, kappa
number, viscosity and bre length). Yield presented in Table 2 con-
siders brous suspension able to produce paper, i.e. it is a screened
yield. It does not take into consideration rejects or uncooked mate-
868 L. Barber et al. / Industrial Crops and Products 34 (2011) 865872
Table 2
Operating conditions of experimental design and results of pulp characterisation in the ethanolamine hemp core pulping.
Time (Xt, min) Temperature (XT,

C) Ethanolamine (XE, %) Yield (%) Rejects (%) Kappa number Viscosity (cm
3
/g) L
L
w
(m)
1 1 1 53.17 0.79 25.26 256 450
1 1 1 28.16 62.57 113.36 764 690
0 0 0 56.11 15.14 66.26 535 590
0 0 1 63.44 13.7 58.48 377 615
0 0 1 54.00 17.65 71.44 413 595
0 1 0 43.56 39.16 90.80 767 635
1 1 1 55.37 0.98 39.33 275 510
1 1 1 59.37 6.69 55.95 498 535
1 0 0 52.32 31.65 82.49 759 680
1 1 1 42.98 42.94 82.19 243 655
1 1 1 55.57 9.63 74.05 639 595
1 1 1 36.99 48.68 70.81 278 655
1 1 1 27.47 61.21 91.56 463 730
1 0 0 57.17 10.17 68.36 607 595
0 1 0 64.30 0.99 41.11 780 480
rial that was calculated using the Sommerville-type equipment,
based on TAPPI T275 standard. There is an inverse relationship
between screened yield and rejects, therefore, cooking conditions
than will favour yield, contradict rejects.
A multiple non-linear regression analysis using JMP software
(version 8.0) was performed on all the results related with organo-
solvhempcorepulpcharacterization. Abackwardstepwisemethod
was applied over all interactions to take into consideration only
the terms with a Snedecors F-values less than 4. The equations
obtained are presented in Table 3. This table also contents statis-
tical values as r
2
, Snedecors F, highest p values and the optimum
(maximum or minimum) values for the dependent variables and
the normalized independent variables needed to achieve them. The
responsesurfacemethodology(Myers andMontgomery, 1995) was
appliedtoequations inorder todeterminetheoptimum(maximum
or minimum) values for the dependent variables over the ranges
studied for the process variables.
Equations presented in Table 3 reproduce the experimental
results for the different dependent variables, as a function of
the independent ones. Quadratic correlation coefcients (r
2
) of
obtained equations for the characterization of pulp samples are
really good (>0.90) and the variations obtained were always lower
than 5% except the viscosity that gave too high values of variation.
The described statistical method applied to yields equation in
order to determine the highest value over the range studied, gave a
maximumyield of 63.3% obtained for a short time and a high tem-
perature (normalised values of 0.04 and 0.75, respectively) and
independent of ethanolamine concentration. Similar yield results
(63.9%) were obtained by Jimnez et al. (2007) when treating
vine shoots with ethanolamine, however at lowest temperatures
(155

C).
Surface representation of proposed yield equation (Fig. 2) by
means of Sigmaplot 8.0 conrmed the importance of temperature
and time as independent variables. The greatest changes in yield
resulted from variation of the temperature, whereas the smallest
ones wereduetoethanolamineconcentration, withaninsignicant
inuence on yield variation. It is a usual behaviour than yield is
more sensitive to changes in temperature than in reaction time or
organosolv concentration (Jimnez et al., 2004).
As it was mentioned before, there is an inverse relationship
between screened yield and rejects, therefore, independent vari-
ables that inuence yield would be the same for the reject analysis.
As it is observed inTable 3, this is conrmed. Time and temperature
are the variables that inuence uncooked material or rejects from
organosolv hempcore samples. Minimumvalue obtainedwithpre-
dicted equation reaches negative values.
Delignication process, expressed as kappa number, increased
with increasing temperature and reached a predicted minimum
Fig. 2. Surface representation of yield (%) in function of temperature (

C) and time
(min) within the normalized range.
level of 28.6at higher temperature, time andethanolamine concen-
tration, as it can be observed in Table 3. More extreme conditions
promoted delignication and thus enhanced the dissolution of
lignin. Frominitial value of acidinsoluble lignin(24.8%) determined
as TAPPI T222, it can be considered than in optimumconditions, a
85% of this lignin is removed during digestion. Poorer conditions
removed only a 43% of total lignin.
The same hempcore rawmaterial was treatedinprevious works
(Cerdn, 2008) using chemical process (i.e., Kraft) and semichem-
ical one (i.e., sodaanthraquinone). Yield obtained ranged from72
to 40% for chemical treatment and from79 to 43% for semichemical
one. Kappa number ranged from 72 to 15 for chemical treatment
andfrom168to21for semichemical one. Comparingall thesetreat-
ments, it canbe concludedthat organosolvtreatment for hempcore
pulps is adequate in terms of pulp characterisation.
Viscosity is a measure of polymerization degree based on dis-
solving the lignin-free pulp in a solvent, typically a standard
solution of cupriethylenediamine. By measuring the viscosity, one
can estimate the extent of degradation of cellulose and undissolved
hemicelluloses thancanaffect brestrengthandmayalsoinuence
papermaking properties. Viscosity of obtained organosolv hemp
core pulps varied from 243 to 780cm
3
/g, i.e., from low to really
high viscosity values. Optimumvalue predicted by the polynomial
equation is even greater (813cm
3
/g). Temperature is not a sig-
nicant variable on viscosity variation while cooking liquor and
L. Barber et al. / Industrial Crops and Products 34 (2011) 865872 869
Table 3
Obtained equations to predict pulp characterization variables (yield, rejects, kappa, viscosity and length) into the range of cooking conditions used.
r
2
F p Optimumvalue Variation (%) Normalized values of the independent variables lead to
optimumvalues of dependent variables.
Time (Xt, min) Temperature (XT,

C) Ethanolamine (XE, %)
Yield(%) = 59.21 +2.28 Xt +
10.86 XT 3.84 Xt XT
6.50 X
2
t
7.31 X
2
T
0.94 33.3 <0.0001 63.3 2.3 0.04 0.75
Rejects (%) = 14.75 6.82 Xt
23.55 XT +7.47 X
2
t
+
6.64 X
2
T
0.97 108.5 <0.0001 0.0 2.8 0.46 +1
Kappa =68.61 13.15Xt
21.30XT 5.56XE
0.91 41.5 <0.0001 28.6 4.9 1 1 1
Viscosity = 663.83 146.4 Xt
53.2 XE 243.23 X
2
E
0.82 18.1 <0.0001 813.1 45.9 1 0.10
L
L
w
= 596.6 36.5 Xt
79.5 XT 14 XE +
42.7 X
2
t
37.3 X
2
T
0.96 49.5 <0.0001 732 11.3 1 1 1
time are reactive. The reactions between the cooking liquor and
reactive lignocellulosic components dissolve some of these compo-
nents resulting in openings that allow the chemicals to penetrate
the hemp structure. As the pulping process proceeds, this results
in further decomposition of hemp core components and transfor-
mation of the hemp structure. The pulping reactions start to spread
fromthe initial reactive sites of the hemp as conrmed by Dang and
Nguyen (2006). The pronounced differences suggest that the peel-
ing reactions, which are responsible for the loss of pulp viscosity,
are more sensitive to the time and organosolv reagent.
Values of kappa number and viscosity for a typical unbleached
eucalyptus Kraft pulp obtained in the same rotator digester using
a proportion of active alkali of 15% were 23.8 and 753.6cm
3
/g,
respectively. It means that organosolv hemp core pulp is not
signicantly different from a hardwood pulp obtained in a Kraft
process.
The information related with morphological characterization
of pulps presented in Table 2 is length weighted in length (L
L
w
),
calculated as follows:
L
L
w
=

n
i
L
2
i

n
i
L
i
This is the most common denition of bre length distribution
because the plain arithmetic average is not applicable when the
sample contains a high proportion of nes (24%) and short bres
as expected in pulps fromnon-wood rawmaterial.
The weighted length (L
L
w
) variation obtained with the differ-
ent experiments using a MorFI compact device, is into the range
of 450730m, in accordance with published values of average
length(510m) of anindustrial hempcore (Hurter, 2006). All inde-
pendent variables are present in L
L
w
predicted equation (Table 3)
witha robust statistical analysis. This equationleads to a maximum
value of bre length of 732machieved at the lowest cooking con-
ditions, i.e. lowtemperature, timeandethanolamineconcentration.
This maximumbre length is slightly lower fromthat obtained by
the eucalyptus kraft pulp, i.e., 870m.
Summarising, chemical and morphological properties of
organosolv hemp core pulp are comparable to a typical eucalyp-
tus Kraft pulp with the exception of some lengths of organosolv
hemp core pulps.
To analyze the suitability for papermaking applications of
the organosolv hemp core pulp obtained at different conditions,
mechanical properties should be evaluated. The most impor-
tant strength properties of paper and board would include:
tensile strength analysed by means of breaking length; inter-
nal bond strength analysed by means of Scott index; tearing
strength; bursting strength analysed by means of Mllen index
and porosity or air resistance analysed by means of Gurley
method. Table 4 summarizes the values obtained on corresponding
handsheets.
The same multiple non-linear regressionanalysis appliedbefore
is used with these mechanical properties. Obtained equations and
statistical parameters are presented in Table 5 and reproduce the
Table 4
Mechanical characterisation of handsheets fromhemp core pulp obtained at different ethanolamine cooking conditions.
Time (Xt, min) Temperature
(XT,

C)
Ethanolamine
(XE, %)
Breaking
length (m)
Scott index
(J/m
2
)
Tear index
(100gf m
2
/g)
Mllen index
(1000
(kg/cm
2
)/(g/cm
2
))
Porosity (s)
1 1 1 5295 527.7 31.5 31.23 274
1 1 1 4865 478.6 30.5 18.63 288
0 0 0 4910 447.0 33.2 19.44 206
0 0 1 5256 436.8 31.4 19.44 302
0 0 1 4763 459.8 31.3 19.10 226
0 1 0 4808 514.1 31.0 17.02 282
1 1 1 4139 276.9 35.4 26.17 44
1 1 1 5153 448.0 33.9 19.68 326
1 0 0 4387 507.5 33.5 17.88 192
1 1 1 4474 454.8 31.3 20.49 384
1 1 1 3865 308.6 32.0 16.26 99
1 1 1 4419 448.4 28.1 17.03 210
1 1 1 5986 542.4 28.3 20.67 420
1 0 0 5107 472.9 31.7 19.95 308
0 1 0 4311 405.9 30.8 20.17 258
870 L. Barber et al. / Industrial Crops and Products 34 (2011) 865872
Table 5
Obtained equations to predict mechanical properties (breaking length, scott index, tear index, burst index and porosity) into the range of cooking conditions used.
r
2
F p Optimumvalue Variation (%) Normalized values of the independent variables lead to
optimumvalues of dependent variables
Time (Xt, min) Temperature
(XT,

C)
Ethanolamine
(XE, %)
Breaking
length=4790.582.2Xt
178.9XT +411.3XE
+296.75XtXT
0.68 5.9 0.0086 5759 243 1 1 +1
Scott
index =448.5347.12XT
+43.74XE +40.0XT XE
0.72 10.13 0.0013 499.4 30.9 1 +1
Tear
index =31.69+1.44XT
0.38 8.71 0.0105 33.13 1.2 1
Mllen index =
18.98 +2.18 Xt +
1.97 XT +1.43 XE +
2.91Xt XT +1.89 X
2
E
0.92 22.0 <0.0001 29.35 0.7 1 1 1
Porosity=251.5658.3XT
+83.9XE
0.77 21.2 <0.0001 (394)max 39.6 1 1
(109.4)
min
1 1
experimental results for the different dependent variables, as a
function of the independent ones. Quadratic correlation coef-
cients (r
2
) of obtained equations for the characterization of pulp
samples are good (0.70) except for tear index (r
2
=0.38). The
variations obtained were lower than 5% only for tear index and
Mllen index. The higher variations presented by breaking length
can be explained by the standard deviation of the analysis itself
that was higher than 300. The same situation was presented by
standard deviation of Scott that in this case, corresponds to the
same variation of statistical analysis (i.e. 31). The porosity was the
only parameter that variation was not well explained in function of
the residuals obtained, based on the variation of real and predicted
values.
The relative inuences of the independent variables are differ-
ent among physical characteristics analysed. From the equation
presented in Table 5 describing the variation of breaking length
it can be assumed that the variable with the highest effect is
ethanolamine concentration, followed by the interaction between
time and temperature. For the Scott index, the most signicant
variable is the temperature, followed by the ethanolamine con-
centration and their interaction. If the equation analysed is that
corresponding to tear index, it can be deduced that the only sig-
nicant variable is the temperature even tough the variation in the
response is not totally attributed to the model (lowest r
2
).
Table 5 also contains proposed equations for Mllen index from
which one can be inferred that the variables with highest effect
are time, temperature and ethanolamine concentration, followed
by the interaction between time and temperature. For porosity,
taking into consideration that was evaluated as the time that air
needed to pass the handsheet, the most signicant variables are
the ethanolamine concentration and temperature.
Breaking length and porosity increased more markedly on
increasing the ethanolamine concentration while increasing tem-
perature affected them negatively. Scott index showed the same
behaviour. Processing time only affected positively burst index
(expressed as Mllen one). However, when assessing pulp char-
acterisation cooking time was a signicant variable for Kappa
number, viscosity and weighted length.
To proceed with the goodness of the results, Eucalyptus Kraft
pulp, recycled liner and recycled uting were used as reference
pulps. This is because the optimum pulp quality depends on the
specic product requirements. Fluting and liner are used to pro-
duce corrugated board, a competitive packaging material. Fluting
is equivalent to corrugated medium, the paperboard grade that is
used in corrugated board as the wave between the two liners.
Because corrugating mediumis a bulk product, price is very impor-
tant for raw materials and the upgrading of nonwood pulps has
a niche in this market. Strength is an important property to ana-
lyze. Table 6 contains their corresponding mechanical properties
obtained using the same standards and equipments, and the range
of experimental values fromethanolamine hemp core cookings.
Ranges of variation of breaking length, Scott index and Mllen
index values are considerable high for an organosolv paper
compared with all other pulp handsheets. These results are in
accordance with published organosolv experiments (Gonzlez
et al., 2008). Tear index values for the ethanolamine pulp are lower
thanother pulps analysed. Porosity values obtainedare out of range
whencomparingwithEucalyptus Kraft pulpor pulps obtainedfrom
recycled Kraft liner or corrugated medium(i.e. uting).
Summarising, it can be inferred that physical properties are
acceptable for a big range of industrial papers some examples of
which are shown in this paper.
Therefore, to upgrade hemp core pulps, is important to decide
which type of paper is the objective and to which additional
treatments will be submitted (i.e. rening process). If the paper
target requires higher brightness, lower kappa numbers have to be
obtained. If the paper target requires important strength proper-
ties, then mechanical parameters have to be evaluated to decide
cooking conditions. The same conclusion could be taken if poros-
ity is an important parameter. In this sense, three different set of
operationconditions are proposedinorder tooptimise certainvari-
ables without affecting too much on the others, using the obtained
equations. These conditions are listed in Table 7.
Pulping conditions more suitable for obtaining sheets withgood
physical properties (set of conditions a) require operation at high
temperature and concentration of ethanolamine (60% and 185

C,
respectively), as well as a cooking time of 85min. Under these con-
ditions all the physical properties of handsheets differ by less than
10%of its optimal value, being the deviation fromthe optimal value
of performance only of 10.31%. However, the intrinsic properties of
pulps (viscosity and bre length) as well as porosity are far from
optimal values.
Pulping conditions corresponding to set b (Table 7) are recom-
mended if the goal of the process is to obtain pulps with optimum
yield, viscosity and bre length, to further undergo a rening pro-
cess. Ethanolamine concentration of 44% for 36min at 174.5

C
are ideal conditions for optimal values of the variables mentioned
above do not differ from 15%. Among the physical properties of
L. Barber et al. / Industrial Crops and Products 34 (2011) 865872 871
Table 6
Mechanical properties of handsheets made with Eucalyptus Kraft pulp, recycled liner and uting, compared with the range of experimental values.
Ethanolamine hemp core pulp Eucalyptus kraft pulp Recycled kraft liner Recycled uting
Breaking length (m) 38655986 2246 2984 3536
Scott index (J/m
2
) 277542 70.8 150 171.2
Tear index (100gf m
2
/g) 2835 52.4 62 92.9
Mllen index (kPa m
2
/g) 1631 10.5 16.2 17.7
Porosity (s) 44420 1 8 27
Table 7
Different sets of recommended operation conditions with values of dependent variables and percentage of deviation with respect to optimum.
Condition Normalized values of the independent variables lead to
optimumvalues of dependent variables
Variable Value Deviation with respect to
optimum(%)
Ethanolamine Time Temperature
a 1 0.85 1 Yield (%) 56.74 10.3
Rejects (%) 0 0
Kappa 30.57 6.9
Viscosity 243 70.1
L
L
w
466 36.4
Breaking length 5205 9.6
Scott index 485.1 2.9
Tear index 33.1 0
Mllen index 28.6 2.6
Porosity 277 (29.6)max/(153.5)
min
b 0.6 0.8 0.3 Yield (%) 56.75 10.3
Rejects (%) 18.52
Kappa 76.08 166
Viscosity 725 10.8
L
L
w
634 13.3
Breaking length 4485 22.1
Scott index 400.9 19.7
Tear index 32.1 3.0
Mllen index 16.95 42.3
Porosity 184 (53.3)max/(68)
min
c 0.13 1 0.4 Yield (%) 55.14 12.8
Rejects (%) 20.68
Kappa 72.52 153.6
Viscosity 799 1.7
L
L
w
636 13.1
Breaking length 4736 17.8
Scott index 437.5 12.4
Tear index 32.3 2.6
Mllen index 16.64 43.3
Porosity 239 (39.3)max/(118.7)
min
handsheets obtained, only the Tear index remained acceptable dif-
fering by only 3% fromoptimal value.
Finally, the proposed operation conditions are intermediate
between those indicated above, getting a loss of physical proper-
ties not very high, and preserving bre properties (set of conditions
c). As seen in Table 7, working with a concentration of 51%
ethanolamine for 30min at 176

C, you can get the properties stud-

ied, differ by less than 15% of its optimal value (17.8% for breaking
length) with the exception of Kappa, Mllen index and porosity.
Under these conditions (set c) nal yield would be 55.14%, but
considering that rejects (20.68%) in a continuous process are recir-
culated and reintroduced to the process, this yield would be higher.
It should be noted that the proposal of cooking at shorter times and
lower temperatures have greatest interest from the point of view
of operational costs.
4. Conclusions
Upgradingof hempcore basedonethanolamine organosolvpro-
cess was achieved in this study. Handsheets obtained from this
process have physical properties similar or even better than hard-
wood Kraft pulps.
Mathematical models obtained reproduce results in an
organosolv cooking process with acceptable errors. The most rec-
ommendedoperatingconditions for highyields are60min at 185

C
using a 60% of ethanolamine. To improve physical properties is
necessary toincrease cooking time. If working conditions are deter-
mined at 51% of ethanolamine for 30min at 176

C, a balance
between physical properties of paper and bre characteristics is
obtained.
Acknowledgments
Authors wish to thanks Spanish Ministry of Education and
Science (MEC) for the grant obtained to develop this study
(CTM2007-66793-C03-01/TECNO).
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