Bioresource Technology 102 (2011) 3504–3511

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Disproportionation of rosin on an industrial Pd/C catalyst: Reaction pathway

and kinetic model discrimination
Juan Carlos Souto, Pedro Yustos, Miguel Ladero ⇑, Felix Garcia-Ochoa
Dpt. Ingeniería Química, Fac. CC. Químicas, Universidad Complutense, 28040 Madrid, Spain

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a phenomenological study of the isomerisation and disproportionation of rosin acids using
Received 18 August 2010 an industrial 5% Pd on charcoal catalyst from 200 to 240 °C is carried out. Medium composition is deter-
Received in revised form 1 November 2010 mined by elemental microanalysis, GC–MS and GC-FID. Dehydrogenated and hydrogenated acid species
Accepted 3 November 2010
molar amounts in the final product show that dehydrogenation is the main reaction. Moreover, both
Available online 12 November 2010
hydrogen and non-hydrogen concentration considering kinetic models are fitted to experimental data
using a multivariable non-linear technique. Statistical discrimination among the proposed kinetic models
Keywords:
lead to the conclusion hydrogen considering models fit much better to experimental results. The final
Rosin acids
Disproportionation
kinetic model involves first-order isomerisation reactions of neoabietic and palustric acids to abietic acid,
Dehydrogenation first-order dehydrogenation and hydrogenation of this latter acid, and hydrogenation of pimaric acids.
Kinetics Hydrogenation reactions are partial first-order regarding the acid and hydrogen.
Pd/C catalyst Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction 200 to 240 °C. It is applied in several industries: adhesives (hot-

Rosin is obtained from living trees (gum rosin), from pine
stumps (wood rosin), and from the alkaline extraction of wood
during the Kraft pulping process (tall-oil rosin). Rosin is mainly a
mixture of C20 monocarboxylic diterpenic resin acids of the
abietic-type acids (mainly abietic, palustric and neoabietic acids)
and of the pymaric acid type (pimaric and isopimaric acids, usu-
ally). It also has a certain quantity of fatty acids (in tall oil) and
other neutral components (5–15%). The main difference between
rosin acids is a conjugated double bond system present in abietic
type resin acids, but not in the pimaric family. Carboxylic and
olefinic functionalities of resin acids are advantageously modified
by hydrogenation, disproportionation, formation of adducts with
dicarboxylic acids, dimerisation, polymerisation, esterification
and saponification (Soltes and Zinkel, 1989). Some applications re-
quire a combination of reactions to obtain the desired product
quality. For example, esterification with polyols, disproportion-
ation and isomerisation reactions occur together, leading to esters
of rosin acids stable towards oxidation and, thus, of a very clear
colour – one of the desired properties of rosin and rosin products.
Disproportionated rosin has good oxidation resistance, low
brittleness, high thermal stability and light color, and maintains
a high softening point, even higher than the original rosin due to
the elimination of turpentine oils during disproportionation at
⇑ Corresponding author. Tel.: +34 913934164; fax: +34 913944179.
E-mail address: mladero@quim.ucm.es (M. Ladero).
melt and pressure-sensitive adhesives), solder flux, printing inks,
paper neutral-size – after saponification – and more (Soltes and
Zinkel, 1989). It has some important applications in the polymeric
industry where abietic acid presence is not adequate, because it
acts as an inhibitor (amounts as low as 0.5% in abietic acid are
looked up) and very high percentages in dehydroabietic acid are
desired (65% or more): as an emulsifier in the production of sty-
rene–butadiene rubber and ABS resin and chloroprene rubber
(Mayer et al., 1995, 1996). New fields where applications are being
developed include the synthesis of non-ionic surfactants (Hu et al.,
2006), applications in the coating industry in antifouling paints
and in the synthesis of new polymers (Duan et al., 2009).
Dehydroabietic acid, as other abietates, is a diterpene acid
important in the defense system of conifers, against potential her-
bivores and pathogens (González et al., 2010). Dehydroabietic acid
(DHA) and its derivatives show a broad spectrum of biological ac-
tion: antiulcer, antimicrobial, anxiolytic, antiviral, antitumor, and
cytotoxic activities (González et al., 2010; Tanaka et al., 2008;
Fonseca et al., 2004). Recently, DHA structure has been proved to
be a new scaffold for BK (large-conductance calcium-activated
K+) channel openers, causing a dramatic increase of the channel-
opening activity. In fact, as it has shown one of the greatest activ-
ities ever reported, it seems that this structure will be the nucleus
for the design of new BK channel modulators, of interest in the
treatment of acute stroke, epilepsy, asthma, hypertension, gastric
hypermotility, and psychoses (Ohwada et al., 2003). Moreover,
DHA seems to be an anti-inflammatory agent with high PPARa/c
dual activation potential and prevent the production of several

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.11.022
 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511
Nomenclature
CAB abietic acid concentration (mol L1)
CD dehydroabietic acid concentration (mol L1)
CDi dihydroabietic acid concentration (mol L1)
CH2 hydrogen concentration (mol L1)
CN neoabietic concentration (mol L1)
CP palustric acid concentration (mol L1)
CPi pimaric acid concentration (mol L1)
DHA dehydroabietic acid
Ea activation energy (J mol1)
EMA elemental microanalysis
GCFID gas chromatography with flame ionization detector
GC–MS gas chromatography–mass spectrometry
H-RMN hydrogen-nuclear magnetic resonance spectroscopy
proinflamatory mediators by activated macrophages and
differentiated adipocytes. Inasmuch as obesity is associated to
low-grade inflammation and the production of the mentioned pro-
inflamatory mediators, DHA seems to be a compound with interest
in the prevention of obesity, and the resistance to insulin associ-
ated to obesity (Kang et al., 2008). This anti-inflammatory activity
can be related to its capacity to reduce cholesterol and
arteriosclerosis.
Disproportionation and isomerisation of rosin acids happen to-
gether as rosin is heated (Soltes and Zinkel, 1989). Disproportion-
ation has been considered to be an exchange of hydrogen between
acid molecules, though percentages of DHA higher than 50% are
commonly reached. This reaction has traditionally been catalysed
by sulphur alone or with some sulphur organic compounds (as
sulphides, and disulphides), iron salts, iodide and iodide alkaline
metals salts, and lithium salts (Soltes and Zinkel, 1989). In the last
decades, due to the toxicity of the gases formed when using sul-
phur as catalyst, palladium supported on activated carbon or alu-
mina has been used, though inactivation by the iron present in
rosin leads to the necessity of reactivating the catalyst (Matsuo
and Tsuchida, 1981). Nickel and selenium have been tested as cat-
alysts, to replace Pd catalysts, being the search for a non-noble me-
tal catalyst one of the most interesting research lines in this field
(Soltes and Zinkel, 1989). Thus, at the present time, Pd catalysts
show much interest due to the good properties that the dispropor-
tionated rosin feature (regarding colour, softening-point, low metal
concentration, and resistance to oxidation).
Several methods of analysis to determine the composition of ro-
sin after disproportionation have been used: UV–vis spectropho-
tometry, GC-FID, GC–MS, HPLC, H NMR and MALDI-TOF (Brites
et al., 1993; Gigante et al., 1995; Rigol et al., 2003; Mitani et al.,
2007; Kumooka, 2008). UV–vis spectrophotometry, using 254 nm
as wavelength, is a simple method able to give an average conver-
sion of abietic acid to dehidroabietic acid, and has been the method
of use during a long period of time. Modern chromatographic tech-
niques have been applied in the rosin industry since the 80s–90s,
allowing, from that date, to determine the exact composition of
the disproportinated product. However, little information can be
obtained in the literature regarding the kinetics of the reactions
involved, with Pd/C or any other catalyst (Song et al., 1985; Vital
and Lobo, 1992; Wang et al., 2009). Song et al. (1985) used gas
chromatography to analyse reaction samples from a three-necked
round-bottom flask in the disproportionation of gum rosin at
543 K, being dehydroabietic acid the main compound found in
the final samples, with a low quantity of dihydroabietic acids (four
of them were identified) and no trace of tetrahydroabietic acids.
Wang et al. (2009) have proposed a kinetic model for the dispro-
portionation of rosin on a home-made Pd 5%/C, based on a complex
3505
HPLC high performance liquid chromatography
ki kinetic constant
k0 preexponential term of the kinetic constant
MALDI-TOF matrix-assisted laser desorption/ionization
RAb disappearance rate of abietic acid (mol L1 min1)
RD appearance rate of dehydroabietic acid (mol L1 min1)
RDi appearance rate of dihydroabietic acid (mol L1 min1)
RN disappearance rate of neoabietic acid (mol L1 min1)
RPi disappearance rate of pimaric acid (mol L1 min1)
T temperature (°C, K)
tR residence time (min)
Xab abietic acid conversion
scheme of disproportionation and isomerisation reactions where
several abietic- and pymaric-type rosin acids are considered. The
reaction runs were performed on a batch reactor (usual in the
industry) featuring a double-tier paddle agitator and reaction con-
ditions were chosen so that kinetic control by chemical reactions
was assured and oxidation was avoided (by using nitrogen). The
kinetic model, able to fit well all data from 483 to 533 K, is of an
empiric nature, as it is not capable of explaining the high quantity
of dehydrogenated species compared to hydrogenated species in
the final product and in samples taken during the kinetic runs.
Being disproportionation the way to get a rosin of interest
in classic and new applications, and a way of obtaining dehydro-
abietic acid of a technical grade, the knowledge of disproportion-
ation kinetics will provide information on the composition of the
reacting mixture under different conditions and time values. An
empirical model can be of use in the design of reactors for a given
catalyst, but a deeper knowledge of the phenomena underlying
disproportionation will give more accurate information on the
activity of each catalyst, being a sounder basis for the comparison
of catalysts. Moreover, the use of commercial catalysts will be of
interest to industry. Thus, in this work, the disproportionation of
rosin with Pd (at 5% concentration) on activated carbon from
Engelhardt, from 473 to 513 K, is studied, leading to the proposal
of a kinetic model based on dehydrogenation, hydrogenation and
isomerisation reaction pathway. Runs were performed at the men-
tioned temperatures and samples were withdrawn and analyzed
by GC-FID and GC–MS. The proposed model and the empirical
model by Wang et al. (2009) are used to fit data obtained with
the Engelhardt catalyst, using a multiparametric and multivariable
non-linear technique with a coupled integration of the ODEs of the
kinetic models.
2. Experimental
2.1. Materials
Rosin and glicerol were of technical and pharmaceutical grade,
respectively, and were kindly supplied by LURESA. N,N-Dimethyl-
formamide dimethyl acetal 92% for gas chromatography was pur-
chased from Acros Organics. Pure oleic acid, from Fluka, was
used as internal standard. The catalyst (Escat 111) was 5%Pd on ac-
tive carbon and was a kind gift from Engelhard.
2.2. Catalyst characterisation
The specific surface area (BET), total pore volume and average
pore diameter were measured in duplicate by nitrogen adsorption
3506 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511

at 77 K in a Coulter SA 3100 Surface Area and Pore Size Analyzer

RAb ¼ k1  C N þ k3  C D  C H2 þ k2  C P  k3  C Ab  k4  C Ab  C H2
(with outgassing of the samples at 573 K during 3 h). The mean
particle size distribution of the catalyst was measured at several
agitation speeds (to avoid aggregation and breakage of the
catalyst) with a Focused Beam Reflectance Measurement with a
LasentecÒ FBRMÒ system model M400L-316K. The morphology of

First order kinetic models (empirical models) and second-order kinetic models (phenomenological models) for the disproportionation of rosin with a Pd 5%/C catalyst used to fit to experimental data in this work.
the catalyst and the EDS was observed in a JEOL JM-6400 scanning
electronic microscope (SEM), using an acceleration voltage of
20 kV. This was also the voltage for the quantitative Electron Dis-
persion Scanning X-ray microanalysis (EDS) controlled by the ISIS
software. Powder X-ray diffraction (XRD) was performed at

 C D  C H2
k = 1.54 nm in a multipurpose PANanalytical diffractometer model
X’Pert MPD with a Cu–K anode, at 40 mV and 200 mA, while scan-
ning the sample over a Bragg angle (2h) from10° to 90°.

k3
0

0
RD ¼ k3  C Ab 

RN ¼ k1  C N
RP ¼ k2  C P
2.3. Esterification runs and sample analysis

Model 5
Kinetic runs were performed between 200 and 240 °C using
0.1% catalyst referred to the rosin mass. Batch runs were started
by charging the reactor with 100 g of rosin into a 250 mL round-
bottom flask with three necks with upper agitation by marine helix
and a distillation head attached designed to condense the tremen-

RAb ¼ k1  C N þ k3  C D  C H2  k3  C Ab  k4  C Ab  C H2
tine. When the reactor was charged a flow of N2 was passed into

RAb ¼ k1  C N þ k2  C P þ k3  C D  k3  C Ab  k4  C Ab
the reactor to avoid oxidation. When reaching 100 °C agitation
was set at 500 r.p.m. At the temperature of reaction, a zero time
sample was withdrawn and catalyst was added, taking more sam-
ples during 6 h.

 C D  C H2
Aliquots of the samples have also been crushed to powder to
analyze their percentual mass content in C and H by elemental
microanalysis (EMA) using each time a 1 mg aliquot and a Perkin

k3
0

0
RD ¼ k3  C Ab þ k2  C P 
Elmer CHN 2400 elemental microanalyser.
RD ¼ k3  C Ab  k3  C D
For a qualitative and quantitative analysis of the rosin acids in-

0
0

volved in the isomerisation and disproportionation reaction net-

RN ¼ k1  C N
RP ¼ k2  C P
work, a GC–MS analytical procedure was also employed. A HP
6890 GC–MS chromatograph equipped with a mass detector MSD
Model 2

Model 4

RH2 ¼ k3  C D  C H2  k4  C Ab  C H2  k3  C D  C H2  k5  C Pi  C H2  k6  C H2
type 5973 was used to analyze the reaction compounds. The sam-
ple constituents were separated with a HP-INNOWAX (crosslinked
PEG) 30 m  0.32 mm ØI  0.25 lm column. Helium (purity
P99.999%) with a flow-rate of 16 mL min1, and a constant pres-
sure of 24 kPa was used as the carrier gas. The oven temperature
was T0 = 150 °C, 1 min, rate 5 °C/min, T1 = 190 °C, rate 10 °C/min,
RAb ¼ k1  C P þ k3  C D  C H2  k3  C Ab  k4  C Ab  C H2

T2 = 240 °C, 25 min, and post run, 249 °C, 5 min. The injection port
temperature was 210 °C, and the detector temperature was 250 °C.
The injection volume was 1 ll (splitless mode). Data acquisition
RAb ¼ k1  C N þ k2  C P  k3  C Ab  k4  C Ab

was performed in scan mode. Mass spectra were recorded from

0
 C D  C H2

m/z 50–550 amu.

To determine the concentration of the main rosin acids, GC-
Second-order kinetic models

FID analyses of withdrawn samples were performed. Samples

First-order kinetic models

k3
0

were methylated with N,N-dimethylformamiddimethylacetal and

RD ¼ k3  C Ab þ k2  C N 

analyzed on a HP model 5890 series II gas cromatograph with a

RPi ¼ k5  C Pi  C H2
RDi ¼ k4  C Ab  C H2

flame ionization detector using a dimethylpolysiloxane capillary

0

column (15 m  0.32 mm  0.5 mm, Zebron 1, Phenomenex).

RPi ¼ k5  C Pi
RN ¼ k1  C N

RN ¼ k2  C N
RDi ¼ k4  C Ab
RP ¼ k2  C P

RP ¼ k1  C P
RD ¼ k3  C Ab

The operating conditions of the gas chromatography were as fol-

Model 1

Model 3

lows: (i) initial oven temperature 453 K for 0 min, program at

1 K min1 to 468 K, then at 20 K min1 to 558 K and hold for
5.5 min, with total run time of 25 min; (ii) N2 was used as carried
gas with GC-FID system; (iii) the injection temperature was 523 K
and the detectors temperature was 573 K (Rigol et al., 2003; HSE,
2006).
Dihydroabietic acids

Dihydroabietic acids
Dehydroabietic acid

Dehydroabietic acid

2.4. Kinetic modelling and simulation

Neoabietic acid

Neoabietic acid
Palustric acid

Palustric acid
Pimaric acid

Pimaric acid
Abietic acid

Abietic acid
Compound

Hydrogen

Two kinetic models were the base of the proposed models to be

fitted to data from the reaction system: a first-order kinetic model
Table 1

(Wang et al., 2009) and a second-order kinetic model that consid-

ers dehydrogenation of abietic-type rosin acids followed by hydro-
 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511
genation of abietic- and pimaric-type rosin acids with the liberated
hydrogen from the previous reactions. In the first-order kinetic
model, it was assumed that the reactions just involve isomeriza-
tion and exchange of hydrogen among molecules of rosin resin
acids, a double bond rearrangement of rosin resin acids molecules
(Wang et al., 2009). In the second-order kinetic model, the concen-
tration of hydrogen able to perform hydrogenation of pimaric and
abietic acids was considered. The proposed kinetic models in-
cluded model 1 (the one by Wang et al.), the same with equilib-
rium between abietic and dehydroabietic acid (model 2) and
three kinetic models based on second-order kinetic laws and the
existence of free hydrogen molecules (models 3–5). Model 3 in-
volves that palustric acid isomerised to abietic acid, while neoabi-
etic acid is directly dehydrogenated. Model 4 considers exactly the
opposite: neoabietic acid isomerise to abietic acid, while palustric
acid is converted to dehydroabietic acid. Finally, model 5 involves
the isomerisation of both acids to abietic acid prior to the dehydro-
genation of the latter. Equations of all kinetic models are included
in Table 1.
Kinetic models were fitted using the Marquardt–Levenberg
algorithm together with a Runge–Kutta method for the numerical
integration of the kinetic equations. The selection of the most
appropriated model was based on the usual physical criteria (posi-
tive value of the kinetic parameters and values for the activation
energies within adequate ranges) and statistical criteria (Student’s
t value for each kinetic parameter, Fischer’s F and SQR values for
each kinetic model).
3. Results and discussion
3.1. Catalyst characterisation
Basic characteristics of the Escat 111 catalyst were obtained in
the Coulter SA 3100 Analyser. BET surface area was 582 m2/g,
while total pore volume was 0.50 ml/g. BET surface area related
to micropores (less than 5 nm diameter) was 200 m2/g, with an in-
ner volume due to micropores of 0.088 ml/g. The pore size distri-
bution shows a high percentage of volume related to the
micropore region, while macropores in the 20–80 nm pore diame-
ter region are present (data corroborated by SEM at 500–15,000
enlargement). Mesopores are also of importance, with a 35% of
the total volume linked to pores in the 2–20 nm pore diameter re-
gion. Thus, pore distribution is almost trimodal, mainly bimodal,
but highly dispersed.
XRD shows little crystallinity but this is linked to the presence
of Pd crystals (as SEM semiquantitative elemental analysis con-
firms). It can be seen that the sample exhibited four peaks at 2h
of 34.04°, 43.53°, 55.05° and 80.01°, ascribed, respectively, to
(1 1 1), (2 0 0), (2 1 0) and (3 1 1) reflections of Pd metal with a face
centered cubic (fcc) structure. The average size of the Pd crystallite
particles was estimated from the full width at half maximum of the
diffraction peaks to be 2.92 nm through Scherrer equation. The dis-
persion values (D), the ratio of number of surface atoms to the total
number of atoms is calculated from the equation D = 1.13/d, where
d is the crystallite size (2.9 nm). Thus, %D = 1.13/2.92  100 = 38.6%
(Pattabiraman, 1997).
Particle size is small, as the FBRM measurements showed, with
an average diameter of 1.6 ± 1.4 nm (high dispersion) and a totally
asymmetric distribution, with a maximum at 0.48 nm. This is con-
firmed by SEM images, with a high number of small particles in the
micro-meter range and some big particles with hydraulic diame-
ters up to 100 lm. EDS measurements give an idea of the distribu-
tion of Pd on carbon particles, with a percentage of Pd between
2.9% and 4.3% depending on the particle and zone of particle
studied.
3507
3.2. Reaction route and kinetic modelling
To fit kinetic models to molar quantities of the involved
rosin acids a non-linear regression technique based on the
Marquardt–Levenberg algorithm has been applied. Several kinetic
models have been considered, based on the isomerisation
pathways in the literature as well as assumptions and facts in
references regarding disproportionation. These kinetic models are
shown on Table 1, based on an empirical first order model (models
1 and 2) and on second-order kinetics, of a more phenomenological
nature (models 3–5). Identified compounds by GC–MS comprised
abietic-type acids (abietic, palustric, neoabietic, dihydroabietic
and dehydroabietic acids) as well as several pimaric and dihydro-
pimaric acids (several peaks for each one, as the inner double bond
can be in several positions inside the cyclic structure). Chromato-
graph profile was identical in GC-FID and GC–MS, so peaks were
assigned in a straightforward way, though during the construction
of the corresponding calibrates in GC-FID with several rosin acid
standards, peak assignations were confirmed.
Disproportionation of rosin involves dehydrogenation of abi-
etic-type acids, as well as hydrogenation and isomerisation reac-
tions, so that the mixture of acids evolves to a final composition
that is more stable from a thermodynamical viewpoint. It is pro-
posed that abietic acid is dehydrogenated to dehydroabietic acid
(which is the actual sought after product in industry), so that
two conjugated double bonds turn into an aromatic ring. At the
same time, palustric and neoabietic acid convert to abietic acid
or one of them can be dehydrogenated. Pymaric type acids (several
of which are identified in the GC–MS chromatograms) are hydroge-
nated to dihydropymaric acids. The double bond external to the
cyclic structure typical of such acids is prone to hydrogenation.
The hydrogen molecules from the dehydrogenation step can re-
act with pymaric and abietic-type acids, or can escape from the li-
quid phase where all reactions happen. Although this latter fact is
more than possible, according to results from all authors (Song
et al., 1985; Wang et al., 2009), it is also thought that hydrogen
atoms are rearranged among the different acids involved so that
dehydrogenation and hydrogenation are synchronized and no
hydrogen leaves the liquid phase and, even, a very recent kinetic
study seems to be based on such assumption (Wang et al., 2009).
The equilibrium between abietic and dehydroabietic acids
shows that the former is really stable at the high temperatures
where disproportionation and other reactions involving rosin take
place. In fact, at 200 °C, more than 80% of the rosin acids not yet
dehydrogenated is abietic acid (in the absence of a disproportion-
ation catalyst), so it is the most stable acid among the abietates.
Moreover, a worse fitting and an even worse value of the F param-
eter are obtained when using a non-equilibrium considering ki-
netic model to fit the experimental data herein presented as well
as the data featured in the paper by Wang et al. (2009), as shown
in Table 2.
If the empirical model involving only the redistribution of
hydrogen atoms among the rosin acid molecules is modified in
such a way that there is a chemical equilibrium between abietic
and dehydroabietic acid, a model that fits considerably better to
experimental data is obtained. (F changes from 1090 to 2649
although two kinetic parameters have to be added to those in mod-
el 1, and SQR is reduced by a factor of 2.5, as given in Table 2). All
these results seem to show that not only abietic acid and pimaric
acid react with free hydrogen molecules, but also that dehydroabi-
etic acid itself is prone to be hydrogenated.
Fitting of the proposed kinetic models to experimental data has
been performed by first calculating parameters at given tempera-
tures. Thus, values of the parameters at each temperature have
been calculated for each model and, afterwards, by linearization
of the Arrhenius equation, values for the neperian logarithm of
3508 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511

Table 2
Fit of the empirical and phenomenological models to experimental data of disproportionation of rosin obtained at several temperatures (from 200 to 240 °C) with an industrial Pd
5%/C catalyst from Engelhardt.

Kinetic parameters Model 1 Model 2 Model 3 Model 4 Model 5

Valor ± STD error Valor ± STD error Valor ± STD error Valor ± STD error Valor ± STD error
k1 Ln k0 21.8 ± 12.21 21.9 ± 8.08 19.4 ± 2.86 13.9 ± 2.43 18.8 ± 2.76
Ea/R 12,221 ± 5768 12,225 ± 3879 11,005 ± 1379 8450 ± 1175 10,797 ± 1333
k2 Ln k0 18.0 ± 5.13 18.5 ± 3.35 13.2 ± 5.21 22.1 ± 8.03 23.0 ± 6.80
Ea/R 10,422 ± 2481 10,635 ± 1619 8066 ± 2509 12,166 ± 3847 12,761 ± 3265
k3 Ln k0 18.7 ± 1.15 18.4 ± 0.70 21.1 ± 0.85 22.2 ± 1.03 19.2 ± 0.76
Ea/R 11,116 ± 558 10,876 ± 340 12,276 ± 418 12,845 ± 504 11,221 ± 371
0
k3 Ln k0 – 5.6 ± 2.60 15.7 ± 8.01 23.2 ± 7.00 18.8 ± 6.83
Ea/R – 5901 ± 1301 8587 ± 3945 12,399 ± 3408 10,361 ± 3342
k4 Ln k0 8.2 ± 2.27 14.0 ± 1.23 17.9 ± 4.89 25.1 ± 4.10 20.0 ± 3.49
Ea/R 6673 ± 1109 9407 ± 602 9472 ± 2392 13,195 ± 1994 10,711 ± 1707
k5 Ln k0 22.3 ± 10.62 22.3 ± 6.59 13.5 ± 8.63 18.8 ± 6.61 14.5 ± 6.36
Ea/R 13,434 ± 5244 13,434 ± 3253 8606 ± 4245 11,066 ± 3235 9041 ± 3129
k6 Ln k0 – – 23.9 ± 7.63 32.1 ± 6.77 28.1 ± 6.33
Ea/R – – 12,327 ± 3751 16,534 ± 3327 14,637 ± 3118
Model statistical F 1090 2649 3604 3292 3724
parameters SQR 6.62  102 2.53  102 1.63  102 1.77  102 1.59  102

Note: k1–k6 in L mol1 min1. Ea/R (K).

the preexponential parameters and for the activation energies have
been obtained. Finally, fitting of the kinetic models to all experi-
mental data (at the several temperature values used) has been per-
formed to calculate the optimal values of the kinetic parameters.
As shown in Table 2, the empirical model based on first-order ki-
netic equations is able to reasonably fit experimental data (F value
higher than the critical one for the given values of data and param-
eter numbers), but more complex models fit much better experi-
mental data, reducing the SQR value by a factor of 4 and
increasing by the same factor the F value when compared to model
1. Thus, both from a statistical and from a physical point of view,
disproportionation of rosin proceeds through the dehydrogenation
of rosin acids of the abietate kind, and the hydrogenation of all
acids involved, affecting mainly to pimaric acids, as the hydrogena-
tion of the exocyclic double bonds is favoured both by thermody-
namics and kinetics (Song et al., 1985; Wang et al., 2009). As
hydrogen molecules diffused fast, a great percentage of this gas
is lost from the reacting mass.
While palustric acid can be dehydrogenated directly, there is no
evidence that it cannot be converted to abietic acid previously
(model 5, SQR = 0.0159, F = 3724). In fact, while model 4 has a
SQR value slightly worse than models 3 and 5 (SQR = 0.0177,
F = 3292), model 3 is statistically equal to model 5 (SQR = 0.0163;
F = 3604). Considering the work on isomerisation of levopimaric
acid by Vital and Lobo (1992), this acid reacted directly to neoabi-
etic, abietic and palustric acids, being these two latter acids related
by a chemical balance. Vital and Lobo (1992) suggest that neoabi-
etic acid is not related directly to abietic acid, but palustric acid
converts to this latter acid, supporting model 3. In this work and
another from some years later (Portugal et al., 1996), results sug-
gest that levopimaric acid is stable only at relatively low tempera-
tures (those of rosin distillation, 150–180 °C), and isomerised
directly to abietic, neoabietic and palustric acid. In fact, levopima-
ric acid is the most abundant rosin acid in fresh oleoresin, while
abietic acid is the prevalent in heat- or acid-treated oleoresin
(Enoki, 1976). On the other hand, abietic acid isomerises to both
palustric and neoabietic acids, with a higher percentage of the
former, remaining the percentage of abietic acid higher than 80%
at temperatures of 200 °C or higher (Takeda et al., 1969). Palustric
acid isomerisation leads to abietic acid, the prevalent, and neoabi-
etic acid (Joye and Lawrence, 1961), though it is suggested that
neoabietic acid comes from levopimaric acid, being a product of
isomerisation of palustric acid by a rearrangement of double bonds
in one of the cycles of the diterpenic structure (Vital and Lobo,
1992). Thus, model 4 can be considered not valid based on
literature and on the statistical analysis in Table 2. Models 3 and
5 are both statistically valid, and there are reasons in the literature
for both of the chemical routes to be realistic. Model 5 involves the
rearrangement of two double bonds in neoabietic acid to render
abietic acid. This isomerisation is supported by some references
in literature (Takeda et al., 1969; Perelson et al., 1990).
This work and the one by Wang et al. (2009) show that abietic
acid is the main acid of gum rosin and converts directly to dehy-
droabietic acid. The statistical study in this work shows that an
equilibrium exists between abietic and dehydroabietic acid. Some
authors suggest that levopimaric acid and palustric acid can be
considered as the intermediates between abietic acid and dehydro-
abietic acid (Enoki, 1976; Portugal et al., 1996), and this seems to
be the case when temperature is lower than 200 °C. The common
industrial practice is, however, to work in the range 200–270 °C,
depending on the catalyst used. Here, abietic acid and dehydroabi-
etic acid seem to be the most stable acids. In fact, when using Pd on
charcoal as catalyst during hydrogenation of abietic acid, the cata-
lyst acts as a hydrogenation catalyst at temperatures lower than
150 °C and as a dehydrogenation catalyst at higher temperatures
(Yu et al., 2005).
Thus, considering the information in the literature and the re-
sults herein presented, model 5 seems to be more reasonable than
model 3 (neoabietic and palustric acids react to abietic acid prior to
the dehydrogenation/hydrogenation steps), and dehydrogenation
is the most important reaction due to the high operational temper-
atures. In Fig. 1, experimental data are shown as points, while the
fitting of model 5 to them is drawn in lines. Moreover, according to
kinetic model 5 and as shown in Fig. 2, hydrogen molar amount
grows initially until a maximum is reached and, afterwards, grad-
ually decreases due to diffusion to the atmosphere, and this pro-
cess is faster the higher temperature is.
All references in literature regarding disproportionation of ro-
sin, as well as the results from this work, lead to the proposal of
simple potential kinetic models, though many reactions are in-
volved in the final reaction scheme. Considering that reactions take
place on or near the catalyst surface, hyperbolic kinetic equations
could be expected (for example, regarding the adsorption and
splitting of hydrogen molecules or the adsorption of rosin acid
molecules). The macroscopic kinetic model shows, however, that
these surface phenomena are too fast to be considered in the
kinetic equations. As sulphur is the homogeneous catalyst with
an activity similar to that of Pd/C, and its activity is related to its
 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511 3509

0.30 0.35

(a) (b)
0.30
0.25

0.25
molar quantity (mol)

0.20

molar quantity (mol)

0.20
0.15
0.15

0.10
0.10

0.05
0.05

0.00 0.00

0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (min) Time (min)

0.35 0.35

(c) (d)
0.30 0.30

0.25 0.25
molar quantity (mol)
molar quantity (mol)

0.20 0.20

0.15 0.15

0.10 0.10

0.05 0.05

0.00 0.00

0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (min) Time (min)

0.35

(e)
0.30

0.25
molar quantity (mol)

0.20

0.15

0.10

0.05

0.00

0 50 100 150 200

Time (min)

Fig. 1. The phenomenological kinetic model fitting to experimental data obtained at (a) 473 K; (b) 483 K; (c) 493 K; (d) 503 K and (e) 513 K. (j) Abietic acid, (N)
dehydroabietic acid, (}) dihydroabietic acid, (s) palustric acid, (H) neoabietic acid, (h) pimaric acid, (–) kinetic model.

ability to withdraw hydrogen atoms and transfer them to other products is taking place near the surface, so the system is acting
molecules, it can be envisaged a similar behaviour for the Pd atoms as a pseudo-homogeneous reacting system (Kanno et al., 1987;
at the charcoal surface. There are a number of reasons why a mac- Zhang et al., 2010).
roscopic kinetic model has simply first-order kinetic equations When comparing kinetic parameters and model to those ob-
even if heterogeneous catalysis is involved. However, all of them tained by Wang et al. (2009), it can be observed that values for acti-
show that only one phenomenon is controlling the overall rate of vation energies lay in the range 80–100 kJ mol1, regardless of the
the process and, what is more, no accumulation of reactants and results considered (ours or those of Wang and coworkers). This
3510 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511

GC–MS not only is employed for the identification of the com-

0.06 pounds in the sample, depending on the value of a quality factor,
473 K but it can also be used to quantify the amount of each compound.
0.05
Here again, dehydrogenation seems to happen, as the mass of the
dehydrogenated species is considerably higher than the sum of
molar amount (mol)

the several dehydrogenated species that have been identified, even

0.04 483 K if both pymaric and abietate structures are taken into account.
For an accurate identification of the several acids involved in
0.03 the reactions taking place, GC-FID has been used, using standards
of the most important rosin acid identified by CC–MS and oleic acid
493 K
0.02 as an internal standard. Through this analytical strategy, quantifi-
cation of the rosin acids concentration in the samples is performed.
503 K By adding amounts of dehydrogenated species on one hand, and
0.01
performing the same calculation for the dehydrogenated ones on
513 K the other, it can be seen that the former is almost three times lar-
0.00
ger than the latter, and this is so independently of the reaction
0 50 100 150 200 250
temperature. Though not so clearly, the same trend is observed
Time (min)
in the paper of Wang and coworkers (2009). This fact is also due
Fig. 2. Simulated hydrogen molar amount temporal evolution in the reaction liquid to the statistically identical values of activation energies in dehy-
using kinetic model 5. drogenation and hydrogenation reactions (Wang et al., 2009). Thus,
dehydrogenation is the prevailing reaction in the reaction network
taking place during rosin disproportionation, and this reaction
could be expected as results from Wang and coworkers and our re-
leads to the most stable rosin acid to oxidative degradation: dehy-
sults are obtained in a similar range of particle size (less than
droabietic acid.
60 mm in diameter) and agitation speed (more than 400 rpm),
Palladium on charcoal catalysts seems to behave as sulphur,
where no hindrance due to mass transfer phenomena are expected
highly increasing disproportionation rates at relatively low tem-
and chemical reactions are the controlling step.
peratures (comparing to other rosin processes, as esterification,
As said previously, despite the empirical model (model 1) not
which proceeds at 260–290 °C). This could be so as Pd atoms act
being the best one, it is able to be fit to all empirical data reason-
as a hydrogen adsorbent, reservoir and a hydrogen-transfer vehi-
ably well: residual sum of squares is low, F value is high and error
cle, while the main reactions take place in the liquid phase, which
ranges for the parameters are narrow. To compare results of both
is a mixture of rosin acids (it is a solvent-less reacting system). In
works, it is necessary to take into account the fact that rosin and
fact, the formation of palladium hydrides and the well-known dis-
catalyst concentration in Wang’s work are 55% the ones used in
ruptive chemisorption of hydrogen on the palladium surface could
this work, as here solvent-less conditions are employed, while
be part of the explanation why there is a higher amount of dehy-
Wang and coworkers dilute rosin by using a mineral oil (oil no.
drogenated than hydrogenated rosin acids (Markus et al., 2007;
200) in a volume ratio 45:55 to rosin. Moreover, catalysts are sim-
Tomaszewska et al., 2008; Weng et al., 2010). On the other hand,
ilar but not identical (crystallinity and dispersion of palladium are
hydrogen escapes from the reacting liquid aided by the nitrogen
different). In this situation, kinetic constants of isomerisation reac-
that flows onto and over the liquid surface, through an irreversible
tions (k1 and k2), the kinetic constant value for the dehydrogena-
process that follows first-order kinetics and that highly depends on
tion reaction (k3), and the kinetic constant for pimaric acids
temperature, as the high activation energy of constant k6 of model
hydrogenation (k5) are similar in both works, while the hydrogena-
5 shows. In a similar way, but involving a chemical reaction, sul-
tion reaction constant for dehydroabietic acid (k4) is eight times
phur withdraws hydrogen atoms from rosin acids yielding hydro-
lower in this work. Thus, conditions in this paper are favourable
gen sulphide, that also desorbs partly from the liquid (Zhao et al.,
to isomerisation and dehydrogenation of abietic acids and less
2008).
favourable for hydrogenation reactions (mostly in the case of abi-
etic acids). In Wang’s paper, the amount of hydrogenated acids
is, more or less, between 60% and 75% that of dehydroabietic acid. 4. Conclusions
Here, hydrogenated acids amount to less than 40% of the dehydro-
genated acid, so, on the whole, both catalysts used are favourable In this paper, the role of hydrogen in rosin disproportionation is
to dehydrogenation. clarified with the aid of recent literature and using several analyt-
ical techniques. Dehydrogenation of abietic acid extent is almost
three times higher than that of hydrogenation reactions pooled
3.3. Hydrogen fate during disproportionation
all together, so, in the presence of Pd/C as a catalyst, dehydrogena-
tion is the prevailing phenomenon.
Two approaches have been considered to prove the role of
Based on this fact, a phenomenological kinetic model is se-
hydrogen in the disproportionation of rosin: elemental microanal-
lected, after discrimination among several kinetic models and reac-
ysis (EMA) and gas chromatography, using both a quadrupole mass
tion schemes was performed by non-linear regression techniques.
detector and a flame ionization detector (FID).
This model considers isomerisation reactions of abietates, as well
The hydrogen to carbon mass ratio percentage can be calculated
as dehydrogenation and hydrogenation of abietic acid and hydro-
from data obtained by EMA and it changes from 1.25 to 1.17 from
genation of pimaric acids.
pure abietic to pure dehydroabietic acid. As the runs at all the tem-
peratures proceed, this ratio changed from 1.22 to 1.19–1.18 in all
cases, showing that certain dehydrogenation of the solid material Acknowledgements
happens in every run. However, as the material is not pure and
some turpentine distilled off while disproportionation proceeds, Financial support from the Spanish Ministry of Education and
this technique allows only for a qualitative assessment of the from L.U.R.E.S.A. (through project PETRI 95-0821.OP) is gratefully
dehydrogenation. acknowledged. Moreover, the authors want to extent this
 J.C. Souto et al. / Bioresource Technology 102 (2011) 3504–3511
recognition to the Spanish Ministry of Environment (project MMA-
0392063-11.2) for further financial support. The authors also want
to express their deepest gratitude to Engelhardt Inc. (now, branch
of BASF) for the kind gift of a 5%Pd/C catalyst, as well as to L.U.R.-
E.S.A. for the generous gift of industrial rosin.
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