Brazilian Journal

of Chemical ISSN 0104-6632

Printed in Brazil
Engineering
Vol. 21, No. 02, pp. 211 - 218, April - June 2004

CATALYTIC WET-AIR OXIDATION OF LIGNIN IN

A THREE-PHASE REACTOR WITH AROMATIC
ALDEHYDE PRODUCTION
F.G. Sales1*, C. A. M. Abreu2 and J. A. F. R. Pereira3
1
Departamento de Engenharia Química, Centro de Tecnologia, Universidade Federal do Ceará,
Fortaleza - CE, 60455-760, Brazil. E-mail: [email protected]
2
Departamento de Engenharia Química, Centro de Tecnologia, Universidade Federal de Pernambuco,
Recife - PE, 50740-520, Brazil. E-mail: [email protected]
3
Departamento de Engenharia de Sistemas Químicos e Informática, Faculdade de Engenharia Química,
Universidade Estadual de Campinas, Campinas - SP,13083-970, Brazil.
E-mail: [email protected]

(Received: February 13, 2003 ; Accepted: December 13, 2003)

Abstract - In the present work a process of catalytic wet air oxidation of lignin obtained from sugar-cane
bagasse is developed with the objective of producing vanillin, syringaldehyde and p-hydroxybenzaldehyde in
a continuous regime. Palladium supported on J-alumina was used as the catalyst. The reactions in the lignin
degradation and aldehyde production were described by a kinetic model as a system of complex parallel and
series reactions, in which pseudo-first-order steps are found. For the purpose of producing aromatic aldehydes
in continuous regime, a three-phase fluidized reactor was built, and it was operated using atmospheric air as
the oxidizer. The best yield in aromatic aldehydes was of 12%. The experimental results were compatible with
those values obtained by the pseudo-heterogeneous axial dispersion model (PHADM) applied to the liquid
phase.
Keywords: catalytic wet air-oxidation, lignin, vanillin, syringaldehyde p-hydroxybenzaldehyde, palladium
catalyst, three-phase fluidized-bed reactor.

INTRODUCTION disadvantage of the additional cost of subsequent

separation of the catalyst and by-products, making
Lignin is a ramified polymer made up of their application impractical.
phenylpropane molecular units which occurs in an Catalytic-wet-air-oxidation (CWAO) using air
amorphous state mixed with holocellulose in the and supported catalysts is an attractive method for
vegetable biomass as a layer covering the cellulose. the treatment of effluents, aiming at removal of the
Of those chemical processes that seek to valorize total organic compounds (TOC) where the
lignocellulosic materials, oxidation has been the concentration of organic polluents is too low to
most promising, since it produces a mixture of justify an incineration process and too toxic for a
aromatic aldehydes which are of great industrial biological treatment (Harmsen et al., 1997). In the
interest, vanillin, syringaldehyde and the p- present work, CWAO was applied to the lignin
ydroxybenzaldehyde. Reasonable yields can be obtained from sugar-cane bagasse by the Organosolv
obtained by catalytic oxidation in an alkaline acid process. The reaction conditions were selected
medium, however limited to the use of homogeneous with the objective of obtaining intermediate
catalytic processes (Mathias, 1994) that have the oxidation products, such as vanillin, syringaldehyde

*To whom correspondence should be addressed

212 F.G. Sales, C. A. M. Abreu and J. A. F. R. Pereira

and p-hydroxybenzaldehyde. Moderated oxygen external heating element together with an internal
partial pressures and short reaction times are used to cooling coil provided temperature control in the reactor
avoid degradativ oxidation of the aldehydes with an accuracy of r 1K. The experimental
produced with formation of acid mixtures (formic, conditions are listed in Table 1. The liquid sample
latic, etc.). These aldehydes have many applications, was collected with a metal filter, and after separation
from galvanization to the production of chemical of the reagent, it was analyzed using a gas
intermediaries for pharmaceutical and agricultural chromatographer (HP 5890 Series II) equipped with
production. a capillary column (HP-1) and a flame ionization
detector (FID).

EXPERIMENTAL DEVELOPMENT Continuous Process Operation

Catalyst Preparation A schematic chart of the experimental setup is

given in Figure 1. The experiments were carried out
The catalyst was prepared from palladium in a fluidized-bed operation in a 0.13m diameter
chloride (Vetec) and J-alumina (Procatalyse) as tubular reactor with a total height of 1.40 m. The
catalytic support, with a superficial area of BET distributor plate has holes with diameter of 0.002 m,
3.65 u 105m2/kg and a particle porosity (Hp) of a triangular pass, with continuous free plate area (M)
0.5878. of 0.85%.
The humid impregnation procedure was used to The gas-phase feed is through a two-stage
prepare the catalyst. After the impregnation step the compressor and the liquid-phase feed with a positive
material was dried at 393K for 12 hours and then displacement pump with a surge tank to avoid line
reduced at 673K for 2 hours. The palladium content pulsation. Before entering the reactor, both fluid
of 2.85% was quantified by atomic absorption. The lines pass through a preheater.
presence of palladium in crystal shape was The experimental procedure was divided into
confirmed through X-ray diffraction (2T = 40.047, three steps: in the first the reactor operated at a
46.609, 68.085 and 82.104). liquid-phase flow rate of 5L/h and temperature of
373K during three hours; in the second step the
Kinetic Evaluation same liquid-phase flow rate and temperature of
393K were maintained during the same period; and
The kinetic experiments (Sales et al., 2001) in the last the liquid-phase flow rate was changed to
were carried out in a high-pressure SS-316 Parr 10L/h and the temperature maintained at 393K
slurry reactor (Model 4843) equipped with a six- during two hours. At the end of each step, reactor
bladed turbine-type impeller mixer and with an operation was verified to be in steady state (Sales,
effective volume of 500mL. A thermal sensor and an 2001).

Table 1: Experimental conditions for the kinetic study

of catalytic wet-air lignin oxidation.

Temperature (K) 373 / 393 / 413

Oxygen partial pressure (bar) 2 / 5 / 10

Total pressure (bar) 20

Reaction volume (L) 0.5

Lignin Concentration(g/L,NaOH 2N) 60

Catalyst (Pd content, wt%) 2.85

Catalyst mass concentration (wt%) 2.5% - 5%

Catalyst granulometry (Pm) 90 - 200

Brazilian Journal of Chemical Engineering

 Catalytic Wet-Air Oxidation of Lignin In a Three-Phase Reactor 213

Figure 1: Schematic diagram of the continuous three-phase fluidized reactor.

RESULTS AND DISCUSSION the present work we did not observe the evolution of
gases at the beginning of the reaction, probably due
The kinetics of catalytic wet-air lignin oxidation to the mild reaction conditions, although two
was studied to determine the influences of reaction steps in lignin oxidation have been
temperature, oxygen partial pressure, mass of recognized for temperatures starting at 393K (Figure
catalyst fed into reactor and catalyst particle 2). For the proposed overall mechanism, we assumed
size, which were detailed in previous work (Sales, that lignin, a macromolecule with a complex
2001). structure, is hydrolyzed forming fragments that
The organic compound mechanism of the produce aldehydes and other products of low
catalytic wet-air oxidation is very complex, even for molecular weight. The second step of the reaction
simple structures such as phenol (Hamoudi et alli., was not studied because the concentration of lignin
1999; Zhang. at all, 1998). This is especially true in did not change significantly.
lignin oxidation with the reaction resulting in the The kinetic profiles for aromatic aldehyde
formation of a large variety of intermediate products. concentrations resulting from the lignin conversion
Generally is assumed that the wet-air oxidation are typical of reactions in series with their production
occurs in two or more steps, with small molecules and subsequent degradation in acids. Typical profiles
such as CO2 and water formed in the first stage. In are shown in Figure 3.

2.0

1.8 373K(exp.)
393K(exp.)
1.6 413K(exp.)

1.4

1.2
-ln(CL/CL )
0

1.0

0.8

0.6

0.4

0.2

0.0
0.0 0.5 1.0 1.5 2.0
time(h)

Figure 2. Experimental (symbols) and theoretical (lines) concentration profiles, according to a

pseudo-first-order model, for catalytic wet-air lignin oxidation, PO2 = 5bar.

Brazilian Journal of Chemical Engineering Vol. 21, No. 02, pp. 211 - 218, April - June 2004
214 F.G. Sales, C. A. M. Abreu and J. A. F. R. Pereira

0.09
VANILIN
0.08 SYRINGALDEHYDE
p-HYDROXYBENZALDEHYDE
0.07

0.06

0.05

0
C/CL 0.04

0.03

0.02

0.01

0.00
0.0 0.5 1.0 1.5 2.0
time(h)

Figure 3: Experimental (symbols) and theoretical (lines) concentration profiles, according to a pseudo-
first-order model, for the reaction products. PO2= 5bar, PT = 20bar, T = 413K, 4wt% catalyst.

Figure 4: Schematic mechanism for catalytic wet-air lignin oxidation.

Process Kinetic Modeling V dC P

k 3C L  k 6C P
m S dt
A schematic pathway of the reactions based on
observations of its behavior, is proposed according to
Figure 4. Considering all the process steps
V dC S
k 4 C L  k 7 CS
represented by first-order reactions, we have m S dt

where V is the reaction volume and ms the

V dC L catalyst mass, while L represents the lignin, V the
k 1  k 2  k 3  k 4 C L
m S dt vanillin, S the syringaldeyde, P the p-
hydroxybenzaldehyde and R the other products of
low molecular weight. ki (i=1, 2, 3, 4, 5, 6, 7)
V dC V represent the pseudo-first-order kinetic constants.
k 1C L  k 5 C V
m S dt
Estimation of Kinetics Parameters

V dC R Figure 2 shows the experimental results of

k 5C V  k 2 C L  k 6 C P  k 7 CS catalytic wet-air lignin oxidation for three
m S dt
temperatures and 5bar of oxygen partial pressure.
Brazilian Journal of Chemical Engineering
 Catalytic Wet-Air Oxidation of Lignin In a Three-Phase Reactor 215

The data obtained were well fitted by a first-order for the lignin and aldehyde concentrations. The
kinetic law, even when they are applied separately in results are presented in Table 3.
each step, as in the case of the reaction temperatures Catalyst activity and seletivity were evaluated by
of 393K and 413K. The rate constants were obtained comparing the rate constants of the catalytic
by the linear regression model and are listed in Table 2. reactions with those of reactions without catalyst.
The differential equations system, representing Through a comparative analysis (Table 4) under
the kinetic model of the reaction, was numerically these conditions, it was observed that the catalyst
solved using a 4th order Runge-Kutta integration increased the lignin degradation rate approximately
method. The calculated values of CL, CV, CS and CP twofold. However, the rate of aldehyde formation
were compared with the experimental results (Figure was completely changed. The catalytic effect
3). The kinetic parameters were obtained through an could also be outstanding compared to the rate
optimization procedure using Box’s complex method constant k2, relative to the formation of other
(Box, 1965), minimizing an objective function, Fob products. The catalyst reduced the formation of
n undesirable products approximately fortyfold,
( Fob exp
> teo
¦ Ci  Ci ),
i 1
@2
constructed from the indicating a significative improvement in the
selectivity for aldehydes associated with the catalytic
experimental ( C iexp ) and the calculated values ( C iteo ) process.

Table 2: Rate constants and activation energy of the catalytic wet-air lignin oxidation.

kx103 (min-1) 'E(KJ/mol)

373K 393K 413K

Initial step 5.86 13.98 23.23 44.26

Final step - 2.03 2.02 0.97

Table 3: Rate constants and activation energy for the catalytic reaction of the first-order kinetic
model for the production of aromatic aldehydes with an oxygen partial pressure of 5bar.

Aromatic
kx103(min-1)
Aldehydes 'E
KJ/mol
373K 393K 413K

Lignin kL 5.39 11.60 23.50 43.76

k1 0.53 2.08 3.83 63.64

Vanillin
k5 23.28 28.73 31.93 10.18

Syringal- k4 1.93 7.93 15.00 66.04

dehyde
k7 70.30 127.0 216.7 35.97

p-Hydroxy- k3 0.60 1.45 4.50 64.11

benzald.
k6 4.67 8.96 18.33 43.62
Others
k2 2.33 0.16 0.17 -
products

Brazilian Journal of Chemical Engineering Vol. 21, No. 02, pp. 211 - 218, April - June 2004
216 F.G. Sales, C. A. M. Abreu and J. A. F. R. Pereira

Table 4. Rate constants and activation energy for the catalytic and non catalytic
processes for the first-order kinetic model for production of aromatic
aldehydes, with an oxygen partial pressure of 5bar.

kx103(min-1)
Components Non
Catalytic
catalytic

Lignin kL 6.53 11.60

k1 0.16 2.08
Vanillin
k5 71.32 28.7
k4 0.18 7.93
Syringaldehyde
k7 61.67 127.0
k3 0.15 1.45
p-Hydroxibenzaldehyde
k6 31.92 8.96
Other products k2 6.04 0.16

Continuous Three-phase Reactor Phenomenological limited quantification to the liquid phase component.
Modeling For these components we have the following:

Having predicted the representation of the For the lignin,

reaction process in the three-phase fluidized-bed 2 x
H L d C L ,l dC L ,l
x
reactor, the pseudo-heterogeneous axial dispersion
model (PHADM) was applied with external mass Pe L dz 2

dz
 St S,l C xL ,l  C Sx ,l   0
transfer to the catalytic pellet, assuming dispersion in
the liquid-phase. The conceptual basis for
For aldehydes,
development of the model involves the following
assumptions: 2 x x
H L d C L,A dC L,A
1) flow of the dispersed phase (gas) and the
continuous phase (slurry) is concurrent and Pe L dz 2

dz
 St S,A C xL,A  C Sx ,A   0
continuous;
2) gas-liquid and liquid-solid mass transfer For the liquid-phase inside the catalyst pellet, we
resistances are described by the two-films theory; have the following:
3) internal mass transfer resistance is described by
the internal effectiveness factor, recognizing the For the lignin,
model as pseudo-heterogeneous;
4) surface reaction with intrinsic kinetics is 
St S,l C xL ,l  C Sx ,l  K l R xl
described according to a pseudo-first order model;
5) mass transport occurs in the axial direction by
For aldehydes,
convection and axial dispersion;
6) catalytic load, component adsorption and oxygen
concentration are taken into account as pseudo-

St S, v C xL,A  C Sx ,A  K O 2 R xA
constants;
7) the system is isothermal with no temperature The boundary conditions of the system are as
gradients in the catalytic pellet or in the reactor; follows:
8) continuous-phase (slurry) vapor pressure was
At the bed inlet, Z=0
much lower than the oxidizer (atmospheric air)
pressure.
H L dC L,l
x
Writing the system equations in dimensionless C xL ,l  C xL ,l,E (lignin)
form, and with the previous simplifications, we Pe L dz

Brazilian Journal of Chemical Engineering

 Catalytic Wet-Air Oxidation of Lignin In a Three-Phase Reactor 217

x
H L dC L,A the three-phase reactor, used as the operational
C xL,A  C xL,A,E (aldehydes) parameters a temperature of 393K, 4bar of pressure,
Pe L dz a palladium catalyst (3 wt%) on J-alumina with a
concentration of 4 wt%, a granulometry in the range
At the bed outlet, Z=1 of 400mm to 500mm and a lignin concentration in
the liquid-phase of 30g/L in NaOH 2M solution.
dC xL,l Atmospheric air was the oxidizer. The other
0 (lignin)
dz parameters are given in Sales (2001). The model
lignin and aldehyde concentration profiles for the
dC xL,A reactor are presented in Figure 5.
0 (aldehydes) The experimental results obtained at a sampling
dz
point located at 80% of the length of the reactor
under the same conditions as those applied in the
In previous equations the concentrations are in
the dimensionless forms based on the bed-inlet lignin simulation were 4.3mmol/L for vanillin and
concentration. The subscripts L and S refer to the 6.3mmol/L for syringaldehyde, both in good
liquid and solid phase, respectively, while l and A agreement with the values predited by the axial
refer to the lignin and aldehydes, respectively. dispersion model. The chromatographic analyses of
The axial dispersion model described by the the samples taken throughout the reactor found that
previous equations is a boundary value problem for sample points did not offer systematic results for the
the group of second-order nonhomogeneous ordinary p-hydroxybenzaldehyde. In some samplings was
differential equations, except for the lignin detected, however, it was not possible to evaluate its
concentration throughout the reactor. Solution of the evolution during the entire time of reactor operation.
equations system was obtained analytically through a Verifying its physical constants, such as of a melting
computational program developed in the MAPLE point of 319K, and the observation that it does not
software, version 6. have a boiling point because it sublimes above this
The simulation of the of catalytic wet-air lignin temperature, this behavior may indicate that this
oxidation process, aiming at describing the lignin aldehyde was being arrested outside the reactor with
and the aromatic aldehyde concentration profiles for the gas-phase during the experiment.

LIGNIN, mmol/L VANILLIN, mmo/L

OH
OCH3

CHO

SYRINGALDEHYDE, mmol/l p-HYDROXYBENZALDEHYDE, mmol/L

OH
OH
H3CO OCH3

CHO
CHO

Figure 5: Concentration profiles for the reactor according to the axial dispersion model
for temperature of 393K, a liquid-phase flow rate of 5l/h, a gas-phase flow
rate of 1000l/h, and a total pressure of 4bar.
Brazilian Journal of Chemical Engineering Vol. 21, No. 02, pp. 211 - 218, April - June 2004
218 F.G. Sales, C. A. M. Abreu and J. A. F. R. Pereira

CONCLUSIONS Oxidation of Aqueous Phenolic Solutions Catalyst

Deactivation and kinetics. Chemical Engineering
Conversion of the process from discontinuous to Science, v 54, pp 3568-3576 (1999).
continuous operation of catalytic wet-air lignin Harmsen, J.M.A., Jelemensjy, L. and van Andel-Scheffer,
oxidation allowed validation of the kinetic model of P.J.M., Kinetic Modeling for Wet Air Oxidation on
series and parallel reactions with pseudo-first-order Formic Acid on Carbon Supported Platinum Catalyst.
steps. The maximum operational yield with the
Applied Catalysis A: General, v 165, pp 499-509
reactor operating with an air-flow rate of 1000L/h, a
liquid phase flow rate of 5L/h, a catalytic loading of (1997).
4 wt% and a pressure of 4bar, was of approximately Mathias, A.L. and Rodrigues, A.E., Production of Vanilin
12% aldehydes in relation to the lignin feed by Oxidation of Pine Kraft Lignins with Oxygen.
concentration. The data obtained from the process Holzforscung (1994).
simulation of the pseudo-heterogeneous axial dispersion Sales, F.G., Pereira, J.A.F.R. and Abreu, C.A.M., Estudo
model are compatible with those values experimentally Hidrodinâmico de um Reator de Leito de Lama
obtained at the point located at 80% of the reactor length. Trifásico. XXVIII Congresso Brasileiro de Sistemas
Particulados, Teresópolis, Brazil, (2000).
Sales, F.G., Oxidação Úmida Catalítica da Lignina em
ACKNOWLEDGMENTS Reatores Trifásicos com Produção de Aldeídos
Aromáticos. Ph.D.diss., Faculdade de Engenharia
The authors acknowledge the financial support Química, Universidade Estadual de Campinas,
received from CAPES for this work. Brazil,(2001).
Zhang, Q., Chuang, K.T., Kinetics of Wet Oxidation of
REFERENCES Black Liquor over a Pt-Pd-Ce/alumina Catalyst.
Applied Catalysis B: Enviromental, v 17, pp 321-332,
Hamoudi, S., Belkacemi, K. and Larachi, F., Catalytic 1998.

Brazilian Journal of Chemical Engineering