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Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

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Journal of Analytical and Applied Pyrolysis


journal homepage: www.elsevier.com/locate/jaap

Upgrading the characteristics of the bio-oil obtained from rapeseed oil cake T
pyrolysis through the catalytic treatment of its vapors
E. Davida, , J. Kopačb

a
National Institute for Cryogenic and Isotopic Technologies, Street Uzinei No.4, P.O Râureni, P.O. Box 7, 240050 Rm.Vâlcea, Romania
b
Faculty of Mechanical Engineering, University of Ljubljana, Askerceva 6, SI-1000 Ljubljana, Slovenia

ARTICLE INFO ABSTRACT

Keywords: The present work is aimed to investigate the upgrading of rapeseed oil cake pyrolysis bio-oil (PBO) through
Fe2O3/ZSM-5 catalyst catalytic treatment of its vapors in a fixed bed reactor. In this regard, HZSM-5 zeolite and promoted Fe2O3/ZSM-
Rapeseed oil cake 5 samples were prepared. The HZSM-5 zeolite was synthesized by NaOH treatment and then it was used as
Fixed bed reactor support material to obtain Fe2O3-ZSM-5 catalysts (2.5–10 wt% Fe2O3 load) produced by metalorganic chemical
Catalytic pyrolysis
vapour deposition (MOCVD). The support material and catalysts prepared were characterized by BET, XRD,
Improved bio-oil
SEM, EDX methods. The Fe2O3-ZSM-5 catalysts were then used in the study on improving the characteristics of
the rapeseed oil cake pyrolysis bio-oil through catalytic treatment of its vapors.The results obtained by non-
catalytic and catalytic pyrolysis experiments showed that bio-oil yields have decreased in the presence of cat-
alysts. In addition, the bio-oil composition was determined by GC/MS method and it was observed that Fe2O3/
ZSM-5 catalyst lead to a significant improved quality of the pyrolysis bio-oil in comparison with product ob-
tained by non-catalytic process. The catalyst improved the oxygen removal process from the organic phase of
pyrolysis bio-oil and further increased the quantity of desirable products such as aromatic and phenolics com-
pounds.

1. Introduction value. These undesirable properties constitute the main disadvantages


and major obstacles to the bio-oil feasibility. Catalytic pyrolysis can be
Liquid fuels, such as gasoline and diesel, are obtained through oil used to largely remove these major problems by converting oxygenated
refining, but the oil reserve is limited. For this reason other sources, compounds directly into hydrocarbons, which can improve the final
cheaper and renewable, must be found from which these fuels could be properties of bio-oil [15,16]. Furthermore, the use of catalysts in bio-
obtained. Therefore, finding of alternatives for energy sources is im- mass thermal processing is an approach that can maximize the yields
portant and becomes interested field for research. Alternatives include and selectivity of the obtained products. The catalysts also improve the
biomass, which has potential to supply energy requirements for next composition of bio-oil and its physico-chemical characteristics [17–20].
decades [1–3]. Biomass is a source of abundant raw material and can be In addition, in the presence of catalysts,there are produced bio-oils
transformed into valuable products through different technologies which contain higher amounts of aromatic compounds and an organic
[4,5], such as catalytic pyrolysis and gasification, steam and super- fraction that can be upgraded to diesel fuels and valuable chemical
critical water gasification [6,7]. Pyrolysis of renewable biomass to substances [21–24]. Catalytic modernization technologies include those
produce bio-oil has attracted attention because bio-oil is easy to based on cracking, hydrogenation, aromatization, deoxygenation re-
transport and store for various uses, such as the energy source (syn- actions [25–29].Wang et al. [29] showed that HZSM-5 has maintained a
thetic fuel or hydrogen) or valuable chemical products (phenolic or high catalyst activity during the cracking and hydrogenation of bio-oil
aliphatic compounds) [8–11]. Bio-oils are totally different from petro- compounds, while the selectivity towards oil phase with an aromatic
leum fuels, they are complex mixtures that include many oxygenated content of around 90% has increased up to 40%. The data presented in
compounds, and contain many important chemicals [12–14]. Im- the literature show that metal-modified zeolite materials can increase
provement of oil features refers to the reduction of undesirable char- the yield of hydrocarbons and high-value chemical substances resulting
acteristics such as high concentrations of oxygen compounds, water from the pyrolysis process of biomass [27,30]. The addition of metals to
content and acidity, corrosivity, high viscosity, and also low calorific zeolite increased its catalytical activity in the conversion of oxygenated


Corresponding author.
E-mail address: elena.david@icsi.ro (E. David).

https://doi.org/10.1016/j.jaap.2019.104638
Received 15 January 2019; Received in revised form 1 June 2019; Accepted 13 June 2019
Available online 20 June 2019
0165-2370/ © 2019 Elsevier B.V. All rights reserved.
E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

compounds from polycyclic aromatic hydrocarbons by favoring the Table 1


formation of monocyclic compounds. In literature are presented data Proximate, ultimate and component analyses of reapseed oil cake (RSOC).
regarding to ZSM-5 zeolite with different Si/Al ratio to produce suitable Proximate (dry,wt%) Ultimate (dry,wt%) Component (dry,
catalyst for methanol conversion to hydrocarbon products, that are analysis analysis analysis wt%)
comparable to petroleum gasoline [18,24,31].The acid sites of ZSM-5
Moisture – C 45.81 Extractivesa 19.51
catalyst determined the catalyst activity and the defects into ZSM-5
Ash 6.67 H 6.17 Cellulose 28.46
zeolite structure can affect the catalyst activity [20]. Veses et al. [20] N 6.85 Hemicellulose 41.58
tested many types of zeolite catalysts for biomass conversion to fuels. S 0.93 Lignin 5.01
Their results proved that for gasoline producing, the performance of O 33.47
ZSM-5 catalyst is much better than other catalysts.Among the metals, H/C molar 1.62
ratio
iron is considered favorable one in catalytic reactions based on its high
O/C molar 0.55
activities and also in terms of economic aspects [17]. ratio
The method of metal-organic chemical vapour deposition (MOCVD), Empirical formula CH1.62 O0.55 N0.128 S0.0076
in which species of metal are deposited on supports using a gaseous GCVb, MJ/kg 25.61
metal precursor, has been used special in semiconductor field [32,33]. a
Toluene/alcohol (2/1, v/v).
In the last time, this method is considered to be used for the catalyst b
Gross calorific value.
preparation, because MOCVD assures the deposition of thin and uni-
form layers on support material at a relatively low temperature [34,35].
according to standard ASTM D240-02. Envolved gasses during ther-
The MOCVD is a one-step preparation method and is able to develop
mocatalytic pyrolysis and thermal characteristics of residual biomass
stable and well-structured catalysts without showing the disadvantages
(RSOC) under inet gas (N2) atmosphere were performed using a ther-
encountered in other methods [19,23]. Catalysts prepared by MOCVD
mogravimetric analyzer (Setaram Setsys Evolution instrument con-
method have a much better metal dispersion, because the metal com-
trolled by a PC) coupled with FTIR-Thermo Nicolet IZ10 analyzer. The
pound is in the vapour phase and its diffusion is much faster than in the
transfer lines from TGA to FTIR has been maintained at 230OC, to avoid
liquid phase [32].
the condensation of volatiles compounds. FTIR spectra were registered
The aim of this work was (i) to prepare novel Fe2O3-ZSM-5 catalysts
at a resolution of 4 cm−1, the sample weighing about 15 mg was heated
which have a good iron dispersion and small iron crystalline size by
to 900°C, with a rate of 10°C /min, under N2 flow rate of 20 mL/min.
MOCVD method, (ii) test the catalytic activity of the prepared catalysts
The scan range of the wave number was 4000-500 cm−1. Also, for se-
in improving of pyrolysis bio-oil through catalytic cracking of its vapors
parated bio-oil and phenolic fraction was performed the Proton Nuclear
in a fixed bed pyrolysis reactor and (iii) the characterization of the
Magnetic Resonance Spectroscopy (1H-NMR), using an analizer type
obtained bio-oil. The role of Fe2O3 loading into HZSM-5 catalyst on the
Agilent 600 MHz NMR.
distribution and yield of pyrolysis products was evaluated and also the
bio-oil characteristics were established.
2.2. Catalyst preparation

2. Experimental part HZSM-5 sample was synthesized by alkali modification for catalytic
pyrolysis process to improve the characteristics of the pyrolysis bio-oil.
2.1. Biomass feedstock As Al and Si sources were used following chemical compounds: alu-
minum hydroxide (Al(OH)3, Aldrich) and tetraethyl orthosilicate
Rapeseed oil cake (RSOC) was used as residual biomass to feed a (TEOS, 98%, Aldrich), respectively. Also,as a template was used tetra-
fixed bed pyrolysis reactor and was procured in the form of extrudates propylammonium bromide (TPABr), 50% aqueous solution. The de-
(Ø of 5–6 mm) from the company Zecasin SA Bucharest. Rapeseed oil tailed synthesis method of HZSM-5 and promoted samples by Fe2O3 are
cake extrudates were maintained at 105°C for 3 h to remove the as follow.
moisture content and after that were crushed, sieved mechanically and
before pyrolysis experiments they were kept in desiccator containing 2.2.1. Synthesis method of HZSM-5
anhydrous calcium chloride. Particles having sizes of (≤ 0.5 mm) were Aluminum hydroxide [Al(OH)3] and distilled water are mixed to-
used all over the experiments. A schematic representation of the cata- gether and stirred at room temperature until it was obtained a clear
lytic pyrolysis process of rapeseed oil cake (RSOC) is given in Fig. 1. The solution, then to the solution was added 0.25gNaOH/100 mL solution
proximate and ultimate analyses were performed and the results are and the mixture was stirred at 80°C for 20 min to obtain solution I. The
shown in Table 1. stirring rate was setted to 150 r.p.m. Solution II was prepared by drop
The moisture, volatile content, fixed carbon and ash amount were addition of TEOS to 50% aqueous solution of TPABr and then stirred at
determined according to ASTM standards (D 2016 74, D3174 89 and room temperature. Solution II was added to solution I and the mixture
D1102 84, respectively). Ultimate analysis was performed to estab- was stirred for 3 h at room temperature till TEOS was completely hy-
lished the content of C,H,N and O and it was used a Carlo Erba 1106 drolyzed.
instrument according to standard ASTM D 5373. The composition was After that, the pH value was adjusted to 11 by drop addition of 20%
determined according to standard ASTM D 3176. The extractives and aqueous solution of H2SO4. The obtained gel was stirred for 10 h and
lignocellulosic content of RSOC was established using TAPPI test then transferred to a PTFE lined stainless steel autoclave, heated at
methods [36]. The gross calorific value (GCV) was calculated in 185°C for 24 h to crystallize the zeolite. The resulted solid was

Fig. 1. Schematic representation of the catalytic pyrolysis


process of rapeseed oil cake (RSOC).

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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

filtered,washed with distilled water and dried at 105°C for 8 h and then diffraction (XRD) using a Philips PW 1710 diffractometer with Ni filter
calcined at 550°C for 2 h to remove the template. Calcined sample was and Cu kα radiation. XRD patterns diffractograms were compared to the
treated two times with 0.8% aqueous solution of NaOH, with a ratio of standards to establish crystalline phases. The morphology of the Fe2O3
25 ml NaOH/1 g solid at a temperature of 65°C and after that the modified ZSM-5 catalysts was analyzed by Scanning Electron
sample was washed with distilled water. The obtained solution was Microscopy (SEM) using a microscope JSM-7500 F (JOEL-Japan), op-
subjected to ion exchanged process using a 8% aqueous solution of erated at 10 kV. Energy dispersive spectroscopy (EDS) was used to
NH4NO3 with the ratio of 20 ml NH4NO3/1 g solid at 65°C. After that study the iron dispersion on catalyst samples.The metal content of
the sample was dried at 105°C for 3 h and then calcinated at 550°C for catalysts (Fe) was calculated from the average of at least six different
8 h to obtain HZSM-5.The composition of prepared HZSM-5 expressed points and was also determined by atomic absorption spectroscopy
in parts by weight is: 0.25 Al(OH)3 : 6.25TEOS : 4 TPABr : 1000 H2O. (AAS), using an analyzer type Analytic Yena Nova 300. The catalyst
All chemicals used were of analytical grade and were provided by degradation by coke formation and deposition into catalyst mass and its
Sigma-Aldrich. regeneration was analyzed by thermogravimetric analysis, using a
Setaram Setsys Evolution thermogravimetric analyzer. The curves of
2.2.2. Fe2O3/ZSM-5 preparation the mass loss were resulted for fresh and coked catalyst by heating
Fe2O3-ZSM-5 catalyst was prepared by metal organic chemical va- 20 mg of catalyst samples from room temperature to 900OC under ni-
pour deposition method (MOCVD). HZSM-5 prepared in accordance trogen gaseous atmosphere, with a flow rate of 50 ml/min. The tem-
with the procedure described in Section 2.2.1, and ferric acet- perature was increased at a heating rate of 5°C /min. The coke removal
ylacetonate [Fe(acac)3] powders were selected as support and iron was performed by keeping of the catalyst samples at temperature of
source precursor, respectively. HZSM-5 support was put inside a Fritsch 900°C for 1.5 h.
planetary ball mill and well mixed by grinding together with Fe(acac)3
precursor for 5 min. After that, the mixture was sieved to obtain a 2.4. Pyrolysis tests and bio-oil characterization
particle size fraction of ≤ 150 μm. This fraction was put into a quartz
tube and during the process an inert gas (N2) was used as protective The experimental tests of thermo-catalytic pyrolysis process were
atmosphere. The deposition temperature was setted at 300 °C with a performed under inert atmosphere (N2) in a fixed bed reactor with a
heating rate of 5 °C/min and the deposition time was 2 h. After de- length of 700 mm, an inner diameter of 12 mm, made of stainless steel
position step, the catalyst material was calcined in air at temperature of and which was heated by electrical furnace to ensure an isothermal
550 °C for a time of 6 h.The heating rate was of 2 °C/ min. The Fe2O3 regime for process. Fig. 3 presents a schematic diagram of the experi-
load into catalyst mass was varied and was obtained through varying mental system.
iron source precursor ratio as follows: 2.5 wt %; 5.0 wt%; 10.0 wt%. The temperature measurement was taken in the middle of the bio-
mass and catalyst bed, with (Cr : Al) thermocouples, in order to control
2.3. HZSM-5 and Fe2O3/ZSM-5 materials characterization the reactor temperature. The N2 flow rate before entry into the reactor
and catalyst bed was established by a fine control using a gas flow-
The specific surface area, total pore volume and micropore volume meter. All the pyrolysis tests were carried out at 500°C with 40°C/ min
of the HZSM-5 and Fe2O3/ZSM-5 materials were determined by N2 heating rate and a N2 gas flow rate of 400 mL/min. For every test 100 g
adsorption-desorption at (−196.15°C), using a surface analyzer of rapeseed oil cake with particle size up to 0.5 mm (≤0.5 mm) and
(Quantachrome Inst., Nova 2200e), BET, BJH and DH methods. Before 10 g of catalyst with particle size up to 150 μm (≤0.15 mm) were in-
the experimental tests to be performed, the samples were degassed in troduced in the reactor. The upper layer is formed of rapeseed oil cake
nitrogen flow, at the temperature of 150OC, for 2.5 h to remove the and lower layer is formed of catalyst (as is shown in Fig. 3). Before of
humidity and other adsorbed molecules. Nitrogen gas (N2) with a high each experiment, all system was stripped with N2 gas to assure inert
purity of 99.99 vol. %, was provided from Linde Company. Fig. 2 (I and atmosphere during the experimental test. Due to the way biomass and
II) shows the N2 adsorption/desorption isotherms (I) and pore struc- catalyst are placed in the reactor, the thermal pyrolysis of rapeseed oil
tures (II) of different material samples.The values of these parameters cake take place first and then the released vapors (primary product)
are shown in Table 2. were improved when they have passed through the bed of catalyst. The
The bulk phases of the catalysts were determined by X-ray obtained catalytic pyrolysis vapors were next passed through a metallic

Fig. 2. (I) - N2 adsorption/desorption isotherms (a) HZSM-5;(b) Fe2O3/ZSM-5 (2.5 wt% Fe2O3); (c) Fe2O3/ZSM-5 (5.0 wt% Fe2O3); (d) fresh Fe2O3/ZSM-5 (10.0 wt%
Fe2O3); (e) used Fe2O3/ZSM-5 (10.0 wt% Fe2O3); (II) - pore diameter for each sample: (a) HZSM-5;(b) Fe2O3/ZSM-5 (2.5 wt% Fe2O3); (c) Fe2O3/ZSM-5 (5.0 wt%
Fe2O3); (d) fresh Fe2O3/ZSM-5 (10.0 wt% Fe2O3); (e)used Fe2O3/ZSM-5 (10.0 wt% Fe2O3).

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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

Table 2
The surface properties of the HZSM-5 and Fe2O3/ZSM-5 materials.
a
Sample SBET(m2/g) b
Vmicro(cm3/g) d
Vmeso(cm3/g) c
Vtotal(cm3/g) a
Dmeso (nm)

HZSM-5 412.23 0.048 0.295 0.343 3.68


Fe2O3/ZSM-5(2.5 wt% Fe2O3) 397.12 0.038 0.276 0.314 3.43
Fe2O3/ZSM-5(5.0 wt% Fe2O3) 327.81 0.032 0.243 0.275 3.28
Fe2O3/ZSM-5(10 wt% Fe2O3) 242.41 0.028 0.210 0.238 3.19
Fe2O3/ZSM-5(10 wt% Fe2O3) used 186.31 0.017 0.187 0.204 3.01

a
BET method.
b
P/Po = 0.95, from BJH method.
c
From N2 adsorption (t-plot method).
d
By difference method.

according to the IP336 method. The carbon residue was established


according to ASTM D 189, the caloric value according to ASTM D 3286-
91a and total acid value according to ASTM D 974. The pH value of bio-
oils was measured with a digital pH meter (Mettler Delta 340) and the
empirical formula, H/C, N/C, O/C molar ratios were calculated from
elemental composition. The viscosity of the bio-oil was measured using
a ARES TA rheometer and the temperature was set at 25 °C and 60 °C.
The surface tension was determined at 25 °C, using Wilhelmy plate
method. The gaseous fraction was collected and analyzed using a
chromatograph (type Varian CP-3800 with TCD and FID detectors)
equipped with a 5 Å molecular sieve column, a Porapak N column and a
Chromosorb column and using as carrier gas argon. The concentrations
of CO2, CO, N2, H2, CH4 and hydrocarbons up to C7 were measured.

2.5. Phenol separation from bio-oil

Bio-oil is organic fraction obtained from pyrolysis liquid phase,


which contains the highest quantity of phenol. The feasible separation
of phenolic fraction from bio-oil is important to enhance the phenolics
production and to upgarde the characteristics of bio-oil for its using as
bio-fuel. To separate the phenol from bio-oil the liquid-liquid extraction
technique was performed and it was used an alkaline solution, an acid
solution and an organic solvent, as it is presented in Fig. 4.
An amount of diethyl ether (C4H10O) and an amount of 10% solu-
Fig. 3. Schematic diagram of experimental setup for biomass pyrolysis and bio-
tion of NaOH were added to bio-oil (as is incated in Fig. 4) and the
oil production. (1)-tank containing nitrogen gas under pressure; (2)- pressure resulting mixture was stirred for 15 min and then left to stand for
controller; (3)- adjusting valve ;(4)-flowmeter; (5)- reactor; (6)-electrical fur- 10 min, to extract the phenol and water from the bio-oil by reacting
nace;(T)- temperature control;(7) and (8)- metallic sieve; (9) and (10)- metallic with phenol, in agreement with the chemical reaction (1) and to form
perforated support; (11)-biomass; (12)-catalyst; (13)-ceramic filter; (14) and sodium phenoxide:
(15)- gas-liquid separator containing liquid product; (16)- cooling bath (85OC);
(17)- cooling bath (10OC) ; (18)-condenser with water (5OC); (19)- two-way NaOH + C6H6O = NaOC6H5+H2O (1)
valve ;(20)-gaseous product. (A)- analizer.
The splitting of the phase was initiated and as a result two phases

sieve and ceramic filter to retain any solid particles and then through
cold traps in order to cool and to collect the liquid phase. The liquid
phase consisting of oil and aqueous fractions,was then separated and
each fraction was weighed. In addition, the solid products consisting of
bio-char and catalyst with coke deposited on and into its mass were
weighed to establish the pyrolysis yields. Each experimental test was
performed at least three times and the measurement error was less than
0.5%. Point values on the diagrams are an average value of these data.
The bio-oil was separated of aqueous fraction and the chemical com-
position of the bio-oil was identified by using GCMS-QP2010SE Gas
Chromatograph/Mass Spectrometer. The identification of the chroma-
tographic peaks was made using the NIST mass spectrum library. The
compositional analysis of the functional groups was carried out by
using a Nicolet 6700 FTIR spectrophotometer and using KBr tablets of
1 mm thickness. The 1H NMR of bio-oil was get using a high NMR
Bruker spectrometer, at 300 MHz frequency. Bio-oil density was de-
termined according to ASTM D 1298. The bio-oil water content was
established by Karl Fischer method according to ASTM D 1744. The ash
content was established according to ASTM D 482 and sulphur content Fig. 4. The scheme for separation of phenol from bio-oil.

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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

weight was observed, a maximum value of weight loss appeared in the


180–545°C temperature range and a total weight loss was determined
as 73.95% for a temperature range between 40 to 900°C. As stated by
the results of the pyrolysis behavior of rapeseed oil cake, the thermal
(without and with catalyst) pyrolysis tests were performed at tem-
perature of 500°C.

3.2. HZSM-5 support and Fe2O3-ZSM-5 catalyst characterization

The nitrogen adsorption-desorption results at (-196OC) for the


HZSM-5 and Fe2O3-ZSM-5 are shown in Fig. 2 (I and II) and the Table 2.
After loading iron oxid, the specific surface area of HZSM-5 support
decreased from 412.23 to 242.41 m2/g and total pore volume also de-
creased from 0.343 to 0.238 cm3/g (Table 2). This results may be due to
Fig. 5. Schematic representation of the reaction mechanism between sodium the iron oxid which dispersed in the pore canal and blocked the pores.
hydroxide and phenol. The micropore volume decreased from 0.048 to 0.028 cm3 /g, proving
that the iron species are loaded into the micropores and the result is the
decreasing of the micropore volume. Pore volume and the average pore
occurred, a bottom one aqueous layer which was slightly more clear,
size also decreased, because of the accumulation of metal species into
light brown and transparent to an upper one layer that was dark and
support material [37,39,40]. As can be seen from Fig. 2, the used cat-
more viscous. The formed bottom layer was separated and an amount of
alyst shows a reduced adsorption capacity (I- isotherm e), as well as a
10% solution of HCl was added to it, to react with sodium phenoxide
decreasing in the pore size, (II-curve e). This decreasing is due to the
(NaOC6H5) in solution to form NaCl and phenol, in agreement with the
deposition of coke on and into the catalyst pores, leading to narrowing
chemical reaction (2):
or blocking of pores [41,42].
NaOC6H5+HCl = C6H6O + NaCl (2) To study the morphology and structure of Fe2O3-ZSM-5 catalysts the
SEM method was used and SEM images are presented in Fig. 7
and after pH measurement, any traces of moisture were evaporated (a,b,c,d,e).
in the oven at 105°C for 30 min and the remaining compound was in- On the SEM image it can be seen that the iron species are uniformly
troduced to NMR to confirm the phenol recovery from bio-oil, as shown distributed on the catalyst surface and that the active metal was suc-
in Fig. 4, while the reactions mechanisms are presented in Fig. 5 cessfully loaded on the support through MOCVD method.
As indicated by the image, the Fe3+ species in prepared Fe2O3-ZSM-
3. Results and discussion 5 catalysts are extra-framework (Fe2O3), which are also placed into the
pores and on the zeolite surface. These results are in agreement with
3.1. Composition and thermal degradation of the rapeseed oil cake EDX data shown in Fig. 7(b,c,d, e).
The EDX elemental analysis spectrum (Fig. 7b,c,d, e), highlights the
In Table 1 are showed the results for the proximate and ultimate existence of Si, Al, O and Fe elements in catalysts.It can be seen that Fe
analyses as well as the components from rapeseed oil cake composition. species are presented on surface of catalyst, confirming that the Fe
An analysis of thermal degradation of the rapeseed oil cake is shown in components were successfully loaded on the HZSM-5 support through
Fig. 6 and analyzing the diagrams can be distinguished three major MOCVD technique. In Fig. 8 are shown the XRD diagrams for HZSM-5
areas of weight loss. used as support and for Fe2O3-ZSM-5 catalyst. It can be seen that both
The first weight loss is due to the moisture removal and has oc- samples show diffraction peaks between 6-9O and 22-24O, which cor-
curred at the temperature value from 40 to 180°C. The next weight loss responds to the standard HZSM-5 model according to literature data
is due to the hemicellulose volatilization and has appeared at the [43].
temperature value from 180 to 250°C. A maximum rate of weight loss, The XRD diagrams show that the crystalline phase of HZSM-5 sup-
represented by the point of inflection corresponds to 235°C. The third port did not change significantly after iron loading, although a decrease
weight loss level appeared between 235 and 545°C was associated to in peak intensity in Fe2O3-ZSM-5 catalyst relative to HZSM-5 intensity
degradation of the cellulose and lignin components. The third weight peak can be observed. According to the other studies [42,43] the iron
loss stage represents the major pyrolysis process and the point of in- loading on HZSM-5 support could enhance the absorption of X-ray on
flection corresponds to temperature value of 330°C. The similar results the zeolite, producing a decrease in the intensity of peaks and so the Fe
were presented in other studies related to the rapeseed oil cake TG peaks can not be highlighted very well for the Fe2O3-ZSM-5 catalyst.On
analysis [37,38]. In the 545–900°C temperature range no further loss of the other hand the peak intensity could be significantly influenced by
the specie size and its dispersion on the HZSM-5 support, or it could be
due to a good dispersion and a small size of crystalline components.

3.3. Characterization of pyrolysis bio-oil (PBO) obtained from rapeseed oil


cake

PBO obtained is a liquid mixture of more than 115 of organic


compounds, viscous and dark color (Fig. 9a).
PBO was collected at two temperature, high temperature of 85OC
(PBOHT) and low temperature of 10OC (PBOLT), respectively (Fig. 3).
The main compounds identified in PBO can be included in the following
categories : hydrocarbons, alcohols, aldehydes, furans, ketones, esters,
phenolics. The results of the GC / MS analysis are shown in Table 3, the
PBO sample is mostly enriched in phenolics, aromatics and aliphatic
Fig. 6. The TG and dTG curves of rapeseed oil cake. groups.

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Fig. 7. SEM images for: (a) HZSM-5; (b) Fe2O3/ZSM-5 (2.5 wt% Fe2O3 loading); (c) Fe2O3/ZSM-5 (5.0 wt% Fe2O3 loading); (d) Fe2O3/ZSM-5 (10 wt% Fe2O3 loading)
and their EDX results.

As can be seen in Table 3, the hydrocarbons (aliphatic and aromatic) content of complex organic compounds. The presence of oxygen is re-
are present in all samples collected (PBO LT, PBO HT and PBOM), for lated to oxygenated compounds identified in bio-oil composition and its
example representing an area of 25.62% for PBOM sample. Aldehydes, presence in the aliphatic, aromatic, or cyclic hydrocarbons represents a
alcohols, ketones, furans, esters,as well as phenolics compounds are major disadvantage of bio-oil. The catalysts used in the bio-oil pro-
also identified in PBO and in these classes, alcohols, furans and phenols duction process can re-arrange the molecules structure of the organic
are more predominant than others components, as is shown in Table 3. compounds by deoxygenation, cracking, reforming, dehydrogenation
The aliphatic and aromatic compounds identified in PBO are presented reactions.The elemental composition and the calorific values of the bio-
in Table 4. oils obtained by pyrolysis process with and without catalyst are shown
As is presented above, the bio-oil is characterized by its highly in Table 5.

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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

Table 3
Distribution of the chemical functional groups in bio-oil produced at 500°C, N2
gas flow rate of 400 mL/min, particle size ≤ 0.5 mm and Fe2O3/ZSM-5(10 wt%
Fe2O3).

a
Compound Area (%)

b
PBO LT PBO HT PBO M

Aldehydes 2.93 4.51 3.44


Alcohols 5.67 6.85 6.52
Esters 1.95 2.18 2.17
Furans 7.74 7.18 7.92
Ketones 2.95 2.86 2.91
Phenolics 50.84 51.79 51.41
Hydrocarbons 27.91 24.62 25.62

a
GC–MS analysis.
b
PBOM – Mixed bio-oil obtained from PBO LT and PBO HT.

Fig. 8. XRD diagram for HZSM-5 and Fe2O3-ZSM-5 catalyst.


Table 4
Some aliphatic and aromatic compounds that were identified in PBO obtained
from rapeseed oil cake pyrolysis at 500OC, 400 mL/min N2 flow rate (without
catalyst).
Compound Formula Retention time (min.)

Aliphatics
Pentanone C5H10O 7.58
Pentanol C5H12O 9.47
Hexanone C6H12O 9.51
Pentadecane C15H32 20.68
Heptadecane C17H32 24.56
Hexadecanitrile C16H31N 46.77
Palmitic acid C16H32O2 47.75
9-Octadecenoic acid, methyl ester C19H36O2 50.15
Oleic acid C18H34O2 51.94
Hexadecanamide C16H33NO 52.21
Aromatics
1 H-Pyrrole C4H5N 10.41
Benzene,1,2-diethyl C10H14 10.68
Benzene,1-methyl-4-(1methylethyl) C10H14 11.31
Toluene C7H8 11.85
2-Methylinden C10H10 13.12
Methyl pyridine C6H7N 14.35
Benzene, hexyl C12H18 15.53
Naphthalene, 1-methyl C11H10 16.31
Ethyl benzene C8H10 17.16
Naphthalene,2-ethyl C12H12 18.58
Phenol C6H6O 22.54
O-cresol C7H8O 25.29
P-cresol C7H8O 26.14
2,4-Dimethyl-phenol C8H10O 27.21
4-Ethyl-phenol C8H10O 29.12
3-Phenyl propionitrile C9H9N 31.43
1,2-A pyrazine C8H8N2 32.51
2,6-Dimethoxy-phenol C8H10O3 33.16
3-Methyl-1H-Indole C9H9N 35.23
Fig. 9. Pirolysis bio-oil obtained from rapeseed oil cake: (a)- without catalyst ; N-Isobutyl aniline C10H15N 36.63
(b)-with Fe2O3-ZSM-5 catalyst (10 wt% Fe2O3 loading). 2,3,5-Trimethoxy toluene C10H14O3 37.76
P-Toluen sulfonic acid, n-heptyl ester C14H22O3S 43.94
2-Hydroxymethyl-5-metoxy-phenol C8H10O3 45.38
Analyzing the data in Table 5, as a result of catalyst using, the
deoxygenation reactions occurred on the catalyst surface and the GC–MS analysis.
oxygen content of bio-oil has decreased from 15.53 to 7.72% while
carbon amount increased from 66.53 to 83.37%. The increase in carbon
content can be justified by the fact that during the pyrolysis process, the increase in carbon content, indicating a superior quality of bio oil.
deoxygenation reactions (removing an important amount of oxygen) In Fig. 10 and Table 6 is presented the distribution of the main
occurred. Also, other reactions specific to the conversion process such products of the bio-oil and extracted phase obtained by pyrolysis with
as cracking, dehydrogenation take place and these probably led and to and witout catalyst.
carbon deposition from organic compounds contained in bio-oil, and As is known,of pyrolysis products, acids determine a high corro-
this extra amount of carbon is added to the amount resulting from the sivity, ethers and esters reduce heating value, PAHs are carcinogenic
decomposition of lignin. In fact, this aspect is presented in the other and all are the undesired products,while hydrocarbons, furans, phenols
studies [42,44].The hydrogen amount remained nearly at the same and alcohols represent desirable compounds to obtain valuable che-
content, this being a result of simultaneous dehydration and dec- micals and fuel. The introduction of Fe3+ into ZSM-5 and the use of the
arboxylation reactions (see Table 5). On the other hand, the heating Fe2O3/ZSM-5 catalyst in pyrolysis process results in an increase in the
value of the bio-oil increased (from 32.97 to 34.58 MJ/kg) with the relative area of phenolic compounds. As can be observed in Fig. 10 the

7
E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

Table 5 By 1H-NMR spectroscopy were analized the bio-oil resulted from


Characteristics of the bio-oils resulted from RSOC pyrolysis with and without catalytic pyrolysis using Fe2O3/ZSM-5 catalyst (10 wt% Fe2O3 content)
catalyst (pyrolysis temperature of 500°C, N2 gas flow rate of 400 mL/min). and its separated phenolic phase. Table 7 shows the results that were
Eement(wt%) Non- With catalyst (Fe2O3/ZSM-5) obtained by 1H-NMR analysis for pyrolysis bio-oil and its phenolic
catalyst phase using Fe2O3/ZSM-5 catalyst (10 wt% Fe2O3 content).
Fe2O3 Fe2O3 (5 wt.%) Fe2O3 (10 wt.%) The content of phenolics (AreOH) increased significantly in the
(2.5 wt.%)
extracted phase, while other functional groups have decreased.
C 66.53 82.23 82.78 83.37 Chemical change region between 4.5 and 3.3 has increased for the ex-
H 8.65 8.84 8.31 8.62 tracted phenolic phase compared to the bio-oil obtained by using
N 8.77 0.23 0.22 0.12 Fe2O3/ZSM-5(10 wt% Fe2O3) catalyst. This increasing could be explained
S 0.52 0.21 0.18 0.17 by the phenolic groups presence that were bonded with hydroxyl,
Oa 15.53 8.49 8.51 7.72
H/C molar ratio 1.56 1.59 1.57 1.57
methyl, ether or methoxy groups [44]. The data from 1H-NMR analysis
O/C molar ratio 0.175 0.21 0.17 0.17 are consistent with the results obtained by GC–MS analysis.
Empirical The bio-oil compositions resulted from the rapeseed oil cake pyr-
formula CH1.56 O0.175N0.112S0.003; CH1.29 O0.077N0.002S0.001 ;CH1.20 olysis were analyzed and it was observed that the catalyst bed presence
O0.077N0.002S0.001 ;CH1.24 O0.069N0.001S0.001
determined a decrease in bio-oil yield. There has also been an increase
H2O content (wt. 5.02 4.68 4.46 4.21
%) in gaseous yield and water amount as a result of catalyst effectiveness
Viscosity at 60OC 0.51 0.47 0.43 0.41 for the deoxygenation reactions. Compared to pyrolysis process without
(Pa s) catalyst, it was observed that the catalyst existence modified sig-
Acidity (mg KOH/ 44.76 44.26 43.64 43.28 nificantly the bio-oil quality.It was found that the use of Fe2O3/ZSM-
g)
Density (g/mL) 1.23 1.21 1.19 1.18
5(10 wt% Fe2O3) catalyst has determined a significantly increase of the
Surface tension, 25.03 24.74 24.12 23.98 phenolic compounds amount, aliphatic and aromatic hydrocarbons in
25OC,(mN/m) bio-oil composition. The data by GC–MS analysis showed that about
GCVb (MJ/kg) 32.97 33.21 34.43 34.58 33.37% phenolics compounds are present in bio-oil composition ob-
a
tained without catalyst, while in the presence of Fe2O3/ZSM-5 catalyst,
Calculated from difference.
b the phenolics fraction was increased and represents over 45% (45.04%
Gross calorific value.
to 51.41% for Fe2O3/ZSM-5(2.5 wt% Fe2O3) and Fe2O3/ZSM-5(10 wt%
Fe2O3), respectively). In the both cases the phenolic fraction can be se-
parated using the extraction method. The average yield of phenolic
fraction, after extraction was ≈ 17.62 wt%, and this is in agreement
with other data presented in the literature [45–47]. The increasing of
the phenolic phase can be due to the dehydrogenation, cracking, or
deoxygenation reactions and the experimental results obtained by this
study show that the use of a catalyst bed such as Fe2O3/ZSM-5 for bio-
oil upgrading represents an efficient tehnique to decrease oxygenated
compounds, to increase the carbon content as well as to keep a constant
hydrogen content in the bio-oil composition.

3.4. Effect of Fe2O3/ZSM-5 on the yields of product

The yield of the products from the catalytic and non-catalytic pyr-
Fig. 10. Distribution of the chemical functional groups in bio-oil and phenolic olysis process is shown in Table 8.
phase (data obtained from GC–MS analysis), pyrolysis temperature of 500°C, N2 The product yields of rapeseed oil cake non-catalytic pyrolysis can
gas flow rate of 400 mL/min and particle size ≤ 0.5 mm with and without be compared with the product yields obtained from catalytic pyrolysis
catalyst.
using Fe2O3/ZSM-5 as catalyst. As can be observed, the highest bio-oil
yield of 31.64 wt%, was obtained from the non-catalytic tests. The use
content of undesired components in bio-oil such as aldehydes, esters of Fe2O3/ZSM-5 catalyst has decreased bio-oil yield and has increased
and ketones decreased in the presence of Fe/ZMS-5 catalyst, more ob- the gas and water yields with the gradual increase of the content of
vious for the catalyst containing 10% Fe2O3 content compared with the Fe2O3 from catalyst. This effect is due to the deoxygenation reactions
bio-oil obtained by pyrolysis without catalyst. The highest amount of that occur on the surface of the catalyst. When the pyrolysis vapour
hydrocarbons (25.62 wt%, Table 3) and phenols (51.41%, Table 6) re- passed through the catalyst bed, the highly oxygenated compounds
sulted when the 10 wt% Fe2O3/ZSM-5 catalyst was used and this effi- with long chain were converted to lower molecular weight compounds
ciency is due to a possible improvement in the deoxygenation and de- (in particular hydrocarbons) by catalytic cracking. Water formation has
hydrogenation reactions on the catalyst. also been stimulated by decarboxylation and dehydration reactions of
Fig. 11 shows the FTIR spectrum of the bio-oil obtained from ra- the oxygenated compounds on the acid sites of catalysts [6,12,19,33].
peseed oil cake pyrolysis using 10 wt% Fe2O3/ZSM-5 catalyst. The fact that biomass and catalyst in the reactor form separate beds, the
The OeH stretching bands between 3100 and 3400 cm−1 indicate char yield are almost constant for all tests, without the formation of
the presence of alcohols and phenols, while the bands between 2840 additional char and coke on the biomass bed.
and 3000 cm−1corespond to a olephinic CeH stretching vibration. Otherwise, during the pyrolysis process it is possible that the coke
These cause unsaturated conditions at the lower intensities in structure formed to be deposited on the catalyst surface causing a decrease in its
while the C]C deformation bands between 1345 and 1475 cm−1 activity by reducing the surface area due to the narrowing and blocking
highlights the alkenes and aromatics presence. The peaks between of the pores. The weight loss curves obtained for fresh and used cata-
1560–1750 cm−1 corespond to the presence of the carbonyl groups. lysts are showed in Fig.12.
These groups may be due by ester, ketones,aldehydes or carboxylic acid It can be observed that the first weight loss (2–2.5 wt%) for both
structure. It has been noted that these functional groups have been catalyst materials has took place in temperature range of 70 to 185OC
identified for all bio-oil samples and is due to moisture removal (H2O molecules volatilization bonded

8
E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638

Table 6
The distribution of phenolic compounds in bio-oils and phenolic phase resulted from GC–MS data of % relative area.
Compound Relative area (%)

No catalyst With catalyst (1Fe2O3/ ZSM-5)

1
Fe2O3: 2.5 wt.% 5.0 wt.% 10.0 wt.% Phenolic phase

Phenol (C6H6O) 1.51 1.89 2.64 2.82 2.96


2-Hydroxyphenol (C6H6O2) 0.37 0.44 0.52 0.65 0.71
Malthol (C6H6O3) 1.23 1.32 1.37 1.41 1.51
O-Cresol (C7H8O) 0.81 0.86 1.23 1.32 2.52
P-Cresol(C7H8O) 1.03 1.36 1.77 1.98 3.05
2-Methoxyphenol(C7H8O2) 2.29 2.45 2.54 2.64 5.02
2-Hydroxy-4-methylphenol(C7H8O) 1.79 1.91 2.26 2.85 1.27
3-Methoxy catechol (C7H8O3) 0.35 0.47 0.61 0.78 1.62
Phenol,2,3-Dimethyl(C8H10O) 0.02 0.36 0.43 0.47 2.75
Phenol,2,4-Dimethyl(C8H10O) 0.96 1.04 1.55 1.47 0.45
Phenol,2,6-Dimethyl(C8H10O) 0.16 0.26 0.33 0.41 0.42
Phenol,3,5-Dimethyl(C8H10O) 0.67 0.31 0.39 0.27 0.97
2,6-Dimethoxyphenol (C8H10O3) 7.93 9.85 8.96 8.61 15.52
Phenol,2-Methoxy-4-(1-propenyl)(C8H8O2)
M-Cresol (C8H10O2) 0.51 0.85 1.18 0.84 0.42
Methyl-syringol (C9H12O3) 0.96 1.44 1.73 1.85 2.02
4-Ethylguaiacol(C9H12O2) 1.18 2.54 2.94 2.41 11.37
2-Methoxy-4-vinylphenol(C9H12O2) 1.16 1.19 1.21 2.11 2.78
Phenol,2-(1-methylethyl) (C10H14O) 2.35 1.78 1.65 1.61 2.65
Phenol,2-methoxy-3-(2-propenyl) – 0.46 0.76 0.86 1.88
(C10H12O2) 0.56 0.62 0.72 0.47 1.11
Phenol,2,6-dimethoxy-4-(2-propenyl)
(C11H14O3) 5.91 8.63 8.12 8.36 8.51
Others phenolics(C7H8O, C8H10O, C8H10O3, etc 0.62 5.06 4.34 7.22 12.54
Total phenolic compounds 33.37 45.04 51.41 47.25 82.05

Table 8
The product yields for non-catalytic and catalytic pyrolysis tests.
Catalyst Product yields (wt%)

Char Bio-oil Gas Water

Non-catalyst 12.21 31.64 35.24 20.91


Fe2O3/ZSM-5(2.5 wt% Fe2O3) 11.86 28.45 37.94 21.75
Fe2O3/ZSM-5(5.0 wt% Fe2O3) 11.35 27.12 38.12 23.41
Fe2O3/ZSM-5(10 wt% Fe2O3) 11.05 25.09 38.48 25.38

into fresh catalyst and the constant weight losing after 950OC demon-
strated that used catalyst regeneration was almost completed.

Fig. 11. The FTIR spectrum for bio-oil resulted from the rapeseed oil cake 4. Conclusions
pyrolysis.
Fe2O3-ZSM-5 catalysts with different loading ratios (2.5, 5.0 and
10 wt%) of Fe2O3 were prepared through MOCVD method and were
on the catalyst surface).The fresh Fe2O3/ZSM-5 catalyst remained at tested in a catalytical reactor for the obtaining of bio-oil from the
same state, without loss any mass, while the used catalyst has continued pyrolysis of the rapeseed oil cake. The use of a Fe2O3-ZSM-5 catalyst
to loss in weight due to coke removal up to about 3.6 wt% until the bed in pyrolysis reactor decreased the bio-oil amount while the gas and
temperature reached a value over 950OC.This difference in the behavior water yield increased, this being a consequence of the catalyst activity
for two catalyst materials approved the coke formation and deposition in the deoxygenation reactions.Compared to non-catalytic pyrolysis
process, the presence of the catalyst considerable reduces the amount of

Table 7
The results obtained by 1H-NMR analysis for pyrolysis bio-oil and its phenolic phase (Fe2O3/ZSM-5 catalyst,10 wt% Fe2O3 content).
Hydrogen type Chem.shift Bio-oil (%)
(δ, ppm)
Fe2O3/ZSM-5(10 wt% Fe2O3) Phenolic phase

R-CHO/R-COOH(Aldehyde/carboxylic acid) 13.0-9.5 0.65 0.35


Ar-H/Ar-OH (Aromatic/phenolic) 9.5-6.5 16.25 26.75
Olefinic proton 6.5-4.5 2.27 5.28
Ar-CH2-Ar (Methylene/methoxy) 4.5-3.3 18.13 29.12
CH3,CH2,CH α(benzylic) 3.3-2.7 39.65 21.58
CH3γ, β ̶ CH3, CH2/CH γ (from aromatic ring) 2.7-0.5 23.05 16.92

9
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