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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
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.
⁎
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
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
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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)
a
BET method.
b
P/Po = 0.95, from BJH method.
c
From N2 adsorption (t-plot method).
d
By difference method.
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
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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638
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
a
GC–MS analysis.
b
PBOM – Mixed bio-oil obtained from PBO LT and PBO HT.
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
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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638
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
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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 (%)
1
Fe2O3: 2.5 wt.% 5.0 wt.% 10.0 wt.% Phenolic phase
Table 8
The product yields for non-catalytic and catalytic pyrolysis tests.
Catalyst Product yields (wt%)
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
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E. David and J. Kopač Journal of Analytical and Applied Pyrolysis 141 (2019) 104638
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