Journal of Environmental Chemical Engineering 9 (2021) 105564

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Journal of Environmental Chemical Engineering

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Pyrolysis of walnut shell residues in a fixed bed reactor: Effects of process

parameters, chemical and functional properties of bio-oil
Mudasir Akbar Shah a, *, N.S. Khan b, Vimal Kumar c, Ahsanulhaq Qurashi d
a
Department of Chemical Engineering, Kombolchia Institute of Technology Kombolchia, Ethiopia
b
Department of Chemical Engineering, National Institute of Technology Srinagar, J&K 190006, India
c
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Uttarakhand 247667, India
d
Department of Chemistry, Khalifa University Abu Dhabi 127788, United Arab Emirates

A R T I C L E I N F O A B S T R A C T

Keywords: In the present work the products and characteristics of bio-yields obtained from pyrolysis of different types of
Biomass walnut shells (WS) by using a fixed bed pyrolyzer. The different walnut shells considered are paper (PSW), thin
Pyrolysis products (TSW), medium (MSW) and hard (HSW) shelled walnut. The biomass samples were pyrolyzed at various tem­
Bioproducts
peratures, particle sizes, heating and sweep gas flow rates. The results revealed that the maximum bio-oil 44.7,
Fixed bed reactor
Bio-oil
biochar 37.6 and gas 40.4 wt% yields have been obtained for HSW, MSW and HSW at a pyrolysis temperature of
550, 375 and 750 ◦ C respectively at heating rate 0.33 K/sec, particle size 0.5–1.5 mm with swept gas flow rate
1.6 × 10− 6 m3/s. The higher heating value (HHV) of bio-oil obtained from different walnut shells are ranged
from 26 to 27.3 MJ/kg. Comprehensive physiochemical characteristics such as density, viscosity, flash point,
pour point and water content of bio-oils have been obtained. Chemical composition analysis of bio-oils revealed
that the pyrolytic bio-oil composition is predominated by oxygenated compounds such as carbonyl, methoxy,
phenols and carboxyl groups determined by GC-MS, FTIR, 1H NMR and 13C NMR. The pyrolysis gas mainly
contained CH4 CO, H2, CO2, and light hydrocarbons. Based on these results and structural analysis of the bio-oil,
it can be concluded that the bio-oil obtained from WS may be used as a feedstock for furnaces, as a fuel, as a
lubricant after modifications and value-added products via pyrolysis.

1. Introduction Pyrolysis is the thermal decomposition process of biomass residue in

the absence of air into bio-oil, biochar and gaseous yields with different
The increases in world population and economic development has proportions [7,8]. Generally, there are various types of pyrolysis; fast,
led to increase energy demand, which has greatly affected the existing slow and intermediate pyrolysis and their distribution of yields depend
limited reserves of fossil fuels. From 2010 onwards there is ≈2.8% per on the process of parameters. Fast pyrolysis was carried out at rapid
year increase in the usage of renewable sources [1] for different appli­ heating rates, temperature around 500 ◦ C with short residence time and
cations. Renewable energy source, such as biomass, has been considered produce 80%, 12% and 13% of bio-oil, biochar and gas respectively.
as an alternative for fossil fuels. Biomass has become an attractive fuel Similarly, slow pyrolysis can produce 30%, 35% and 35% bio-oil, bio­
because of its unique nature and as a major renewable energy source to char and gas respectively with a temperature up to 400 ◦ C and residence
control CO2 emissions [2,3]. It is mainly comprised of cellulose, hemi­ time up to 120 s [2,9–10]. For intermediate pyrolysis, about 20–30%
celluloses, lignin and extractives; and the composition of biomass vary gas, 15 – 25% biochar and 40–60% bio-oil of the total product yield are
significantly due to diverse origins and types. In last few decades, with obtained with the vapor residence time 10–30 s and temperature
the advent of technologies, such as liquifaction, pyrolysis, gasification 500–650 ◦ C [2,11–13].
and combustion, the biomass can be converted into gas, solid and liquid Bio-oil from biomass pyrolysis is a mixture of light hydrocarbons,
fuels (or bio-oil). The high heating value of a typical biomass residues oxygenated compounds, phenols and traces of sulfur and nitrogen
varies from 1.5 to 19 MJ/kg, and it can be further improved (≈1.25–2 compounds. The bio-oil fuel produced lower NOx, SOx, CO and partic­
times) by converting a biomass residue into liquid fuel [4–6]. ulate matters (PMs) as compared to diesel oil in a gas turbine. Therefore,

* Corresponding author.
E-mail address: shahmudasir22@[Link] (M.A. Shah).

[Link]
Received 5 January 2021; Received in revised form 17 April 2021; Accepted 20 April 2021
Available online 1 May 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

bio-oil fuel produce is less smoky, a clean burning fuel with high calo­ further use. The four types of walnut shells which were used in the study
rific value and are more reactive as compared to the respective biomass as: paper (PSW), thin (TSW), medium (MSW), and hard (HSW) shelled
residue fuels [8,14–19]. walnut.
The yield of bio-oils through pyrolysis technology of various biomass
residues have been thoroughly investigated by various researchers in the 2.2. Pyrolysis Experiments
past, such as are wheat straw, Corn cob, deodar, Corn stalk, rice husk
and rice straw and peanut shell [9–12] etc. The results of these in­ Pyrolysis of walnut shells (PSW, TSW MSW, and HSW) residues was
vestigations revealed the feasibility of pyrolysis technology for the carried out by using a fixed bed pyrolyzer (reactor) in an inert atmo­
bio-oil fuel production from biomass residues for different applications, sphere of nitrogen. The reactor was made up of stainless steel (SS316)
such as in boilers, diesel engines and gas turbines [8,13]. A pathway to material having 1200 mm length and 122 mm internal diameter. The
liquid fuel can be selected depending on the pyrolysis gas composition design temperature and pressure of the reactor were 950 ◦ C and
and economics of the available catalysts [20]. 1.2 × 106 N/m2, respectively. It was surrounded by electric furnace with
Walnut shells are one of the important biomass residues which are P&ID controller. Ni-Cr thermocouple was used to sense the temperature
mostly wasted without proper utilization. The shells are obtained from inside the reactor. A batch of 0.3 Kg of the individual feedstock was
the dry fruit, walnut which comprises 60% kernel (the oily material) and charged to the reactor for pyrolysis. The temperature was increased from
40% shell the hard covering [21]. In India during the year 2013–2014 ambient to 375, 450, 550, 650 and 750 ◦ C for particle sizes of 0.5–1.5,
the total production of walnut was 38,000 MT [21], which resulted into 1.5–2.5 and 2.5–3.0 mm, respectively, at a heating rate of 0.17, 0.33 and
the walnut shell production of ≈15,200 MT. The average heating value 0.83 K/sec. Nitrogen at a flow rate of 0.8 × 10− 6, 1.6 × 10− 6 and
of walnut shells is 20.18 MJ/kg [22]. However, the walnut shells almost 2.5 × 10− 6 m3/s was supplied to keep the environment inert and
remain as a waste or sold at throw away price by the walnut processing oxygen-free, and also to carry along the condensable vapors which were
industries. It is marginally used as a fuel in rural areas for heating passed through condensers I and II to collect oil and water scrubbing
purposes. With the help of the conversion technologies, such as gasifi­ tank to collect gas, as shown in Fig. 2. The reaction was performed for
cation, combustion, liquefaction and pyrolysis, energy can be extracted 2100 s, or till no further release of gas was observed. There after the bio-
from walnut shell residues and can further be upgraded for production of oil and biogas samples were stored in airtight bottles and gas kits,
various types of chemical feedstock, solid, liquid and gaseous fuels. respectively, for further investigation. Condensed pyrolysis vapors were
In the present work, the pyrolysis of the different walnut shell resi­ collected as liquid fuel (bio-oil) is dark brown and viscous, thick portion
dues (paper, thin, medium and hard shelled walnut) has been carried seem at the bottom and light portion at the top. Two phases were
out. The heating values, density, flash and pour point, water content and separated (aqueous phase and organic phase) using a centrifuge, which
viscosity of the bio-oils produced from different walnut shells at 550 ◦ C was operated at 4000 rpm for 2100 s. After centrifugation, the two
were analyzed and compared with the respective biomass residues. The phases, the upper aqueous phase (less viscous) and lower organic phase
effects of temperatures, size of the residual particle, swept gas flow rates (more viscous) were separated. Physico-chemical characteristics of bio-
and heating rates on bio-oil, bio-char and gases yields were also deter­ oils obtained at 550 ◦ C with particle size of 1.5 – 2.5 mm and heating
mined. The bio-oils were characterized using Gas chromatography–mass rate 0.33 K/s were characterized and analyzed.
spectrometry (GC-MS), 1H and 1 3C NMR (Nuclear Magnetic Resonance)
and Fourier Transform Infrared Spectroscopy (FTIR). The composition 2.3. Physicochemical characteristics of bio-oils
of the gaseous mixture obtained during pyrolysis was also determined
using Gas chromatography (GC). Density of bio-oils was measured using a specific gravity bottle at
18 ◦ C, ASTM D4052 [23] method. The viscosity of bio-oil was deter­
2. Experimental mined by Rheometer (MCR 100) at 40 ◦ C using ASTM D445 method
[24]. Water Content was obtained by Karl-Fisher titration method. Flash
2.1. Materials and methods points of bio-oils were performed according to Pensky− Martens closed
cup tester method. The bio-oil is heated at a constant rate with stirring
The walnut shells were obtained from the local walnut industry, continuously at regular intervals of time. The pour point of bio-oil was
Srinagar, Jammu & Kashmir, India and were dried for three days at investigated using ASTM D 93 [25]; during this method preheated
average temperature of 25 ◦ C under 47% humidity to remove the excess bio-oil sample was cooled at specific rate and checked at intervals of 3 ◦ C
moisture before storage. The dried walnut shells were crushed with high for flow analysis. The minimum temperature, at which bio-oil mobility
speed ball mill and sieved by standard screens in order to get particle was noticed, was reported as the pour point. For heating value mea­
sizes of 0.5–1.5, 1.5–2.5 and 2.5–3.0 mm as shown in Fig. 1. Fine surement 0.001 Kg of bio-oil sample was implanted in the calorimeter
powdered feedstock was packed in air tight containers and stored for (CC01/M3; Toshniwal, India) and ignited in the presence of oxygen

Fig. 1. Four types of walnut shell powder are paper (a) (PSW) (b) thin (TSW) (c) medium (MSW) and (d) hard (HSW) shelled walnut.

2
M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Fig. 2. Schematic diagram of experimental setup.

using ASTM procedure D2015-85 [26]. with single taper and quartz wool was used. The temperature of transfer
The bio-oil showed maximum yields at 550 ◦ C and the characteristics line was controlled at 280 ◦ C. All bio-oil samples were investigated in
of bio-oil like water content, flash point, pour point, viscosity, density splitless mode at an injection temperature of 250 ◦ C. In the present
and high heating values revealed on the basis of standard test methods in study, 5 × 10− 9 m3 micro-syringes were used for injection volume of
the same temperature. 1 × 10− 9 m3. The temperature of electron ionization was set at 230 ◦ C at
70 eV and the quadruple was 150 ◦ C. Mass spectral database was used to
2.4. Chemical composition analysis of bio-oils identify the organic compounds in a selected ion monitoring (SIM) and
full scan mode. The assessment of organic compounds in the bio-oil
2.4.1. FTIR analysis samples and extracts were calculated from the GC peak areas of the
Functional group analysis of organic and aqueous bio-liquid phases unsaturated and precise signals (including derivatives) of signal to noise
obtained during pyrolysis was carried out using Fourier Transform (S/N) ratio of at least 6:1.
Infrared Spectroscopy (Nicolet 8700-Thermo Fisher Scientific FTIR
spectrometer, USA) with the sample diluted in 1% potassium bromide 2.4.4. Gas chromatography analysis
(KBr). Thin uniform layers of both organic and aqueous oils were placed The analysis of gaseous products was carried out using a Varian CP-
on a sample cell. The FTIR spectrum in the range of 500–4000 cm− 1 was 3800 gas chromatograph, (Australia) equipped with two thermal con­
measured with a resolution of 4 cm− 1 and an accumulation of 64 scans. ductivity detectors (TCD) and one flame ionization detector (FID).
Argon was used as a carrier gas with a flow rate of 5 × 10− 7 m3/s. TCD
2.4.2. 1H and 13C NMR analyses was used to analyze hydrogen and nitrogen gases; whereas FID for the
Integrated intensities of different protons and carbon types in the analysis of hydrocarbons.
bio-oil related with an average molecule can be found 1H and 13C NMR
spectra. The one dimensional (1D) 1H and 13C NMR spectra of organic 3. Results and discussion
bio-oils were recorded on a NMR spectrometer (Bruker, Avance III NMR
500 MHz, AV 500, Germany) equipped with BBO, TXI, solid state and 3.1. Effect of pyrolysis temperature
cryoplatform probe resonating at the frequency of 500 and 125 MHz, for
1
H and 13C, respectively. 0.001 Kg of sample was prepared and dissolved The results were varied for various walnut shell sizes. The bio-oil
in 600 µl of D2O (concentration 26.95 mM). Before recording the data, yields increased from 26.8% to 43.0% for PSW, 25.4–40% for TSW,
baseline and phase were corrected in the given spectra and separated 24.6–37% for MSW and 28.8–44.7% for HSW. The maximum of HSW
into various regions, which correspond to different types of carbons and (44.7%) and minimum MSW (37%) of bio-oil yields were obtained at
protons according to their position in the molecule. Simultaneously, all temperature 550 ◦ C, heating rate 0.33 K/s, particle size 1.5–2.5 mm and
spectrums were integrated four times and averaged within the indicated swept gas flow rate at 1.6 × 10− 6 m3/s. From the Fig. 3(a), It can be
regions. 13C NMR is much capable of directly observing the carbon observed that the initially the bio-oil products increases with respect to
skeletal. temperature touches maximum and decreases thereafter.
Similarly the bio-char yield decreased from 35.1% to 19%, for PSW,
2.4.3. GC/MS analysis 37–22.1% for TSW, 37.6–25% for MSW and 30.4–14% for HSW. It can
Mass spectrometric analyses was carried out with a varian GC–MS be seen that the bio-char yield gets decreased from 35% to 41% as the
instrument (Perkin Elmer USA; SQ8 Series) using an analytical column temperature gets increased from 375 to 750 ◦ C as shown in Fig. 3(b).
Elite 5MS (0.25 mm i.d. × 30 m length × 0.25 µm film thickness). The The observations for bio-gas showed, more or less, the same trend.
initial temperature of GC oven was set as 50 ◦ C (grip for 90 s) and The biogas yields also increased with increasing temperature as shown
increased to 240 ◦ C (hold for 600 s) at 0.33 K/sec. Helium was used as a in Fig. 3(c). It was found to be maximum (40.4%) for HSW and minimum
carrier gas at a constant flow rate of 2 × 10− 8 m3/s. A splitless inlet liner (29.1%) for MSW at 750 and 375 ◦ C respectively.

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

This is due to the high temperature, secondary reactions of the liquid

fraction of the volatile components or decompositions of char residues in
the reactor results in increased bio-oil and bio-gas and reduction in the
bio-char products.
Similar investigations were reported by Demiral and Kul, [19] Mis­
hra and Mohanty [27], Gable [28], Saif et al. [29], and Raja et al., [30].
They concluded that, 18–34% reduction of bio-oil from 277 to 750 ◦ C
may be due to extra cracking leading to high gas and low bio-oil con­
version. Also, the pyrolysis of Jatropha showed that the oil yield
increased from 42.15% to 64.25% with an increase in temperature from
350 to 550 ◦ C and then decreased to 57.69% after 550 ◦ C.

3.2. Effect of heating rate

The experiments were done with different heating rates (0.17, 0.33
and 0.83 K/sec) to investigate the effect of heating rates on product
yields at a particle size 1.5–2.5 mm, sweep gas flow rate of 1.6 × 10− 6
m3/s and constant temperature at 550 ◦ C. Fig. 4(a-c) shows that at all
heating rates, the overall conversion of the pyrolysis was slightly
different. As we move from 0.17 to 0.33 K/s, we observe there is an
increase in bio-oil and bio-gas yield but decrease in bio-char yield. It can
be observed that the bio-oil and bio-gas yields gets increased almost 10%
and bio-char gets decreased upto17% when heating rate changes from
0.17 to 0.33 K/s as shown as shown in Fig. 4(a–c). However at 0.83 K/s,
it can be analyzed that almost constant values are obtained in all the
yields. For the current study, it can be visualized that bio-oil and bio-gas
yields is observed maximum at temperature of 550 ◦ C with heating rate
of 0.33 K/s.
The increase in bio-oil, bio-gas and reduction in the bio-char yields is
due to high heating rate, which may be leads to a rapid depolymeriza­
tion to primary volatiles, prevents the secondary reactions and reduces
the mass and heat transfer limitation during pyrolysis. These in­
vestigations are well revealed with the other researchers [31–33].

3.3. Effect of particle size

The experiments were repeated at different particle sizes, to observe

the effect of particle size on bio-oil, bio-char and gas yields at a heating
rate of 0.33 K/s, sweep gas flow rate of 1.6 × 10− 6 m3/s and constant
temperature at 550 ◦ C as shown in Fig. 5(a–c).
As the particle size was increased from dp < 0.5–1.25 < dp
< 2.5 mm, we observe a slightly an increase in the bio-oil (1.0–6%) and
biochar (1–4%) but reduction in gas (7–11%) yields of all walnut shells.
Moreover, as we increases further the particle size dp < 2.5< dp
< 3.0 mm, we observe a reduction in the bio-oil and gas but increase in
biochar product yields. According to pyrolysis experimental in­
vestigations maximum bio-oil (44.7%) of HSW and bio-char (26.8%) of
MSW is obtained for the particle size of 1.5–2.5 and 2.5–3.0 mm
respectively.
It is observed that with an increase in particle size bio-oil yield
decreased, because large size particle causes higher temperature gradi­
ents inside the particle, and as such, the core temperature is low as
compared to the surface temperature, and it results into the high yield of
solid fuel and less yield of gases and liquid fuel. These investigations are
in good agreement with others researchers for maize stalk [32] and
chestnut cupulae [33].

3.4. Effect of nitrogen flow rate on product yields

The effect of different sweep nitrogen (N2) gas flow rates on the
yields at a pyrolysis temperature 550 ◦ C, heating rate of 0.33 K/s and
particle size 1.5–2.5 mm is shown in Fig. 6(a–c). N2 flow rate decreases
Fig. 3. (a-c). Influence of temperature on bio-oil, biochar and gas yields at the residence time and creates an inert atmosphere for pyrolysis. Also it
particle size of 1.5–2.5 mm, heating rate 0.33 K/s and swept Gas (N2) velocity
may lower the re-polymerization of vapors to increase the bio-oil yield
of 1.6 × 10− 6 m3/s.
[31]. The product yield of bio-oil increases 25–30%, and decreases
nearly 27–33% when a swept gas flow rate increases from

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Fig. 4. (a-c). Influence of heating rate on bio-oil, biochar and gas yields at Fig. 5. (a-c). Influence of particle size on bio-oil, biochar and gas yields at a
particle size of 1.5–2.5 mm, sweep gas flow rate of 1.6 × 10− 6 m3/s and con­ heating rate of 0.33 K/s, sweep gas flow rate of 1.6 × 10− 6 m3/s and constant
stant temperature at 550 ◦ C. temperature at 550 ◦ C.

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

0.8 × 10− 6–1.6 × 10− 6 and 1.6 × 10− 6–2.5 × 10− 6 m3/s respectively.
The maximum and minimum bio-oil yield is recorded as 44.7% of HSW
and 37.0% of MSW respectively. It is the facts, that at higher nitrogen
flow rate large amount of volatile components are coming out from the
pyrolyzer without condensing properly and reduces the secondary re­
actions like partial oxidation, thermal cracking and de-polymerization
[32–35].
The bio-char yield decreases from 24.8% to 22%, 24.3–21% and
23–20.8% as N2 flow rate increases from 0.8 × 10− 6–1.6 × 10− 6 and
1.6 × 10− 6–2.5 × 10− 6 m3/s respectively. Similarly for gas yield in­
creases from 33.7% to 38.2%, 34.8–39.4% and 35.2–42.4% as N2 flow
rate increases from 0.8 × 10− 6 - 1.6 × 10− 6 and 1.6 × 10− 6–2.5 × 10− 6
m3/sec respectively. So, it can be concludes that bio-gas and bio-char
yield increases and decreases respectively with increases in sweep gas
flow rates.
Table 1 illustrates the comparative analysis of the pyrolysis of
various types of biomass in fixed bed reactor. It reports the optimum
operating parameters such as heating rate, particle size, N2 flow rate and
temperature for pyrolysis of different walnut shell residues and other
biomass for maximum bio-oil yield. It is found that the optimum py­
rolysis heating rate, N2 flow rate, particle size and temperature mainly
vary in the range of 0.17–0.83 K/s, 1.67–3.33 K/s, 0.5–0.02 mm and
500–600 ◦ C respectively. In the present investigations, the values are
comparable with the values reported by other researchers as reported in
Table1 and support the biomass suitability for pyrolysis.

3.5. Density, viscosity, water content, flash, pour point and high heating
value (HHV)

The density of bio-oils obtained from various walnut shells varied

from 1025 to 1041 kg m− 3 at 18 ◦ C. The bio-oil obtained from HSW
showed the highest value, 1041 kg m− 3. While in case of PSW, the
lowest density of 1025 kg m− 3 was recorded. Almost similar values were
reported by various researchers as reported in Table 2 for bio-oils ob­
tained from almond shell, walnut shell, pine needles, soyabean cake and
sugarcane bagasse, [43–45]. High density of bio-oil is directly related to
heavy fractions and energy contents [46]. The range of bio-oil density is
found between 1000 and 1240 kg m− 3 for the temperatures between 15
and 40 ◦ C for most of the bio-mass residues. However, few biomass
residues, like saw dust may rise up to 1300 kg m− 3 as reported by Feng
et al. [47]. For oils obtained from palm fruit and chañar, lower density
<1000 kg m− 3 has been reported [48].
Viscosity plays important role for the design of engines where a bio-
liquid fuel is used. In the present work, the viscosity varied from 1.27 to
2.99 cSt at 40 ◦ C, where HSW showed the highest value and PSW the
lowest. All the above results are also supported by the investigations of
Gupta et al., [43] and Ahmed et al. [44] for the viscosity of almond shell
oil, palm residue oil and scrap tire oil are 1.68, 2 and 2.04 cSt respec­
tively at 40 ◦ C as depicted in Table 2.
The water content of the different types of bio-oils obtained from
WSs is very high (23–28%) when compare to other bio-oils it’s compa­
rable as shown in Table 2. Due to high water content, this leads low HHV
of the bio-oils.
The flash point of bio-oil is recorded to signify the high temperature
at which bio-oil can be easily handled and stored without any fire haz­
ards. Continuous flashing, explosion and ignition may be caused due to
low flash point. The forest biomass pyrolysis liquids (40–50 ◦ C) possess
low flash point due to large quantity of low boiling volatile mixtures and
also specifies a high vapor pressure [48,49]. Flash points of bio-diesels,
diesels and vegetable oils, exhibit large variations may be due to the
Fig. 6. (a -c). Influence of sweep nitrogen (N2) gas flow rates on bio-oil, biochar different product variations and processes in the final chemical
and gas yields at a heating rate of 0.33 K/s, particle size 1.5–2.5 mm and composition [43].
constant temperature at 550 ◦ C. The pour point of a bio-oil is an evidence of the minimum temper­
ature at which the bio-oil samples can be moved [50]. The pour point for
forest residues, softwood and hardwood pyrolysis liquids ranged from
− 12 to − 33 ◦ C. For the pyrolysis bio-oils revealed the low viscosity

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Table 1
Comparative analysis of various types of biomass for pyrolysis.
Biomass Temperature (◦ C) Heating rate (K/sec) Particle size mm N2 flow rate (m3/sec) Bio-oil yield/mass (%) References
− 6
PWS 550 0.33 1.5–2.5 1.6 × 10 31.4 Present work
TWS 32.7
MWS 33.3
HWS 35.4
6
Pine needles 550 0.83 0.6–0.01 1.6 × 10− 43.76 [31]
6
walnut shell 500 0.5 0.1–0.2 2.5 × 10− 48.2 [36]
6
Napier grass stem 600 0.5 0.2–0.02 0.5 × 10− 32.26 [37]
6
Perennial grass 500 0.67 0.2 2.5 × 10− 26.18 [34]
6
Hornbeam shell 550 0.83 0.5–1 1.6 × 10− 24.67 [38]
6
Jatropha curcas cake 550 0.08 5–8 1.6 × 10− 45 [39]
6
Sugarcane bagasse 560 0.5 0.5–0.85 1.9 × 10− 53.38 [40]
6
Mahua seed 525 0.33 0.55–1 0.5 × 10− 49 [41]
6
Paulownia wood 500 0.83 0.425–1 1.6 × 10− 54 [42]

Table 2
Physicochemical characteristics of bio-oils obtained at 550 ◦ C with particle size of 1.5–2.5 mm and Heating rate 0.33 K/s.
Types of bio-oil Density at 18◦ C (Kg/ Viscosity (cSt Flash point Pour Water content (wt HHV of Bio-oil MJ Reference
m3) (40◦ C) (K) point %) kg− 1

PWS 1025 1.27 121 20 28.5 26.0 Present

TWS 1026 1.22 114 17 26.7 26.5 work
MWS 1027 2.92 108 13 25.1 26.8
HWS 1041 2.99 104 8 23.5 27.3
Pine needles 1062 1.25 61 - 10 – 26.25 [31]
Almond shell 1106 1.68 110 − 15 22.3 12.4 [43]
Scrap tire 1100 2.04 < 30 41.3 [44]
Walnut 1094 30 31.94 21.53 [45]
Perennial grass 951 – 43 +4 – 24.7 [34]
Calophyllum inophyllum wood 1190 1.86 96 10.7 21.7 34.89 [51]
bark
Jatropha 1100 – 180 -6 – 25.91 [52]
Diesel 820–850 2–5.5 53–80 - 40 to – 1 – 42–45 [53]

which results a low pour point [50]. 3.6. FTIR for pyrolytic organic and aqueous oils
The high heating values varied from 26 to 27.3 MJ/kg, HSW drew
highest and the lowest for PSW. When compared HHVs of the walnut FTIR spectrums of pyrolytic bio-oils yields obtained at 550 ◦ C py­
shells, 30–48% increase was observed for bio-oils as shown in the rolysis temperatures were shown in Fig. 7(a-b). The band assignments
Table 2. When compared with the HHVs of corn cobs and stover bio-oils for different stretching under various band frequencies have been re­
[35], the bio-oils in the present investigation was found to possess 18% flected in the Table 3. Band spectra for organic and aqueous bio-oils
more energy contents per unit volume. All the above observations draw have been taken in the range of 500 – 4000 cm− 1 with a resolution of
to the conclusion that bio-oils are much more efficient and cost effective 4 cm− 1. The spectra identify the qualitative composition of bio-oil yields
for transportation than the bio-mass. and dependent on the constituent of biomass but independent of

Fig. 7. (a). FTIR spectra of the organic bio-oil with indexes of the estimated functional structure. (b). FTIR spectrum of the aqueous bio-oil with indexes of the
estimated functional structure.

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Table 3
FTIR spectra band assignments of different types of bio-oils formed after pyrolysis of walnut shell residues at 550 ◦ C.
Band assignment Band frequency (cm¡1)

PSW TSW MSW HSW

Organic Aqueous Organic Aqueous Organic Aqueous Organic Aqueous

O–H stretching 3417, 3437 3670–3250 3437 3438 3336 3433 3424 3425
C–H stretching 2933, 2852 – 2934, 2854 – 2849 – 2933, 2852 –
HC˭O stretching (ester) 1716 – – – 1716
HC˭O stretching (ketone) 1712 1751 1712 – 1720 – 1712 1715
C–C/C˭C stretching vibrations in aromatic structure 1610 1610,1660 1619 1639 – 1639 1616 1638,1521
Aromatic skeletal vibrations and C–O–H in-plane bending – 1550, 1390 – 1397 – – – 1401
CH deformation and OH bending vibrations – – – 1398 – – – –
C–O and C–C stretch of guaiacyl unit in lignin 1270,1218 1195- 1270,1215 – – – 1270,1212 –
C–OH stretch and C–H in-plane deformation in syringyl 1114 1113 1114 1113
C–OH and O–CH3 stretching 1030 1029 1029 1030
C–H out-of-plane stretching 975 971 965
C–H out-of-plane stretching 817, 755 865, 634 821 818 818

temperature. It is identified that the oil yields contains condensed vol­ Walnut, Abnisa et al. [54] for palm shell and polystyrene, Chukwuneke
atiles emitting from hemicellulose and cellulose which may decompose et al. [55] for mahogany wood and Sugumaran et al. [56] for non-edible
completely at temperatures near 350 ◦ C [36]. Hence, the spectra ach­ seed-cake oils.
ieved at 550 ◦ C pyrolysis temperatures were almost similar.
As to examine the spectra, The most prominent intensive and wide 1 13
3.7. H and C NMR characterization
band peaks are in the range of 3320–3600 cm− 1 of the organic and
aqueous bio-oils, represent the stretching vibration of hydroxyl (–OH)
Characteristic spectra of aromatic fractions and saturates of bio-oil
groups of water, phenol, carboxylic acids or alcohols due to the presence
yields in carbon chain were found with the help of proton (1H) and
of carbohydrates and lignin. The band peaks for organic and aqueous
carbon (13C) NMR and are shown in Fig. 8(a-b). The integral values
bio-oils were almost similar at the wave numbers in the range between
(relative amounts) of various intensities of selected regions of the
3417 and 3437 cm− 1 for PSW, TSW, MSW and HSW, where TSW and
spectra on a percentage basis are presented in Table 4. It was observed
HSW organic and aqueous bio-oils coincide. However, PSW and MSW
that the bio-oil showed extensively differences in the overall chemical
bio-oils showed slight variation. The methyl (CH3) and methylene (CH2)
makeup from the various types of walnut feedstock’s. Table 4 subdivides
groups were detected by –CH stretching at a wave number of 2933,
the proton content into Hα, Hβ and Hγ within each chemical shift range
2852 cm− 1 for PSW, 2934, 2854 cm− 1 for TSW, 2849 cm− 1 for MSW and
and describes it in terms of the percentage of protons with different
2933, 2852 cm− 1 for HSW organic oils [24]. In the present study, the
proton substitution numbers. The upfield spectra region from 0.4 to
C˭O stretching vibrations were observed at band peaks of 1712 cm− 1 for
1.1 ppm, depicting aliphatic protons with aromatic rings attached to
all organic bio-oils except MSW which was found at 1720 cm− 1 and
carbon atoms, for the PSW and TSW bio-oils (~37%), indicating highest
1715 cm− 1 for all aqueous oils, respectively, indicating the presence of
aliphatic content as compared to MSW and HSW bio-oils. Also, HSW bio-
carboxylic acids, ketones, and aldehydes. The peak bands at 1610, 1619
oil does not showed any aliphatic content in this region. The next inte­
and 1616 cm− 1 for PSW, TSW and HSW organic oils, respectively, and at
grated region was from 1.1 to 2.0 ppm and investigated protons on
1638, 1639, 1639 and 1638 cm− 1 for PSW, TSW, MSW and HSW
aliphatic carbon atoms that may be bonded to a CH and CH2 (aromatic
aqueous bio-oils, respectively, showed the presence of alkenes. Peak
or olefinic) from a heteroatom. From these investigation bio-oils, such as
band between 1550 and 1490 cm− 1 indicates -NO2 stretching in the
HSW (50%), TSW (~35%) and MSW (12.5%) showed protons however
nitrogenous compounds, which was found in all organic and aqueous
no protons were shown in PSW bio-oil. It can be clearly seen that HSW
oils at 1514 and 1521 cm− 1. The peak bands at 1514 and 1461 cm− 1
bio-oil showed dominant number of protons in this region. It can be
were observed in all types of organic bio-oils, whereas 1390, 1339, 1398
pretended that aliphatic molecules, even those are very near to het­
and 1401 cm− 1 were noticed in PSW,TSW, MSW and HSW aqueous
eroatoms or bonded to aromatic portions, are more prevalent for the
bio-oils, supporting the presence of – CH bending of alkanes. Various
higher energy containing bio-oils. The next spectrum lies between 2.05
peaks for organic oils were found at 1270, 1218, 1114, 1030 cm− 1 for
and 4.5 ppm and indicates the presence of protons in all type of bio-oils,
PSW, 1270, 1215, 1113, 1029 and 971 cm− 1 for TSW, 1114, 1029 and
which shows highest for HSW bio-oil (50%) and lowest in TSW bio-oil
965 cm− 1 for MSW and 1270,1212, 1113 and 1030 cm− 1 for HSW
(~28%). This region of the spectrum may indicate protons on carbon
indicating the presence of primary secondary and tertiary alcohols, es­
chain next to an aliphatic alcohol or a methylene group or ether that
ters, phenols and ether due to OH bending and – CO stretching vibra­
joins two aromatic rings. The spectrum in the range varying from 6.0 to
tions. The peaks of 756, 614 cm− 1 for PSW, 820 and 755 cm− 1 for TSW,
9.0 ppm indicated the presence of mono-, di- and poly- aromatics,
817 and 756 cm− 1 for MSW and 817 and 756 cm− 1 for HSW organic
containing 0.78–12.5% of protons in bio-oils, which contains hydrogen
bio-oils were found showing the presence of aromatic groups. Band
atoms in benzenoids and also hetero aromatics containing O and N.
peaks were found to be broader in organic bio-oils as compared to
Small quantities of mono-, di- and poly- aromatics was observed in TSW
aqueous oils. All the above observations are also supported by the in­
bio-oil (0.78%) and highest in MSW bio-oil (12.5%). Interestingly,
vestigations of Ahmed et al. [44] for scrap tire, Gupta et al. [45] for
neither the percentage of aromatic protons was observed within the

8
M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Fig. 8. (a). 1H NMR and (b) 13

C NMR spectrum of organic bio-oils.

9
M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

lignin contents of the biomass nor the energy content of the bio-oils, used. Large number of organic and aqueous bio-oil compounds con­
although lignin content of the feedstock and energy content of the bio- sisting of hydrocarbons, alcohols, organic acids, ketones, phenols, al­
oil often are linked. The only downfield spectral regions occur in MS dehydes, esters, furans, guaiacols, sugars and other multifunctional
bio-oil and contains 12.5% proton, which indicated that the resonances compounds were extracted as shown in Tables 5 and 6 respectively.
arise from aldehydes, although carboxylic acids may also be present in Some complicated peaks cannot be observed perfectly on the chro­
this region. matogram because of its low concentration and volatile in nature. It was
The spectra of the 13C NMR spectrum investigated that CH3 reso­ observed that the hydrocarbons are dominant followed by other
nances showed variation from 5 to 25 ppm, CH2 showed 20–40 ppm and carbonyl compounds. GC peak areas of the chemical compounds sepa­
CH varies from 25 to 60 ppm. Besides these, humps comparable to CH2 rated into their respective carbon families were estimated for the overall
and CH naphthenic carbons in the region 25–60 ppm are clearly sepa­ distribution of organic and aqueous bio-oils. The mains constituents of
rated in the CHn sub-spectra and contains maximum percentage of biomass are cellulose, hemicellulose, lignin and others with different
carbons (23–31%). The presence of aliphatic carbon atoms attributes to proportionality [59]. The similar compounds found are phenol, 2,
the energy content of bio-oils. On compare different bio-oils, it was 6-dimethoxy-, acetate, tri-methoxy amphet amine, 2,3,5-, propylphos­
observed that PS-oil showing maximum resonance peaks in aromatic, phonic acid, ethyl isopropyl E, 2,3,4-Trimethoxy phenyl ethyl amine,
aliphatic as well as oxy shift regions. Various bio-oil samples, region benzene ethane amine, 3,4,5-trimethoxy-, 2,4,5-Trimethoxy phenyl
50–110 ppm and 120–160 ppm were contributed by cellulosic com­ ethyl amine, 9-octadecenoic acid, 2-trimethylsilyl, formic acid,
pounds as in 13C NMR spectra. Also, for region 165–185 ppm ester 2-methoxy phenyl ester, 2,4(3 h,5 h)-thiazoledione, 5–3,4-dimeth in
carbons were dominant. From these observations, a very simplified and Table 4 and Table 5. Hence, hemicellulose, and cellulose gets decom­
clear picture was shown for complex hydrocarbon mixtures with a large posed easily during pyrolysis, which leads into gases, ketones, hydro­
range of components. In 13C aromaticity of the bio-oil was dominant in carbons, carboxylic acids/aliphatic aldehydes, furans and other
TSW oil (25.9%) and present in all bio-oils as compared to proton, which compounds identified in bio-oil. However the lignin was incompletely
were present only in PSW oil. In 13C NMR aromatic, protonated, bridged decomposed and may be methoxy phenols were remained in the bio-oil.
and substituted aromatic carbons were present in all different types of These investigations were supported by the earlier results for bio-oil
bio-oil. Similar observations were made for 1H and 13C NMR for bio-oil, observations [44, 52, 59, 61–63].
obtained from corncob [5], different pyrolysis oils [57], pinewood,
wheat straw and rapeseed cake [58], cedar residuals [59], fast pyrolysis 3.9. GC analysis of gaseous products
oil [60] and jatropha [52].
The components of the gases released during pyrolysis of walnut
shells residues were identified as H2, CO, CO2 and light hydrocarbons as
3.8. GC/MS characterization of bio-oils CH4, C2H6, C2H4, C3H8, C4H10, C4H8, C3H6 and C5H12. Their average
composition has been presented in Fig. 10. O2, N2, and H2O vapors were
In order to estimate the degree of partitioning of organic/aqueous not analyzed because N2 and O2 were always in the similar proportion as
compounds of all the chemical classes present in bio-oils, GC/MS anal­ in air; and H2O vapor was condensed during pyrolysis to form liquid
ysis was carried out as illustrated in Fig. 9(a-b). Benzene and hexane H2O product. The formation of CO2 and CO during the pyrolysis can be
were used as solvents. NIST database were used for compilation of mass due to the degradation of cellulose and hemicelluloses at lower tem­
spectra, Probability based matching of the individual GC signals was perature. The production of methane and light hydrocarbons could be
due to the degradation of lignin at higher temperature up to 500 ◦ C [64,
Table 4 65]. Further, CH4 and CO were found as most abundant gas produced
Chemical shift regions and results of bio-oil 1H NMR and 13C NMR of protons and (~27% and ~21%, respectively) and followed by CO2 and H2 showing
carbons. 22% and 17%, respectively. Pyrolysis gas produced in different types of
Proton and Symbol Chemical Bio-oil (mol% of total hydrogen walnut shells showed irregular pattern. The yields of the major com­
carbon shift range and carbon) ponents of the gas mixture: CO2, CH4, CO, and H2 were observed in the
assignment (ppm)*
PSW TSW MSW HSW following orders:
Aromatic proton Har 6–9 8.45 – – – CO2 ⇒MSW > TSW > HSW > PSW CH4 ⇒ TSW > PSW > MSW
Mono aromatic Hmar 6–7.25 7.97 0.78 12.5 – > HSW.
proton CO ⇒ HSW > TSW > MW S> PSW H2 ⇒ PSW > HSW > MSW
Di + poly Hpar 7.25–9 7.97 0.78 – – > TSW.
aromatic
proton
The gas mixtures have adequate contents of combustible fractions.
Hα to aromatic Hα 2.05–4.5 37.81 27.55 62.5 50 Mahmood et al., [66] used post-treatments, like post catalytic reforming
ring in order to increase the energy content of the observed permanent gases.
Hβ to aromatic/in Hβ 1.1–2.05 – 34.64 12.5 50 Therefore, the gases obtained in the present research may be recom­
paraffinic CH
mended as potential gas fuel and also be upgraded for high quality
and CH2
Hγ to aromatic Hγ 0.4–1.1 37.81 36.22 12.5 – syngas.
ring/terminal
CH3 4. Conclusion and recommendations
Aliphatic carbon Cali 5–10 17.31 8.18 – 30.77
Aromatic carbon Car 100–160 22.5 25.9 25 15
Naphthenic CN 25–60 – 31.36 25 23
The products and analysis of bio-oil, biochar and gas generated from
carbon pyrolysis of PSW, TSW, MSW and HSW were examined using fixed bed
Protonated p
Car 100–130 25.03 9.09 12.5 7.7 reactor. In the experiment, the highest bio-yields was obtained using
aromatic optimum operating conditions, like temperature, particle size, heating
carbon
Br rate and the N2 flow rate. Walnut shell samples were pyrolyzed at
Bridgehead Car 124–133 25.03 8.63 12.5 15.4
aromatic temperatures of 375,450,550,650 and 750 ◦ C under specific conditions.
carbon The results showed that the bio-oil yields had more influence of the
Substituted S
Car 133–160 10.11 1.36 25 7.7 pyrolysis temperature. The bio-oil yields obtained from different types
aromatic of walnut shells increases up to 550 ◦ C, after which there were a sig­
carbon
nificant decrease in the bio-oil yields, but enhance the gas yields after

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Fig. 9. (a). GC/MS chromatograms of organic bio-oils, (b). GC/MS chromatograms of aqueous bio-oils.,.

11
M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Fig. 9. (continued).

550 ◦ C. The maximum conversions of the oil, char and gas were obtained investigate testing standards. The advanced bio-refinery methods and
for HSW, PSW and HSW at temperature, heating rate, particle size and catalytic upgradation should be well established to substitute non-
nitrogen flow rate of 550 ◦ C, 0.33 K/sec, 1.5–2.5 mm and 1.6 × 10− 6 renewable fuels with renewable fuels. However, the utilization of
m3/sec respectively. The pyrolytic bio-oil showed that the composition biomass residues may be captivating factors for the production of
was predominated by oxygenated compounds such as carbonyl and different biochemical and fuel products for future uses.
carboxyl groups, phenol, and methoxy groups as revealed by GC-MS.
The pyrolytic bio-oils possess high water content leads to low HHV. CRediT authorship contribution statement
Pyrolysis gases obtained at temperature of 550 ◦ C mainly contained CO,
CH4, CO2, and H2 and light hydrocarbons. Based on these results, the Mudasir Shah: carried out experiments and compiled the results and
pyrolysis bio-oil can be considered as a potential fuel and may substitute manuscript, N.S. Khan: monitored the work and helped in manuscript
to petroleum based fuel in future. drafting, Vimal Kumar: supported in analytical measurements and
In future for the sustainability of the biofuel, there are challenges and helped in draft revision, Ahsanulhaq Qurashi: revised and improved
opportunities with the implementation of commercial applications. the manuscript.
Therefore to examine the quality of the bio-yields there is a need to

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M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

Table 5
Identification of the hydrocarbons in the organic bio-oils using GC/MS technique.
Organic oil Peak Name of the compound Molecular formula Molecular weight Area%

PSW 8.521 Cyclohexene,3-hexyl C 12 H22 166 3.8

Bicyclo[4.1.0]heptane, 7-pentyl 5.1
Cyclohexene,1-hexyl- 5.6
Naphthalene, decahydro-2,6-dimethyl 6.92
Trans, Trans-2-ethylbicyclo[4.4.0] decane 9
Cyclododecene, (E)- 9.3
5,7-Dodecadiene, (E,E)- 10.5
9.236 2(1 h)-Benzocyclooctenone, decahydro-10a- C13H22O 194 11
18.257 9-Eicosyne C20H38 278 12.2
20.153 Z,E-2-Methyl-3,13-octadecadien-1-Ol C19H36 O 280 13.1
TSW 4.699 2-Cyclohexen-1-One, 4,4,6-Trimethyl- C9H14O 138 2.8
2-Cyclohexen-1-One, 4,4,5-Trimethyl- 4.8
2-Cyclohexen-1-one, 3,4,4-Trimethyl- 5.2
Bicyclo[5.3.0]decane (Cis) C10H18 6.0
Cyclohexane, 1-Methyl-4-(1-Methylethenyl 6.9
Cyclohexane, 1-Methyl-4-(1-Methylethylid 7.8
11.394 Benzeneacetic Acid,. Alpha.-Hydroxy-2-Me C9H10O4 182 8.6
12.914 Phenol, 2,6-Dimethoxy-, Acetate C10H12O4 196 9.5
15.800 Trimethoxyamphetamine, 2,3,5- C12H19O3N 225 10.9
24.017 Fumaric Acid, Dodecyl Tetradec-3-Enyl Es C30H54O4 478 11.1
MSW 8.734 1-Propanone, 1-(1-Cyclohexen-1-Yl)- C9H14O 138 4.6
11.413 Benzenemethanol,. Alpha.-Methoxy-, Aceta C10H12O3 180 6.9
12.912 Phenol, 2,6-Dimethoxy-, Acetate C10H12O4 196 7.4
Phenol, 2,6-Dimethoxy-, Acetate 8.0
14.585 Propylphosphonic Acid, Ethyl Isopropyl E C8H19O3 194 8.4
15.803 2,3,4-Trimethoxyphenylethylamine C11H17O3N 211 8.8
Benzeneethanamine, 3,4,5-Trimethoxy- 9.5
2,4,5-Trimethoxyphenylethylamine 10.1
18.426 2-(2,5-Dimethoxy-4-Propylphenyl)Ethanam C13H21O2N 223 11.1
24.109 9-Octadecenoic Acid, 2-[(Trimethylsilyl) C27H56O4Si2 500 14.5
HSW 4.662 2-Decyne C10H18 138 2.8
9-Methylbicyclo[3.3.1]Nonane 5.2
6-Methyl-Bicyclo[4.2.0]Octan-7-One C9H14O 6.1
8.655 Formic Acid, 2-Methoxyphenyl Ester C8H8O3 152 6.9
11.376 Phosphonic Acid, Bicyclo[2.2.1]Hept-5-En C9H15O3P 194 7.7
18.424 2,4(3 h,5 h)-Thiazoledione, 5-[(3,4-Dimeth C19H17O4NS 355 11.1
23.020 Oleyl Alcohol, Heptafluorobutyrate C22H35O2F7 464 14.8
24.142 Benzene, [3-(2-Cyclohexylethyl)− 6-Cyclop C25H14O 340 13.9

Table 6
Identification of the hydrocarbons through GC/MS of the aqueous bio-oils.
Aqueous oil Peak Name of the compound Molecular Formula Molecular weight Area%

PSW 5.053 13-Methyltetradec-9-Enoic Acid Methyl Es C16H30O2 254 3.04

8.710 Formic Acid, 2-Methoxyphenyl Ester C8H8O3 152 5.27
10.213 2-Methoxy-5-Methylphenol, Acetate C10H12O3 180 6.18
12.859 Phenol, 2,6-Dimethoxy-, Acetate C10H12O4 196 7.7
Phenol, 3,4-Dimethoxy-, Acetate
15.780 2,3,4-Trimethoxyphenylethylamine C11H17O3N 211 9.56
Benzeneethanamine, 3,4,5-Trimethoxy-
2,4,5-Trimethoxyphenylethylamine
18.447 2,4(3 h,5 h)-Thiazoledione, 5-[(3,4-Dimeth C19H17O4NS 355 11.18
23.792 9-Octadecenoic Acid, 2-[(Trimethylsilyl) C27H56O4Si2 500 14.41
1-Monooleoylglycerol Trimethylsilyl Ethe 500
TSW 5.090 Methyl 3,4-Ethylidene-. Alpha.-D-Galactop C9H16O6 220 3.1
7.906 Trans-2-Methyl-4-N-Butylthiane, S,S-Diox C10H20O2S 204 4.8
Cis-2-Methyl-4-N-Butylthiane, S,S-Dioxid
MSW 12.855 Phenol, 2,6-Dimethoxy-, Acetate C10H12O4 196 7.8
15.781 Trimethoxyamphetamine, 2,3,5- C12H19O3N 225 9.6
24.011 I-Propyl 5,9,19-Octacosatrienoate C31H56O2 460 14.55
HSW 4.725 Furan, 2,5-Dimethyl- C6H8O 96 2.86
Furan, 2,5-Dimethyl-
2,4-Dimethylfuran
2-Cyclopenten-1-One, 3-Methyl-
Furan, 2,5-Dimethyl-
5.127 1,3:2,4-Dimethylene-D-Epirhamnitol C8H14O5 190 3.1
5.376 Furan, Tetrahydro-2,5-Dimethoxy- C6H12O3 132 3.2
7.888 Cis-2-Methyl-4-N-Butylthiane, S,S-Dioxid C10H20O2S 204 4.8
Trans-2-Methyl-4-N-Butylthiane, S,S-Diox
8.692 Phenol, 2-Methoxy- C7H8O2 124 5.3
Mequinol
10.243 1,3-Benzenediol, 4-Propyl- C9H12O2 152 6.2
12.866 Formic Acid, 2,6-Dimethoxyphenyl Ester C9H10O4 182 6.6

13
M.A. Shah et al. Journal of Environmental Chemical Engineering 9 (2021) 105564

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