Journal of Analytical and Applied Pyrolysis 169 (2023) 105828

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Journal of Analytical and Applied Pyrolysis

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

Novel photothermal pyrolysis on waste fan blade to generate bisphenol A

Qiangqiang Ren a, 1, Zhiwen Lei a, 1, Song Hu a, b, *, Yong Ding c, Limo He a, Sheng Su a, b,
Yi Wang a, b, Long Jiang a, b, Jun Xu a, b, Jun Xiang a, b
a
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b
China-EU Institute for Clean and Renewable Energy, Huazhong University of Science and Technology, Wuhan 430074, China
c
China Shenhua Energy Jiujiang Power Generation Company Ltd., Jiujiang 332599, China

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

Keywords: Waste fan blade would explosively grow with the life time of wind power machine is ended. Developing new low
Waste fan blade carbon-emission method to treat waste fan blade and achieving high resource recovery is promising. In this work,
Photothermal pyrolysis a novel photothermal pyrolysis method was developed and firstly applied to treat waste fan blade. A typical
Base material
waste fan blade was cut, crushed and screened to separate base material and reinforcing fiber, whose mass ratio
Bisphenol A
was 74.36:25.64. The base material was pyrolyzed at varied conditions of pyrolysis temperature, heating rate,
Mechanism
gas flow rate respectively. The study showed that bisphenol A was significantly acquired in tars (relative contents
were commonly over 40%), and its generation can be promoted by increasing pyrolysis temperature, heating rate
and gas flow rare. The generation mechanism of bisphenol A was revealed during photothermal pyrolysis pro­
cess: The main chain of 2,2-bis(4-glycidyloxyphenyl)propane resin in base material undergone random or chain
cracking reaction to produce bisphenol A rigid skeleton, phenoxy, alkane, hydroxyl and other active groups.
Bisphenol A rigid skeleton was the precursor of bisphenol A. Bisphenol A was formed after receiving hydrogen
atoms, accompanied by the formation of tetrahydrofuran, 4,4-(propane-2,2-diyl)bis(methoxybenzene) and other
substances. Bisphenol A undergone decomposition via secondary reactions, and it was mainly decomposed into
phenol and 4-isopropylphenol, 4-isopropylphenol was then dehydrogenated to produce 4-isopropenylphenol.

1. Introduction
As an important clean and renewable energy, wind power has
developed rapidly to effectively curb global warming, and its global
installed capacity has reached to 7.42 GW in 2020 [1,2]. The wind
power machine is responsible for wind power, and fan blade is key in
wind power machine. However, the expected service life of wind power
machine is 20–25 years, and it would be destroyed when the life time is
ended. The situation would bring out a large quantities of waste fan
blades and great pressures to the environment, because 10 tons com­
posite material is required to manufacture fan blades for each additional
1 MW capacity [3], which indicates the waste fan blades are also
important resources. Therefore, it is urgent and promising to dispose
waste fan blades with high resource recovery [4,5].
Taking the compositions of waste fan blade for analysis, it is made by
thermosetting composite materials (bisphenol A epoxy resin) reinforced
by some glass fibers [6]. According to some published works [7,8], it is
easy to recovery the glass fibers by mechanical, chemical and heat
treatment methods. Among various recovery methods, the combined
treatment method of mechanical and pyrolysis has been regarded as
most promising due to the high recovery quality, easy operation and
good material adaptability [9,10]. Besides, as a hydrocarbon organic
compound, bisphenol A epoxy resin can be also disposed by pyrolysis
effectively to generate abundant products such as gas, oil and char
[11–13]. High resource treatment of bisphenol A epoxy resin is key for
disposing waste fan blades to achieve recovery.
Bisphenol A epoxy resin is a high molecular compound refined by
condensation of bisphenol A and epichlorohydrin, whose monomer
molecule is 2,2-bis(4-glycidyloxyphenyl)propane. Bisphenol A is widely
used industrial compound, and mainly in the production of polymer
materials (epoxy resin, polycarbonate and unsaturated polyester resin)
and chemical products (plasticizers, flame retardants, antioxidants,

* Corresponding author at: State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology,
Wuhan 430074, China.
E-mail address: husong_hust@hotmail.com (S. Hu).
1
The authors contributed equally to this work.

https://doi.org/10.1016/j.jaap.2022.105828
Received 9 October 2022; Received in revised form 27 November 2022; Accepted 10 December 2022
Available online 14 December 2022
0165-2370/© 2022 Elsevier B.V. All rights reserved.
Q. Ren et al.
pesticides and coatings) [14,15]. Little researches reported the prepa­
ration of bisphenol A during waste fan blades pyrolysis and it is valuable
to study recovery of bisphenol A by the method.
Presently, most works concentrated on generation of bisphenol A
during pyrolysis of brominated epoxy resin in printed circuit board [16,
17]. It can be inferred from them that the during pyrolysis process, a
large number of rigid skeletons of bisphenol A are generated at the
beginning, and would destruct with the pyrolysis reaction proceeding.
This is because that some rigid skeleton of bisphenol A can be decom­
posed during high temperature treatment. Besides, there are a large
number of small molecule debris and various active groups in the
high-temperature zone. These small molecule debris and active groups
will undergo many secondary reactions with the rigid framework of
bisphenol A, which will destroy the rigid framework of bisphenol A. This
also leads to a low content of bisphenol A in the pyrolytic tar, which
would hinder the high resource utilization. Developing method to
reduce the decomposition of bisphenol A to increase its yield and con­
tent could further promote the high resource treatment of waste fan
blades.
It has been proved by us that photothermal pyrolysis can reduce
complex secondary reactions, because it can produce a limited high-
temperature zone and quickly separate volatile [18–20]. Therefore, it
can be inferred that when photothermal pyrolysis is applied to treat the
waste fan blade, it can effectively reduce the fracture of the rigid skel­
eton of bisphenol A, improving its yield and content. Besides, photo­
thermal would use sun light in the practical applications, which is also
clean, renewable, and can reduce CO2 emission.
As part of our ongoing efforts, a novel photothermal system was
developed to pyrolyze waste fan blade in this work. A typical waste fan
blade was cut and crushed to separate the fibers to collect the base
material. In order to close to practical application process, the experi­
ments at different key operation pyrolysis parameters (pyrolysis tem­
perature, heat rate and gas flow rate) were conducted using the base
material as reactant [18,19,21]. The products were thus collected and
analyzed to study the pyrolysis characteristics and mechanism. The
products yields, tar compositions, yields and relative contents of
bisphenol A were studied systematically. The correlations between tars
compositions and bisphenol A were analyzed by spearman correlation
analysis method, the formation and decomposition mechanisms of
bisphenol A during photothermal pyrolysis of waste fan blade were
revealed.
2. Experiments and analysis methods
2.1. Experimental raw material
Waste fan blade used in this work was produced by Baoding Huayi
Blade Company. The raw material was then cut, crushed, and screened
into yellow base material and reinforcing fiber, which are shown in
Fig. 1 and their mass ratio was 74.36:25.64 by repeated experiments.
The proximate and ultimate analysis of base material were averagely
determined by a Proximate Analyzer (Thermostep, ELTRA) and an
Element analyzer (Vario micro cube, Element) for two times, and the
results are given in Table 1.
2.2. Photothermal pyrolysis experiments of base material
The photothermal pyrolysis system used in this work (Fig. 2) was
upgraded based on our previous system [19]. The gas supply system
contained a gas cylinder, a pressure reducing valve, a mass flow meter
and a silicone tube, and the internal supply system of the reactor pro­
vided nitrogen with a purity of 99.999%, which was used as a protective
atmosphere during the pyrolysis process, and the supplied nitrogen was
fed into the condenser heating system through the mass flow meter
control flow after passing through the pressure reducing valve. The
concentrated heating system was composed by a DC power supply, a
2
Journal of Analytical and Applied Pyrolysis 169 (2023) 105828
Fig. 1. The main components from mechanical separation of the waste
fan blade.
four condenser cup, a quartz reactor (internal cavity dimensions
300 mm long, 30 mm wide and 30 mm high), a dark crucible, a ther­
mocouple, a signal collector, a computer and a signal control line, and
the system enabled the temperature to be precisely controlled with a
heating rate between 5 ℃/min and 500 ℃/min. The tar collection
system consisted of three empty washing cylinders and liquid nitrogen
buckets, and the generated gaseous tar was captured by the method of
cryogenic condensation. The exhaust treatment system was a glass
apparatus equipped with cotton, silica gel, lime and other substances,
and the gases that have been subjected to the exhaust treatment were
emptied by passing into the ventilation system.
The Control method of the photothermal pyrolysis system was as
below: the heating rate and pyrolysis temperature were set in the
computer firstly, the computer controlled a DC power supply to provide
voltage to the beaker, the beaker condenser heated the material in the
crucible, the thermocouple fixed near the focal area measured the real-
time temperature of the material inside the crucible, this real-time
temperature was input to the computer by the signal collector, the
computer contrast the difference between the real-time temperature and
the temperature target value, LabVIEW based PID temperature control
program was utilized to implement negative feedback regulation of the
lamp cup voltage for accurate temperature control. The signal acquisi­
tion frequency was 5 times per second.
During the experiment, 0.35 ± 0.02 g base material was firstly
spread out in the crucible and the crucible was placed in the focal area of
the quartz reactor with a thermocouple fixed just above the crucible
close to the sample. After the end cover was sealed and connected with
the quartz reactor, high-purity nitrogen was switched on at the front end
of the end cover, and a tar collection and exhaust treatment apparatus
was attached at the end of the quartz reactor. Purge nitrogen gas was
supplied for 10 min before the start of the reaction and verify overall gas
tightness. Then, the control temperature program of the condenser
heating system was set up as well as the carrier gas flow rate, and the
specific experimental operating conditions are shown in Table 2. In
photothermal pyrolysis experiments, the heating rate and gas flow rate
were 200 ℃/min and 200 mL/min when studying the effects of pyrol­
ysis temperature; the pyrolysis and gas flow rate were 600 ℃ and
200 mL/min when studying the effects of heating rate; the pyrolysis and
heating rate were 600 ℃ and 200 ℃/min when studying the effects of
gas flow rate. The selections of the controlled parameters were based on
the reasons below: in traditional pyrolysis, the pyrolytic tar can achieve
Q. Ren et al. Journal of Analytical and Applied Pyrolysis 169 (2023) 105828

Table 1
Proximate and ultimate analysis results of the base material in waste fan blade.
Proximate analysis (wt%, as received basis) Ultimate analysis (wt%, as received basis)

Moisture Volatile Fixed Carbon Ash C H Oa N S

0.98 82.67 1.62 14.73 55.61 6.14 19.65 2.87 0.02

a
Calculated by difference.

Fig. 2. Photothermal pyrolysis experimental system.

dichloromethane is 1:4) and the pyrolytic tar was collected with

Table 2
washing gas cylinder [21,22]. This part containing a large amount of
Experimental conditions in this work.
washing liquid was recorded as Mtar. Based on the tar quantitative
Variate Specific values of experimental conditions experiment [22], the tar concentration was determined as Xtar, and then
Pyrolysis Heating rate Gas flow rate the yield of tar can be obtained. In order to close to the actual situations,
temperature (℃) (℃/min) (mL/min) the final result of the pyrolytic products yields were the average value
Pyrolysis 400 200 200 from two repeated experiments. The standard deviation of the data was
temperature 600 200 200 used as the error bars to reflect the stability and reliability of the data.
800 200 200 The calculation formulas of char yield and tar yield are shown as Eqs. (1)
Heating rate 600 100 200
and (2):
600 200 200
600 400 200 Mchar
Gas flow rate 600 200 200 Char yield(%) = × 100% (1)
600 200 400
Mmaterial
600 200 600
Mpure− tar + Mtar ⋅Xtar
Tar yield(%) = × 100% (2)
Mmaterial
relatively high yield when the pyrolysis temperature is about 600 ℃; the
effects of heating rate are obviously varied for different materials, thus 2.3. Quantitative analysis of bisphenol A yield
we chose intermediate value (200 ℃/min); relatively small gas flow rate
would be beneficial for collecting tars, so it can be chosen as 200 mL/ The pyrolytic tars were analyzed by a Gas Chromatography-Mass
min. The specific selection of gas flow rates (200, 400 and 600 mL/min) Spectrometer (GC-MS) combined by GC (Thermo Scientific, Trace
was based on our previous study [21], where the parameter was be­ 1300) and MS (Thermo Scientific, ISQ QD) equipped with a HP-5MS
tween 200 and 1000 mL/min. After our thoughts, 800 and capillary column (length: 30 m, inner diameter: 0.25 mm, film thick­
1000 mL/min were relatively large and thus not used. Besides, the ness: 0.25 µm). The bisphenol A yields were accurately analyzed by
traditional pyrolysis experiments at different temperatures (400, 600 external standard method like some published works [21,23], and the
and 800 ℃) were also finished to compare with photothermal pyrolysis. method was shown below in details: using the 99.0 wt% purity
After the experiment, the mass of char was weighed with a balance to bisphenol A with the washing solution used in the experiment was
calculate the char yield. The tar produced was divided into two parts: configured into a series of standard solutions with concentrations of
one part was the pyrolytic tar remaining on the silicone tube and end 0.52, 1.02, 1.93, 4.16, 6.69 mg/g respectively. The precipitate peak
cap, the mass of this part is recorded as Mpure-tar by weighing the front areas of bisphenol A in different concentrations of bisphenol A solutions
and rear mass of the end cap and silicone tube. Washing the tube wall of were measured using GC-MS, and the fitting curve of the concentration
quartz reactor with a mixed liquid (volume ratio of methanol: of bisphenol A solution to the precipitate peak area of bisphenol A was

3
Q. Ren et al.
plotted in Fig. 3. Y is the precipitation peak area of bisphenol A and X is
the mass concentration of bisphenol A (mg/g). The equation of the fitted
curve is shown in Eq. (3) and the peak area of bisphenol A evolution
from pyrolytic tars at different conditions measured by GC-MS is
denoted as Yi, then the mass yield of bisphenol A is calculated using Eq.
(4):
8 8 2
Y = 2.98121 × 10 ∗ X + 1.35332 × 10 R = 0.99218 (3)
Yi − 1.35332 × 108 Mpure− tar
Bisphenol A yield(wt%) = × (Mtar + ) (4)
2.98121 × 108 × 103 Xtar
2.4. Spearman correlation analysis for components by GC-MS
The current analysis of the generative decomposition mechanism of a
certain ingredient in tar using GC-MS data are mostly obtained by
analyzing the variation of the proportion of each ingredient measured by
GC-MS [24–26]. However, the components of tar from waste fan blades
are complex, and it is subjective to compare the products related to
bisphenol A in many components only through GC-MS results. Spearman
correlation analysis method has been applied to analyze the chemical
reactions pathways [27,28]. The evolution of bisphenol A in the pyrol­
ysis process will result in some certain correlations between the content
of bisphenol A and other products in tars. Therefore, the Spearman
correlation analysis method was adopted to screen the substances
related to bisphenol A in tars, which can be used as a reference for
analyzing the formation and decomposition mechanisms of bisphenol A
in photothermal pyrolysis process.
IBM SPSS statistics 26 software was used to screen and sorted out the
correlations of GC-MS data, and in-depth analysis. The significance test
was carried out by using the two tailed t-test model. Rho value is the
correlation coefficient, between -1 and 1. Greater than 0 means positive
correlation, and less than 0 means vice versa. The substances with
positive correlation with bisphenol A can be considered to be associated
with the formation of bisphenol A, which is related to its formation.
Substances negatively related to bisphenol A can be considered to be
produced by the decomposition of bisphenol A, which is related to its
decomposition. The greater the absolute value, the greater the degree of
correlation. The size of P value represents the significance level of cor­
relation. If *P < 0.05, it means statistically significant correlation, and if
* *P < 0.01, it means more significant [29].
Fig. 3. The relation between concentration and peak are in GC-MS of bisphe­
nol A.
4
Journal of Analytical and Applied Pyrolysis 169 (2023) 105828
3. Results and discussion
3.1. Effects of pyrolysis temperature on products compositions and
bisphenol A
The pyrolytic products yields of waste fan blade based material at
different pyrolysis temperatures (400 ℃, 600 ℃, 800 ℃) from photo­
thermal and traditional pyrolysis are shown in Fig. 4. As it can be seen,
the error bar results are relatively small, suggesting the experimental
results are reliable and can be used to analyze the trend. As for the
photothermal pyrolysis, with increase of pyrolysis temperature, the tar
yield increases significantly, the char yield decreases, and the gas yield
does not change significantly. It indicates that the higher the degree of
thermal cracking of base material, the more sufficient the release of
volatile component after the increase of pyrolysis temperature [18].
While for traditional pyrolysis, as the pyrolysis temperature rises, the
char yield is decreased, the gas yield increases, the tar yield shows a
tendency of first increase and subsequent decrease, and the phenomenon
is consistent with biomass pyrolysis [30,31]. The yields differences are
caused by the reason below: in this photothermal pyrolysis system, the
high-temperature zone of concentrated pyrolysis is in the cube area with
a side length of less than 20 mm, so the volatile can quickly escape from
the high-temperature zone, effectively avoiding the secondary reactions
of volatile and cracking into small molecular gaseous substances [19],
and the volatile separated from the high-temperature zone condenses to
form tar, resulting in the gas yield does not change significantly and tar
yield can be promoted at higher pyrolysis temperature.
Fig. 5 shows the compositions of tars at different pyrolysis temper­
atures derived from photothermal and traditional pyrolysis. The results
showed that there are 8 kinds of substances in the tars. While as for the
results of traditional pyrolysis, no bisphenol A signal is detected in tars
derived from traditional pyrolysis. However, bisphenol A is abundant in
photothermal pyrolytic tars, which also suggests that the gas secondary
reactions for bisphenol A decomposition are significantly reduced. Be­
sides, most of the photothermal pyrolytic tars are phenolics (more than
80%), the major phenolics are bisphenol A, phenol, 4-isopropylphenol
and 4-isopropylphenol. While all of them are less than 5% except
nitrogenous compounds, and esters and acylates could only be detected
in tar obtained at 400 ℃. The contents of various substances changes
with the pyrolysis temperature as follows: the content of phenolic sub­
stances firstly decreases and then increases, and the change trend of
nitrogen-containing compounds is opposite to that of phenolic sub­
stances; the contents of silicon compounds, acyls, esters and aliphatic
hydrocarbons decrease; the contents of ethers and aromatic hydrocar­
bons increase. Actually, the relative content of phenolic compounds is
finally decided by the generation and decomposition processes. As a
whole, the generation and decomposition of phenolic compounds would
both be promoted when the input energy is more, and the decomposition
can be promoted when the gas secondary reactions are stronger. By
analyzing the results of traditional pyrolysis in Fig. 5(b), it can be found
that the relative content of phenolic compounds would be decreased
with pyrolysis temperature increasing. While higher pyrolysis temper­
ature can offer more energy, thus the gas secondary reactions are the
main factor to for the reduction. It is known that the photothermal py­
rolysis can significantly reduce the gas secondary reactions due to the
limited heat zone [19]. Therefore, as for photothermal pyrolysis in Fig. 5
(a), the gas secondary reactions would be reduced obviously, leading to
the reduction degree from 400 ℃ to 600 ℃ is less, and the relative
content at 800 ℃ is even higher than that at 600 ℃. The reason why
there are nitrogen compounds in tar is that the epoxy resin is a viscous
liquid or brittle solid before curing, and the nitrogen-containing sub­
stance is highly sensitive to temperature, and its content will fluctuate
significantly with increase of pyrolysis temperature. Silicon compounds
and esters have poor thermal stability, and their proportion in tar will
decrease significantly when the temperature increases. The increase of
pyrolysis temperature is conducive to the formation of aromatic
Q. Ren et al.
Fig. 4. Products yields from base material at different pyrolysis temperatures: (a) photothermal pyrolysis; (b) traditional pyrolysis.
Fig. 5. Compositions of tars at different pyrolysis temperatures.
hydrocarbons and ethers.
The bisphenol A yields and relative contents at different pyrolysis
temperatures are shown in Fig. 6. It can be seen that with increase of
pyrolysis temperature, bisphenol A yield increases from 4.66 wt% to
6.22 wt%, and its relative proportion in tar increases from 37.65% to
45.46%. The relative contents of bisphenol A in tars determined by GC-
MS can effectively reflect the selectivity. Thus the results in Fig. 6 show
that the increased pyrolysis temperature is conducive to the formation of
bisphenol A and improve its selectivity in tar [32]. However, high
temperature is not conducive to the stable existence of bisphenol A rigid
skeleton, and the reasons for this phenomenon may be as following: 1)
5
Journal of Analytical and Applied Pyrolysis 169 (2023) 105828
Fig. 6. Yields and relative contents of bisphenol A in tars at different pyrolysis
temperatures.
although the increase of pyrolysis temperature can increase the range of
high-temperature zone, the high-temperature zone is still concentrated
in a small area. As a result, the impact of the increased pyrolysis tem­
perature on the enhancement of the secondary reactions outside the
particles is weak, so the residence time of the volatile released from
thermal interpretation in the high-temperature zone is still very short.
The energy absorbed by bisphenol A rigid skeleton in the
high-temperature zone is enough to produce the fracture of chemical
bonds; 2) the increase of pyrolysis temperature will significantly pro­
mote the degree of thermal cracking, so that more volatile components
are released, and the bisphenol A rigid skeleton plays a dominant role in
the 2,2-bis(4-glycidyloxyphenyl)propane molecule. Therefore, the in­
crease of bisphenol a molecule in volatile component is greater, and the
content of bisphenol A in tar is increased.
3.2. Effects of heating rate on products compositions and bisphenol A
When the heating rates are 100, 200 and 400 ℃/min respectively,
the pyrolytic products yields of waste fan blade base material are shown
in Fig. 7. With increase of heating rate, the tar yield firstly increases
significantly and then levels off, the gas yield firstly decreases and then
basically remains unchanged, and the char yield has not changed
significantly. This shows that the increase of heating rate can signifi­
cantly increase the tar yield, but when the heating rate exceeds 200 ℃/
Q. Ren et al.
Fig. 7. Products yields from base material at different heating rates.
min, the improvement effect basically disappears; the effect of heating
rate on the gas yield is opposite to that of tar; the heating rate has little
effect on the char yield, and temperature is the main factor affecting its
yield. The main reason for this phenomenon is that the heating rate
increases, the heat absorbed by the sample increases per unit time, and
the release amount of volatile component per unit time increases. That
is, the release rate of volatile component increases, which greatly re­
duces the secondary reactions of volatile molecules in the particles, so
the small molecular gaseous substances generation will be reduced.
However, the heating rate is too high, which is limited by the thermal
conductivity of the sample, so it cannot absorb more heat per unit time,
and the influence of the heating rate on the products yields is weakened.
Therefore, the increase of the heating rate from 200 ℃/min to 400 ℃/
min cannot cause a significant change in the pyrolytic products yields.
Fig. 8 shows the compositions in tars at different heating rates, and
there are 8 kinds of substances in the tars obtained at different heating
rates. According to the contents of substances from high to low, they are
phenolic compounds, nitrogen compounds, ethers, aromatics, silicon
compounds, alcohols, esters and aliphatic hydrocarbons. Among them,
phenols account for the majority, and the maximum content in tar can
exceed 90%. The content of other substances, except nitrogen com­
pounds and ether compounds, is less than 5%, and alcohol compounds
and silicon compounds only exist in tar with a specific heating rate.
The heating rate has the greatest impact on the content of phenolic
Fig. 8. Compositions of tars at different heating rates.
6
Journal of Analytical and Applied Pyrolysis 169 (2023) 105828
substances. The heating rate increases from 100 ℃/min to 400 ℃/min,
and the relative content of phenolic compounds decreases from 90.11%
to 78.34%, which indicates that excessive heat absorption in a short time
will destroy the phenolic hydroxyl groups of some phenols. The contents
of other substances change with the heating rate as follows: the content
of alcohol substances decreases significantly; the contents of aromatic
hydrocarbons and ethers increase; the contents of other substances
fluctuate. By comparing the tar compositions obtained at different
temperatures and heating rates, it is not difficult to find that the two are
roughly the same in the overall distribution of the material. The main
difference lies in the change of phenolic substances contents, which
shows that the high temperature resistance of phenolic substances is
stronger than the heat shock resistance in the photothermal pyrolysis.
Incorporating the analysis above, high heating rate has a strong ability
to destroy phenolic hydroxyl, which significantly reduces the relative
proportion of phenolic substances at high heating rate. This part of
phenols that cannot withstand high heat shock mainly evolve into ethers
and aromatic hydrocarbons.
The bisphenol A yield and its relative contents in tars at different
heating rates are shown in Fig. 9. It can be seen that with increase of
heating rate, the bisphenol A yield increases from 3.94 wt% to 6.50 wt
%, and its relative content increased from 40.58% to 43.39%. The
phenomenon suggests that the increase of heating rate is also beneficial
for formation of bisphenol A and improving its selectivity in tar. From
the tars compositions at different heating rates, the content of phenols
decreases with increase of heating rate, which does not conflict with
increase of bisphenol A. There are two reasons: 1) the high heating rate
causes the phenolic substances receive more heat in a short time, leading
to the destroy of phenolic hydroxyl groups of some phenolic substances,
while the bisphenol A rigid skeleton makes it have better heat shock
resistance; 2) the release rate of volatile component will also increase
significantly at high heating rate, which significantly reduces the surface
secondary reactions of volatile matter in the particles, so that the
bisphenol A rigid skeleton is largely retained and the formation of
bisphenol A is promoted.
3.3. Effects of gas flow rate on products compositions and bisphenol A
When the gas flow rates are 200, 400 and 600 mL/min respectively,
the pyrolytic products yields of resin components in waste fan blades is
shown in Fig. 10. With increase of gas flow, the tar yield firstly increases
and then decreases, the gas yield firstly decreases and then increases,
and the char yield has not changed significantly. This shows that the gas
flow mainly affects the pyrolytic tars and gases, and has almost no effect
Fig. 9. Yields and relative contents of bisphenol A in tars at different heat­
ing rates.
Q. Ren et al.
Fig. 10. Products yields from base material at different gas flow rates.
on the char yield. Therefore, the gas flow mainly affects the mutual
conversion reactions between tars and gases. Fig. 11 shows the tar
compositions at different gas flow rates. Compared with the tars ob­
tained at different pyrolysis temperatures and heating rates, there are
more kinds of substances in the tars, but the content of phenolic sub­
stances decreases. As for Fig. 11, when the gas flow rate increases from
200 mL/min to 400 mL/min, the gas flow rate brings some thermal
energy, leading to the decrease of phenolic compounds generation and
decomposition. Besides, the increase of gas flow rate also reduces the gas
secondary reactions. In this situation, the decrease degree is more
obvious as for generation, so the relative content shows a decrease from
200 mL/min to 400 mL/min. However, when the gas flow rate increases
from 400 mL/min to 600 mL/min, the gas secondary reactions can be
further obviously reduced, leading to the phenolic compounds de­
compositions in gas phase can be hugely reduced. Thus the relative
content of phenolic compounds in GC-MS shows the tendency of
increase.
The bisphenol A yields and the relative contents in tars at different
gas flow rates are shown in Fig. 12. It is known the bisphenol A yield
increases from 5.86 wt% to 6.46 wt% with increase of gas flow rates,
and its relative contents are all about 41%. The results shows that the
increase of gas flow rate could promoted the formation of bisphenol A,
and has no obvious effect on its selectivity in tar. The gas flow rate has an
effect on the secondary reactions occurring inside and outside the par­
ticles. The cross-sectional area of the quartz reactor is constant. The
Fig. 11. Compositions of tars at different gas flow rates.
7
Journal of Analytical and Applied Pyrolysis 169 (2023) 105828
Fig. 12. Yields and relative contents of bisphenol A in tars at different gas
flow rates.
larger the flow rate of the carrier gas means the greater the flow rate of
the carrier gas in the reactor. Then the carrier gas can bring the volatiles
produced by pyrolysis away from the high-temperature zone quickly, so
that the bisphenol A rigid skeleton has fewer secondary reactions in the
high-temperature zone, thereby promoting the formation of bisphenol
A.
3.4. Generation mechanism of bisphenol A during photothermal pyrolysis
In Sections 3.1–3.3, the experiments at three different pyrolysis pa­
rameters were conducted, and pyrolytic tars were collected and char­
acterized. In this section, the correlation between the tar components
and bisphenol A would be analyzed to conclude the generation mech­
anism of bisphenol A, the correlation results were shown in Fig. 13.
Ethers and bisphenol ring phenols show a significant positive correla­
tion, indicating that bisphenol ring phenols are produced concomitantly
with the production of bisphenol A, the production of ethers is related to
the ring opening reaction of the epoxide groups at both ends of the 2,2-
bis(4-glycidyloxyphenyl)propane, and the bisphenol ring phenols have a
Fig. 13. Correlation analysis results between tar components and bisphenol A.
Q. Ren et al.
molecular structure that is mostly similar to that of bisphenol A and can
be produced from the bisphenol a backbone by substitution reactions,
ring forming reactions, or other reactions.
High contents of phenol and 4-isopropylphenol both show a signif­
icant negative correlation with bisphenol A, indicating that phenol and
4-isopropylphenol are the main products of bisphenol A decomposition.
Analysis shows that there are mainly two possible reasons: 1) the
chemical properties of phenol and 4-isopropylphenol are relatively
stable; 2) 2,2-bis(4-glycidyloxyphenyl)propane molecules can produce
phenol and 4-isopropylphenol. The relative content of 4-isopropenyl­
phenol is also high, but it has no statistical correlation and its molecu­
lar structure is very similar to with bisphenol A. The difference is that 4-
isopropenylphenol has carbon-carbon double bond, so it can be inferred
that 4-isopropenylphenol is obtained by dehydrogenation of 4-
isopropylphenol.
Incorporating the results and analysis above, the formation and
decomposition mechanisms of bisphenol A during photothermal pyrol­
ysis can be obtained as shown in Fig. 14. Polymer pyrolysis includes the
cracking of the main chain and the elimination of side groups. The main
component of the base material is 2,2-bis(4-glycidyloxyphenyl)propane,
which has two epoxy functional groups and hydroxyl groups on its
branch chain, and the main chain contains bisphenol a rigid skeleton, C-
O bond and C-C bond.
During the initial stage of pyrolysis process, the epoxy group and
hydroxyl group on the branch chain will undergo side group elimination
reaction to produce free highly active hydroxyl and ether bonds, and a
small part of hydroxyl will combine with hydrogen atoms to produce
Fig. 14. Formation and decomposition mechanism of bisphenol A during photothermal pyrolysis of base material in waste fan blade.
8
Journal of Analytical and Applied Pyrolysis 169 (2023) 105828
water. With further increase of pyrolysis temperature, the pyrolysis re­
action is significantly strengthened, and main chain of 2,2-bis(4-glycidy­
loxyphenyl)propane begins to crack, producing bisphenol a rigid
skeleton, phenoxy, alkane and other active groups. Subsequently, most
of the hydroxyl and ether bonds will combine with alkyl groups to form
ethers, alcohols, esters and other oxygen-containing functional group
compounds. Most phenoxy groups will evolve into phenols, and a small
amount of phenoxy groups will lose oxygen atoms in the secondary re­
actions and convert into aromatic hydrocarbons. After, part of the
bisphenol A rigid skeleton are destroyed to form phenoxy, but most of
them will quickly enter the cold zone to avoid secondary reactions with
other active groups and thus be retained. The retained bisphenol a rigid
skeleton mainly reacts with hydrogen atoms to form bisphenol A, and a
few evolve into substances with similar molecular structure to bisphenol
A, such as 4,4-(propane-2,2-diyl)bis(methoxybenzene) and 4-(2-(4-
methoxyphenyl)propan-2-yl)phenol. In addition, bisphenol A molecule
will also generate a small amount of substances such as 5-isopropyl-2-
methylphenol, 2-(tert-butyl)− 4-(2-phenylpropan-2-yl)phenol, o-
cresol, aromatic hydrocarbons and so on through substitution reaction
and the fracture of phenoxy bond. The generation mechanism shown in
Fig. 14 is mainly based on the original inner connection. While the ef­
fects of the three pyrolysis parameters are as below: the higher pyrolysis
temperature can offer more input energy, and it can promote all the
chemical reactions by strengthening their effective collisions; the larger
heating rate can also promote the change of reaction system and break
the chemical balance, affecting many chemical reactions; when the gas
flow rate is increased, the volatile can be quickly brought out from high-
Q. Ren et al.
temperature zone, thus reducing gas secondary reactions.
4. Conclusions
A novel photothermal pyrolysis system was developed and firstly
applied to treat waste fan blade, which was mainly composed by the
based material and reinforcing fiber (mass ratio was 74.36:25.64). By
pyrolyzing the base material, bisphenol A was significantly acquired,
and its generation can be promoted by increasing pyrolysis temperature,
heating rate and gas flow rare. The pyrolysis of 2,2-bis(4-glycidyloxy­
phenyl)propane resin included the breaking of the main chain and the
elimination of side groups. During the photothermal pyrolysis process,
the main chain undergone random or chain cracking reaction to produce
bisphenol A rigid skeleton, phenoxy, alkane, hydroxyl and other active
groups. Bisphenol A rigid skeleton was the precursor of bisphenol A.
Bisphenol A was formed after receiving hydrogen atoms, accompanied
by the formation of tetrahydrofuran, 4,4-(propane-2,2-diyl)bis
(methoxybenzene) and other substances. Bisphenol A undergone
decomposition via secondary reactions, and it was mainly decomposed
into phenol and 4-isopropylphenol, 4-isopropylphenol was then dehy­
drogenated to produce 4-isopropenylphenol.
Funding
This research was financially supported by National Natural Science
Foundation of China (NSFC) (52076097), and Strategic International
Scientific and Technological Innovation Cooperation Special Funds of
National Key Research and Development Program of China
(2018YFE0127500).
CRediT authorship contribution statement
Qiangqiang Ren: Methodology, Formal analysis, Investigation,
Writing – original draft, Visualization. Zhiwen Lei: Formal analysis,
Investigation, Writing – original draft. Song Hu: Writing – review &
editing, Supervision, Project administration, Funding acquisition. Yong
Ding: Writing – review & editing. Limo He: Writing – review & editing.
Sheng Su: Validation, Writing – review & editing. Yi Wang: Validation,
Writing – review & editing. Long Jiang: Writing – review & editing. Jun
Xu: Writing – review & editing. Jun Xiang: Writing – review & editing,
Supervision, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
The authors do not have permission to share data.
Acknowledgments
The assistance from Analytical and Testing Center of Huazhong
University of Science and Technology is highly acknowledged. Also,
thanks to the facility support of Equipment Center in State Key Labo­
ratory of Coal Combustion, Huazhong University of Science and
Technology.
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