Journal of Hazardous Materials 426 (2022) 127783

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Journal of Hazardous Materials

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Degradation of urea-formaldehyde resin residues by a hydrothermal

oxidation method into recyclable small molecular organics
Tianhang Ren a, Yan Wang b, Nan Wu c, Yan Qing a, Xingong Li a, Yiqiang Wu a, Ming Liu a, *
a
College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410000, China
b
College of Engineering and Design, Hunan Normal University, Changsha 410000, China
c
Guangxi Fenglin Wood Industry Group Co. Ltd., Nanning 530000, China

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

Editor: Haizhou Liu-CHAZL Urea-formaldehyde (UF) resin residues and the related product wastes as organic hazardous wastes are difficult
to be biodegraded or recycled. In this research, a hydrothermal oxidation method using hydrogen peroxide
Keywords: (H2O2) solution has been developed for the degradation and recycling of UF resin residues. The effects of solution
Hazardous wastes concentration, temperature, and time on the degradation efficiency and products of UF resin residues were
UF resin
studied. Under optimal conditions, i.e., 140 ◦ C and 5 wt% H2O2 solution, over 75% of UF resin residues was
Hydrothermal treatment
degraded after 3 h. The degradation efficiency is much higher than that of the traditional hydrothermal treat­
Hydrogen peroxide
Harmless disposal ment or acid hydrolysis method. In addition, results from Fourier transform infrared spectroscopy (FTIR), gas
chromatography–mass spectroscopy (GC–MS), nuclear magnetic resonance spectroscopy (NMR), and X-ray
diffraction (XRD) confirmed that H2O2 solution degrades UF resin residues to low molecular compounds, such as
alcohols, methylal, and amides. This research provides a novel and high-efficient hydrothermal oxidization
process for the degradation of UF resin residues, which might be a promising environmentally friendly and low-
cost method for the disposal and recycling of industrial UF resin residues.

1. Introduction As an organic waste treatment technology used worldwide, inciner­

As one of the essential formaldehyde-based wood adhesives, urea-
formaldehyde (UF) resin is widely used in wood-based panels because of
its excellent bonding properties and low cost (Dunky, 1998). China is the
largest wood-based panel manufacturing country, produces and con­
sumes large amounts of wood-based panels and related products every
year (Park et al., 2013). Although wood-based panels are widely
accepted in the construction and packaging markets, UF resin residues
hinder the sustainable development of the wood-based panel industry.
As a polymeric condensation product formed by chemical reactions
between formaldehyde and urea, UF resin residues is difficult to be
biodegraded, which may take many years to decompose once buried in
land (Zhong et al., 2017). For many years, organic resin residues have
been recognized as hazardous wastes in many countries. European
countries have issued many regulations to limit the treatment of organic
resin residues (Karazipour, 2007; Mitchell, 2008; Piekarski et al., 2018).
The UF resin residues also hinder the reuse of wood components in
wood-based panels. Degrading and recycling UF resin residues or ma­
terials containing UF resin in an environmentally friendly way is urgent.
ation causes violent oxidation and reduces the waste volume. Although
the thermal energy generated by waste incineration can be stored for
further utilization, the generation of noxious nitrogen oxides (NO and
NO2) during the UF resin residues combustion process causes severe
environmental issues such as acid rain (Skodras, 2004;
Risholm-Sundman and Vestin, 2005). Therefore, incineration is an un­
economical and not environmentally friendly disposal method for UF
resin residues.
Alternatively, pyrolysis is used for organic wastes disposal. Pyrolysis
could convert organic wastes into high-value fuels or chemical products,
thus has received extensive attentions from researchers in recent years
(Wang et al., 2020; Cesprini et al., 2020; Chen et al., 2012). Although
pyrolysis of UF resin residues under oxygen-limited conditions could
eliminate the formation of noxious nitrogen oxides, toxic
nitrogen-containing gases such as HCN and HNCO are usually found in
exhaust gases (Chen et al., 2015). Recent studies have been focusing on
suppressing the formation of toxic nitrogen-containing gases during the
pyrolysis of UF resin residues. For instance, Becidan et al. shows that the
slow pyrolysis of waste fiberboard significantly reduces the generation

* Corresponding author.
E-mail address: liumws@126.com (M. Liu). HCN hydrogen
https://doi.org/10.1016/j.jhazmat.2021.127783
cyanide
Received 31 July 2021; Received in revised form 16 October 2021; Accepted 10 November 2021
Available online 14 November 2021
0304-3894/© 2021 Elsevier B.V. All rights reserved.
T. Ren et al.
of HCN (Becidan et al., 2007). Girods et al. presents that
low-temperature pyrolysis of waste wood containing UF resin at
250 − 300 ◦ C effectively inhibits the production of HCN (Girods et al.,
2008). However, pyrolysis requires dry feedstocks, the cost of the
treatment is relatively high. Therefore, pyrolysis is not an ideal method
for the treatment of organic wastes containing UF resin.
Hydrothermal treatment is a chemical process that decomposes
organic substances using hot-compressed water. Compared with pyrol­
ysis, it barely produces harmful gases for the disposal of organic wastes
(Lubis et al., 2017). Moreover, since the whole process is conducted in
an aqueous condition, there are no requirements for the moisture
removal of the feedstock. This saves energy for raw materials drying that
is required in incineration and pyrolysis processes (He et al., 2008).
Therefore, the hydrothermal pretreatment process has a wide applica­
tion range and low operation difficulty for organic wastes disposal
(Ching et al., 2020). Relevant studies show that the hydrolysis reaction
of UF resin residues is the reverse reaction of its synthetic process (Lubis
and Park, 2018). Water molecules penetrate the junction of the UF resin
that initiates the hydrolysis reaction. Due to the existence of hydrox­
ymethyl and methylene ether bonds in UF resin, the hydrolysis of UF
resin residues is easier to occur in the hydrothermal environment (Ching
et al., 2020; Lubis and Park, 2018; Grigsby et al., 2015). Research by Liu
et al. shows that a 30% formaldehyde solution at 140 ◦ C for 2 h degrades
about 85% of UF resin residues, the hydrolyzed product could be
directly used in formaldehyde solutions for new UF resin synthesis (Liu
et al., 2018). However, the use of hazardous formaldehyde solution for
the degradation of UF resin residues is considered less environmentally
friendly.
Hydrothermal oxidation is a mature pollutant treatment technology
widely used to treat refractory pollutants. The reaction conditions for
wastes treatment are at the temperature of 100 − 320 ◦ C and pressure at
0.5 − 20 MPa, using ozone, hydrogen peroxide, and air as oxidants (Yin
et al., 2011; Poyatos et al., 2009; Kaczmarek et al., 1998). Studies on
hydrothermal treatment of UF resin residues and related wastes mainly
focus on hydrolysis treatment using HCl and formaldehyde. However,
there are no reports on the oxidative degradation of UF resin residues in
hydrogen peroxide (H2O2) solution. From an environmentally friendly
perspective, compared to other chemical reagents, the only by-product
from the oxidation of H2O2 solution is water (Yin et al., 2011)⋅H2O2 is
widely used to treat industrial pollutants in the oxidative degradation
treatment at low temperature and pressure.
This study explores the hydrothermal oxidation treatment of UF resin
residues using H2O2 as the advanced oxidation reagent. The effects of
hydrothermal oxidation conditions on the degradation efficiency and
products of UF resin residues were studied. The degradation efficiency of
this method is evaluated by measuring the mass loss ratio of the treated
UF resin residues. The hydrolysates were analyzed using Fourier trans­
form infrared spectroscopy (FTIR), gas chromatography− mass spec­
troscopy (GC− MS), nuclear magnetic resonance spectroscopy (NMR),
and X-ray diffraction (XRD). A considerable amount of small molecular
products, such as methylal and amide, can be obtained after the hy­
drothermal oxidation process. These products can be recycled and used
as high-value raw materials for chemical synthesis. The hydrothermal
oxidation process improves the degradation efficiency of UF resin resi­
dues, which is an energy-saving and environmentally friendly method
for the disposal and recycling of UF resin residues.
2. Materials and methods
2.1. Materials
Analytical-reagent grade urea (99%), formaldehyde (37%) aqueous
solutions, formic acid (98%), NaOH (99%), H2O2 (30%), HCl (37%)
were purchased from Sinopharm Chemical Reagent Co., Ltd, China. All
chemicals were used as received without further purification except for
dilution to achieve different desired concentrations.
2
Journal of Hazardous Materials 426 (2022) 127783
2.2. UF resin preparation
Approximately 560 g of formaldehyde solution was mixed with 200 g
urea for an addition reaction. The pH was controlled around 8.0 during
the reaction. After that, the pH value of the solution was adjusted to 5.0
for a condensation reaction to occur. After reaching the target viscosity
(T-4 cup viscosity), 95 g of urea was added. The solution was reacted for
an additional 30 min at 70 ◦ C. Then 108 g of urea was added, the pH was
controlled between 7.0 − 7.5 to complete the reaction. The measured
average viscosity for all the resins was 29.02 mPa⋅s, with an average
solid content of 53.0%.
UF resin residues were prepared by adding 1 wt% of NH4Cl based on
the resin’s solid content. Subsequently, all the UF resins were cured at
120 ℃ for 3 h. Then, the cured UF resins were ground to particles (≤ 20
mesh) with a ceramic mortar and pestle for further experiments.
2.3. Degradation of UF resin residues by HCl and H2O2 solution
To explore the degradation process of the UF resin residues using
hydrothermal treatment, about 2 g of pretreated UF resin residues and
1 − 5 wt% HCl or H2O2 solutions were put into 50 ml hydrothermal
autoclaves as shown in Fig. 1. The autoclaves were heated at
100 − 140 ℃ for 1 − 5 h, respectively. The detailed experimental
conditions are listed in Table 1. After the hydrothermal treatment, the
remained UF resin residues were collected and measured. The degra­
dation efficiency of UF resin residues was measured by the mass loss
ratio using Eq. (1):
Mass loss ratio(%) =
Mi − Me
× 100 (1)
Mi
Where：.
Mi = weight of UF resin residues before hydrothermal treatment,
and.
Me = weight of UF resin residues after hydrothermal treatment.
2.4. Design of experiment (DOE)
DOE was performed using the central composite design (CCD)
experiment. This method is useful in response surface methodology for
building a second-order (quadratic) model for the response variable
without needing a complete five-level factorial experiment. To analyze
the effect of different reaction conditions on the degradation efficiency
of UF resin residues, a 3-factor and 5-level design resulted in 20 exper­
iment runs, includes 8 cubic test points, 6 asterisk test points, and 6
central test points. The value of α is the default value of Minitab 19
software. The parameter range was determined based on preliminary
runs. The detailed conditions are listed in Table 2. All the data were
analyzed using Minitab 19 software (Spreadsheet Software, USA).
2.5. Characterization of chemical products from the degradation of UF
resin residues
2.5.1. FTIR analysis
cured UF
Fourier transform infrared spectroscopy (FTIR, SHIMADZU IRTrace-
100, Japan) was used to characterize the chemical groups of the UF
resin. Before measurement, the samples were pressed into a pellet with
anhydrous KBr powder (2 mg sample with 200 mg KBr). The IR spec­
trometer was operated over 4000 − 400 cm-1 at a 4 cm-1 data interval.
cured UF
2.5.2. XRD analysis
The crystallinity of UF resin residues was characterized using an X-
ray diffractometer (XRD, Ultima IV, RIGAKU, Japan) with a Cu Kα ra­
diation source (λ = 0.15406 nm). Each sample was dried at 103 ℃ for
3 h. The samples were scanned at room temperature from 5 − 90◦ with
0.02◦ min-1. The crystallinity of the samples was calculated from the
T. Ren et al. Journal of Hazardous Materials 426 (2022) 127783

Fig. 1. Pathway of the hydrothermal treatment of UF resin residues.

can oxidize organic compounds (RH), producing organic radicals (⋅R),

Table 1
which are highly reactive and can be further oxidized (Xu et al., 2013;
Factors and levels of the hydrothermal oxidation process of UF resin
Wibowo et al., 2020a). The degradation pathways of UF resin residues
residues.
using H2O2 solutions include both hydrolysis and oxidation. UF resin
Factors Levels residues were treated at different temperatures, times, and solution
Time (h) 12345 concentrations. In this study, mild reaction conditions were used for the
Temperature (℃) 100 120 140 potential of industrial applications.
H2O2 and HCl Concentration (wt%) 135
To compare the degradation efficiency, the weights of UF resin res­
idues before and after the hydrothermal treatment with H2O2 and HCl
solutions were measured. The mass loss ratios were calculated according
Table 2 to Eq. (1). As shown in Fig. 2, the mass loss ratio increases significantly
Factors and levels for central composite design experiment. with the increase of the reaction time at 120 ℃ and 3 wt% H2O2 solu­
Factors Code Levels (α = 1.68) tion. Previous studies show that water reacts with the hydroxymethyl
-α -1 0 1 α end groups on the molecule chain of UF resin residues, which destroys
the methylene bond and degrades the UF resin residues into formalde­
Temperature (℃) A 86.36 100 120 140 153.63
Time (h) B 0.63 2 4 6 7.36 hyde and other oligomers (He et al., 2008). However, the degradation of
Concentration (wt%) C 0.32 1 3 5 6.46 UF resin residues in H2O2 solution is not noticeable compared with the
HCl solution for 1 h treatment. It might relate to the initiation and
diffusion of free radicals on the surface of UF resin residues. The mass
XRD patterns using Jade MDI 6.5. loss ratio reaches 25% when the treatment time was extended to 2 h,
which is significantly higher than that of the HCl solution. This indicates
2.5.3. GC-MS analysis liquid product that the oxidation reaction was initiated in the H2O2 solution during the
The liquid products obtained from the hydrothermal treatment of UF degradation of UF resin residues. Free radicals, such as⋅OH, have higher
resin residues were analyzed using a gas chromatography− mass spec­ reactivity than that of HCl solution, which leads to a rapid degradation
trometry (GC–MS, 7890 A− 5975 C, Agilent, America). A capillary col­ of resin residues (Xu et al., 2013). Sufficient reaction time may ensure
umn (DB− WAX, 30 m × 0.25 mm × 0.25 µm) was employed to separate enough free radicals to initiate and diffuse on the surface of UF resin
the solutions. The GC oven temperature was programmed to start at residues.
40 ℃, held for 5 min, then raised to 120 ℃ at a rate of 5 ℃, held for The reaction temperature is a crucial factor of the hydrothermal
3 min. Then increase to 230 ℃ at a rate of 10 ℃/min, held for 10 min. process for the degradation of UF resin residues. As shown in Fig. 3(a),
The injection port temperature was 60 ◦ C, while the injections were the degradation of the UF resin residues in H2O2 and HCl solutions is
conducted in a split mode with a split ratio of 70. The end of the column improved to varying degrees with the increase of the temperature. With
was directly introduced into the ion source of MS mass detector operated
with electron impact ionization mode at 230 ◦ C. The mass scan ranged t increases, mass loss increases @T=120C
from 35 to 500 m/z.
liquid product
2.5.4. NMR analysis
The 1H and 13C NMR spectroscopy were used to characterize the
chemical structure of products from the hydrothermal treatment of UF
resin residues. The liquid products were dissolved in D2O (400 μL
sample liquid in 40 μL D2O). All the NMR spectra were performed on a
Bruker 400 MHz spectrometer (NMR, Bruker, Billerica, USA). Data for
1
H and 13C NMR were reported as chemical shifts (δ ppm).

3. Results and discussion

3.1. Effects of hydrothermal treatment of UF resin residues using HCl and

H2O2 solutions

In this part, UF resin residues were treated using three different so­
lutions: water, 3 wt% HCl and H2O2. The UF resin residues contain
hydrophilic groups such as methylol, which causes the resin to decom­
pose during the hydrothermal treatment process. On the other hand, the
H2O2 system generates hydroxyl radicals (⋅OH), which is a strong
oxidizing material (Hiroki, 2005; Zhang et al., 2018). Hydroxyl radicals Fig. 2. Mass loss ratios of UF resin residues after hydrothermal treatment with
solutions of water, 3 wt% HCl and H2O2 at 120 ℃ for 1 − 5 h.

3
T increases, Mass loss increases @t=3h conc. increases, mass loss increases @T=140C, t=3h
T. Ren et al. Journal of Hazardous Materials 426 (2022) 127783

Fig. 3. Mass loss ratios of UF resin residues after hydrothermal treatment (a) with water, 3 wt% HCl and H2O2 at 100 ℃, 120 ℃ and 140 ℃ for 3 h; (b) with 1, 3 and
5 wt% of HCl and H2O2 solutions at 140 ℃ for 3 h.

an increased treatment temperature, the degradation efficiency of UF

Table 3
resin residues in H2O2 solution is much higher than that in HCl solution.
Results from the central composite design experiment.
When the temperature is increased from 100 ◦ C to 140 ◦ C, the mass loss
ratio of the UF resin residues in H2O2 solution is increased from 21% to Run # Time (h) Concentration (wt%) Temperature (℃) Yield (%)
55% after 3 h of treatment. This might attribute to the free radical re­ 1 6 5 100 43.5
actions, which requires energy in the reaction system for initiation. 2 2 1 100 15.5
Higher treatment temperature provides more energy to the system and 3 4 3 120 43.5
4 6 5 140 83.5
increases the probability of intermolecular collisions. On the other hand, 5 4 3 120 43.5
higher treatment temperature promotes the generation of⋅OH radicals 6 2 5 140 58.5
and free radical reactions of molecule chains, thus promoting the 7 4 3 86.36 24.0
degradation process (Yin et al., 2011; Xu et al., 2013). 8 2 5 100 20.5
9 6 1 100 25.5
The solution concentration also has a significant effect on the mass
10 4 0.36 120 25.5
loss ratio of the UF resin residues. According to the results in Fig. 3(b), 11 4 3 153.63 97.0
the mass loss ratio of UF resin residues is increased from 25% to 45% 12 7.36 3 120 45.0
with the increase of the HCl concentration. Similarly, the mass loss ratio 13 0.63 3 120 14.5
is increased from 45% to 75% with the increase of H2O2 solution con­ 14 4 3 120 44.5
15 4 6.36 120 48.0
centration. During the hydrothermal treatment of the UF resin residues, 16 6 1 140 64.5
the increase of H+ concentration promotes the hydrolysis process (Liu 17 4 3 120 43.5
et al., 2018). Similarly, higher H2O2 concentration provides more⋅OH 18 4 3 120 43.5
radicals in the hydrothermal oxidation process of UF resin residues. 19 4 3 120 42.5
20 2 1 140 37.0
More⋅OH radicals could accelerate the initiation and transfer of free
radical reactions, which significantly improves the degradation effi­
ciency of the UF resin residues in H2O2 solution. Mass loss ratio = 1⋅854 + 0⋅0583 × Time − 0⋅0115 × Conc − 0⋅03726 ×
In a short reaction time, the HCl solution could hydrolyze UF resin Temp
residues with a good efficiency. But it inevitably causes many environ­ − 0⋅012060 × Time × Time − 0⋅005873 × Conc × Conc + 0⋅000178 ×
mental problems such as water pollution. In contrast, water is the only Temp × Temp
side product from the hydrothermal treatment of UF resin residues using
H2O2 solution. In addition, 5 wt% HCl is not cost-effective compared + 0⋅003125 × Time × Temp + 0⋅000625 × Time × Conc + 0⋅000563 ×
with 5 wt% H2O2. Hence, dilute H2O2 solution outperforms HCl solution Conc × Temp
for recycling and disposal of UF resin residues. In summary, H2O2 so­
In addition to the developed regression equation, graphical pareto
lution might be more suitable for the hydrothermal treatment of UF
analysis was performed to show the effect of each operating parameter
resin residues.
on response. The pareto chart is given in Fig. 4. According to the Pareto
chart, the most effective parameter of UF resin residues degradation
3.2. Optimization of the hydrothermal process using a design of
through the hydrothermal oxidation process is temperature, followed by
experiment (DOE)
time and solution concentration. The parameters interaction also shows
little effects on the degradation efficiency of UF resin residues. The result
The experiment was aimed to further explore the influence of process
from Pareto analysis is consistent with the regression equation. The
parameters on the hydrothermal oxidation efficiency of UF resin resi­
formed mathematical equation, which gives erroneous results or model,
dues, including temperature (Temp), time (Time), solution concentra­
may not be able to properly define the domain. Therefore, variance
tion (Conc), and the interaction between these variables. The results of
analysis is a more reliable way to evaluate model quality in data
the CCD experiment is shown in Table 3. The obtained experimental
analysis.
data was analyzed using Minitab 19 software, the fitted regression
Table 4 shows the ANOVA test results for the influence of the used
equation was obtained as follows:
variables in UF resin residues degradation. The P value less than 0.0500
indicates that the model term is significant (as commented S in the
table). A higher significant level of model term is defined when the P

4
T. Ren et al. Journal of Hazardous Materials 426 (2022) 127783

are less than 0.00001. The values of F and P obtained for both processes
show that the model term is significant. The significance of the model
terms can be seen in Table 4. The results confirm that temperature has
the most significant influence on the degradation efficiency of UF resin
residues during the hydrothermal process, followed by time and solution
concentration.

3.3. Chemical analysis of UF resin residues after the hydrothermal

treatment

As a polymer, the study of the degradation mechanism of UF resin

Fig. 4. Pareto chart of process parameters’ effects on UF resin residues
degradation.
value is less than 0.0001. While an insignificant (as commented NS in
the table) model term is defined when the P value is larger than 0.1. The
more F value corresponds to less P value. The larger of the P value also
explains the higher of the insignificance level of the variable. In this
study, as shown in Table 4, the model F value is 816.51. The values of P
residues is beneficial to optimize the reaction conditions and to improve
the degradation efficiency. The hydrothermal oxidation process of UF
resin residues includes two parts of hydrolysis and oxidation. The
degradation pathway and product distribution are greatly affected by
the hydrothermal treatment conditions. As shown in Fig. 5(a), 3350 cm-
1
and 1388 cm-1 represent -NH- and -NHCH2- in the UF resin residues
(Kaczmarek et al., 1998). Intensities of these bonds are not changed. It
indicates that the main chain of the UF resin was not broken after the
hydrothermal treatment with HCl or H2O2 solution. This suggests that
the functional groups of the residual substance do not change in the
hydrolysis and oxidation process of UF resin residues. However, the
intensity of the C– – O bond at 1633 cm-1 is significantly enhanced,
indicating more oligomers were formed on the surface of UF resin res­
idues after the hydrothermal treatment (Wibowo et al., 2020a; Qu et al.,
2015). Compared to the HCl solution treatment, the C-N bond at
1436 cm-1 and 1136 cm-1 is significantly enhanced with H2O2 treatment
after the hydrothermal process. It is believed that UF resin residues

Table 4
ANOVA results of the response surface model applied for the hydrothermal oxidation process of UF resin residues.
dF SS MS F P Comment

Model 9 0.815835 0.090648 816.51 < 0.00001

Linear 3 0.678625 0.226208 2037.57 < 0.00001 S
A-Time 1 0.116794 0.116794 1052.02 < 0.00001 S
B-Concentration 1 0.060424 0.060424 544.26 < 0.00001 S
C-Temperature 1 0.501407 0.501407 4516.42 < 0.00001 S
AA 1 0.033537 0.033537 302.09 < 0.00001 S
BB 1 0.007953 0.007953 71.64 0.000007 S
CC 1 0.072819 0.072819 655.91 < 0.00001 S
AB 1 0.00125 0.00125 11.26 0.007297 S
AC 1 0.005 0.005 45.04 0.000053 S
BC 1 0.00405 0.00405 36.48 0.000125 S
Residual 10 0.00111 0.000111
Lack of Fit 5 0.00091 0.000182 4.55 0.060906 NS
Pure Error 5 0.0002 0.00004
Cor Total 19 0.816945

Fig. 5. FTIR (a) and XRD (b) patterns of UF resin residues after hydrothermal treatment with 3 wt% HCl and H2O2 solutions at 140 ℃ for 3 h.

5
T. Ren et al. Journal of Hazardous Materials 426 (2022) 127783

generate more linear oligomers and amides after the hydrothermal Table 5
oxidation treatment (Wibowo et al., 2020a, 2020b). This indicates that Liquid products of UF resin residues after the hydrothermal treatment by 3 wt%
the hydrothermal oxidation degradation of UF resin residues may H2O2 solution at 140 ◦ C for 3 h.
gradually proceed from surface to inside. The UF resin molecules on the No. Compound tR MF MW RPA
surface are destroyed by water or free radicals, which generates oligo­ 1 Propylene Glycol 11.40 C3H8O2 76.05 8.92
mers. Then, the oxidation reaction is initiated to generate small mo­ 2 N,N-Dimethylformamide 13.20 C3H7NO 73.05 5.69
lecular compounds with the combination of free radicals and the groups 3 Methylal 20.00 C3H8O2 76.05 8.53
at the end of the linear oligomers. This shows that the H2O2 solution has 4 Piperonylamine 28.50 C8H9NO2 264.25 10.19
5 2,4-Bis(1,1-dimethylethyl)- 30.28 C14H22O 206.17 2.00
a higher degradation efficiency for UF resin residues than HCl solution.
phenol
It further proves that the hydrothermal oxidation treatment is suitable
for the disposal or recycling of UF resin residues. tR, retention time; MF, molecular formula; MW, molecular weight; RPA, relative
The crystalline region has a higher chemical stability than that of the peak area (%)
non-crystalline region of UF resin. The increase of crystalline regions
also enhances the water resistance of UF resin. The crystalline features of from the oxidation of the amide group in the UF resin residues. The
UF resin residues before and after the hydrothermal treatment are structure with a benzene ring is mainly due to the cyclization reaction in
shown in Fig. 5(b). The XRD patterns of UF resin residues after the the hydrothermal environment, which causes the condensation of small
treatment with HCl or H2O2 solutions are similar to the untreated resin molecular organics to form phenol and aniline (Kaczmarek et al., 1998;
samples. The crystallinity calculation of all the samples was conducted Wibowo et al., 2020a). These products could be recycled and reused. For
using the MDI Jade 6.5 software. It shows that the crystallinity of the example, dimethylformamide is widely used as a solvent for the reaction
untreated UF resin residues is 36.51%. The crystallinity of the resin and an important intermediate chemical in organic synthesis. Methylal
residues after the treatment of HCl and H2O2 solutions are increased is mainly used for the production of anion-effect exchange resins, as well
slightly to 45.38% and 45.74%, respectively. Other research works also as solvents and fuels. These products are useful chemical materials,
explore the relationship between the morphological structure and the which are easier to handle than HCN and HNCO from the thermal
degradability of UF resin (Park and Jeong, 2011a, 2011b; Liu et al., disposal of UF resin residues. Acidic hydrolysis of UF resin residues also
2017). Due to the irregular arrangement of the amorphous regions, the generates NH4Cl with an incomplete decomposition (Liu et al., 2018).
physical and chemical properties of the UF resin residues are unstable. The products of UF resin residues from the hydrothermal oxidation
Therefore, the crystallinity of UF resin residues is increased with the process have a wide range of applications.
treatment of hydrolysis or oxidation since the degradation of more Fig. 7 shows the 1H and 13C NMR spectrum of the chemicals from the
amorphous regions. But the crystallinity increase of UF resin residues hydrothermal oxidation process of UF resin residues with 3 wt% H2O2
after H2O2 solution treatment is slightly higher than that of the HCl solutions under 140 ◦ C for 3 h. The sharp peak in 1H NMR chemical
solution. This also indicates that the degradation reaction of UF resin shifts at 4.6 ppm is attributed to H2O of the solution. The other sharp
residues in H2O2 solution is more severe than that of HCl solution. chemical shifts, such as 4.10 and 2.80 ppm, are assigned to substituted
Compared to HCl solution, H2O2 solution has a better degradation effi­ -NH2 and -CH2- from Piperonylamine. The weak chemical shift at
ciency in treating UF resin residues. 3.50 ppm is assigned to substituted -CH2-O-CH2- from methylal (Oliver
Fig. 6 shows the GC− MS spectrum of liquid product of UF resin et al., 2014; Tataurova et al., 2012). The 13C NMR spectrum makes up
residues after the hydrothermal treatment with H2O2 solution under for the deficiencies of the 1H NMR spectrum. It gives information about
140 ℃ for 3 h. The obtained main products are ethers, acetals, amides, various carbon-containing functional groups. The sharp peak in 13C
and phenols as shown in Table 5. The produced fragments of UF resin NMR chemical shifts is 171.44 ppm, which is attributed to -CO-N- of N,
residues could be easily oxidized into short-chain organics. Since the N-Dimethylformamide (Xie et al., 2010). The other sharp chemical
free radicals in H2O2 solution are easy to react with oligomers, the shifts, such as 71.81 ppm are assigned to substituted -CH2-OH from
products after the hydrothermal process are mostly small molecular propylene glycol. The weak chemical shift at 162.98 ppm is attributed to
compounds. Ethers and acetals are mainly derived from the methylene the benzene ring structure from 2,4-bis(1,1-dimethylethyl)-phenol
ether bond structure in the UF resin residues. These components are (Chandrashekhar et al., 2008). Combined with all the chemical anal­
oxidized into ethers and aldehydes in the hydrothermal oxidation pro­ ysis, it is reasonable that UF resin residues could be hydrolyzed into
cess (Liu et al., 2017). The N, N-Dimethylformamide is mainly derived intermediate chemicals first. The intermediate chemicals could be

Fig. 6. GC-MS spectrum of liquid products of UF resin residues after the hydrothermal treatment by 3 wt% H2O2 solutions at 140 ◦ C for 3 h.

6
T. Ren et al. Journal of Hazardous Materials 426 (2022) 127783

Fig. 7. 1H and 13
C NMR spectrum of liquid products of UF resin residues after hydrothermal treatment by 3 wt% H2O2 solutions at 140 ◦ C for 3 h.

further oxidized into harmless small molecular compounds, which could

be reused in the subsequent recycling process.

3.4. Hydrothermal oxidation pathway of UF resin residues

According to the characterization results, the degradation process of

UF resin residues in H2O2 solution is divided into hydrolysis and
oxidation. As a polymer, due to the existence of hydrophilic groups, such
as hydroxymethyl, the hydrolysis reaction of UF resin residues occurs in
the hydrothermal environment. Formaldehyde is usually generated first
during the resin hydrolysis process. Subsequently, water molecules
further destroy the methylene and ether bond linkages in the UF resin
residues, resulting in small molecules of resin fragment (Nuryawan and
Park, 2018). In the hydrolysis process of UF resin residues, the resin Fig. 8. The degradation process of UF resin residues in H2O2 solution.
molecules will only degrade to produce resin fragments and NH4Cl (Liu
et al., 2018). However, during the oxidation process, the resin fragments
destroyed and generate more radicals such as⋅OOH,⋅NH,⋅CH2 and⋅NH, as
produced by the hydrolysis of the UF resin further reacts with⋅OH to
shown in Fig. 9. Free radicals also produce small molecules such as
generate a variety of recyclable small molecular organics.
methylal and amines. In the hydrothermal treatment process, small
As shown in Fig. 8, hydrothermal oxidation process of UF resin can
molecular substances may undergo further reactions to form substances
be divided into three steps: initiation, propagation, and termi­
containing ring structures, such as phenols. The increase of the tem­
nation⋅H2O2 generates⋅OH radicals under heating conditions. The
perature also promotes the progress of hydrolysis and free radical re­
decomposition reaction occurs between the solid and the liquid, a het­
actions in the system. It improves the degradation efficiency of UF resin
erogeneous reaction, the aqueous solution plays a vital role in the re­
residues. Therefore, the increase in temperature has a significant pro­
action system. Only when active radicals contact with the resin surface
motion effect on the hydrolysis and oxidation of UF resin residues.
can the transfer of free radical reactions be induced. The reaction
Under sufficient reaction time and temperature, the free radical reaction
gradually proceeds from the surface of the resin residue particle to the
makes it possible to degrade more UF resin residues at a lower con­
inside. First,⋅OH diffuses on the surface of the UF resin residues and
centration of H2O2 solution. This research provides a new method for the
initiates a free radical chain reaction at the end of the molecule chain.
harmless degradation and recycling of UF resin residues. The products
The molecules of UF resin residues are destroyed by free radical re­
from the hydrothermal treatment with H2O2 solution can be recycled as
actions and degraded into small molecular products. As the reaction
chemical feedstock while avoiding environmental pollution problems
temperature is increased, the hydrolysis reaction of UF resin residues is
that traditional treatment methods may cause. The degradation
continued, which forms more small fragments. Then, the fragments are

7
T. Ren et al.
Fig. 9. Possible oxidative reaction scheme of UF resin residues based on FTIR, XRD NMR, and GC-MS analysis of the products from the hydrothermal oxida­
tion process.
mechanism of the hydrothermal oxidation process of UF resin residues is
complicated and will be studied in subsequent research.
4. Conclusions
In this research, a hydrothermal oxidation process was studied to
simulate the disposal and recycling of UF resin residues. Compared with
pyrolysis, the hydrothermal oxidation treatment of UF resin residues
produces no harmful gases. The reaction temperature was found to be
the crucial factor affecting the degradation efficiency of UF resin resi­
dues. The optimized condition of the hydrothermal treatment was
140 ◦ C and 3 h with 5 wt% H2O2 solution. This condition generated 75%
mass loss of UF resin residues, which was much higher than that of the
conventional hydrothermal methods or acid hydrolysis under the same
conditions. The products from the hydrothermal oxidation of UF resin
residues includes propylene glycol, N,N-Dimethylformamide, methylal,
amides, and phenols. These compounds could be reused for producing
value-added chemical products. Hydrothermal oxidation method gen­
erates no harmful pollutants and needs no pretreatment, which proves
its applicability for the disposal and recycling of UF resin residues.
CRediT authorship contribution statement
Tianhang Ren: Conceptualization, Methodology, Investigation and
Writing – original draft. Yan Wang: Validation and Data curation. Nan
Wu: Resources and Visualization. Yan Qing: Investigation and Meth­
odology. Xingong Li: Project administration. Yiqiang Wu: Funding
acquisition. Ming Liu: Supervision, Formal analysis, Funding acquisi­
tion, Review and editing.
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.
Acknowledgements
This work was supported by National Natural Science Foundation of
China [32001262]; Outstanding youth project of Hunan Education
8
Journal of Hazardous Materials 426 (2022) 127783
urea formaldehyde
UF
Department [18B18]; Changsha Science and technology project
[kq2004096]; Forestry science and Technology Extension Project
[2019:23]; Science and technology innovation project of Shengxiang
group− Shengxiang Industry (Jiangsu) Co., Ltd. [G.
YF− QH− 201905001]; the Key Projects of Hunan Science and Tech­
nology Plan [2016SK2032]; Guizhou Science and Technology Support­
ing Plan [2018:2196]; Introduced Talents Start-up Project of Central
South University of Forestry and Technology [2018YJ007].
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