http://pubs.acs.

org/journal/acsodf Article

Ion-Exchange Resins for Efficient Removal of Colorants in

Bis(hydroxyethyl) Terephthalate
Rong Huang, Qi Zhang, Haoyu Yao, Xingmei Lu,* Qing Zhou,* and Dongxia Yan
Cite This: https://doi.org/10.1021/acsomega.1c01477 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Bis(hydroxyethyl) terephthalate (BHET) obtained

from waste poly(ethylene terephthalate) (PET) glycolysis often
have undesirable colors, leading to an increased cost in the
decoloration of the product and limiting the industrialization of
chemical recycling. In this work, eight types of ion-exchange resins
Downloaded via 191.101.87.121 on April 30, 2021 at 01:30:54 (UTC).

were used for BHET decoloration, and resin D201 showed an

outstanding performance not only in the decoloration efficiency
but also in the retention rate of the product. Under the optimal
conditions, the removal rate of the colorant and the retention
efficiency of BHET were over 99% and 95%, respectively. D201 showed outstanding reusability with five successive cycles, and the
decolored BHET and its r-PET showed good chromaticity. Furthermore, the investigations of adsorption isotherms, kinetics, and
thermodynamics have been conducted, which indicated that the decoloration process was a natural endothermic reaction.
Adsorption interactions between the colorant and resin were extensively examined by various characterizations, revealing that
electrostatic force, π−π interactions, and hydrogen bonding were the dominant adsorption mechanisms.

1. INTRODUCTION oxidation, and active carbon adsorption.15−17 Among these

Glycolysis is the most promising method in waste poly-
(ethylene terephthalate) (PET) recycling.1,2 It has been
practiced by well-known enterprises such as DuPont, Kodak,
Dow Chemicals, and Goodyear.3,4 The main glycolysis product
of PET is the monomer bis(hydroxyethyl) terephthalate
(BHET), which is the monomer of PET and can be used
directly as a raw material for the synthesis of PET to form a
closed loop. Moreover, BHET, an important chemical and
industrial material, has been widely used in scientific research
and industrial production. For example, it is used for the
production of various high-value products such as polyur-
ethane, hydrophobic textile dyes, alkyd resins, and waterborne
coating.5 Although the recovery method of PET via glycolysis
is promising,6 there are still some problems worth attention.
In general, catalyst development, BHET purification, and its
decoloration are the main difficulties in glycolysis industrializa-
tion. Nowadays, many researchers focus on the first two,7−11
while the bottleneck problem is the high chromaticity of
BHET, but it has attracted little attention. The heavy-colored
BHET limits its high-value usage, and the r-PET regenerated
from it is usually substandard in chromaticity. To reduce the
chromaticity, traditional decoloration methods are adopted,
which greatly increase the process cost and hinder the
industrialization process. However, the problems related to
BHET decoloration has not been solved yet.12−14 Bearing in
mind the aforementioned dilemma, the decoloration of BHET
is pressing.
In this regard, various measures have been attempted for the
decoloration of BHET, including recrystallization, distillation,
© XXXX The Authors. Published by
American Chemical Society
A ACS Omega XXXX, XXX, XXX−XXX
methods, the recrystallization process is quite simple, but the
solvent separation is difficult; the additives from the polymer
still exist and BHET loss is large. The oxidation method can
achieve significant decoloration efficiency, whereas it also
causes secondary pollution and even result in the destruction
of BHET’s molecular structure. The vacuum distillation
method is desirable with less waste generation and low
requirements for raw materials. However, BHET refining is not
feasible due to the likelihood of repolymerization. 11
Adsorption, a common physicochemical measure, is very
popular because of its excellent efficiency, minimal cost, and
super less sludge accumulation. Among many adsorbents,
active carbon is the most common one, while it is far from
ideal due to the difficult reproduction which leads to high cost.
As a result, the majority of used active carbon is treated as solid
waste, which is contrary to the concept of sustainable
development.18−20 The existing conventional decoloration
methods and adsorbents are generally problematic. Therefore,
searching for a new adsorbent that can effectively remove the
colorant from BHET and can be regenerated easily is an urgent
issue.
Received: March 19, 2021
Accepted: April 23, 2021
https://doi.org/10.1021/acsomega.1c01477
ACS Omega http://pubs.acs.org/journal/acsodf
Recently, resins have been widely used in the decoloration
and separation of sugar liquors,21−23 medicine,24,25 foods26 and
so on,27−29 owing to its easy regeneration and high selectivity.
Qiang et al. used resins to removal the hydrophobic caramel
pigments from cane molasses, and the anion exchange resin
can achieve 99% decoloration rate.30 The colorants used in
PET products, especially in textile, are mainly disperse dyes
and reactive dyes, among which, reactive dyes are more
difficult to treat.31,32 The reactive dyes usually appear in an
ionic state in solution, which makes the decoloration through
ion-exchange resins highly advantageous. However, the
theoretical research is lacking, and we hope to reveal a gentle
and effective method for removing colorants from BHET and
usher in the new plastic economy.
Therefore, eight ion-exchange resins were used to evaluate
the decoloring performance according to their color removal
rate and BHET retention rate for the first time. The
decoloration factors and the interactions between the
adsorbent and colorant were investigated. The adsorption
isotherm, kinetic, and thermodynamic experiments together
with different adsorption models were analyzed. Numerous
characterization methods were employed to discover the
interactions between the adsorbent and colorant. A compre-
hensive and detailed recognition of the decoloration
mechanism was obtained via this theoretical study.
2. RESULTS AND DISCUSSION
2.1. Adsorption Parameters and Reusability. 2.1.1. Ad-
sorbent Selection. Ion-exchange resins with different func-
tional groups were carried out to select the most suitable
adsorbent for the decoloration and purification of the PET
glycolysis product. As shown in Figure 1, the decoloration rate
Figure 1. Properties of different ion-exchange resins for BHET
decoloration.
and loss ratio of BHET on different resins were distinct.33,34
Among these resins, D201, JK206, and D202 showed decent
efficiencies in the decoloration process, which can achieve
99.16%, 99.87%, and 83.65%, respectively. Moreover, the
decoloration rates of strong base ion-exchange resins were
higher than those of weak base resins: strong [JK206 (99.87%)
> D201 (99.16%) > D202 (83.65%) > D296 (74.95%) > IRA-
410 (69.33%)] > weak [D301 (51.98%) > D900 (43.44%) >
D392R (31.09%)]. Thus, the functional group played a vital
role in the decoloration stage, and the more basic the
functional group of the resin, the better its decoloration
performance. Besides, the superiority in the decoloring
performance of D201 and JK206 may be caused by its pore
B https://doi.org/10.1021/acsomega.1c01477
Article
diameter distribution. In addition, in separate and purification
technology, product selectivity is also an essential evaluation
index. Li et al. used modified activated carbon to remove the
color of BHET, and the decoloration rate was 97%. However,
the retention efficiency of BHET was not mentioned.17 In this
study, the loss ratio of BHET was investigated for the first
time. All these resins caused BHET loss in a more or less
amount. The loss ratio of BHET was JK206 > D202 > D201.
Therefore, to reduce the loss of BHET, further investigations
on the decoloration of BHET were carried out using D201.
2.1.2. Influence of Temperature. Temperature’s impact on
BHET decoloration by D201 was investigated using a fixed
original concentration in 1 h (Figure 2a). The increase in
temperature was in favor of the sorption process of the
colorant, which hinted that the adsorption of the colorant onto
D201 was a natural endothermic reaction. On the one hand,
the increased temperature endowed colorant molecules with a
much higher kinetic energy; hence, the adsorbates can reach
active sites with a higher energy. On the other hand, the
boundary layer thickness around the resin decreased with an
increase in temperature; hence, the mass transfer resistance of
the colorant decreased consequently.35 Therefore, the increase
in temperature promoted adsorption. However, the loss degree
of BHET was also sensitive to temperature change, and heating
was not conducive to the retention of BHET. Hence, room
temperature was the relatively optimal condition, which can
not only save energy but also achieve the ideal purification goal
in both the decoloration and selectivity of BHET.
2.1.3. Influence of Resin Dosage. An optimal concentration
of the adsorbent not only can achieve the ideal effect but can
make the process more economic. As evident from Figure 2b,
the adsorption rate of the colorant increased dramatically with
an increase in the adsorbent dosage, and from 0.1 g/50 mL to
0.15 g/50 mL, the prominent changeless decoloration rate over
99% kept constant with an increase in the dosage. In contrast, a
slight increase in BHET loss was caused with an increase in the
mass of resin. These trends probably caused by the available
active adsorption sites and the competition intensity between
the colorant and BHET. First, with a larger amount of resin,
redundant effective adsorption sites were provided, and the
colorant was preferentially adsorbed on the resins rapidly.
Then, with an excess amount of adsorbent and an extremely
low concentration of the colorant after adsorption, the
adsorption competitiveness of the colorants was largely “lost”
even the interaction between BHET and the adsorbent was
quite weak.36 Hence, the loss rate of BHET was increased to
some extent.
2.1.4. Influence of Contact Time. Figure 2c shows the effect
of time on adsorption. The decolorization rate increased in the
first 3 h and for this period, colorant adsorption onto the resins
occurred quickly. The motor force of this stage may be caused
by abundant blank active sorption sites and the huge difference
of the colorant concentration between the liquid−solid
interphase.37 After this, the colorant concentration difference
gradually decreased, the active sites on the adsorbent surface
tended to saturation, and the decolorization rate of the resin
increased more slowly and flattened out at 4 h; at this time, the
decoloration rate was nearly 99%, and the BHET retention
efficiency was over 95%. Then, the colorant adsorption
achieved equilibrium at 4 h. After 4 h, there was an increased
loss in the BHET product while the decoloration rate remained
constant.
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf
Figure 2. Different effects on the decoloration of BHET: (a) contact temperature, (b) resin dosage, (c) contact time, and (d) the influence of
regeneration cycles via D201.
2.1.5. Reusability. In general, the recyclability of the
selected resin should be fully studied to gain economic
viability when applied in practical application.38 As shown in
Figure 2d, D201 showed outstanding reusability with a slight
decrease in the desorption rate and the decoloration rate after
five cycles can still exceed 99%. Besides, the appearance of the
reused D201 after five cycles was almost unchanged compared
to fresh D201 at low magnification, and only a slight change
was observed at a higher magnification with tiny cracks (Figure
S1). Thus, D201 resin showed outstanding performance and
reusability for colorant removal, which makes it a potential
candidate for the decoloration of BHET.
2.2. Adsorption Isotherms. Adsorption isotherms show
the distribution of adsorbates in two phases in terms of
concentration and pH under uniform temperature.39 To
further elucidate the mechanism of colorant adsorption using
D201, adsorption isotherm experiments were carried out. As
shown in Figure 3a, it was noteworthy that all the isotherms
showed the same trends and shapes, and the higher the
temperature, the stronger the adsorption capacity of the
colorant, suggesting that the decoloration process was
endothermic. To have a more comprehensive understanding
of the decoloration mechanism, Temkin, Freundlich, and
Langmuir isotherm models were proposed, which were
expressed in the following equation, respectively.40,41
qe = B ln A + B ln Ce
(1)
1 process were in the range of 0−1 (Table S1), indicating that
ln qe = ln kF + ln Ce
n (2)
C https://doi.org/10.1021/acsomega.1c01477
Article
Ce 1 C
= + e
qe kLqmax qmax (3)
In these equations, Ce and qe are the equilibrium
concentration and the adsorption capacity of the colorant,
respectively; A is the binding constant of equilibrium relevant
to maximum binding energy; and B equals to RT /b (T is the
temperature in kelvin, R is the molar gas constant (8.314 J·
mol−1·K−1), and b is the adsorption heat). Both n and kF are
Freundlich constants, reflecting the sorption amount and
intensity, respectively. The kL is the Langmuir constant
concerning the affinity of binding sites. qmax is the maximum
sorption capacity (mg·g−1). The fitting parameters of the
adsorption isotherm are summarized in Table 1.
According to the fitting correlation coefficients, the Temkin
and Freundlich isotherms did not describe the experimental
data well, while the correlation coefficient R2 of the Langmuir
isotherm was above 0.991. This suggested that the Langmuir
model can depict the adsorption data well and indicated that
the decoloration process was uniform monolayer adsorp-
tion.42,43 Besides, the equilibrium capacity qe from the
experiments and the calculated maximum capacity qmax from
the model were very close. From 288.15 to 328.15 K, the
values of qe were 117.79, 129.37, 143.04, 172.05, and 232.01
mg·g−1, respectively. The values of qmax were 107.41, 131.58,
142.05, 173.31, and 231.48 mg·g−1, respectively. The values of
the separation factor RL that are related to the adsorption
the adsorption was favorable. The pH value of solution is a
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 3. Adsorption isotherm of the BHET decolorization system via D201: (a) adsorption isothermal curve, (b) Temkin, (c) Freundlich, and (d)
Langmuir.

Table 1. Isotherm Model Parameters of Colorant

Adsorption onto D201
Temkin isotherm model
temperature (K) A (L·g−1) B (J·mol−1) R2
288.15 38.07 11.15401 0.9784
298.15 1722.80 9.02364 0.8705
308.15 3.29 × 105 7.51728 0.9616
318.15 2.21 × 1015 4.17278 0.9833
328.15 7.42 × 106 11.06643 0.8890
Freundlich isotherm model
temperature (K) N kF ((mg·g−1)(L·mg−1)1/n) R2
288.15 6.23 43.26 0.9938
298.15 10.63 69.95 0.9301
308.15 15.43 95.80 0.9736 Figure 4. Adsorption isotherm at various pH values.
318.15 38.52 147.73 0.9872
328.15 18.11 175.28 0.8962 As shown in Figure 4, with an increase in the pH value, the
Langmuir isotherm model equilibrium adsorption capacity decreased rapidly and then
temperature (K) kL (L·mg−1) qmax (mg·g−1) R2 tended to be flat. This may be caused by a change in resin’s
288.15 0.00109 107.41 0.9910 surface charge properties. As shown in Figure S2, the point of
298.15 0.00089 131.58 0.9911 zero charge (pHpzc), in which the surface of the resin was
308.15 0.00034 142.05 0.9962 electrically neutral, was determined, and the pHpzc of D201 was
318.15 0.00009 173.31 0.9998 found to be 6.70. When pH < pHpzc, the D201 surface was
328.15 0.00003 231.48 0.9987 occupied by excess H+ ions and in a positive charge state.
Besides, the colorant was anionic and contained deprotonated
sulfonic clusters in solution.44 Hence, a strong electrostatic
significant factor that affects the equilibrium, and the force occurred between the colorant and D201.20 When pH >
adsorption isotherm under different pH values is shown in pHpzc, the resin was occupied by excess OH− ions and in a
Figure 4. negative charge state; hence, the electrostatic repulsive force
D https://doi.org/10.1021/acsomega.1c01477
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 5. Adsorption kinetics study of the decolorization system.

Table 2. Kinetic Parameters of Colorant Adsorption onto D201 Ion-Exchange Resin

model temperature (K) k1 (h−1) R2
pseudo-first-order 288.15 0.94 0.9710
298.15 1.35 0.9875
308.15 1.58 0.9823
318.15 2.38 0.9847
328.15 1.62 0.9809
temperature (K) k2 (g·mg−1·h−1) H (mg·g−1·h−1) R2
pseudo-second-order 288.15 0.03 28.59 0.9909
298.15 0.04 100.32 0.9995
308.15 0.06 210.07 0.9961
318.15 0.07 202.81 0.9973
328.15 0.09 192.00 0.9989
temperature (K) kdif1 (mg·g−1·h−1/2) kdif2 (mg·g−1·h−1/2) kdif3 (mg·g−1·h−1/2) R12
intraparticle diffusion 288.15 19.36 16.66 8.85 1.0000
298.15 58.11 20.79 2.54 0.9984
308.15 63.02 13.34 2.34 0.9685
318.15 62.73 12.83 0.98 0.9962
328.15 58.78 10.55 0.88 0.9997

was observed between the resin and colorant, and the
adsorption attraction was very week.45 An increase in the
equilibrium capacity at a lower pH implied that decoloration
was probably due to electrostatic force along with ion
exchange.
2.3. Adsorption Kinetics. Adsorption kinetics is an
important factor reflecting chemical reaction and mass-transfer
processes. The colorant adsorptions via D201 resin with time
were investigated. Pseudo-first-order and pseudo-second-order
kinetic models were used to fit the experimental data.46,47
i k y
and Table 2 show the fitting results. Both the pseudo-first-
order and pseudo-second-order kinetic models can elucidate
the adsorption behavior of the colorant onto the anion
exchange resin properly. In detail, the decoloration process of
BHET was more in line with the second model (R2 > 0.990),
which suggested that the adsorption process was dominated by
chemiadsorption.48 The value of H for decoloration increased
rapidly with a higher temperature and then decreased slightly,
which also reflected that the adsorption rate at higher
temperature was significantly faster than that at lower one.

log(qe − qt ) = log(qe) − jjj 1 zzzt

The diffusion of the colorant into the pores of fresh D201 is

k 2.303 {
of great significance. Thus, the intraparticle diffusion model
(4) was taken into consideration. According to the fitting result of
the intraparticle diffusion model, all plots in three linear parts
t t
= (k 2qe2)−1 + showed similar characteristics (Figure 6). The deviations of the
qt qe (5) straight lines from the origin in Figure 6 indicated that the
intraparticle diffusion was not the only rate-limiting step.
H = k 2qe2 (6) Moreover, the higher the intercept C value, the more
important role the external diffusion played in the decoloration
qt = kdif t + C (7) process. Moreover, the values of kdif in every segment followed
the order: kdif1>kdif2>kdif3; they represent the exterior surface
where qe and qt are the sorption capacity in equilibrium and at adsorption step, the interior surface adsorption step, which is
time t, respectively; k1 and k2 refer to first-order and second- controlled by intra-particle diffusion, and the equilibrium
order rate constant, respectively; H is the indicator of the adsorption step for which the colorant moves from larger pores
initial adsorption rate; and kdif and C represent the diffusion to micropores in a tardy rate, respectively.40 In the initial
coefficient and the intercept of the curve, respectively. Figure 5 segment, as a result of vastly available adsorption sites on the
E https://doi.org/10.1021/acsomega.1c01477
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 6. Intraparticle diffusion model.

surface of D201, the removal rate of the colorant was Figure 7. FTIR spectra of the decoloration system.
instantaneous. Besides, the maximum value of kdif1 hinted
that the external diffusion played a dominant role in the cm−1, which represented that the resin still had a small
decoloration dynamics. adsorption effect on BHET.50 A new strong absorption peak
2.4. Thermodynamic Study. The increased value of qe appeared at 1130 cm−1, which was the characteristic
with a higher temperature elucidated that the decoloration absorption peak of the sulfonate S=O, and the peak in 1486
process was endothermic. The thermodynamic parameters ΔH cm−1 was attributed to the methyl C−H of the quaternary
, ΔS , and ΔG related to the decoloration were calculated from ammonium group in D201 resin; the increase in intensity
the van’t Hoff plot equation. The activation energy Ea was hinted that the quaternary ammonium played an indispensable
calculated by the Arrhenius equation (eq 11), where K is equal role in the decoloration process. The new vibration absorption
to k2 in the pseudo-second-order model.47 peak of C−Cl at 615 cm−1 further proved the adsorption of the
q colorant. The peak at 1630 cm−1 red-shifted to 1607 cm−1, and
Kc = e the width of the peak also expanded significantly, suggesting
ce (8) that the benzene ring in D201 and colorant showed π−π
interactions during the decolorization process. Thus, the
ΔS ΔH
ln Kc = − adsorption process was mainly influenced by electrostatic
R RT (9) forces, π−π interactions, etc. In addition, according to the
ΔG = ΔH − T ΔS (10) molecular structure of BHET, colorant, and D201, hydrogen

1 ij Ea yz
jj− zz
bond could work. However, this interaction is too weak to be

Tk R {
proved by FTIR. Thus, the possible decoloration mechanism is
ln K = ln A +
(11) shown in Figure 8.
As shown in Table 3, the value of ΔH was positive and
exceeds 40 kJ·mol−1, indicating a chemical adsorption process,
and a higher temperature was conducive to decoloration.49
The enhancement in the randomness of the decoloration
system can be confirmed by the positive value of entropy ΔS .
Above room temperature, the negative value of ΔG hinted the
spontaneous decoloration process and ΔG gradually decreased
with a higher temperature, which indicated that within the
scope of experimental investigation, the temperature was one
of the controlling factors of the decolorization rate, and the
increase in temperature can promote the spontaneous reaction.
The Ea value for the colorant adsorption was found to be 21.52
kJ·mol−1, indicating that the BHET decoloration procedure
was favorable.20
2.5. Characterization. Figure 7 shows the FTIR results of Figure 8. Schematic diagram of the decolorization mechanism.
BHET, colorants, and D201 before and after adsorption. A
small stretching vibration peak of carbonyl appeared at 1715

Table 3. Thermodynamics Parameters and Activation Energy

R2 △H (kJ·mol−1) △S (J·K−1·mol−1) △G (kJ·mol−1) Ea (kJ·mol−1)

288.15 K 298.15 K 308.15 K 318.15 K 328.15 K
0.9988 40.02 134.80 1.18 −0.17 −1.52 −2.87 −4.22 21.52

F https://doi.org/10.1021/acsomega.1c01477
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 9. SEM images of ion-exchange resin (a) before adsorption and (b) after adsorption.

To better understand the physicochemical characteristics of

D201 resin before and after the decoloration process, SEM and
BET were also performed. As observed in Figure 9, the
appearance and structure of the D201 particle did not change
at a low magnification, which indicated that the resin had
strong mechanical properties and did not break easily. At a
higher magnification, the fresh D201 had a smooth surface and
a large number of pores, while the one after adsorption
appeared much rougher and its pores became smaller. Table 4

Table 4. Physicochemical Properties of D201 before and

after Adsorption
surface area pore volume pore diameter
resin (m2·g−1) (cm3·g−1) (nm)
Figure 10. BHET and r-PET: (a and c) before decoloration and (b
D201 6.933 0.0484 31.96
and d) after decoloration.
D201 after 6.857 0.0435 29.21
adsorption
Table 5. Chroma Analysis Results of BHET and r-PET
sample chromaticity
presents the BET characteristics of anion exchange resins, and
it shows that the D201 resin had a large average pore size, L a B
which could be conducive to the colorant diffusion.27 BHET before decoloration 72.48 25.73 −6.34
Moreover, according to the BET analysis, the pore diameter BHET after decoloration 94.12 −0.10 0.79
and pore volume of fresh D201 were larger than those of the r-PET from colored BHET 78.99 2.55 13.87
used one, which was consistent with the phenomenon r-PET from decolored BHET 94.05 −0.39 1.44
observed in Figure 9.
2.6. Chroma Analysis. The BHET samples before and
after decolorization with D201 and the regenerated r-PET are colorant and loss ratio of BHET) for the first time. Under the
shown in Figure 10, and their chroma analysis results are optimal condition (25 °C, 0.1 g·50 mL−1, and 4 h), the
shown in Table 5. Evidently, the color of BHET changed decoloration rate of the colorant and the retention rate of
significantly from red to white after decoloration, and the color BHET were over 99% and 95%, respectively. The regeneration
of r-PET regenerated from undecolorized BHET was yellow, performance of D201 was outstanding with five successive
while the one from the decolored BHET was obviously white, cycles, and the decolored BHET and its r-PET showed good
and its whiteness value L ≥ 80 and b value ≤ 2, which met the chromaticity. The interaction between the resin and colorant
requirements of the bottle-grade PET. Moreover, when was mainly attributed to electrostatic forces, π−π interactions,
compared with other decolorization methods, decolorization and hydrogen-bonding interactions. Finally, the investigation
method using the D201 resin not only can show an excellent of the adsorption isotherms at various concentrations and pH
decoloring performance but also can achieve a good quality in values, kinetics, and thermodynamics indicated that the
r-PET (Table S2).11,17,51 Thus, the decoloration method of sorption was a monolayer endothermic chemical sorption
BHET by the D201 resin was feasible. conformed to the pseudo-second-order model. In conclusion,
the aforementioned excellent performances of D201 resin
3. CONCLUSIONS provide a good prospect for BHET decoloration, and we
An efficient decoloration method for waste PET glycolysis believe that this green and effective decoloration method can
product BHET was developed using ion-exchange resins with provide waste PET glycolysis product a wider area of
two main evaluation indexes (the decoloration rate of the application.
G https://doi.org/10.1021/acsomega.1c01477
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf
4. EXPERIMENTAL
4.1. Materials. PET particles were obtained from Jingdong
Commercial Co., Ltd. Zinc acetate, urea, ethylene glycol,
methanol, hydrochloric acid (HCl), sodium chloride (NaCl),
sodium hydroxide (NaOH), active carbon, and ethylene glycol
antimony (C6H12O6Sb2) were obtained from Kepujia Reagent
Co., Ltd. The colorant (Reactive Red X-3B, the chemical
structure is shown in Figure S2) was purchased from Karma
Reagent Co. Ltd. The reagents were directly used without
purification. Ion-exchange resins (IRA-410, D201, D301,
D900, D392R, JK206, D202, and D296) were obtained from
Langfang Sennart Chemical Company, and their basic
properties are listed in Table S3. The resins were used after
pretreatment.25
4.2. Preparation of BHET and r-PET. The glycolysis
product BHET was obtained from the waste PET decom-
position using the depolymerizing agent EG and catalyst. The
synthesis of the catalyst (n(urea)/n(ZnCl2) 4/1) was the same
as reported previously, and the mass of the catalyst and EG was
0.05 and 4 times of waste PET, respectively.9 A three-necked
rounded-bottom glass flask with a reflux condenser, magnetic
stirrer, and thermometer was employed. The reaction was
conducted at 449.15 K until the complete degradation of PET.
Then, deionized water was used for the separation of BHET
from the reaction mixture, and the obtained crude BHET
products were purified by active carbon treatment and water
recrystallization several times, and then they were dried at
343.15 K for 24 h. Then, the colored glycolysis product
solution was simulated by adding the colorant (Reactive Red
X-3B) to control it as the only colorant source, since it was
commonly used in polyester blended fabrics and was an
important source of color. The concentrations of BHET and
the colorant were 10 g/L and 100 mg/L (the volume of
methanol was equal to that of distilled water), respectively.
The synthesis of r-PET was carried out in a sealed flask under
mechanical agitation. The usage amount of the catalyst
(ethylene glycol antimony) was 0.1 wt % of BHET. The
reaction conditions were kept at a nitrogen atmosphere and
heated and evacuated.
4.3. Adsorbent Performance Test. A fixed mass of ion-
exchange resins (IRA-410, D201, D301, D900, D392R, JK206,
D202, and D296) of 0.1 g were put into Erlenmeyer flasks
containing 50 mL of colored BHET solution. The flasks were
shaken at 298.15 K for 12 h with a constant agitated rate. The
supernatant after adsorption was determined by UV and
HPLC to obtain the concentration of the colorant and BHET,
respectively. The equilibrium adsorption capacity of the
colorant, qe (mg·g−1), decoloration rate (R%), and the loss
ratio of BHET (L%) were calculated by the following
equations:
V Engineering, State Key Laboratory of Multiphase Complex
qe = (C0 − Ce) ×
m (12)
C0 − Ce
R% = × 100
C0 (13)
C BHET·0 − C BHET·e
L% = × 100
C BHET·0 (14)
where C0 (mg·L−1) and C BHET·0 (g·L−1) are the initial
concentrations of the colorant and BHET, respectively; Ce
(mg·L−1) and C BHET·e (g·L−1) are the residual concentrations
H https://doi.org/10.1021/acsomega.1c01477
Article
of the colorant and BHET after reaching adsorption
equilibrium, respectively; m (g) is resin mass; and V (L)
represents the volume of colored BHET solution.
4.4. Batch Adsorption and Desorption. The adsorption
experiments of the colorant and BHET onto resin were carried
out and possible influence factors including sorption time,
temperature, and resin dosage were analyzed. The temperature
range was 288.15−328.15 K. The resin dosage was varied from
0.02 g/50 mL to 0.15 g/50 mL. The contact time was in the
range of 0.5−6 h. The sorption−regeneration cycles were
repeated five times under constant conditions. Desorption
experiments were conducted with 20 wt % HCl solution (the
usage amount was 1 g of resin for 1 L of eluent and the volume
of methanol was equal to distilled water) for a day. Then, the
resin was removed, washed to neutral, and reused in the
following decoloration tests. The efficiency of regeneration
(RE%) was computed via eq 15.
Ce2V2
RE% = × 100
(C0 − Ce)V (15)
where C0, Ce , and V are defined as in eq 12; Ce2 is the colorant
concentration in the regeneration liquid after desorption; and
V2 is the desorption liquid volume.
4.5. Isotherm and Kinetic Experiments. Decoloration
isotherm studies using D201 as an adsorbent were investigated
at different initial colorant concentrations and pH values,
which were in range of 100−700 mg/L and 1−11, respectively.
The adsorption temperature was in the range between 288.15
and 328.15 K. Decoloration kinetics studies were carried out
by placing D201 contacted with colored BHET solution at
different temperatures and time intervals. The adsorbed
amounts of the colorant on resin were determined by eq 12,
where the adsorption capacity qt at time t (mg/g) replaces qe .
Other parameters of eq 12 represent the same meaning.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.1c01477.
SEM characterization of the fresh D201 and reused
D201, determination of point of zero charge, informa-
tion about the colorant, RL values of the adsorption
isotherm, comparison of different BHET decoloration
methods, and resin’s basic information (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Xingmei Lu − Beijing Key Laboratory of Ionic Liquids Clean
Process, CAS Key Laboratory of Green Process and
Systems, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, P. R. China; School of Chemical
and Engineering and Sino Danish College, University of
Chinese Academy of Sciences, Beijing 100049, P. R. China;
Innovation Academy for Green Manufacture, Chinese
Academy of Sciences, Beijing 100190, P. R. China;
orcid.org/0000-0003-4712-656X; Phone: +86-010-
82544800; Email: xmlu@ipe.ac.cn
Qing Zhou − Beijing Key Laboratory of Ionic Liquids Clean
Process, CAS Key Laboratory of Green Process and
Engineering, State Key Laboratory of Multiphase Complex
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf
Systems, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, P. R. China; School of Chemical
and Engineering, University of Chinese Academy of Sciences,
Beijing 100049, P. R. China; Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
P. R. China; orcid.org/0000-0002-0850-8584;
Phone: +86-010-82544800; Email: qzhou@ipe.ac.cn
Authors
Rong Huang − Beijing Key Laboratory of Ionic Liquids Clean
Process, CAS Key Laboratory of Green Process and
Engineering, State Key Laboratory of Multiphase Complex
Systems, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, P. R. China; School of Chemical
and Engineering, University of Chinese Academy of Sciences,
Beijing 100049, P. R. China
Qi Zhang − Beijing Key Laboratory of Ionic Liquids Clean
Process, CAS Key Laboratory of Green Process and
Engineering, State Key Laboratory of Multiphase Complex
Systems, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, P. R. China; School of Chemical
and Engineering, University of Chinese Academy of Sciences,
Beijing 100049, P. R. China
Haoyu Yao − Beijing Key Laboratory of Ionic Liquids Clean
Process, CAS Key Laboratory of Green Process and
Engineering, State Key Laboratory of Multiphase Complex
Systems, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, P. R. China; School of Chemical
and Engineering, University of Chinese Academy of Sciences,
Beijing 100049, P. R. China
Dongxia Yan − Beijing Key Laboratory of Ionic Liquids Clean
Process, CAS Key Laboratory of Green Process and
Engineering, State Key Laboratory of Multiphase Complex
Systems, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.1c01477
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Key
Research and Development Program of China (no.
2019YFC1908204), the National Natural Scientific Fund of
China (nos. 21776289, 21978291, 21878292, and 21908232),
the Innovation Academy for Green Manufacture, Chinese
Academy of Sciences (nos. IAGM2020C21 and
IAGM2020C12), and the K. C. Wong Education Foundation
(no. GJTD-2018-04). The authors sincerely thank Prof.
Suojiang Zhang (IPE, CAS) for his careful academic guidance
and great support.
■
REFERENCES
(1) Wang, Y.; Zhang, Y.; Song, H.; Wang, Y.; Deng, T.; Hou, X.
Zinc-catalyzed ester bond cleavage: Chemical degradation of
polyethylene terephthalate. J. Cleaner Prod. 2019, 208, 1469−1475.
(2) Han, M. 5-Depolymerization of PET bottle via methanolysis and
hydrolysis. In Recycling of Polyethylene Terephthalate Bottles; Thomas,
S., Rane, A., Kanny, K., Abitha, V. K., Thomas, M. G., Eds.; William
Andrew Publishing, 2019; pp 85−108.
(3) Raheem, A. B.; Noor, Z. Z.; Hassan, A.; Hamid, M. K. A.;
Samsudin, S. A.; Sabeen, A. H. Current developments in chemical
I https://doi.org/10.1021/acsomega.1c01477
Article
recycling of post-consumer polyethylene terephthalate wastes for new
materials production: A review. J. Cleaner Prod. 2019, 225, 1052−
1064.
(4) George, N.; Kurian, T. Recent developments in the chemical
recycling of postconsumer poly(ethylene terephthalate) waste. Ind.
Eng. Chem. Res. 2014, 53, 14185−14198.
(5) Yun, X.; Xin-yi, Y.; Dun-hong, G.; Yong-bo, D.; Liang, S.
Preparation and characterization of waterborne alkyd-amino baking
coatings based on waste polyethylene terephthalate. R. Soc. Open Sci.
2020, 7, No. 191447.
(6) Viana, M. E.; Riul, A.; Carvalho, G. M.; Rubira, A. F.; Muniz, E.
C. Chemical recycling of PET by catalyzed glycolysis: Kinetics of the
heterogeneous reaction. Chem. Eng. J. 2011, 173, 210−219.
(7) Sert, E.; Yılmaz, E.; Atalay, F. S. Chemical recycling of
polyethlylene terephthalate by glycolysis using deep eutectic solvents.
J. Polym. Environ. 2019, 27, 2956−2962.
(8) Liu, B.; Lu, X.; Ju, Z.; Sun, P.; Xin, J.; Yao, X.; Zhou, Q.; Zhang,
S. Ultrafast homogeneous glycolysis of waste polyethylene tereph-
thalate via a dissolution-degradation strategy. Ind. Eng. Chem. Res.
2018, 57, 16239−16245.
(9) Wang, Q.; Yao, X.; Geng, Y.; Zhou, Q.; Lu, X.; Zhang, S. Deep
eutectic solvents as highly active catalysts for the fast and mild
glycolysis of poly(ethylene terephthalate)(PET). Green Chem. 2015,
17, 2473−2479.
(10) Eriksen, M. K.; Christiansen, J. D.; Daugaard, A. E.; Astrup, T.
F. Closing the loop for PET, PE and PP waste from households:
Influence of material properties and product design for plastic
recycling. Waste Manage. (Oxford) 2019, 96, 75−85.
(11) Ekart, M. P.; Pell, T. M., Jr. Process including glycolysis and
subsequent purification for recycling polyester materials. No. 5635584,
March 6, 1997.
(12) Li, M.; Li, Y.; Lu, J.; Li, X.; Lu, Y. Decolorization and reusing of
PET depolymerization waste liquid by electrochemical method with
magnetic nanoelectrodes. Environ. Sci. Pollut. Res. Int. 2018, 25,
34531−34539.
(13) Chikawa, Y.; Tokashiki, M.; Suzuki, N. Process for the
purification of crude bis-(β-hydroxyethyl) terephthalate. No. 3666791,
May 30, 1972.
(14) Smith, B. L.; Nayar, P.; Shaw, G.. Process for recycling polyester
materials. No. 7192988, Mar 20, 2007.
(15) Goh, H. W.; Ali, S.; Abdullah, N.; Idris, A. Time, temperature
and amount of distilled water effects on the purity and yield of bis(2-
hydroxyethyl) terephthalate purification system. Bull. Chem. React.
Eng. Catal. 2015, 10, 143.
(16) Raheem, A. B.; Hassan, A. B.; Noor, Z. Z.; Samsudin, S. B.;
Hamid, M. A.; Bello, A.; Oladokun, O.; Sabeen, A. H.; Shamiri, A.
Process simulation of bis (2-hydroxyethyl) terephthalate and its
recovery using two stage evaporation systems. Chem. Eng. Trans.
2018, 63, 655−660.
(17) Li, M.; Lu, J.; Li, X.; Ge, M.; Li, Y. Removal of disperse dye
from alcoholysis products of waste PET fabrics by nitric acid-modified
activated carbon as an adsorbent: Kinetic and thermodynamic studies.
Text. Res. J. 2020, 90, 2058−2069.
(18) Ahmad, A.; Mohd-Setapar, S. H.; Chuong, C. S.; Khatoon, A.;
Wani, W. A.; Kumar, R.; Rafatullah, M. Recent advances in new
generation dye removal technologies: Novel search for approaches to
reprocess wastewater. RSC Adv. 2015, 5, 30801−30818.
(19) Zang, Y.; Yue, Q.; Kan, Y.; Zhang, L.; Gao, B. Research on
adsorption of Cr(VI) by poly-epichlorohydrin-dimethylamine (EPI-
DMA) modified weakly basic anion exchange resin D301. Ecotoxicol.
Environ. Saf. 2018, 161, 467−473.
(20) Manzar, M. S.; Waheed, A.; Qazi, I. W.; Blaisi, N. I.; Ullah, N.
Synthesis of a novel epibromohydrin modified crosslinked polyamine
resin for highly efficient removal of methyl orange and eriochrome
black T. J. Taiwan Inst. Chem. Eng. 2019, 97, 424−432.
(21) Liang, L.; Liu, G.; Yu, G.; Song, Y.; Li, Q. Simultaneous
decoloration and purification of crude oligosaccharides from pumpkin
(Cucurbita moschata duch) by macroporous adsorbent resin. Food
Chem. 2019, 277, 744−752.
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf Article

(22) He, B. L.; Guo, L. Q.; Zheng, Q. W.; Lin, S. X.; Lin, J. F.; Wei, (40) Wang, M.; Ma, Y.; Sun, Y.; Hong, S. Y.; Lee, S. K.; Yoon, B.;
T.; Ye, Z. W. A simple and effective method using macroporous resins Chen, L.; Ci, L.; Nam, J. D.; Chen, X.; Suhr, J. Hierarchical porous
for the simultaneous decoloration and deproteinisation of Cordyceps chitosan sponges as robust and recyclable adsorbents for anionic dye
militaris polysaccharides. Int. J. Food Sci. Technol. 2019, 54, 1741− adsorption. Sci. Rep. 2017, 7, No. 18054.
1751. (41) Zhao, W.; Tang, Y.; Xi, J.; Kong, J. Functionalized graphene
(23) Zhang, H.; Luo, J.; Liu, L.; Chen, X.; Wan, Y. Green production sheets with poly(ionic liquid)s and high adsorption capacity of
of sugar by membrane technology: How far is it from industrializa- anionic dyes. Appl. Surf. Sci. 2015, 326, 276−284.
tion? Green Chem. Eng., in press. DOI: 10.1016/j.gce.2020.11.006 (42) Wang, A.; Zheng, Z.; Li, R.; Hu, D.; Lu, Y.; Luo, H.; Yan, K.
(24) Yin, L.; Xu, Y.; Qi, Y.; Han, X.; Xu, L.; Peng, J.; Sun, C. K. A Biomass-derived porous carbon highly efficient for removal of Pb(II)
green and efficient protocol for industrial-scale preparation of dioscin and Cd(II). Green Energy Environ. 2019, 4, 414−423.
from Dioscorea nipponica Makino by two-step macroporous resin (43) Wang, T.; Zhao, P.; Lu, N.; Chen, H.; Zhang, C.; Hou, X.
column chromatography. Chem. Eng. J. 2010, 165, 281−289. Facile fabrication of Fe3O4/MIL-101(Cr) for effective removal of acid
(25) Shi, Y.; Liu, T.; Han, Y.; Zhu, X.; Zhao, X.; Ma, X.; Jiang, D.; red 1 and orange G from aqueous solution. Chem. Eng. J. 2016, 295,
Zhang, Q. An efficient method for decoloration of polysaccharides 403−413.
from the sprouts of Toona sinensis (A. Juss.) Roem by anion exchange (44) Lai, K. C.; Lee, L. Y.; Hiew, B. Y. Z.; Yang, T. C.-K.; Pan, G.-T.;
macroporous resins. Food Chem. 2017, 217, 461−468. Thangalazhy-Gopakumar, S.; Gan, S. Utilisation of eco-friendly and
(26) Albert, I.; Víctor, F.; Salvador, G.; Alfonso, G. Discoloration low cost 3D graphene-based composite for treatment of aqueous
kinetics of clarified apple juice treated with Lewatit S 4528 adsorbent reactive black 5 dye: Characterisation, adsorption mechanism and
resin during processing. Food Bioprocess Technol. 2012, 5, 2132−2139. recyclability studies. J. Taiwan Inst. Chem. Eng. 2020, 114, 57−66.
(27) Wu, J.; Li, Q.; Li, W.; Li, Y.; Wang, G.; Li, A.; Li, H. Efficient (45) Gao, X.; Zheng, M.; Zhao, X.; Song, S.; Gao, Z. Ultra-high-
capacity adsorption of rhodamine B in a carboxyl-functionalized
removal of acid dyes using permanent magnetic resin and its
metal−organic framework via surface adsorption. J. Chem. Eng. Data
preliminary investigation for advanced treatment of dyeing effluents. J.
2020, 66, 669−676.
Cleaner Prod. 2020, 251, No. 119694.
(46) Meng, L.; Zhang, X.; Tang, Y.; Su, K.; Kong, J. Hierarchically
(28) Greluk, M.; Hubicki, Z. Effect of basicity of anion exchangers
porous silicon-carbon-nitrogen hybrid materials towards highly
and number and positions of sulfonic groups of acid dyes on dyes efficient and selective adsorption of organic dyes. Sci. Rep. 2015, 5,
adsorption on macroporous anion exchangers with styrenic polymer No. 7910.
matrix. Chem. Eng. J. 2013, 215−216, 731−739. (47) Yang, M.; Bai, Q. Flower-like hierarchical Ni-Zn MOF
(29) Ochando-Pulido, J. M.; Vellido-Pérez, J. A.; González- microspheres: Efficient adsorbents for dye removal. Colloids Surf., A
Hernández, R.; Martínez-Férez, A. Optimization and modeling of 2019, 582, No. 123795.
two-phase olive-oil washing wastewater integral treatment and (48) Du, H.; Xie, Y.; Zhang, H.; Chima, A.; Tao, M.; Zhang, W.
phenolic compounds recovery by novel weak-base ion exchange Oxadiazole-functionalized fibers for selective adsorption of Hg2+. Ind.
resins. Sep. Purif. Technol. 2020, 249, No. 117084. Eng. Chem. Res. 2020, 59, 13333−13342.
(30) Qiang, X.; Luo, J.; Guo, S.; Cao, W.; Hang, X.; Liu, J.; Wan, Y. (49) Ouyang, L.; Wang, Y.; Zhang, P.; Wang, X.; Yuan, S.
A novel process for molasses utilization by membrane filtration and Heterostructured MWCNTs@PANI@TiO2 nanocomposites for
resin adsorption. J. Cleaner Prod. 2019, 207, 432−443. enhanced adsorption of As(III) from aqueous solution: adsorption
(31) Markandeya, S.; Shukla, P.; Mohan, D. Toxicity of disperse and photocatalytic oxidation behaviors. Ind. Eng. Chem. Res. 2020, 59,
dyes and its removal from wastewater using various adsorbents: a 11743−11756.
review. Res. J. Environ. Toxicol. 2017, 11, 72−89. (50) Zhou, X.; Lu, X.; Wang, Q.; Zhu, M.; Li, Z. Effective catalysis of
(32) Hassan, M. M.; Carr, C. M. A critical review on recent poly(ethylene terephthalate) (PET) degradation by metallic acetate
advancements of the removal of reactive dyes from dyehouse effluent ionic liquids. Pure Appl. Chem. 2012, 84, 789−801.
by ion-exchange adsorbents. Chemosphere 2018, 209, 201−219. (51) Asakawa, Y.; Asano, S. Method of purifying bishydroxyalkyl
(33) Sarkar, A. K.; Bediako, J. K.; Choi, J.-W.; Yun, Y.-S. terephthalate. No. US 6642350 B1, May 10, 2001.
Functionalized magnetic biopolymeric graphene oxide with out-
standing performance in water purification. NPG Asia Mater. 2019,
11, No. 4.
(34) Yang, H.; Bai, L.; Wei, D.; Yang, L.; Wang, W.; Chen, H.; Niu,
Y.; Xue, Z. Ionic self-assembly of poly(ionic liquid)-polyoxometalate
hybrids for selective adsorption of anionic dyes. Chem. Eng. J. 2019,
358, 850−859.
(35) Wawrzkiewicz, M.; Hubicki, Z. Equilibrium and kinetic studies
on the sorption of acidic dye by macroporous anion exchanger. Chem.
Eng. J. 2010, 157, 29−34.
(36) Zhou, Y.; Lu, J.; Zhou, Y.; Liu, Y. Recent advances for dyes
removal using novel adsorbents: A review. Environ. Pollut. 2019, 252,
352−365.
(37) Rashid, S.; Shen, C.; Chen, X.; Li, S.; Chen, Y.; Wen, Y.; Liu, J.
Enhanced catalytic ability of chitosan−Cu−Fe bimetal complex for
the removal of dyes in aqueous solution. RSC Adv. 2015, 5, 90731−
90741.
(38) Liu, Y.; Hua, X.; Wang, M.; Yang, R. Purification of the mother
liquor sugar from industrial stevia production through one-step
adsorption by non-polar macroporous resin. Food Chem. 2019, 274,
337−344.
(39) Guediri, A.; Bouguettoucha, A.; Chebli, D.; Chafai, N.; Amrane,
A. Molecular dynamic simulation and DFT computational studies on
the adsorption performances of methylene blue in aqueous solutions
by orange peel-modified phosphoric acid. J. Mol. Struct. 2020, 1202,
No. 127290.

J https://doi.org/10.1021/acsomega.1c01477
ACS Omega XXXX, XXX, XXX−XXX