Brazilian Journal of Chemical Engineering

https://doi.org/10.1007/s43153-022-00258-y

ORIGINAL PAPER

Chemical recycling of polyurethane foam waste and application

for antibacterial and removal of anionic and cationic dyes
Elhossein A. Moawed1   · Hala A. Kiwaan1 · Shireen K. El‑Zakzouk1 · Mervat A. El‑Sonbati2 · Mohamed M. El‑Zahed3

Received: 19 April 2022 / Revised: 16 June 2022 / Accepted: 12 July 2022

© The Author(s) 2022

Abstract
The large amounts of polyurethane foam wastes (PUFWs) produced in the automobiles, buildings, and furniture industries
cause many environmental problems. Therefore, the recycling of PUFWs has acquired great interest worldwide. In this study,
the PUFWs were converted to new nanocomposite. The chemical modification of PUFWs was conducted through reflux
with potassium permanganate in 0.1 M H ­ 2SO4. The produced PUF-COO@MnO2 nanocomposites was characterized by
scanning electron microscope, energy-dispersive X-ray spectrometry, X-ray diffraction, and Magnetic susceptibility. PUF-
COO@MnO2 has been used for the removal of cationic (Methylene blue) and anionic (Trypan blue) dyes from industrial
wastewater. The antibacterial effect of PUF-COO@MnO2 was also examined against Gram-positive and Gram-negative
bacterial strains. The adsorption capacities of PUF-COO@MnO2 for tested dyes were 277 and 269 mg/g. Moreover, PUF-
COO@MnO2 showed a potent antibacterial action against B. cereus (8.8 mm) followed by S. aureus (7.5 mm) and E. coli
(7.1 mm). It was concluded that PUF-COO@MnO2 can be employed as antibacterial low-cost material and for the removal
of synthetic dyes from industrial effluents.

Keywords  Polyurethane wastes · Industrial wastewater · Methylene blue · Trypan blue · Antibacterial effect

Introduction
Polyurethane foam (PUF) has special properties such as high
resilience, good mechanical property, abrasion resistance,
and good flexibility (Moawed and El-Shahat 2016; Zhou
et al. 2022). Therefore, it is widely used in the automotive,
building industries, footwear, furniture, construction, and
electronics (Bergamonti et al. 2018; Dou et al. 2014; Moon
et al. 2020). PUF represent almost 8% of produced.
plastics (annual production of up to 360 million tons)
which place them as the sixth most used polymer in
the world (Kemona & Piotrowska 2020). Owing to the
considerable development in the production of polyure-
thane foam, large amounts of polyurethane foam wastes
* Elhossein A. Moawed
eamoawed@yahoo.com
1
Chemistry Department, Faculty of Science, Damietta
University, P.O. Box 34517, New Damietta City, Egypt
2
Environmental Sciences Department, Damietta University,
New Damietta City, Egypt
3
Botany and Microbiology Department, Faculty of Science,
Damietta University, New Damietta City, Egypt
(PUFWs) are produced which are not used optimally and
cause many environmental problems (Gómez-Rojo et al.
2019; Lei et al. 2019). PUFWs belong to white pollution
and affect living organisms. At the same time, the pile-
up density of polyurethane foam plastics is small (about
30  kg/m 3), thus, stockpiling will take up a large area.
In addition, it will cause adverse effects on the ecologi-
cal environment because of the difficulty of degradation
(Kemona and Piotrowska 2020). However, various gov-
ernmental regulations have been implemented to reduce
the waste creation through solid waste management which
is usually controlled by the “Ladder of Lansink” (reduce,
reuse, recycle, energy recovery, incineration, and land-
fill) (Nikje et al. 2011). Landfilling is the most common
approach to processing polyurethane waste but a great
amount of air contained inside foam cells may provide
oxygen for deep-seated fires and impede efforts to extin-
guish flames (Kemona and Piotrowska 2020). As a result,
recycling of PUFWs or scraps has acquired a great interest
worldwide. PUFWs can be recycled by various methods,
all have their advantages and drawbacks. Physical recy-
cling will be an effective means due to the simple opera-
tion and relatively active application, in the short term.

1 3 Vol.:(0123456789)

Chemical recycling (hydrolysis, hydroglycolysis, aminoly-
sis, phosphorolysis, gasification, pyrolysis, hydrogenation,
and glycolysis) is difficult to achieve large-scale industri-
alized production in the short term due to higher techni-
cal difficulty but in the long run, it will be the ultimate
and effective recycling method (Kemona and Piotrowska
2020). Thus, chemical treatment of PUFW for convert-
ing to valuable products is one of the main challenges of
today’s society (Abdel-Rahman et al. 2019; Simón et al.
2018).
Water resources, being the substantial foundation for
the existence of humans, become seriously polluted due
to anthropogenic activities, particularly rapid industriali-
zation (Graca et al. 2020; Hasanpour and Hatami 2020;
Schmidt et al. 2020; Zheng et al. 2021). The emergence of
new chemical and microbial contaminants in the aquatic
environment is an issue of increasing concern (Chinoune
et al. 2016; Joseph et al. 2020; Maleki et al. 2017). The
wastewater generated from chemical industries carries a
large number of deleterious pollutants such as synthetic
dyes which have a serious environmental impact as toxic-
ity, mutagenicity, and carcinogenicity (Kong et al. 2016;
Krishnamoorthi et al. 2021). Therefore, removing of dye-
stuff from wastewater before discharging into a water body
becomes a must (Kumar et al. 2019). Various techniques
have been developed for the removal of dyes from waste-
waters such as chemical precipitation, nanofiltration mem-
brane, electro coagulation, adsorption, reverse osmosis,
and biological treatment (Gopakumar, et al. 2019; Bhat
et al. 2020; Deshpande et al. 2020; Yang et al. 2020). The
adsorption process was regarded as superior as it is sim-
ple, economic, and most effective (Bazan-Wozniak and
Pietrzak 2020; Raza et al. 2020).
Many studies elucidated that polyurethane is an efficient
sorbent for various dyes which can be applied without any
pretreatment, the effectiveness of this adsorbent can be
enhanced by optimizing the experimental conditions (Sul-
tan 2017; Fakhry et al. 2022).
Few reports were available on recycling PUFWs and
remain for removal of synthetic dye from wastewater.
This has inspired the authors to prepare new adsorbents
by recycling of PUFWs with available materials. Among
the various approaches, the chemical oxidation route is a
robust and dependable method, low cost, and requires a
short period of time to prepare. Thus, the aim of this work
is to prepare a novel adsorbent from polyurethane foam
wastes by a simple method and investigate the capability
for industrial wastewater treatment. This can be achieved
through: (i) Recycling of PUFWs by chemical oxidation
process using potassium permanganate in 0.1 M ­H2SO4.
(ii) Application of the produced (PUF-COO@MnO 2 )
for the removal of methylene blue and trypan blue dyes
(models for basic and acidic dyes) from wastewater. (iii)
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Brazilian Journal of Chemical Engineering
Small cubes of
PUFWs
0.1M of HCl
Boiling for 3h
Washing with
distilled water
Drying at room
temperature
Fig. 1  Flow process chart for the pre-treatment of polyurethane foam
Examination the antibacterial effect of PUF-COO@MnO2
composite.
Experimental
Materials
All chemicals used throughout the work were of analyti-
cal reagent grade quality without further purification. Stock
solutions (500 mg/L) of MB (Sigma Aldrich: CI 52015,
CAS 122965-43-9, purity ≥ 82%) and TB (Sigma Aldrich:
CI 23850, CAS 72-57-1, purity ≥ 75%) were prepared by
dissolving 0.05 g of each dye in 100 mL distilled water.
­KMnO4, ­CuSO4, ­Fe2(SO4)3, ­K2Cr2O7, ­Na2S2O3 and N ­ a2S2O8
were purchased from Sigma-Aldrich (Germany), ­HNO3,
­H2SO4 and HCl were brought from scientific office for
laboratory supplies (Damietta, Egypt). Polyurethane foam
remains were collected from upholstery stores and furniture
factories from Damietta City, Egypt.
Synthesis of PUF‑COO@MnO2 nanocomposite
The white and color industrial polyurethane foam remains
and wastes (PUFWs) were collected from a scrap of house-
hold, upholstery stores, and furniture factories from Dami-
etta City, Egypt. The two types of PUFWs were cut to simi-
lar small cubes, boiled for 3 h in HCl, squeezed, washed with
distilled water and left to dry (Fig. 1).
PUF-COO@MnO2 nanocomposite was prepared as fol-
lowing: A 5 g of dried PUF remains were blended into small
particles then refluxed with 5 g K ­ MnO4 in round bottom
flask with 200 mL H ­ 2SO4 (0.1 M) for 3 h with vigorous
stirring. As the reaction progresses, the purple permanga-
nate color was gradually changed to brown. The produced
Brazilian Journal of Chemical Engineering
Blended small particles of the
pretreated PUF (5 g)
200 mL of 0.1 M KMnO (5 g)
H SO
2 4
4 where Ci and Ce are the initial and final dye concentra-
Refluxing for 3 h
with stirring
Washing with
0.1 M oxalic acid
Washing with
distilled water
Air drying
Fig. 2  Schematic diagram for preparation of PUF-COO@MnO2 com-
posite
PUF-COO@MnO2 was washed with 0.1 M oxalic acid solu-
tion to remove excess K ­ MnO4 followed by distilled water
and then air dried (Fig. 2). The PUF-COO@MnO2 were
finally blended, sieved, and stored in suitable container for
use (Kiwaan et al. 2020).
In case of PUF scrap, PUF were washed with tap water to
remove impurities, then with NaOH (0.1 M) for 1 h and HCl
(0.1 M, 1 h), finally with distilled water and air dried then
treated as similar as the industrial PUF remains.
Various oxidizing agents e.g. ­HNO3, ­CuSO4, ­Fe2(SO4)3,
­K2Cr2O7, ­Na2S2O3 and ­Na2S2O8 were examined for oxida-
tion of PUF and treated as previously mentioned for prepara-
tion of PUF-COO@MnO2 composite. The oxidized PUFW
cubs were blended in a food-processing blender and sieved.
The particles (90 -250 μm size) were adopted for adsorption
studies.
Adsorption experiments
To accomplish the optimum adsorption conditions,
0.2 ± 0.01 g of PUF-COO@MnO2 in 100 mL glass bottle
was shaken for 2 h with 25 mL of MB and TB dyes aque-
ous solution individually at required pH adjusted by diluted
HCl and/or NaOH. Blank solutions were run under the same
experimental conditions. After phase separation, a 5 mL of
the aliquot solution of each dye was assayed by direct spec-
trophotometry at 668, 607 nm for MB and TB, respectively.
Effect of various parameters such as time, dye concentration
and temperature on the removal efficiency of MB and TB
was carefully investigated. The removal percentage (E) and
capacity (Q, mg/g), were calculated according to the follow-
ing equations (Fakhry et al. 2022):
( )
C − Ce
%Removal = i × 100 (1)
Ci
Qe = (Ci − Ce)V∕m) (2)
tion, V (mL) is the volume of solution and m is mass of the
PUF-COO@MnO2.
Antibacterial activity of PUF@MnO2 composite
The antibacterial activity of the PUF-COO@MnO2 was
examined employing the agar well diffusion method (Barry
2007) at concentration 150 μg/mL in DMSO. The nutri-
ent agar medium was used against Gram-positive bacterial
strains (Bacillus cereus and Staphylococcus aureus) and
Gram-negative bacterial strain (Escherichia coli). About
200 μg/mL of PUF-COO@MnO2, Penicillin G (150 μg/mL);
as a positive control and DMSO as a negative control were
added separately into three wells (10 mm) that were made
in the inoculated agar plates. The agar plates were incubated
at 37 °C for 48 h. The antibacterial activities were assayed
in terms of zones of inhibition (ZOI) diameters (mm ± SD).
Characterization of the prepared PUF‑COO@MnO2
composite
All characterizations were conducted in Petroleum Research
Institute (Cairo City, Egypt).
FTIR Spectrum
FTIR spectrum was performed using a JASCO-410
spectrometer (JASCO, Easton, MD) at a resolution of
4 ­cm−1 from 400–4000 ­cm−1. Disks made of a mixture of
0.6–1.0 mg of composite and 100 mg of KBr were vacuumed
for 1 min, pressed at 350 MPa for 2 min, and oven-dried for
48 h at 110 °C before analysis.
SEM analysis
The morphological characteristics and elemental composi-
tion of the proposed composite surface was characterized
using SEM, EDX (JEOL model JSM-6510LV, USA), at
an accelerated voltage of 20 kV in the secondary electron
mode. The sample was cut into 4 × 4 mm, dried in an oven
at 40 ℃ for 10 h, and bent in liquid nitrogen. The fracture
surface was vacuum coated with gold and examined at dif-
ferent magnifications.
Magnetic susceptibility
It was measured with a Johnson Matthey magnetic suscep-
tibility balance (120 V power supply). The sample tube was
13

placed in the balance and get an immediate digital read-out
then 250 mg the sample was put in the tube and measured.
The mass magnetic susceptibility was calculated using the
following equation:
Xg = CL(R − RO )∕m × 109 (3)
where L sample height (cm), m sample mass (g), C bal-
ance calibration constant, RO and R are the reading of empty
tube and the tube plus sample, respectively.
UV/Vis spectra
A UV–Vis spectrophotometer (JASCO, V-630 UV–Vis
Spectrophotometer, Japan) was employed for absorbance
measurements of the dye solutions.
XRD patterns
The structure of PUF-COO@MnO2 nanocomposite was
investigated by XRD patterns using an X-ray diffractom-
eter (D8-Brucker Model) equipped with Cu Kα radiation
(λ = 1.54 Å) at 40 mA and 40 kV in the 2θ range of 5–90°,
using a step size of 0.02° and a counting time of 1 s. Samples
were ground under ethanol to minimize loss during grinding
and to mitigate structural damage.
TGA and DTA analysis
Thermo-gravimetric analysis was performed using Shi-
madzu (DTA/TGA-50, Japan) in a Pyrex furnace coupled
to a Mettler balance. The sample (10 mg) was maintained in
nitrogen atmosphere (20 ­cm3 ­min−1), from room temperature
to 1000 °C with a heating rate of 10 °C ­min−1. Temperature
and mass data were processed by a computer connected to
the system.
BET data
The BET surface areas of the suggested adsorbent was deter-
mined by the liquid N ­ 2 adsorption–desorption approach
(ASAP 2000, Micromeritics, France) at liquid nitrogen
temperature (77 K). The sample was degassed at 80 °C for
12 h under vacuum prior to measurements. The surface area
was calculated using the BET equation and the total pore
volumes were estimated as the liquid volume of adsorbate
adsorbed ­(N2) at a relative pressure of 0.99.
pH point of zero charge ­(pHPZC)
Determination the pH point of zero charge was performed
by adding 0.2 gm of the prepared composite to 40.0 mL of
0.1 M ­NaNO3 in ten 120 ml bottle. The pH was adjusted to 2,
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Brazilian Journal of Chemical Engineering
3, 4, 5, 6, 7, 8, 9, 10 and 11 by 0.1 M HCl and 0.1 M NaOH,
then the solutions were shaken for 24 h to reach equilibrium.
The final pH ­(pHf) was measured and the initial pH ­(pHo)
vs. the difference between the ­pHo and ­pHf values (ΔpH)
was plotted. The pzc was taken as the point (intercept with
X axis) where pH = 0 (Fakhry et al. 2022).
Regeneration and reusability
To examine the stability of the synthesized composite, a
cyclic test was performed. In each cycle, the adsorbent was
separated from the dye solution, washed with distilled water,
and dried at 50 °C for 2 h. The regenerated composite sam-
ples were used several times in dye adsorption experiment to
determine the reusability of the samples (Fakhry et al. 2022).
Statistical analysis
The concentrations plot of MB (0.3–10  mg/L) and TB
(0.05–10 mg/L) against absorbance was carried out to cal-
culate the mean value, standard deviation and relative stand-
ard deviation. Thus, the final results were expressed as the
mean ± relative standard deviation.
Application
The suggested PUF-COO@MnO2 composite was success-
fully tested for antibacterial activity. Moreover, the PUF-
COO@MnO2 was assessed in batch mode for detection and
removal of MB and TB from industrial wastewater in New
Damietta and Ezbat EL-Borg cities. A 25 mL of industrial
wastewater samples from different locations were individu-
ally spiked with 100 μg of MB and TB dyes, shaken for
30 min with 0.1 g of PUF-COO@MnO2, then the recov-
ery percentage was calculated. The lower detection limits
(LDL) of MB and TB dyes was established using precon-
centration of 100 mL of different spiked wastewater samples
then recovered with 5 mL of HCl (0.1 mol/L) under dark
conditions.
Results and discussion
Chemical modification of PUFWs with different
oxidizing agent
The white PUFWs before and after treatment with various
oxidizing agents were displayed in Fig. 3. It is clear that the
effect of ­HNO3, ­Fe2(SO4)3, and ­CuSO4 is non-significant on
the PUFWs matrix. Both ­Na2S2O8 and K ­ 2Cr2O7 oxidized
the PUFWs which is clear from color change. Moreover,
the color of PUFWs was converted to brown-black after
oxidation with K
­ MnO4. Figure S1 represents the mixture of
Brazilian Journal of Chemical Engineering

Fig. 3  The white (A) and different color and densities (B) polyurethane foam wastes before and after treatment with oxidizing agents

different color and densities PUFWs before and after treat-
ment with the oxidizing agents. It is obvious that H ­ NO3,
­Fe2(SO4)3, ­CuSO4, and N ­ a2S2O8 had no effect on the color
or matrix of PUFWs in contrast to K ­ 2Cr2O7. Finally, the
color and matrix of PUFWs were completely changed on
oxidizing with ­KMnO4.
Table 1 represents the FTIR spectra of PUFWs and the
treated PUFWs using N ­ a2S2O8, ­K2Cr2O7, ­HNO3, ­Fe2(SO4)3,
and ­CuSO4. The data revealed that the PUFWs was slightly
affected by ­Na2S2O8, ­HNO3, ­Fe2(SO4)3, and ­CuSO4 oxidiz-
ing agents as no significant changes in the peak position
before and after treatment of PUFWs. FTIR spectrum of
­KMnO4treated PUFWs (PUF-COO@MnO2) was displayed
in Fig. 4. The characteristic absorption peaks of PUFWs are
observed at 3810–2996 ­cm–1 (OH, NH), 2935, 2850 ­cm–1
(C–H), 1654 ­cm–1 (C=O) and 1586 ­cm–1 for C=C (Fakhry
et al. 2022). Comparing the spectrum of PUF and PUF-
COO@MnO 2 showed appearance of two broad bands
of carboxylate and manganese oxide at 3656–1781 and
709–401 ­cm–1, respectively (Hatchett et al. 2005). In addi-
tion, the –NH, C ­ HAr, and C­ HAlp were disappeared due to
coupling in the broad band with OH group (Mahmood and
Waisi 2021). This result indicates that the carbonyl group
of PUF matrix was oxidized to carboxylic and then coupled
with ­MnO2 which produced from the reduction of ­KMnO4
(Fig. 4).
Figures 5 and 2S show the examination of the treated
PUFWs with different oxidizing agents for the removal
of pollutants from wastewater. The removal percentages
of MB and TB dyes from wastewater were displayed. The
maximum removal percentages of MB and TB dyes (~ 97%)
were obtained using the treated PUFWs with KMnO4. Thus,
PUFWs treated with KMnO4 were better than other oxidiz-
ing agents and adopted in the subsequent work.
Characterization of PUF‑COO@MnO2 nanocomposite
The novel PUF-COO@MnO2 adsorbent was characterized
by various physical and chemical techniques to identify the
surface morphology, structural properties and detect sorp-
tion efficiency.

Table 1  Infrared spectra Group PUFWs ­(cm−1) PUFWs after treatment with oxidizing agent ­(cm−1)
of PUFWs before and after
treatments with different K2Cr2O7 K2S2O8 HNO3 Fe2(SO4)3 CuSO4
oxidizing agents
OH 3222 3383 3288 3304 3294 3297
CHAr 2919 2918 2971 2971 2972
CHAlp 2850 – 2874 2882 2871 2872
C=O 1670 1649 1642 1717 1713 1641
C=C 1569 1604 1598 1603 1599 1602
M–O – 550 – – – –

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Fig. 4  FTIR spectra of polyu-

rethane foam wastes before and
after treatment

Fig. 5  Removal percentage
of MB (a) and TB (b) dyes
from wastewater by the treated
PUFWs with different oxidizing
agents

Fig. 6  EDX spectrum and elemental composition of PUF-COO@MnO2

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Brazilian Journal of Chemical Engineering
Fig. 7  SEM image of PUF-COO@MnO2 matrix at magnifications of 250–25,000 ×
Energy-dispersive X-ray spectrometry (EDX) was used
to determine the elemental composition of the proposed
adsorbent (Fig. 6) and evaluate the effect of ­KMnO4 on the
PUFWs matrix. The weight percentages of PUF-COO@
MnO2 were carbon (42%), oxygen (34%), manganese (19%)
and potassium (1.7%). The calculated M­ nO2 in PUF-COO@
MnO2 was 30.4%. The cross-sectional profile of C and O
content in the PUF-COO@MnO2 EDX spectrum revealed
that the matrix of PUFWs was partially oxidized. Besides,
the presence of manganese and potassium elements in the
PUF-COO@MnO2 increased surface activity. Thus, PUF-
COO@MnO2 can be used as a powerful tool for the removal
of pollutants from industrial wastewater. The weight per-
centages of Mn, K, and other metal in PUF-COO@MnO2
were also determined using gravimetric procedure. A 1 g
of PUF-COO@MnO2 was ignited at 500 °C, cooled and
weighed. It is found that the total weight percentages of
metal oxide in composite were 34%.
Surface morphology of PUF-COO@MnO2 was investi-
gated using SEM at magnifications from 250 ×  to 25,000×.
Figure 7A represents SEM image of PUF-COO@MnO2
matrix at magnifications of 250×. It is clear that the matrix
contains many spaces, channels, and cells, which are
Table 2  Magnetic data of solid‐state ­MnO2 and PUF-COOH@MnO2
composite at 298 K
Material L (cm) m (g) R Xg
MnO2 0.9 0.16  + 1055 8.5 × ­10–6
PUF-COO@MnO2 1.7 0.08  + 820 2.5 × ­10–5
irregular in size and shape. The particles of M ­ nO2 were
randomly distributed inside the spaces of the PUF matrix
(Fig. 7B, 1000 ×). Higher SEM images magnification of
PUF-COO@MnO2 nanocomposite (20,000 × and 25,000 ×)
showed that the crystals of ­MnO2 were aggregated on the
surface of PUF-COO@MnO2 (Fig. 7B–D) (Ma et al. 2021).
Magnetic susceptibility data of solid‐state ­MnO2 and
PUF-COO@MnO2 composite (at 298 K) are summarized
in Table 2. PUF-COO@MnO2 is found to be paramagnetic
corresponding to an unpaired electron with positive value of
R (+ 820). It is obvious that PUF-COOH@MnO2 Xg value
(2.5 × ­10–5 erg/G2 g) is higher than that of ­MnO2 value
(8.5 × ­10–6 erg/G2 g) due to the presence of trace elements
e.g. Fe and Cu in PUF-COO@MnO2.
The electronic spectra of PUFWs and PUF-COO@MnO2
were tested using Nujol mulls method (Ghatge and Jadhav
1983). The PUFWs spectrum showed that the absorption
peaks were appeared at 369, 337, 336, 218, and 209 nm due
to π–π ∗ transition localized on the conjugated system. The
spectrum of PUF-COO@MnO2 shows short peaks from 372
to 376 nm and higher band at 353–369 nm that may attrib-
uted to n–π ∗ transition which indicate successful addition of
­MnO2 into the PUFWs matrix (Moawed et al. 2019).
To probe surface crystallization of PUFWs and PUF-
COO@MnO2, XRD analyses were performed; the results
are displayed in Fig. 8. The XRD pattern of PUFWs was
retrieved and a significant broad diffraction band at 2θ,
20.8°, which was identified as a characteristic peak of amor-
phous PUF; usually observed for the aromatic isocyanate-
based PUF. In comparing PUFWs and PUF-COO@MnO2,
the latter has lower band intensity, indicating the formation
13

Fig. 8  XRD patterns of PUFWs
and PUF-COO@MnO2
of the composite with a significant change of the amorphous
phase; no obvious crystalline material was formed on the
surface of PUFWS modified by K ­ MnO4, and manganese
oxide existed in an amorphous form (Wei et al. 2021).
The thermal stability of any polymer is essentially deter-
mined by the strength of the covalent bonds between the
atoms forming the polymeric chains in addition to, the
adhesion forces between different phases. The TGA curve
of PUF-COO@MnO2 shows a smooth stepwise manner
containing five steps (A, B, C, D, F) of thermal decomposi-
tion at temperature range 29–1000 °C as shown in Fig. 9
and  Table  3. The total weight losses percentages at the
detected temperatures was 66.6, the remaining weight per-
cent (33.4%) represents the metal content in PUF-COO@
MnO2. The weight loss of PUF-COO@MnO2 in the first
step may be attributed to evaporation of adsorbed water
molecules. The other decomposition steps have the major
weight losses (45.2%) at temperature ranged between 103
and 403 °C due to the decomposition of PUF matrix. It was
Fig. 9  Thermal Gravimetric
analysis (TGA) of PUF-COO@
MnO2
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Brazilian Journal of Chemical Engineering
reported that the weight loss of (what is the adsorbent) was
99.8% at 27–400 °C (Bazan-Wozniak and Pietrzak 2020).
The Differential Thermal Analysis (DTA) curve of PUF-
COO@MnO2 showed two endothermic peaks at 52 and
126 °C while these peaks were appeared at 58 and 156 °C
in Differential Scanning Calorimetry (DSC) curve (Fig. 3S).
Surface area, pore diameter and pore volume of PUF-
COO@MnO2 were determined using BET and BJH tech-
niques. The N ­ 2 adsorption/desorption isotherm of PUF-
COO@MnO 2 was nearly similar to III type of IUPAC
classification which belong to mesopores dominated prop-
erty (Fig. 10, S4). It is clear that the amount of adsorbed ­N2
gas increases gradually with increasing the relative pressure.
In addition, the calculated surface area of PUF-COO@MnO2
was 14.3 m ­ 2/g which is higher than that obtained (2.8 m
­ 2/g)
for PUF (Bazan-Wozniak and Pietrzak 2020); this indicated
that the ­MnO2 was efficiently grafted with PUF matrix. The
total mean pore volume and pore diameter at (P/Po = 0.990)
Brazilian Journal of Chemical Engineering
Table 3  Weight loss (%) of PUF-COO@MnO2 at different decompo-
sition temperatures
Temperature (°C) Weight loss %
29–102 3.4
103–186 4.7
187–255 14.6
256–403 25.9
404–1000 18.0
were 0.07 c­ m3/g and 19.7 nm, respectively for PUF-COO@
MnO2. (how can be interpreted and what is the significant).
Finally, the IR spectrum showed the appearance of
two broad bands of carboxylate and manganese oxide at
3656–1781 and 709–401  ­c m –1, respectively. The SEM
images magnification nanocomposite showed that the
crystals of M­ nO2 were aggregated on its surface. Also, the
remaining weight percent (33.4%) of TGA represents the
metal content. Therefore, we suggested that the structure of
the new composite was PUF-COO@MnO2.
Optimum conditions for removal of MB and TB dyes
from aqueous solutions
The removal of MB and TB dyes from aqueous media were
studied through batch modes in dark condition. The param-
eters included are pH, contact time, dye concentration, and
solution temperature.
To depict the surface charge of the proposed sorbent, the
zero-point charge ­(pHZPC) was determined. The estimated
­pHZPC values of PUFWs and PUF-COO@MnO2 were 7.4
and 7.9. At pH lower than ­pHZPC, the sorbents surface is
positively charged and can attract anions from the solu-
tion where, at pH higher than p­ HZPC, the sorbents surface
becomes negatively charged and attracts cations. The effect
of pH (1–14) on the removal of MB and TB dyes using
Fig. 10  BET isotherm curve for
adsorption of ­N2 onto PUF-
COO@MnO2
PUF-COO@MnO2 was investigated and the results showed
that the maximum removal percentages of MB and TB were
achieved at pH 3–13 and 1–3, respectively.
The removal of MB and TB dyes from aqueous solu-
tion increased with increasing contact time. The maximum
removal percentages of MB and TB dyes (where are the
removal percent’s) using PUF-COO@MnO2 were achieved
at 5 and 60 min, respectively. It was noticed that the initial
removal rate of MB dye is very rapid then slowed down with
time till the equilibrium is established. This may be due to
availability of a large number of active sites for occupation
at the initial stages which were not easily accessible after a
period of time as the solute molecules on the solid and bulk
phases repel and the binding sites become saturated with dye
molecules (Gagliano et al. 2020; Narkkun et al. 2019). These
results indicate that the removal of tested dyes, at the early
stages, would mainly depend on the porosity of PUF-COO@
MnO2. Therefore, the fast removal of dyes and establishing
equilibrium in a short period of time signifies the efficiency
of the adsorbent for application in wastewater remediation.
The removal of MB dye is higher percent and more rapid
than that of TB dye due to the nature and molecular size
of dyes. The obtained results are basically agreed with that
recorded by Fakhry et al. (2022) who studied the removal
of MB and methyl orange (MO) by polyacrylonitrile/poly-
vinylpyrrolidone coated polyurethane foam membrane and
achieved removal percent of 97% and 95% for MB and MO,
respectively. Similar data were recorded by Seddiki et al.
(2020) who used nanocomposites hydrogels for removal of
methylene blue and basic red 46 from water.
The data for plotting of the amount of dye per unit mass
(capacity, Q) of PUF-COO@MnO2 against the concentra-
tions of MB or TB was shown in Table 4. Linear curves
with correlation coefficients (R2, 0.999 and 0.984) were
obtained (Table 4, Fig. 11). Moreover, the capacities (Q)
of PUF-COO@MnO2 for adsorption of MB and TB were
277 and 269 mg/g, respectively.
13
 Brazilian Journal of Chemical Engineering

Table 4  Characteristics of isotherm curves for the sorption of MB sulfoxide, tetrahydrofuran, 2 methoxy ethanol, 1,4 dioxane
and TB dyes and methylene chloride. A 0.5 g of the PUF-COOH@MnO2
Dye Least square equation Removal (%) Capac- was soaked in 25 mL of solutions with different pH or 25 mL
ity organic solvent for 24 h then filtrated, dried, and weighted.
(mg/g) The results showed that there is no significant change in the
Slope Intercept R2 weights of PUF-COOH@MnO2. These results indicate that
MB 0.24 2 × ­10–4 0.999 99.3 277 the PUF-COOH@MnO2 has good chemical stability in wide
TB 0.18 7 × ­10–4 0.984 88.6 269 range of pH and organic solvents.
The stability of PUF-COO@MnO2 was also confirmed by
examination after many times use in batch mode. A 1 g of
0.12 PUF-COOH@MnO2 was shaken with 25 mL of methylene
blue dye (MB) aqueous solution for 30 min. The average
0.1
removal percentages of MB were 99–100%. Regeneration
Capacity, mmol/g

0.08 of PUF-COO@MnO2 was achieved by recovery of dye

molecules from PUF-COO@MnO2 using hydrochloric acid
0.06 (0.1 M). The obtained results indicated that the capacities
of PUF-COO@MnO2 are nearly the same after ten-time
0.04
recyclability.
MB
0.02
TB Applications
0
0 0.1 0.2 0.3 0.4 0.5
The suggested PUF-COO@MnO2 composite was success-
[Dye], mol/L fully tested for antibacterial activity. Moreover, the PUF-
COO@MnO2 was assessed in batch mode for detection and
Fig. 11  The plot of the amount of dye per unit mass (q, mmol/g) of removal of MB and TB from industrial wastewater in New
PUF-COO@MnO2 against the concentrations of MB or TB (mol/L) Damietta and Ezbat EL-Borg cities.

Antibacterial activity test

Temperature influences the adsorption rate by adjusting
the molecular interactions and the solubility of adsorb-
ate. The effect of temperature on the adsorption of MB
and TB onto PUF-COO@MnO2, was investigated through
batch experiments conducted in the range of 20–80 °C.
The results showed that the removal percentage of MB
increased slightly with increasing temperature due to the
reduction in solution viscosity which led to a fact diffu-
sion of adsorbate molecules toward adsorbent pores and
increase removal process, whereas the removal percentage
of TB reached to maximum value at room temperature
(25 °C) and decreased with increasing temperature due to
deformation of bonds between the TB dye molecules and
the active site of PUF-COO@MnO2 and increasing solu-
bility of the dye in aqueous solution, indicating exothermic
adsorption process (Moawed et al. 2015). The Gibbs free
energy (∆G° = −RTlnK) were −5.4 and −2.1 kJ/mol for
the adsorption of MB and TM, respectively. The negative
values of ΔG° demonstrated that the removal process of
MB and TB was spontaneous.
The chemical stability of PUF-COOH@MnO2 composite
was studied in different pHs (1–14) and various organic sol-
vents e.g., methanol, ethanol, acetone, diethyl ether, petro-
leum ether, benzene, toluene, p-xylene, cyclohexanol, chlo-
roform carbon tetrachloride, dimethylformamide, dimethyl
The ZOI sizes of the PUF-COO@MnO2 against B. cereus,
E. coli and S. aureus are shown in Fig. 12. B. cereus is a
Gram-positive, rod-shaped, facultatively anaerobic and spore
forming bacteria. It is responsible for a minority of foodborne
illnesses (2–5%), causing severe nausea, vomiting, and diar-
rhea. Among the pathogenic bacteria, S. aureus which is a
leading cause of gastroenteritis, Staphylococcal food poi-
soning and pneumonia. S. aureus is an important pathogen
due to a combination of toxin-mediated virulence, invasive-
ness, and antibiotic resistance. In addition, the species E. coli
causes enteric diseases, such as diarrhea or dysentery, and
other pathotypes cause extra-intestinal infections. The PUF-
COO@MnO2 showed a potent antibacterial action against B.
cereus (8.8 mm) followed by S. aureus (7.5 mm) and E. coli
(7.1 mm). The antibacterial effect of M ­ nO2/single crystalline
ZnO nanorod hybrids against E. coli and S. aureus were 14.4
and 10.29 mm, respectively. Also, Yu et al. (2016) reported
that ­MnO2/ZnO nanorod hybrids had a good antibacterial
activity against S. aureus and E. coli.

13
Brazilian Journal of Chemical Engineering
Fig. 12  Inhibition zones of the antibacterial activity for PUF-COO@MnO2 against B. cereus, E. coli and S. aureus
Detection of MB and TB dyes in industrial wastewater
The lowest concentrations of synthetic dyes in aquatic envi-
ronment represents high risk for all living organisms so they
should be detected and removed. The concentrations plot of
MB and TB against absorbance give good straight lines with
correlation coefficient of 0.998 and 0.997, respectively (Fig-
ure 1S). Calibration curve obeys Beer-Lambert law at that
concentration range, with intercept value of 0.003 and 0.010.
The lower detection limits (LDL) of MB and TB dyes was15.0
and 2.5 μg/L, respectively.
Removal of MB and TB dyes from industrial wastewater
The validity of the proposed method for removal of MB and
TB dyes from wastewater samples was critically examined. A
25 mL of industrial wastewater samples from different loca-
tions were individually spiked with 100 μg of MB and TB dyes
then the solutions were shaken for 30 min with 0.1 g of PUF-
COO@MnO2. The Average removal percentages of MB and
TB dyes were 97% and 89% with relative standard deviation
(RSD%) of 0.92% and 3.27%, respectively.
 
Conclusion
Recycling of polyurethane foam wastes with ­KMnO4 in
0.1 M ­H 2SO 4 was achieved and reused for the removal
of methylene blue and trypan blue dyes from wastewater.
Also, the new product (composite) was used for antibacte-
rial activity. The influence of pH, temperature, dye con-
centration, and time on the removal percentages of dyes
from water using the batch technique. At pH ˃3 maximum
removal of methylene blue dye (97.5–100%) was achieved,
whereas the maximum removal percent of Trypan blue
(85–87%) was in the pH range of 1–3. The experimental
kinetic data were well-fitted to the pseudo-second-order
supporting a chemisorption mechanism as evident by the
shift of the FTIR bands of the functional groups of the
PUF-COO@MnO2 after dye sorption. It was concluded
that the synthesized PUF-COO@MnO 2 composite is a
promising material for environmental remediation.
Supplementary Information  The online version contains supplemen-
tary material available at https://​doi.​org/​10.​1007/​s43153-​022-​00258-y.
Funding  Open access funding provided by The Science, Technology &
Innovation Funding Authority (STDF) in cooperation with The Egyp-
tian Knowledge Bank (EKB).
13

Open Access  This article is licensed under a Creative Commons Attri-
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References
Abdel-Rahman HA, Younes MM, Khattab MM (2019) Recycling of
polyurethane foam waste in the production of lightweight cement
pastes and its irradiated polymer impregnated composites. J Vinyl
Addit Technol 25(4):328–338
Barry AL (2007) An overview of the Clinical and Laboratory Stand-
ards Institute (CLSI) and its impact on antimicrobial susceptibil-
ity tests. In: Schwalbe R et al (eds) Antimicrobial susceptibility
testing protocol. CRC Press, Boca Raton, pp 1–6
Bazan-Wozniak A, Pietrzak R (2020) Adsorption of organic and inor-
ganic pollutants on activated bio-carbons prepared by chemical
activation of residues of supercritical extraction of raw plants.
Chem Eng J 393:124785
Bergamonti L, Taurino R, Cattani L, Ferretti D, Bondioli F (2018)
Lightweight hybrid organic-inorganic geopolymers obtained using
polyurethane waste. Constr Build Mater 185:285–292
Bhat SA, Zafar F, Mondal AH, Mirza AU, Haq QMR, Nishat N (2020)
Efficient removal of Congo red dye from aqueous solution by
adsorbent films of polyvinyl alcohol/melamine-formaldehyde
composite and bactericidal effects. J Clean Prod 255:120062
Chinoune K, Bentaleb K, Bouberka Z, Nadim A, Maschke U (2016)
Adsorption of reactive dyes from aqueous solution by dirty ben-
tonite. Appl Clay Sci 123:64–75
Deshpande BD, Agrawal PS, Yenkie MKN, Dhoble SJ (2020) Pro-
spective of nanotechnology in degradation of waste water: a new
Challenges. Nano-Struct Nano-Objects 22:100442
Dou ZJ, Cheng M, Qin YF, Chen L, Qin ZY (2014) Simultaneous
improvement of mechanical properties and thermal stability of
polyurethane by polyethylene glycol grafted cellulose nanocrys-
tals. Adv Mater Res 1052:249–253
Fakhry H, El-Sonbati M, Omar B, El-Henawy R, Zhang Y, EL-Kady
M (2022) Novel fabricated low-cost hybrid polyacrylonitrile/pol-
yvinylpyrrolidone coated polyurethane foam (PAN/PVP@PUF)
membrane for the decolorization of cationic and anionic dyes. J
Environ Manage 315:115128. https://​doi.​org/​10.​1016/j.​jenvm​an.​
2022.​115128
Gagliano E, Sgroi M, Falciglia PP, Vagliasindi FGA, Roccaro P
(2020) Removal of poly-and perfluoroalkyl substances (PFAS)
from water by adsorption: role of PFAS chain length, effect of
organic matter and challenges in adsorbent regeneration. Water
Res 171:115381
Ghatge ND, Jadhav JY (1983) Synthesis, characterization, and proper-
ties of novel poly (ether urethanes). J Polym Sci Polym Chem Ed
21(7):1941–1950
Gómez-Rojo R, Alameda L, Rodríguez Á, Calderón V, Gutiérrez-
González S (2019) Characterization of polyurethane foam waste
for reuse in eco-efficient building materials. Polymers (Basel)
11(2):359
Gopakumar DA, Arumukhan V, Gelamo RV, Pasquini D, Morais LC,
Hermawan SRD, Nzihou A, Abdul Khalil HPS (2019) Carbon
13
Brazilian Journal of Chemical Engineering
dioxide plasma treated PVDF electrospun membrane for the
removal of crystal violet dyes and iron oxide nanoparticles from
water. Nano-Struct Nano-Objects 18:100268
Graca CAL, Lima RB, Pereira MFR, Silva AMT, Ferreira A (2020)
Intensification of the ozone-water mass transfer in an oscillatory
flow reactor with innovative design of periodic constrictions: opti-
mization and application in ozonation water treatment. Chem Eng
J 389:124412
Hasanpour M, Hatami M (2020) Photocatalytic performance of aero-
gels for organic dyes removal from wastewaters: review study. J
Mol Liq 309:113094
Hatchett DW, Kodippili G, Kinyanjui JM, Benincasa F, Sapochak L
(2005) FTIR analysis of thermally processed PU foam. Polym
Degrad Stab 87(3):555–561
Joseph J, Radhakrishnan RC, Johnson JK, Joy SP, Thomas J (2020)
Ion-exchange mediated removal of cationic dye-stuffs from
water using ammonium phosphomolybdate. Mater Chem Phys
242:122488
Kemona A, Piotrowska M (2020) Polyurethane recycling and dis-
posal: methods and prospects. Polymers (Basel) 12(8):1752.
https://​doi.​org/​10.​3390/​POLYM​12081​752
Kiwaan HA, Elsonbati MA, Elzakzouk SK, Elghamaz NA, Moawed
EA (2020) Equilibrium studies of the removal of trypan
blue using modifier polyurethane foam. Int J Sci Eng Res
11(6):558–562
Kong L, Qiu F, Zhao Z, Zhang X, Zhang T, Pan J, Yang D (2016)
Removal of brilliant green from aqueous solutions based on
polyurethane foam adsorbent modified with coal. J Clean Prod
137:51–59
Krishnamoorthi R, Anbazhagan R, Tsai H-C, Wang C-F, Lai J-Y (2021)
Preparation of caffeic acid-polyethyleneimine modified sponge
for emulsion separation and dye adsorption. J Taiwan Inst Chem
Eng 118:325–333
Kumar P, Gihar S, Kumar B, Kumar D (2019) Synthesis and characteri-
zation of crosslinked chitosan for effective dye removal antibacte-
rial activity. Int J Biol Macromol 139:752–759
Lei W, Zhou X, Fang C, Li Y, Song Y, Wang C, Huang Z (2019) New
approach to recycle office waste paper: reinforcement for polyu-
rethane with nano cellulose crystals extracted from waste paper.
Waste Manage 95:59–69
Ma J, Wang C, Xi W, Zhao Q, Wang S, Qiu M, Wang J, Wang X (2021)
Removal of radionuclides from aqueous solution by manganese
dioxide-based nanomaterials and mechanism research: a review.
ACS ES&T Eng 1(4):685–705
Mahmood OAA-Q, Waisi BI (2021) Crystal violet dye removal from
aqueous water using polyacrylonitrile precursor beads. Mater
Today Proc 42:2185–2192
Maleki A, Hamesadeghi U, Daraei H, Hayati B, Najafi F, McKay G,
Rezaee R (2017) Amine functionalized multi-walled carbon nano-
tubes: single and binary systems for high capacity dye removal.
Chem Eng J 313:826–835
Moawed EA, El-Shahat MF (2016) Equilibrium, kinetic and thermo-
dynamic studies of the removal of triphenyl methane dyes from
wastewater using iodopolyurethane powder. J Taibah Univ Sci
10(1):46–55
Moawed EA, Abulkibash AB, El-Shahat MF (2015) Synthesis and
characterization of iodo polyurethane foam and its application in
removing of aniline blue and crystal violet from laundry waste-
water. J Taibah Univ Sci 9(1):80–88
Moawed E, Elhagrasy M, Kamal M (2019) Detection and removing of
lead from wastewater using chemical treatment of polyurethane
foam waste: batch and column experiments. Desalin Water Treat
159:338–345
Moon J, Kwak SB, Lee JY, Kim D, Ha JU, Oh JS (2020) Recycling
of bio-polyurethane foam using high power ultrasound. Polymer
(guildf) 186:122072
Brazilian Journal of Chemical Engineering
Narkkun T, Boonying P, Yuenyao C, Amnuaypanich S (2019) Green
synthesis of porous polyvinyl alcohol membranes functionalized
with l-arginine and their application in the removal of 4-nitro-
phenol from aqueous solution. J Appl Polym Sci 136(31):47835
Nikje MMA, Garmarudi AB, Idris AB (2011) Polyurethane waste
reduction and recycling: from bench to pilot scales. Des Mono-
mers Polym 14(5):395–421
Raza N, Raza W, Gul H, Azam M, Lee J, Vikrant K, Kim K-H (2020)
Solar-light-active silver phosphate/titanium dioxide/silica hetero-
structures for photocatalytic removal of organic dye. J Clean Prod
254:120031
Schmidt PJ, Anderson WB, Emelko MB (2020) Describing water treat-
ment process performance: why average log-reduction can be a
misleading statistic. Water Res 176:115702
Seddiki N, Aliouche D, Boudhene I (2020) Preparation of nanocompos-
ite hydrogels with nanoclay: Characterization, swelling properties
and dye adsorption behavior. Rev Roum Chim 65(2):119–133.
https://​doi.​org/​10.​33224/​r rch.​2020.​65.2.​01
Simón D, Borreguero AM, De Lucas A, Rodríguez JF (2018) Recycling
of polyurethanes from laboratory to industry, a journey towards
the sustainability. Waste Manage 76:147–171
Sultan M (2017) Polyurethane for removal of organic dyes from textile
wastewater. Environ Chem Lett 15(2):347–366. https://d​ oi.o​ rg/1​ 0.​
1007/​s10311-​016-​0597-8
Wei Z, Liu Z, Fu X, Wang Y, Yuan A, Lei J (2021) Effect of crystal-
line structure on water resistance of waterborne polyurethane. Eur
Polym J 157:110647
Yang C, Xu W, Nan Y, Wang Y, Chen X (2020) Novel negatively
charged nanofiltration membrane based on 4, 4′-diaminodiphenyl-
methane for dye removal. Sep Purif Technol 248:117089
Yu W, Liu T, Cao S, Wang C, Chen C (2016) Constructing M ­ nO2/sin-
gle crystalline ZnO nanorod hybrids with enhanced photocatalytic
and antibacterial activity. J Solid State Chem 239:131–138
Zheng J, Du L, Gao P, Chen K, Ma L, Liu Y, You S (2021) Mino-
modified biomass for highly efficient removal of anionic dyes
from aqueous solutions. J Taiwan Inst Chem Eng 119:136–145
Zhou M, Zhao S, Zhou K, Mei F, Qian X, Shi C (2022) Flexible
polyurethane foams surface-modified with FeOOH for improved
oil-water separation and flame retardancy. Mater Chem Phys
276:125408
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