Environmental Technology

ISSN: 0959-3330 (Print) 1479-487X (Online) Journal homepage: http://www.tandfonline.com/loi/tent20

Carbon/FexOy magnetic composites obtained

from PET and red mud residues: paracetamol and
dye oxidation

Leonardo S. Sousa, Poliane Chagas, Luiz Carlos Alves de Oliveira & Cinthia
Soares de Castro

To cite this article: Leonardo S. Sousa, Poliane Chagas, Luiz Carlos Alves de Oliveira &
Cinthia Soares de Castro (2018): Carbon/FexOy magnetic composites obtained from PET
and red mud residues: paracetamol and dye oxidation, Environmental Technology, DOI:
10.1080/09593330.2018.1457723

To link to this article: https://doi.org/10.1080/09593330.2018.1457723

Accepted author version posted online: 26

Mar 2018.

Submit your article to this journal

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=tent20
Publisher: Taylor & Francis & Informa UK Limited, trading as Taylor & Francis
Group
Journal: Environmental Technology
DOI: 10.1080/09593330.2018.1457723

Carbon/FexOy magnetic composites obtained from PET and red mud

residues: paracetamol and dye oxidation

Leonardo S. Sousaa, Poliane Chagasb, Luiz Carlos Alves de Oliveirab,

Cinthia Soares de Castroa,b*

a
Science and Technology Institute, Federal University of Alfenas, Rodovia José Aurélio Vilela,

11999, BR 267, Km 533, CEP 37715-400, Poços de Caldas, MG, Brazil.

b
Department of Chemistry, Federal University of Minas Gerais. Av. Antônio Carlos 6627 –

UFMG, Pampulha, 31270901 - Belo Horizonte, MG - Brazil.

Corresponding author: Tel.: +55 31 3409-5631

E-mail address: cinthia.soares.castro@gmail.com

Abstract

Composite materials from PET and red mud (RM) wastes were used as catalysts for

environmental application such as the wastewater treatment. The PET-RM catalysts

were obtained by mechanical mixture of the residues followed by thermal treatment

under N2 atmosphere (300oC/1h). An additional activation of the composites with CO2

was investigated (at 800-900oC) to reduce the red mud basicity. The CO2 activation

affected the composites surface area and reduced their carbon content. XRD revealed

that the hematite (-Fe2O3) and maghemite/magnetite are the main iron oxides present

in the composites. Mössbauer characterization indicated the formation of reduced iron

species (Fe2+), highly reactive, after the composites heat treatment. The materials were

very active catalysts for methylene blue (MB) and paracetamol (PRC) removal from

aqueous solution. The catalytic activity revealed to be dependent on the surface area and

1
mainly of the presence of reduced iron species in the catalysts. The MB removal

reached 97% for both PET-RM 800/2h and PET-RM 800/5h, after 1 h of reaction. In the

case of PRC, the highest removal was also obtained for PET-RM 800/2h and PET-RM

800/5h, of  25 and 40%, respectively. The contaminants removal mechanism likely

occurred through combined adsorption and Fenton-like oxidation processes.

Keywords: PET waste; red mud; Heterogeneous Fenton; oxidation; paracetamol

2
1- Introduction

Paracetamol (PRC), N-(4-hydroxyphenyl)acetamide, also known as

acetaminophen, is a common analgesic and antipyretic drug, widely used throughout the

world for humans and animals. Despite its high metabolization in the organism

(up to 90%) [1], PRC is not completely eliminated in conventional biological

wastewater treatment and is one of the most frequently detected pharmaceuticals in

rivers, lakes and groundwater, in low concentrations (μg L-1 to ng L−1) [2–4].

Considering the potential impacts of pharmaceutical products on human health and

environment, additional treatments for paracetamol oxidation has been widely

investigated. Several advanced oxidation processes have been proposed for paracetamol

removal from water such as: ozonation and H2O2/UV oxidation [1–3,5], oxidation by

sulfate radical SO4- [4], electrochemical oxidation [6,7] and the Fenton-like process

[8,9]. In addition, the textile industry generates large quantities of color wastewaters

that requires specific treatment before its discard into water bodies, according to

legislation [10]. The dyes used in the textile coloration and printing industries can cause

environmental damage to living organisms by blocking sunlight and reducing the water

reoxygenation capacity, thus affecting the natural growth of aquatic life [11].

The aim of the present work is the production of composite materials based on

PET and red mud residues to be evaluated as catalysts for wastewater treatment for

paracetamol drug and methylene blue dye removal. The red mud is an important solid

residue, highly alkaline, generated during bauxite (Al2O3) beneficiation through the

Bayer Process to produce aluminum metal. This residue is one of the largest industrial

by-products in modern society, with global levels at around 3,000 million tonnes at the

end of 2010, according to the International Institute of Aluminum. The red mud is

3
mainly composed of oxides (such as Fe2O3, un-dissolved Al2O3, SiO2, TiO2) and

hydroxides (like Al(OH)3 and residual soluble NaOH). Considerable effort has been

expended in finding a suitable disposal and reutilization for the bauxite residue but

several key factors affect the feasibility and economics of its adoption. The main

potential applications for red mud are: cement and brick production, road construction,

soil amelioration, acid mine drainage and heavy metal absorption, iron production and

catalyst manufacture [12]. The major component of red mud is Fe2O3 (25-45%) [12,13],

which indicates that this residue can be potentially used as a catalyst for the

heterogeneous Fenton Process. Indeed, the hydroxyl radicals (OH) generated during

the Fenton Process are reported as principally responsible for the paracetamol

degradation, due to its high oxidation potential of +2.8 V, compared to other species

like OOH and O2- [6,14].

Another important industry that also generates a large amount of residues is the

PET [poly(ethylene terephthalate)] industry. According to ABIPET, the Brazilian PET

consumption increased from 255,000 tonnes in 2000 to 572,000 tonnes in 2012 and

around 840,000 tonnes were estimated for 2016. However, the increasing PET

production is also accompanied by a large generation of residues. For example, a

portion of the PET bottles is collected and recycled after use ( 274,000 tonnes in 2016)

[15]. During recycling, the grinding of the PET bottles produces fragments called

“flakes” used to produce the PET resin, but also generates an undesired by-product PET

powder which has no further destination [16].

Therefore, this paper describes the transformation of the highly available and low

cost residues (red mud and PET powder) into composite materials to be used as

catalysts for environmental application. The catalytic potential of the iron oxides present

4
in the red mud and the adsorption properties of the PET carbon allows the organic

removal from water by combined processes of adsorption and Fenton-like oxidation.

Currently, a number of papers describe the use of adsorbents and solid catalysts for

wastewater treatment and oxidation reactions [17–22]. In our previous work [23], we

prepared catalysts based on PET-RM by mechanical mixture followed by calcination in

air at 400oC/1h. These materials presented a low organic contaminants removal

(methylene blue removal lower than 40% after 1 h of reaction, using a diluted

methylene blue solution of only 10 mg L-1). Here, we investigate the effect of the

controlled atmosphere (under N2) during the synthesis of the PET-RM composites and

an additional activation with CO2(g) that affected their physical-chemical properties and

considerably increased the catalytic performances for organic removal.

2. Material and Methods

2.1. Synthesis of the PET-RM catalysts

The composites based on PET powder and red mud (PET-RM) were prepared by

mechanical mixture of the residues, using 1/1 weight proportion. The mixture was then

thermally treated in a tubular furnace (Sanchis), under inert N2 atmosphere (flow  100

mL min-1) and a heating rate of 10oC min-1 until 300oC for 1 h. The pyrolysis

temperature was based on thermogravimetric analysis of the precursors. Afterwards, the

obtained materials were activated with CO2 (flow  100 mL min-1) at elevated

temperatures with the objective to reduce the basicity of the red mud and increase the

surface area of the catalysts.

5
 The PET-RM composites were activated using a heating rate of 10oC min-1 until

800oC for 2 h and 5 h (denoted as PET-RM 800/2h and PET-RM 800/5h, respectively)

and at 900oC for 5 h (named PET-RM 900/5h).

FIGURE 1

The composites photos (Fig. 1) showed that the PET-RM 900/5h (Fig. 1-d)

present typical reddish color of red mud, due to the presence of hematite, α-Fe2O3, the

major component of red mud [12]. The black color of the other composites, PET-RM

(Fig. 1-a), PET-RM 800/2h (Fig. 1-b) and PET-RM 800/5h (Fig. 1-c), possibly indicates

the presence of a carbonaceous material obtained from PET decomposition (initially of

light grey color) besides iron phases such as magnetite/maghemite. The attraction to a

permanent magnet attested to the formation of magnetic phases in all PET-RM catalysts

[24]. The presence of magnetite/maghemite phases were further detected by XRD

(Fig. 3). The existence of magnetic iron phases in the composites enables its easily

separation from wastewater in an external magnetic field.

2.2. Characterization of the catalysts

The materials were characterized by X-ray diffractometry (XRD) in a D8

Advance DaVinci using Cu K radiation ( = 1.5406 Å) and LynxEye detector. The

crystalline phases were identified using Powder Diffraction File (PDF) database

(JCPDS, International Centre for Diffraction Data). The textural properties of the

catalysts were investigated by Nitrogen (N2) physisorption at 196oC in a Autosorb 1-C

Quantachrome equipment. The apparent surface area was determined by Brunauer-

6
Emmett-Teller (BET) equation utilizing the adsorption branch. The pore size

distribution plot was obtained by the BJH method and the total pore volume (Vt) from

the volumes of nitrogen adsorbed at a relative pressure of 0.95. The thermal stability of

the precursors and catalysts was studied by thermogravimetric analysis (TGA,

Shimadzu DTG-60AH) under N2 and air atmosphere (gas flow of 30 cm3 min-1) with a

heating rate of 10oC.min−1. The materials morphology was studied by scanning electron

microscopy (SEM) on a FEI Quanta 200 FEG, 840A microscope and the elemental

composition was studied by energy dispersive X-ray spectroscopy (EDS) at 15 KV on a

Shimadzu microscope, SSX-550. The PET-RM materials were also characterized by

Mössbauer spectroscopy using a spectrometer with transducer and CMTE function

generator, model MA250 and 57CO/Rh energy source. The α-Fe was used as calibration

standard and obtained at room temperature (298 K) with a velocity of 10,089 mm s-1,

the data were adjusted with Lorentzian lines in the IgorforNormos program. Moreover,

the Fourier transform infrared spectroscopy - Attenuated total reflectance (ATR-FTIR)

spectra a were recorded on IRPrestige-21 Fourier transform infrared spectrophotometer

(SHIMADZU) in the region of 400–4000 cm-1. The analysis was performed for the

PET-RM before and after the oxidation reaction to understand the interaction of the

organic contaminant with the catalyst surface.

2.3. Catalytic oxidation tests

The catalytic tests were initially carried out for the methylene blue dye (MB)

oxidation, as a model compound. The experiments were performed according to the

procedure described in [23][25][26]. Briefly, the reaction occurred in 20 mL volumetric

capacity batch reactors, using 10 mg of the catalysts and 0.2 mL of the oxidant agent

7
H2O2 (30% v/v), added into 9.8 mL of MB solution (100 mg L-1). After reaction, the

catalysts were removed from reaction medium by centrifugation. The MB removal from

water was monitored for 60 min at regular intervals by UV-vis spectroscopy at 665 nm

(Edutec – 752/752 N). Afterwards, the PET-RM composites were also evaluated as

catalysts for paracetamol (PRC) oxidation with H2O2 under mild reaction conditions

(25oC and nearly neutral pH) using a similar procedure described for MB oxidation.

However, after reaction, the solid catalysts were removed from suspension by Millipore

syringe filters (0.22 µm pore size). The reactions were also monitored at regular

intervals for 30 min and the PRC concentrations were determined by UV-vis

spectroscopy at 242 nm (Edutec – 752/752 N). It is important to mention that, as the

paracetamol and H2O2 absorb UV in a similar wavelength range, a blank experiment

(containing only the catalyst, water and H2O2) was used as reference in each reaction

time. In order to verify the accuracy of the results obtained for paracetamol oxidation

monitored by UV-Vis spectroscopy and eliminate the H2O2 interference, the reactions

were also monitored by HPLC (Shimadzu, detector SPD-20A, LC-20AT pumps, C18

column of 250 mm in length and 4.6 mm of inner diameter, at room temperature). The

method used for PRC analysis by HPLC was based on Brazilian Pharmacopoeia [27]

using a water methanol (75:25) mixture as mobile phase and flow of 1.5 mL min-1. The

mechanism of PRC removal from water was also investigated and, for this purpose, an

additional adsorption experiment was performed using the same procedure described for

the oxidation tests but without H2O2.

8
 3. Results and Discussion

3.1. Characterization of the materials

The thermal stability of the PET powder and RM residues were investigated by TG

analysis under N2 atmosphere (Fig. 2-a) to determine the suitable temperature for the

PET-RM composites pyrolysis.

FIGURE 2

For PET powder, it is possible to observe an abrupt weight loss at temperatures

above 350°C whereas for RM, two regions of weight loss are clearly detected, with a

total weight loss of about 28%. The first weight loss (under 100ºC) can be associated to

physically adsorbed water. The second (250-300ºC), can be attributed to the gibbsite

decomposition [2 Al(OH)3  Al2O3 + 3 H2O], goethite decomposition

[2 FeOOH  Fe2O3 + H2O], besides the loss of chemically adsorbed water [28][29].

Therefore, in order to obtain composite materials based on PET carbon and iron oxides

(from red mud), the temperature of 300oC for 1 h (lower than the PET decomposition

temperature and higher than the temperature of water loss by red mud) was selected as

the pyrolysis temperature for the synthesis of the PET-RM composites under N2

atmosphere. The average yield of the pyrolysis step of the precursors (PET and RM),

prepared by mechanical mixture, was 39 wt.%. After pyrolysis, the PET-RM was

submitted to CO2 activation in a tubular furnace. The yield of the activation process was

64% for PET-RM 800/2h, 60% for PET-RM 800/5h and 50% for PET-RM 900/5h.

Thus, the activation yield tends to decrease as the temperature and time of activation

with CO2 increased. This result was expected since the CO2 used as activation agent is

9
known to react with the carbonaceous material from PET, according to Eq. 1, creating

most of the pores of the catalysts [30].

𝐶 + 𝐶𝑂2 ⇋ 2𝐶𝑂 𝐸𝑞. 1

∆𝐻 = +159 𝑘𝐽𝑚𝑜𝑙−1

The thermal stability of the catalysts was investigated under air atmosphere

(Fig. 2-b) to identify the presence of the carbonaceous material from PET in the

PET-RM composites. The catalysts without activation (PET-RM) showed a total weight

loss of about 40% that occurred gradually until 350oC when a sudden weight loss was

observed. This last weight loss is possibly attributed to the carbonaceous material from

PET, as observed from TGA of the PET powder (Fig. 2-b). The weight loss of the

catalyst without activation (PET-RM) was considerably higher than that obtained for the

catalyst activated with CO2. For the catalysts activated at 800oC (PET-RM 800/2h and

PET-RM 800/5h), a total weight loss was  6%, irrespective of the activation time (2 or

5 h). However, the observed weight loss occurred at over 500oC. This can be related to

the siderite (FeCO3) decomposition [31][32], possibly formed by the reaction of the iron

oxides from RM and the CO2 during the catalysts activation. Another possible

explanation would be the decomposition of the carbonaceous material from PET, with a

strong interaction with RM. It is worth mentioning that the RM does not present

significant weight loss at temperatures over  400oC (Fig. 2-b). In the case of PET-RM

900/5h, the total weight loss was less than 1% (Fig. 2-b), which indicates that the whole

carbon formed during the PET pyrolysis was completely lost during the activation step

with CO2 (Eq. 1), leading to a material composed mainly of a modified RM. In our

10
previous work [23], the addition of different amounts of PET into RM also affected the

thermal stability of the calcined composites due to the PET carbon decomposition.

The crystalline structure of the PET-RM catalysts was investigated by XRD

(Fig. 3).

FIGURE 3

The heat activation under CO2 atmosphere caused changes in the crystalline

structure of the materials (Fig. 3-a). The XRD profiles revealed that the materials are

composed of a complex mixture of phases obtained from RM, considering that the

activated carbons are typically amorphous materials [30]. The XRD of the calcined RM

showed that this is composed mainly of sodalite (3Na2O.3Al2O3.6SiO2.Na2SO4) [96-

900-3330], hematite (-Fe2O3) [96-901-4881], gibbsite (Al(OH)3) [96-900-3875] and

SiO2 [96-101-1173]. As already mentioned, the RM composition can vary to some

extend according to the mineral (bauxite) region and processing conditions used in the

Bayer Process [13].

The PET-RM presented the same crystalline phases: sodalite [96-900-3330],

hematite (-Fe2O3) [96-900-0140], SiO2 [96-101-1173], besides magnetite (Fe3O4)

[96-900-5815] and/or maghemite (γ-Fe2O3) [96-900-68-13]. Magnetite and maghemite

present cubic structure and similar diffraction profiles, difficult to be distinguished by

XRD (26). The PET-RM 800/2h and PET-RM 800/5h presented similar crystalline

phases along with nepheline (NaAlSiO4) [96-900-9818] and siderite (FeCO3) [96-900-

4187]. This last phase of iron carbonate could have been formed by the reaction of

CO2(g), used in the activation step of the catalysts, with the iron species from RM. The

11
XRD of PET-RM 900/5h is similar to the catalysts activated at 800oC, except that no

diffraction of siderite (FeCO3) was detected. This can be explained by its decomposition

(leading to Fe2O3 and CO2) during the high temperature and treatment time. Fig. 3-b

present the diffractions deconvolution clearly showing the iron phases transformations

from hematite (-Fe2O3) in the pure calcined RM and maghemite

(γ-Fe2O3) and/or magnetite (Fe3O4) in the PET-RM composites (e.g. PET-RM 800/2h).

The iron phases in the composites were additionally characterized by Mössbauer

Spectroscopy (Fig. 4).

FIGURE 4

57
The Fe Mössbauer spectrum for the PET-RM (treated under N2) present a

doublet with isomer shift ( = 0.33 mm.s-1), which indicates the presence of only Fe3+

species. On the other hand, the PET-LV 800/2h clearly presents a second doublet with

isomer shift ( = 1.59 mm.s-1), typical of Fe2+ species, along with Fe3+ species ( = 0.26

and 0.36 mm.s-1), Fig. 4-b. This result suggests the partial transformation of Fe3+ to Fe2+

during heat treatment employed for the catalyst activation and indicates that the PET

decomposition promoted the chemical reduction of the iron present in the red mud. In

other words, during activation, the carbonaceous material obtained from PET reacted

with oxygen atoms of the iron oxides present in RM, releasing CO or CO2 and reducing

the iron oxide, in agreement with the literature [33]. This result is also in good

agreement with the XRD data and indicates a more active material for H2O2

decomposition and a better catalytic activity for the Fenton Process, since Fe2+ is the

most active specie in the process [34]. The Mössbauer spectra of the PET-RM 800/5h

12
and PET-RM 900/5h samples present a profile similar to that described above, but the

percentage corresponding to Fe2+ is less, 19 and 6%, respectively. The spectrum for

PET-RM 900/5h clearly indicates the formation of a sextet (Fig. 4-d), which suggest an

increase in the crystallite size of the iron phases. This effect can be observed when high

treatment temperatures are employed, due to the sintering of the crystals. Moreover, it is

possible that the total decomposition of the PET has occurred, as observed by TGA,

leading to the iron particles agglomeration.

The textural properties of the materials were investigated by adsorption/desorption of

N2 at 77 K (Fig. 5).

FIGURE 5

According to IUPAC classification [35], the N2 adsorption/desorption isotherms

for all the catalysts resemble Type IVa. Such an isotherm is identified by the presence

of hysteresis, which is clearly noted for PET-RM and indicates that the prepared

catalysts are mesoporous materials. The BET apparent surface area and the pore volume

of the catalysts are presented in Table 1.

TABLE 1

The pyrolysis process of the PET-RM composite (300oC/1h under N2)

considerably increased its surface area compared to its RM and PET powder precursors.

Moreover, the activation process with CO2 at 800oC/2h caused a slight increase in the

surface area and pore volume compared to the composite without activation (PET-RM).

13
However, the increase in the activation time from 2 to 5 h at 800oC slightly decreased

the surface area, possibly due to the collapse of the formed pores (Table 1). Finally, the

further increase in the activation temperature to 900oC (PET-RM 900/5h) caused an

abrupt reduction in the surface area, which possibly indicates the complete removal of

the carbonaceous material by the reaction with CO2 (Eq. 1), besides the collapse of the

pores at high temperature. These results agree with the TG analysis, which revealed that

most of the PET carbon formed during pyrolysis were decomposed in the activation step

at 900oC/5h.

The morphology and elemental analysis of the catalysts were investigated by

SEM-EDS (Fig. 6).

FIGURE 6

The morphology of the materials changed after heat treatment at different times

and activation temperatures with CO2. The PET-RM presents particles of irregular

shape and irregular surface (Fig. 6-a). On the other hand, the PET-RM 800/2h (Fig. 6-b)

and PET-RM 800/5h (Fig. 6-c), present irregular forms with spongy-like texture. In the

case of PET-RM 900/5h (Fig. 6-d), this is composed of particles of different sizes and

of round forms [29,36]. This is possibly related to the loss of carbon and the sintering

effect occurring at high temperatures (as also demonstrated by Mössbauer analysis, Fig.

4) which resulted in a material composed mainly of a modified red mud [23,31].

The qualitative chemical analysis of the composites was performed by EDS

(Fig. 6-a1 to 6-d1). The results revealed that the catalysts contain mainly C, Al, Fe, Ca,

K, Na, P, O and Si. Except for the carbon, these elements are commonly found in the

red mud residue [13]. For the PET-RM, an intense C peak can be associated with the

14
presence of PET carbon, although the C signal can also be related to the carbon tape

used to prepare the samples prior to SEM analysis. The PET-RM 800/2h and PET-RM

800/5h presented similar chemical composition. For the PET-RM 900/5h, a low intense

peak for C was detected, which indicates that the PET carbon in this composite was lost

through decomposition during activation with CO2.

3.2. Catalytic tests

The prepared catalysts were initially evaluated in the removal of the model organic

compound methylene blue dye (MB) from water (Fig. 7). Furthermore, kinetic data of

the reactions are displayed in Table 2. The initial reaction rate of the MB consumption

(-r0MB, mol/min.gcatalyst) was calculated by the initial slop of the graphic of the

conversion (X) as function of the parameter t.W/N0MB (in which t is the reaction time,

W is the catalyst weight and N0MB is the initial mol of methylene blue), according to Eq.

2 [37][38].

 dX 
 r 0 MB    (Eq. 2)
 d (t.W / N MB )  t .W / N 0 MB 0
0

FIGURE 7

TABLE 2

All the catalysts were effective for MB removal (Fig. 7). Particularly, the

PET-RM 800/2h and PET-RM 800/5h were quite active, even at short reaction times

(< 5 min). These catalysts presented the highest MB removal capacity (about 97%

15
removal after 60 min of reaction, Fig. 7) and high initial reaction rates (Table 2). This is

possibly related to the CO2 activation treatment increasing the materials reactivity by

the formation of reduced iron species such as Fe2+, attested by Mössbauer spectroscopy

(Fig. 4). The difference observed in the MB removal in the short reaction time for

PET-RM 800/2h and PET-RM 800/5h can be attributed to the slightly higher surface

area of PET-RM 800/2h (Table 1). The activity of the catalysts described in this work is

quite satisfactory for instance when compared to our previous work, in which PET-RM

composites without activation (calcined at 400oC/1h) were prepared and presented a

MB removal of less than 40% after 1 h of reaction, using a diluted MB solution of only

10 mg L-1.

It is interesting to observe that the catalyst without activation, PET-RM, also

revealed to be very active (about 75% of MB removal after 60 min of reaction, Fig. 7).

For PET-RM 900/5h, the lowest activity and initial rate (Table 2) can be related to its

having low amount of Fe2+ (Fig. 4), low specific area (8 m2 g-1) and absence (or low

amount) of carbon, confirmed by TGA (Fig. 2-b). The PET-RM 800/5h and PET-RM

present similar surface areas (78 and 84 m2 g-1, respectively) but the PET-RM 800/5h

was more active than the catalyst without activation. This is also evidence that the heat

activation in CO2 atmosphere caused changes in the reactivity of the catalysts,

generating reduced iron species, Fe2+, more active for the Fenton process. It is well

known from literature that the MB removal by catalysts based on carbon and iron oxides

occurs through a complex mechanism that involves adsorption and oxidation by the

heterogeneous Fenton process [23,25,39]. Therefore, it is likely that the MB removal

from water in the presence of the PET-RM catalysts prepared in this work occurred by

adsorption and Fenton-like oxidation, due to the iron oxides present in red mud. The

16
most active catalyst (PET-RM 800/2h) presents the highest surface area, which can

contribute to the MB removal by adsorption, besides the Fenton oxidation, in agreement

the literature [26]. In fact, experiments without H2O2 confirmed the MB adsorption by

PET-RM 800/2h (pink line in Fig. 7). The addition of H2O2 increased the MB removal

(red line) though, which suggest that the contaminant removal mechanism occurs via

adsorption/oxidation processes.

In order to deeply investigate the MB removal mechanism, the effect of the solution

initial pH on the adsorption and oxidation of the dye is shown in Fig. 8. The

experiments were performed in the presence of the PET-RM, varying the pH of the MB

solution from 5.0 until 9.0, which are the pH range values required for the effluent

discard into water bodies [10].

FIGURE 8

The PET-RM presents the highest amount of carbonaceous material obtained

from PET decomposition ( 35%, observed by TGA in Fig. 2). This carbon can be the

reason for the high MB removal by adsorption (tests without H2O2) for all the initial pH

of the MB solution. However, the RM itself can also adsorb the MB dye [40][41]. The

higher MB removal by adsorption and oxidation at pH = 9.0 can be possibly due to the

electrostatic attraction between the predominant negative charge (FeO- surface groups)

of the iron oxides (hematite and maghemite) present in this catalyst and the MB cationic

dye [42]. On the other hand, the addition of H2O2 in the reaction medium increased the

MB removal in all the pH values thus suggesting that MB removal also occurs through

oxidation by heterogeneous Fenton process.

17
 It is important to highlight that, although a slightly higher MB removal was

obtained in pH = 9, the practical use of this catalyst for industrial wastewater treatment

at neutral pH  7.0 would reduce the costs related to the addition of an acid/base to

adjust the solution pH.

An additional ATR-FTIR characterization of the catalysts may help to understand

the interaction of the organic contaminant (i.e., methylene blue) with the solid surface

and the reaction mechanism. Fig. 9 compares the FTIR spectra of the PET-RM before

and after reaction at neutral pH. After reaction, it is possible to observe that the catalyst

kept unaltered and two new small bands at 2930 and 2855 cm-1 appeared, attributed to

the CH3 stretching vibrations of the terminal dimethylamino groups of the MB molecule

adsorbed on the catalyst surface [43]. This result support the suggested mechanism in

which the MB removal occurs through combined adsorption/oxidation processes. The

large bands at the 3300 - 3400 cm−1 region is attributed to surface hydroxyl stretching.

The bands in the 1555 - 1390 cm-1 range are likely related to carbonate ions in different

bonding [44] and the strong band at 980-995 cm-1 are due to SiO2 from the red mud

[45], consistent with the XRD.

FIGURE 9

Finally, the catalysts were tested for paracetamol removal from water (Fig. 10).

FIGURE 10

The paracetamol removal (Fig. 10) in the presence of PET-RM and PET-RM

900/5h was quite similar (about 18%, after 30 min of reaction). It is important to

18
emphasize that the paracetamol removal in the presence of the studied catalysts can also

occur through combined processes of adsorption and oxidation by the heterogeneous

Fenton process, in agreement with similar catalysts reported in the literature [26,46,47].

The PET-RM 900/5h presents the lowest surface area (8 m2g-1), considerably lower than

PET-RM (84 m2g-1) and a lower amount of carbonaceous material. Therefore, these

results also suggest that, in the case of PET-RM 900/5h, the paracetamol removal

occurred mostly by oxidation through the Fenton heterogeneous process (by the iron

oxides from red mud). However, it is well established in the literature that red mud can

adsorb organic and inorganic contaminants from water [40,41,48], showing that the red

mud present in the composites can also contribute to paracetamol adsorption.

Moreover, it is possible to observe that the catalysts activation at 800°C

increased the drug removal capacity (Fig. 10). After 2 min of reaction, the PET-RM

800/2h removed about 25% of paracetamol and remained almost constant until the end

of the reaction. The higher paracetamol removal by this catalyst over a short reaction

time can be explained by its high surface area (114 m2 g-1) and the presence of the

highly active Fe2+ species attested by MÖssbauer spectroscopy. For PET-RM 800/5h,

the paracetamol removal gradually increased to reach the highest removal of 40% after

30 min of reaction. Comparing the activity of PET-RM and PET-RM 800/5h, of similar

surface areas (84 and 78 m2 g-1, respectively), a higher paracetamol removal was

observed for PET-RM 800/5h (Fig. 10). This result was also observed for the MB

removal, attesting that the activation of the catalyst with CO2 cause changes in the

reactivity of the materials. Table 2 compares the contaminants removal after 30 min of

reaction showing that all the catalysts are more effective for the oxidation of the

methylene blue dye.

19
 The mechanism of paracetamol removal from water was also investigated and,

for this, an adsorption experiment (without addition of H2O2) was carried out with the

PET-RM 800/2h (Fig. 9). The results showed that the composite is able to remove

paracetamol by adsorption ( 16% of PRC removal after 5 min of reaction). However,

after H2O2 addition (red line), the PRC removal increased sharply, reaching about 28%

after 5 min. It is worth mentioning that the adsorbed PRC molecule can also be oxidized

on the catalyst surface by the radical attack formed by the H2O2 decomposition.

The catalytic tests for PRC oxidation was also monitored by HPLC. As the

paracetamol absorption wavelength is λ = 242 nm, very close to H2O2 (λ = 240 nm), the

catalytic tests were also monitored by HPLC to eliminate the H2O2 interference that

occur in the UV-Vis analysis.

FIGURE 11

The results of paracetamol removal monitored by HPLC (Fig. 11) were very close

to those of the removal obtained by UV-Vis spectroscopy (Fig. 10).

From recent literature, Do et al., 2018 prepared a Fe3O4@SiO2 yolk-shell catalyst

decorated with copper for heterogeneous Fenton oxidation of paracetamol. A high

paracetamol removal was reached (about 100% after 30 min of reaction) but using a

very low initial concentration of the paracetamol (2 mg L-1) compared to 100 mg L-1 of

paracetamol concentration used in this work [49].

Another important property of a heterogeneous catalyst is its stability during

reaction. Particularly for the PET-RM catalysts, the solution pH was analyzed (after 60

min of reaction), in order to evaluate a possible base leaching of the highly alkaline red

20
mud present in the catalyst to solution. In the case of RM (dried at 60oC/24h, used as

reference material), the base leaching to solution occurred, increasing the pH of the

paracetamol aqueous solution to about 10. Nevertheless, for the PET-RM catalysts, the

solution pH clearly decreased to reach values near neutrality (pH = 7.5 for PET-RM, 7.9

for PET-RM 800/2h and 8.2 for PET-RM 900/5h). This indicates that the pyrolysis and

activation with acidic CO2 used to prepare the catalysts reduced the basicity of the

catalysts, preventing the base leaching to solution. Thus, the PET-RM catalysts can be

satisfactory used for wastewater treatment, without base leaching to solution.

Fig. 12 presents a schematic illustration proposed for the steps involved in the

organic contaminants removal (e.g. paracetamol) in the presence of the activated

PET-RM composites.

FIGURE 12

The paracetamol removal by oxidation is only possible due to the presence of

Fe3+ and Fe2+ species present in the catalyst, identified by Mössbauer spectroscopy (Fig.

4), that react with H2O2 to produce hydroperoxide (•OOH) and hydroxyl (•OH) radicals,

respectively. The hydroxyl radicals present a higher oxidizing potential able to attack

the organic contaminants in water (Fig. 12). Moreover, the drug removal revealed to be

related to the surface area of the catalysts, due to the presence of carbonaceous material

obtained from PET which contributes to the organic removal through adsorption

process.

The results presented here demonstrate that the PET-RM composites can be

potentially used as catalysts for wastewater treatment for the removal of recalcitrant

21
compounds (such as dyes) and emergent contaminants (e.g. paracetamol), for which

there is no specific treatment in the sewage treatment stations. In this case, an additional

unit operation for heterogeneous Fenton process (after the conventional biological

treatment) would be required.

Conclusions

The red mud and PET residues were effectively converted into composite materials by

pyrolysis followed by heat activation in presence of CO2. The PET-RM composites are

mainly composed of a mixture of oxides present in red mud and PET carbon. The

different activation conditions with CO2 (temperature and time) affected the surface

area and reactivity of the catalysts. The PET-RM composites revealed to be very active

as catalysts for removal of the organics (paracetamol and methylene blue dye) from

water. The removal occurs through combined processes of adsorption and oxidation by

the heterogeneous Fenton process due to the presence of Fe3+ and Fe2+ in the catalysts.

The catalysts activated at 800oC (PET-RM 800/2h and 800/5h) presented the highest

removal of organics. The CO2 activation of the PET-RM catalysts reduces its basicity

and prevents the base leaching to the water. Therefore, the use of PET powder and red

mud residues as catalysts precursors can be considered an interesting environmental

application for wastewater treatment, providing an alternate destination for the residues

by their conversion into catalysts for the adsorption/oxidation of organic contaminated

effluents.

Acknowledgements The authors are grateful to CNPq and FAPEMIG for financial

support and to Microscopy Center of UFMG for the MEV analyses.

22
4- References
[1] Hamdi El Najjar N, Touffet A, Deborde M, et al. Kinetics of paracetamol
oxidation by ozone and hydroxyl radicals, formation of transformation products
and toxicity. Sep. Purif. Technol. 2014;136:137–143.

[2] Andreozzi R, Caprio V, Marotta R, et al. Ozonation and H2O2/UV treatment of

clofibric acid in water: A kinetic investigation. J. Hazard. Mater. 2003;103:233–
246.

[3] Kim I, Yamashita N, Tanaka H. Performance of UV and UV/H2O2 processes for

the removal of pharmaceuticals detected in secondary effluent of a sewage
treatment plant in Japan. J. Hazard. Mater. 2009;166:1134–1140.

[4] Tan C, Gao N, Fu D, et al. Efficient degradation of paracetamol with nanoscaled

magnetic CoFe2O4 and MnFe2O4 as a heterogeneous catalyst of
peroxymonosulfate. Sep. Purif. Technol. 2017;175:47–57.

[5] Skoumal M, Cabot PL, Centellas F, et al. Mineralization of paracetamol by

ozonation catalyzed with Fe2+, Cu2+ and UVA light. Appl. Catal. B Environ.
2006;66:228–240.

[6] Arredondo Valdez HC, García Jiménez G, Gutiérrez Granados S, et al.

Degradation of paracetamol by advance oxidation processes using modified
reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3.
Chemosphere. 2012;89:1195–1201.

[7] Taei M, Hasanpour F, Dinari M, et al. Synthesis of 5-[(2-hydroxynaphthalen-1-

yl)diazenyl]isophthalic acid and its application to electrocatalytic oxidation and
determination of adrenaline, paracetamol, and tryptophan. Chinese Chem. Lett.
2017;28:240–247.

[8] Carrasco-Díaz MR, Castillejos-López E, Cerpa-Naranjo A, et al. Efficient

removal of paracetamol using LaCu1−xMxO3 (M = Mn, Ti) perovskites as
heterogeneous Fenton-like catalysts. Chem. Eng. J. 2016;304:408–418.

23
[9] Carrasco-Díaz MR, Castillejos-López E, Cerpa-Naranjo A, et al. On the textural
and crystalline properties of Fe-carbon xerogels. Application as Fenton-like
catalysts in the oxidation of paracetamol by H2O2. Microporous Mesoporous
Mater. 2017;237:282–293.

[10] Izabella Teixeira. Resolução n° 430 do Conselho Nacional do Meio Ambiente -

CONAMA. 2011 p. 1–9.

[11] Wang S. A Comparative study of Fenton and Fenton-like reaction kinetics in

decolourisation of wastewater. Dye. Pigment. 2008;76:714–720.

[12] The International Aluminium Institute (IAI). Bauxite Residue Management: Best
Practice www.european-aluminium. 2015.

[13] MARTA CRISTINA SUAREZ GARCIA. Modificação do resíduo de bauxita

gerado no processo Bayer por tratamento térmico. Tese Doutorado. Universidade
de São Paulo; 2012.

[14] Yang L, Yu LE, Ray MB. Photocatalytic oxidation of paracetamol: Dominant

reactants, intermediates, and reaction mechanisms. Environ. Sci. Technol.
2009;43:460–465.

[15] Abipet. Indústria do PET no Brasil. 2012;20.

[16] José Wellingtons de Melo. Produção e caracterização de pó de PET – Poli (

Tereftala- to de etileno ), obtido a partir de garrafas pós-consumo . Produção e
caracterização de pó de PET – Poli ( Tereftala- to de etileno ), obtido a partir de
garrafas pós-consumo . Universidade Federal de Ouro Preto; 2004.

[17] Cheng S, Zhang L, Xia H, et al. Adsorption behavior of methylene blue onto
waste-derived adsorbent and exhaust gases recycling. RSC Adv. 2017;7:27331–
27341.

[18] Cheng S, Zhang L, Xia H, et al. Crofton weed derived activated carbon by
microwave-induced KOH activation and application to wastewater treatment. J.
Porous Mater. 2016;23:1597–1607.

24
[19] Oliveira LCA, Portilho MF, Silva AC, et al. Modified niobia as a bifunctional
catalyst for simultaneous dehydration and oxidation of glycerol. Appl. Catal. B
Environ. 2012;117–118:29–35.

[20] Cheng S, Zhang L, Xia H, et al. Ultrasound and microwave-assisted preparation

of Fe-activated carbon as an effective low-cost adsorbent for dyes wastewater
treatment. RSC Adv. 2016;6:78936–78946.

[21] Coelho J V., Guedes MS, Prado RG, et al. Effect of iron precursor on the fenton-
like activity of Fe2O3/mesoporous silica catalysts prepared under mild
conditions. Appl. Catal. B Environ. 2014;144:792–799.

[22] Nogueira FGE, Lopes JH, Silva AC, et al. Catalysts based on clay and iron oxide
for oxidation of toluene. Appl. Clay Sci. 2011;51:385–389.

[23] Bento NI, Santos PSC, de Souza TE, et al. Composites based on PET and red
mud residues as catalyst for organic removal from water. J. Hazard. Mater.
2016;314:304–311.

[24] Bowles, J. F. W. Schwertmann U. Iron Oxides in the Laboratory. Second. Wiley

- VCH, editor. Mineral. Mag. New York; 2000.

[25] Castro CS, Guerreiro MC, Oliveira LCA, et al. Remoção de conpostos orgânicos
em água empregando carvão ativado impregnado com óxido de ferro: ação
combinada de adsorção e oxidação em presença de H2O2. Quim. Nova.
2009;32:1561–1565.

[26] Castro CS, Guerreiro MC, Oliveira LCA, et al. Iron oxide dispersed over
activated carbon: Support influence on the oxidation of the model molecule
methylene blue. Appl. Catal. A Gen. 2009;367:53–58.

[27] BRASIL M das SAN de VS. Farmacopéia Brasileira. 5a. Diário Of. da União.
2010.

[28] Dodoo-Arhin D, Konadu DS, Annan E, et al. Fabrication and Characterisation of

Ghanaian Bauxite Red Mud-Clay Composite Bricks for Construction

25
 Applications. Am. J. Mater. Sci. 2013;3:110–119.

[29] Mercury JMR, Galdino LG, Vasconcelos NSLS, et al. Estudo do comportamento
térmico e propriedades físico-mecânicas da lama vermelha. Rev. Mater.
2010;15:445–460.

[30] Teresa J. Bandosz. Activated Carbon Surfaces in Environmental Remediation. 1°.

Elsevier: Oxford, editor. 2006.

[31] Liu Y, Lin C, Wu Y. Characterization of red mud derived from a combined

Bayer Process and bauxite calcination method. J. Hazard. Mater. 2007;146:255–
261.

[32] SONG S, JIA F, PENG C. Study on Decomposition of Goethite/Siderite in

Thermal Modification Through Xrd, Sem and Tga Measurements. Surf. Rev.
Lett. 2014;21:1450019.

[33] Guimarães IR, Giroto AS, De Souza WF, et al. Highly reactive magnetite
covered with islands of carbon: Oxidation of N and S-containing compounds in a
biphasic system. Appl. Catal. A Gen. 2013;450:106–113.

[34] Gonçalves M. Preparação de carvão ativado e impregnação com ferro ou cromo

para aplicação em processos de descontaminação ambiental. Universidade
Federal de Lavras; 2008.

[35] Thommes M, Kaneko K, Neimark A V., et al. Physisorption of gases, with

special reference to the evaluation of surface area and pore size distribution
(IUPAC Technical Report). Pure Appl. Chem. 2015;87:1051–1069.

[36] Jarlbring M, Gunneriusson L, Hussmann B, et al. Surface complex characteristics

of synthetic maghemite and hematite in aqueous suspensions. J. Colloid Interface
Sci. 2005;285:212–217.

[37] Díez VK, Di Cosimo JI, Apesteguía CR. Study of the citral/acetone reaction on
MgyAlOx oxides: Effect of the chemical composition on catalyst activity,
selectivity and stability. Appl. Catal. A Gen. 2008;345:143–151.

26
[38] Díez VK, Apesteguía CR, Di Cosimo JI. Aldol condensation of citral with
acetone on MgO and alkali-promoted MgO catalysts. J. Catal. 2006;240:235–
244.

[39] Resende EC De, Gissane C, Nicol R, et al. Synergistic co-processing of Red Mud
waste from the Bayer process and a crude untreated waste stream from bio-diesel
production. Green Chem. 2013;15:496–510.

[40] Wang S, Ang HM, Tadé MO. Novel applications of red mud as coagulant,
adsorbent and catalyst for environmentally benign processes. Chemosphere.
2008;72:1621–1635.

[41] Sahu MK, Sahu UK, Patel RK. Adsorption of safranin-O dye on CO 2 neutralized
activated red mud waste: process modelling, analysis and optimization using
statistical design. RSC Adv. 2015;5:42294–42304.

[42] Cornell RM, Schwertmann U. The iron oxides: structure, properties, reactions,
occurrences and uses. 2nd ed. WILEY-VHC, editor. 2003.

[43] Ovchinnikov O V., Evtukhova A V., Kondratenko TS, et al. Manifestation of

intermolecular interactions in FTIR spectra of methylene blue molecules. Vib.
Spectrosc. 2016;86:181–189.

[44] Liang W, Couperthwaite SJ, Kaur G, et al. Effect of strong acids on red mud
structural and fluoride adsorption properties. J. Colloid Interface Sci.
2014;423:158–165.

[45] Yadav VS, Prasad M, Khan J, et al. Sequestration of carbon dioxide (CO2) using
red mud. J. Hazard. Mater. 2010;176:1044–1050.

[46] Besov AS, Vorontsov A V. Fast elimination of organic airborne compounds by

adsorption and catalytic oxidation over aerosol TiO2. Catal. Commun.
2008;9:2598–2600.

[47] Palominos RA, Mora A, Mondaca MA, et al. Oxolinic acid photo-oxidation using
immobilized TiO2. J. Hazard. Mater. 2008;158:460–464.

27
[48] Oliveira LCA, Gonçalves M, Guerreiro MC, et al. A new catalyst material based
on niobia/iron oxide composite on the oxidation of organic contaminants in water
via heterogeneous Fenton mechanisms. Appl. Catal. A Gen. 2007;316:117–124.

[49] Do QC, Kim DG, Ko SO. Catalytic activity enhancement of a

Fe3O4@SiO2yolk-shell structure for oxidative degradation of acetaminophen by
decoration with copper. J. Clean. Prod. 2018;172:1243–1253.

28
 TABLE LIST

Table 1 – BET apparent surface area and BJH pore volume for the catalysts.

BET apparent surface area BJH Pore volume

Catalysts (m2g-1) (cm3 g-1)
PET powder <2 -
Dried RM* 7 -
PET-RM 84 0.2015
PET-RM 800/2h 114 0.2096
PET-RM 800/5h 78 0.1314
PET-RM 900/5h 8 0.0277
*RM dried in an oven at 60oC/24 h.

Table 2 – Kinetic analysis of the methylene blue oxidation and the comparison between
the methylene blue and paracetamol removals by the PET-RM catalysts.

Initial MB MB removal* Paracetamol

consumption rate (%) removal**
0
Catalysts -r MB (molMB/min. gcatalyst) (%)
PET-RM 100 63 20
PET-RM 800/2h 210 90 26
PET-RM 800/5h 160 85 40
PET-RM 900/5h 60 33 18
* From Fig. 7 and ** From Fig. 10, after 30 min of reaction.

29
 FIGURE LIST
Figure 1. Photos and composites attraction to a permanent magnet: PET-RM

(a and a-1), PET-RM 800/2h (b and b-1), PET-RM 800/5h (c and c-1) and PET-RM

900/5h (d and d-1).

Figure 2. TGA analyses of the catalyst precursors (PET powder and RM) under N2

atmosphere (a) and TGA analyses of the catalysts and precursors under air atmosphere

(b).

Figure 3. XRD of (a) PET-RM catalysts and calcined RM and (b) diffractions

deconvolution for calcined RM and PET-RM 800/2h.

1 – Sodalite, 2 – Hematite, 3 – Gibbisite, 4 - SiO2, 5 – Magnetite, 6 – Maghemite,

7 – Siderite, 8 – Nepheline.

Figure 4. Mössbauer spectra for the PET-RM (a), PET-RM 800/2h (b), PET-RM

800/5h (c) and PET-RM 900/5h (d) composites.

Figure 5. N2 adsorption/desorption isotherms for PET-RM and catalysts after activation

with CO2.

Figure 6. SEM for PET-RM (a), PET-RM 800/2h (b), PET-RM 800/5h (c), PET-RM

900/5h (d) and EDS spectra for the micrographs on the left.

Figure 7. Catalytic tests for the removal of methylene blue (MB) dye from water in the

presence of H2O2 and the PET-RM catalysts. Conditions: 10 mg of catalyst, 9.8 mL of

MB solution (100 mg L-1) and 0.2 mL of H2O2 30% (v/v).

Figure 8. Effect of the initial MB solution pH on the adsorption and oxidation of the

dye in the presence of the PET-RM catalyst.

Figure 9. ATR-FTIR spectra of the PET-RM before and after methylene blue oxidation

reaction.

30
Figure 10. Catalytic tests for the paracetamol removal from water in the presence of the

PET-RM catalysts. Conditions: 10 mg of catalyst, 9.8 mL of paracetamol solution

(100 mg L-1) and 0.2 mL of H2O2 30% (v/v).

Figure 11. Catalytic tests for paracetamol removal monitored by HPLC using the

PET-RM catalysts. Conditions: 10 mg of catalyst, 9.9 mL of paracetamol solution

(100 mg L-1) and 0.2 mL of H2O2 50% (v/v).

Figure 12. Schematic illustration of the steps involved in the organic contaminants

oxidation in the presence of PET-RM composites.

FIGURE 1.

31
FIGURE 2.

100 100

80 80 (b)
(a)
Weight/%

60
Weight/%

60
Red mud
PET-RM
PET residue PET-RM 800/2h
40 40
PET-RM 800/5h
PET-RM 900/5h
20 20 PET residue
Red mud

0 0
100 200 300 400 500 600 700 800 900 100 200 300 400 500 600 700
Temperature/°C Temperature/°C

FIGURE 3.

32
 (a) 8
5
6
6 PET-RM
82 2 46 4 5
88 1 4 8 2 15 2 5 22 900/5h
7
7 6 6 PET-RM
5
2 4 88 2 46 4 6 57
88 81 15 2 5 2 2 8 800/5h
7
Intensity

6
7 5 6 PET-RM
2 4 88 2 46 4 6 57
88 8 1 15 2 5 2 2 8 800/2h
4 6 6
2 5 4
4 5
1 4 1 2 1 2 22
PET-RM
2
1 1 4 2 2 4 4
33 4 21 2 2 22 RM 300/1h

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
2

Hematite RM 300/1h
(b)
Intensity

34,0 34,5 35,0 35,5 36,0 36,5 37,0 37,5

2
Hematite PET - RM 800/2h
Magnetite/Maghemite
Intensity

34,0 34,5 35,0 35,5 36,0 36,5 37,0 37,5

2

FIGURE 4.

33
 PET-RM

3+
Fe
PET-RM 800/2h

3+
Fe
Transmittance

2+
Fe
PET-RM 800/5h

3+ 2+
Fe Fe
PET-RM 900/5h

2+
Fe
3+
Fe
-10 -5 0 5 10
-1
Doppler speed / mm.s

FIGURE 5.

34
 140

120 PET-LV
N2 adsorbed amount (cm3g-1)

PET-LV 800/2h
100 PET-LV 800/5h
PET-LV 900/5h
80

60

40

20

0
0,0 0,2 0,4 0,6 0,8 1,0
P/P0

FIGURE 6.

35
FIGURE 7.

36
 100

80
Methylene blue removal (%)

60

40
PET-RM
20 PET-RM 800/2h
PET-RM800/2h - adsorption
PET-RM 800/5h
0 PET-RM 900/5h
0 10 20 30 40 50 60
Time (min)

FIGURE 8

37
 PET-RM
70
MB adsorption
60 MB oxidation
MB removal/% 50

40

30

20

10

0
5.0 7.0 9.0
Solution pH

FIGURE 9

38
 PET-RM
Transmittance

2855 1555 1390

2930

-CH3 groups
PET-RM from adsorbed MB 980

After reaction

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber/cm

FIGURE 10

39
 50
PET-RM
PET-RM 800/2h
40 PET-RM 800/2h - adsorption
PET-RM 800/5h
Paracetamol removal (%)

PET-RM 900/5h
30

20

10

0
0 5 10 15 20 25 30
Time (min)

FIGURE 11

40
 100
PET-RM
PET-RM 800/2h
80 PET-RM 800/5h
Paracetamol removal (%)

PET-RM 900/5h

60

40

30 min
30 min
5 min

5 min
30 min

30 min
5 min
5 min

20

0
Time (min)

FIGURE 12

Paracetamol solution
H2O2

Fe+3 Fe+2 + H+ + •OOH

-
( )

H2O2 •OH Paracetamol

Red mud oxidation

Fe+2
Paracetamol

Paracetamol adsorption ( ) Carbon from PET decomposition

41