J Therm Anal Calorim (2017) 130:1939–1951

DOI 10.1007/s10973-017-6551-6

Polyethylene catalytic cracking by thermogravimetric analysis

Effects of zeolitic properties and homogenization process

Vinı́cius P. S. Caldeira1 • Anne G. D. Santos1 • Daniele S. Oliveira1 •

Rafael B. Lima1 • Luiz D. Souza1 • Sibele B. C. Pergher2

Received: 6 March 2017 / Accepted: 21 June 2017 / Published online: 3 July 2017
Ó Akadémiai Kiadó, Budapest, Hungary 2017

Abstract Polymer degradation by the catalytic cracking ysis. Among the zeolites with large pore diameters, the
process has been investigated as an important way of hierarchical Beta showed superior external area due to the
hydrocarbon recovery with high added value. In addition, use of a bulky silanized agent (phenylaminopropyl-
the effects of the catalyst properties and their behavior trimethoxysilane) in the synthesis. In cracking reactions,
during the catalytic degradation of polyolefins have been the polymeric macromolecules mainly react in the external
studied using thermogravimetric analysis. In this context, surface of the catalysts due to the several diffusional lim-
the present work compares the interactions between the itations imposed. Thus, the zeolitic catalysts exhibited
polymeric molecules and the contact surface of zeolitic behaviors respective to a combination of accessibility to
catalysts (hierarchical and standard Beta zeolites, Y zeolite, the active centers and selectivity in function of the acid
ZSM-5, ZSM-12 and MCM-22) with different properties, strength of the centers. So, based on this process, zeolites
in the catalytic cracking reactions of low-density with larger external area values (hierarchical Beta, standard
polyethylene. It was also possible to evaluate distinct Beta, ZSM-5 and MCM-22) promoted the lower values of
reaction mechanisms in function of the thermal homoge- degradation temperature with high efficiency of
nization procedure employed by thermogravimetric anal- conversion.

& Vinı́cius P. S. Caldeira

vinicius_psc@yahoo.com.br
1
Department of Chemistry, State University of Rio Grande do
Norte, Mossoró, RN 59610-210, Brazil
2
Institute of Chemistry, Federal University of Rio Grande do
Norte, Natal, RN 59078-970, Brazil

123
1940 V. P. S. Caldeira et al.

Graphical Abstract
Polyethylene SEXT/m2 g–1
Macromolecules 50 100 150 200 250 300 350
800

ZSM-12
750

TDEGRAD/K
MCM-22
700

400
Zeolitic Catalysts Y Zeolite ZSM-5
BETA 650
350 Beta ZSM-5
Adsorbed volume/cm3 g–1

h-Beta ZSM-12
600
h-BETA
300 Y Zeolite MCM-22

250

Normalized DTG/% K–1

200

150
Polyethylene
100
Catalytic
50
Cracking
0
0.0 0.2 0.4 0.6 0.8 1.0
473 523 573 623 673 723 773 823
Relative pressure/p/p0
Temperature/K

Keywords Hierarchical zeolite
Catalytic cracking
Chemical degradation procedures have been investi-
Polyethylene
Thermogravimetry gated lately as a promising route to reduce landfilling rates
and obtaining chemical raw materials and/or fuels, which
are products of high added value [7, 14]. Many papers in
Introduction the literature report the catalytic cracking of polymers as an
important way of plastic recycling and fuel-like hydrocar-
Plastics are one of the most widely used materials due to bon recovery [15–17].
their various advantages and numerous applications in our The catalytic effect of a zeolite on polymer decomposition
day-to-day life. Plastic production has increased by an can be evaluated using different techniques and reactors, but
average of almost 10% every year on a global basis since thermogravimetric analysis is one of the most frequently
1950 [1, 2]. The increase in the production of plastics is used techniques [18–20]. The information provided by this
due to a higher standard of living and to their availability at technique allows the kinetic data obtained, and the effect of
a relatively low cost. Nevertheless, this increase in the the polymer structure, composition and operating variables
production of materials with progressively shorter periods on the pyrolysis process to be studied [21]. Garforth et al.
of use that are not biodegradable generates serious envi- [22] have shown that the catalytic degradation of polyolefins
ronmental problems [3, 4]. Plastic waste management is a can be investigated using thermogravimetric analysis (TG)
subject of deep concern in western societies. The national as a potential method for screening catalysts, and they
and international laws are becoming more stringent about showed too that the presence of a catalyst led to a decrease in
landfilling [3, 5]. the apparent activation energy.
The conventional recycling treatments show some The isoconversional methods by thermogravimetry have
drawbacks, such as the limited applicability of the recycled been extensively used to obtain the activation energy by the
plastics due to their progressive loss of quality (mechanical catalytic degradation of polymers [23]. Gobin and Manos
recycling) or the possible emission of toxic compounds [24] studied the catalytic decomposition of low-density
(incineration with energy recovery). On the other hand, polyethylene (LDPE), polypropylene (PP) and high-density
chemical treatments have appeared as a promising alter- polyethylene (HDPE) using several catalysts such as USY,
native to deal with the millions of tons of polymeric waste HZSM-5 and FCC in a thermobalance. The microporous
produced every year [5, 6]. Chemical recycling processes zeolite material has high thermal stability and acid sites
are especially interesting because of the valuable products whose strength and concentration can be controlled. Thus,
obtained: monomers [7–9], chemical feedstocks [10, 11] or the selection of the zeolite should be based on a target
fuels [12, 13]. selectivity: HZSM-5 zeolite promotes the production of

123
Polyethylene catalytic cracking by thermogravimetric analysis 1941

olefins (original monomers), while h-Beta and HY zeolites as a porous solid catalyst with high potential in processes
maximize the production of middle distillates [5]. involving bulky molecules [39]. The functionality of the
Park et al. [25] investigated the liquid-phase catalytic introduced mesoporosity in the hierarchical BEA crystals
degradation of HDPE on the BEA, FAU, MWW, MOR and has been demonstrated by the improved performance in the
MFI zeolites with different pores to illustrate the effect of catalytic pyrolysis of LDPE [40].
pore shape on their catalytic activities. High conversions of In this context, the present work compares the interac-
HDPE were obtained on BEA and MFI zeolites, because tions between the polymeric molecules and the contact
bent pores retarded catalytic deactivation due to carbon surface of zeolitic catalysts (hierarchical and standard Beta
deposit suppressing the formation of longer molecules. On zeolites, Y zeolite, ZSM-5, ZSM-12 and MCM-22) with
the other hand, the slow diffusion of cracked products in different properties, in the catalytic cracking reactions of
MWW zeolite due to its repeated larger spaces brought low-density polyethylene (LDPE). It also makes possible to
about further cracking, enhancing the yield of small evaluate distinct reaction mechanisms in function of the
hydrocarbons. thermal homogenization procedure employed by thermo-
Aguado et al. [6] studied the catalytic activity of various gravimetric analysis.
acid solids, including ZSM-5 and Beta zeolites, in the
cracking of HDPE and LDPE, as well as of waste poly-
olefins of agricultural and urban origins. Based on ther- Experimental
mogravimetric experiments, they showed a good
correspondence between the catalytic activities of the Zeolites synthesis
solids and their acid and textural properties. The catalytic
cracking process over traditional zeolitic catalysts (X, Y, Hierarchical Beta zeolite (h-Beta) was synthesized accord-
ZSM-5, Beta, among others) can be restricted by the ing to the strategy published in the literature [41], with the
inaccessibility of bulky molecules to the pores of small following stoichiometric molar ratio: 1.5Al2O3/60SiO2/
diameter, making it difficult to molecular diffusion within 15.5TEAOH/1000H2O and silicon/aluminum molar ratio
the structure [25]. equal to 20. Initially, a solution containing aluminum flakes
An approach to favoring the diffusion of large molecules (Aldrich, 99.9%), fumed silica (Aldrich), tetraethylammo-
in zeolitic structure is the development of a hierarchical nium hydroxide (TEAOH, Alfa, 35% aqueous solution) and
porosity, which contains mesopores or macropores well distilled water was aged at room temperature for 20 h and
interconnected with the microporous framework [26, 27]. precrystallized in Teflon-lined steel autoclave reactors at
Hierarchical zeolites exhibit at least two levels of pore sizes 408 K for 3 days in order to obtain a gel containing Beta
and have attracted great interest in the last few years seeds. The silanization agent employed was phenylamino-
[28–30]. These materials combine the typical zeolitic propyl-trimethoxysilane (PHAPTMS, C6H5NH(CH2)3-
micropores with the occurrence of additional secondary Si(OCH3)3, Aldrich, ?97%). The PHAPTMS amount of
porosity (e.g., supermicropores, mesopores, macropores), 8 mol% (with regard to the silicon content) was added to the
which is an advantage when these catalysts are applied in Beta seeds and left reacting at 363 K for 6 h under reflux.
reactions involving bulky compounds [31]. Hierarchically Finally, the samples were crystallized in autoclave reactors
structured zeolites attract growing attention due to their at 408 K for 7 days.
superior performance in traditional and emerging catalytic Beta zeolite (Beta) synthesis occurred employing the
applications of industrial relevance. This is due to several same chemical composition and procedure previously
elements: an improved diffusion of reactants and products mentioned for hierarchical Beta, but in this case, the
within the microporous crystals due to the presence of wider silanization step was omitted, according the method
mesopores and/or shorter diffusion paths [28, 32], an described in the literature [41, 42]. Both zeolites above-
enhanced selectivity toward desired products in some mentioned with BEA zeolitic phase were calcined in static
reactions [33, 34] and substantial improvements in deacti- air at 823 K for 5 h.
vation phenomena by coke deposition [35, 36]. ZSM-5 zeolite (ZSM-5) was synthesized in presence of
Some studies have shown that hierarchical zeolites organic template with a silicon/aluminum molar ratio of
present high catalytic activity in the cracking of low-den- 25, according to the literature [43, 44]. The synthesis gel
sity polyethylene (LDPE), revealing quite higher activity was obtained with amorphous silica gel (Acros Organics,
than conventional zeolites because of the lower steric 0.035–0.070 mm), sodium hydroxide (Merck), aluminum
constraints and enhanced diffusion of the bulky plastic sulfate hexadecahydrate (Reagen) and tetrapropylammo-
macromolecules [16, 37, 38]. nium bromide (Sigma-Aldrich) as sources for Si, Na, Al
Through improvements in textural properties, accessi- and the organic template, respectively. The synthesis gel
bility and acidity, the hierarchical BEA can be considered had the following stoichiometric proportion: 5.3TPABr/

123
1942 V. P. S. Caldeira et al.

7.15Na2O/1Al2O3/50SiO2/1000H2O. Afterward, the gel values of the samples were determined by XRF measure-
was transferred to Teflon-lined steel autoclave reactors and ments with an EDX-7000 Shimadzu equipment. The sam-
heated to 423 K under autogenous pressure and static ples were supported on a plastic holder sample covered
conditions for 7 days (168 h). The sample was heated at with an LDPE film for analyses. The acid properties of the
823 K for 10 h to obtain the zeolite in calcined form, as catalysts were determined by ammonia temperature pro-
described in the literature [44]. grammed desorption (TPD) in a Micromeritics AutoChem
The method applied for the synthesis of ZSM-12 zeolite 2910 system using He as carrier gas. Previously, the
was proposed by Araujo et al. [45], with a silicon/alu- samples were outgassed under a helium flow
minum molar ratio of 25. The chemical materials employed (50 mL min-1), with a heating rate of 15 K min-1 up to
to obtain the synthesis gel were: silica gel (Aldrich), 833 K, and kept at this temperature for 30 min. After
sodium hydroxide (Aldrich), pseudoboehmite (Catapal cooling to 453 K, an ammonia flow of 35 mL min-1 was
B-Vista) and methyltriethylammonium chloride passed through the sample for 30 min. Once the physi-
(MTEACl–Sigma) as organic template. The synthesis gel sorbed ammonia was removed by flowing helium at 453 K
formed has this stoichiometric proportion: 20MTEACl/ for 90 min, the chemisorbed ammonia was determined by
10Na2O/1Al2O3/100SiO2/2000H2O. Then, the synthesis increasing the temperature with a heating rate of
gel was heated at 413 K into Teflon-lined steel autoclave 15 K min-1 up to 823 K, holding this temperature for
reactors during 6 days (144 h) in static conditions. The 30 min. The ammonia concentration in the effluent helium
calcination process to ZSM-12 zeolite was conducted at stream was monitored with a thermal conductivity detector
823 K for 10 h. (TCD).
The MCM-22 zeolite was synthesized following the
methodology described in the literature [46, 47]. The Polyethylene catalytic cracking
chemical materials employed to obtain the synthesis gel
were: silica Aerosil (Degussa), sodium hydroxide (Merck), The low-density polyethylene (LDPE) used in catalytic
anhydrous sodium aluminate (56% Al2O3; 37% Na2O— cracking reactions was provided by Alcudia-REPSOL/ES,
Riedel-de-Haen) and hexamethyleneimine (HMI–Sigma) in powder form. The LDPE/catalyst mixtures and pure
as organic template. The chemical materials were com- LDPE were placed directly in an alumina pan for ther-
bined to form the pMCM-22 layered precursor, with this mogravimetric analysis. The thermogravimetry (TG) and
stoichiometric proportion: 15 HMI/2.4 Na2O/1Al2O3/ derivative thermogravimetry (DTG) techniques of analysis
30SiO2/1350 H2O and silicon/aluminum molar ratio of 15. were carried out in Netzsch equipment, STA 449 F3 Jupiter
The synthesis gel was placed in Teflon-lined stainless steel model. The catalyst proportion was of 20 mass% in the
autoclave reactors and then heated to 423 K under stirred LDPE/catalyst mixtures, and it is important to observe that
conditions for 7 days (168 h). After calcination treatment this proportion reaches a percentage more than enough to
of pMCM-22 material at 813 K, the three-dimensional evaluate the physicochemical properties of the catalyst in
layered structure (MWW) was obtained and coded as the process, according to saturating effects described in the
MCM-22 zeolite. literature [19]. The LDPE/catalyst mixtures, using LDPE
The Y zeolite applied in this study was acquired in the powder ([210 lm), were weighed in analytical balance
calcined form by Micromeritics (CODE—004-16844-00), as a and prepared with mortar and pestle at room temperature in
standard sample of a zeolite with large microporous diameter. order to obtain around 30 mg of total mixture.
The thermogravimetric analyses of LDPE degradation
Catalysts characterization were conducted on two distinct procedures, in order to
evaluate the interactions of contact surfaces between the
XRD patterns of the different zeolitic catalysts were catalyst and the polymer macromolecules. Both procedures
obtained with a Rigaku diffractometer, Mini Flex II model, were carried out under nitrogen with a continuous flow rate
using Cu (k = 1.5406 Å) Ka radiation. The measurements of 60 mL min-1 and a sample mass of about 3 mg. The first
were taken through scanning method, in 5°–50° 2h range, one was performed using a heating rate of 10 K min-1, with
with step of 0.028 s-1. N2 adsorption–desorption isotherms temperature increase from ambient temperature up to
at 77 K of the calcined catalysts were measured with a 1073 K, and this temperature was maintained for 5 min. The
Micromeritics ASAP 2020 instrument. Prior to the mea- other procedure has an additional step of thermal homoge-
surements, the individual samples were outgassed at 573 K nization at a temperature slightly above of the LDPE melt-
for 10 h under vacuum. The specific area was determined ing temperature (393 K). Thus, the samples were heated
applying the Brunauer–Emmett–Teller (BET) equation. from room temperature to 393 K, under a heating rate of
The micropore volume and area were calculated by t-plot 10 K min-1; at this temperature, the sample remained in an
method. The aluminum content and Si/Al molar ratio isotherm for 6 h, and then the sample was heated to 1073 K

123
Polyethylene catalytic cracking by thermogravimetric analysis 1943

under a heating rate of 30 K min-1. The representation of

this procedure is shown in Fig. 1. Beta

Normalized intensity/a.u.
h-Beta
Results and discussion
Y Zeolite
Zeolites physicochemical properties
ZSM-5
The physicochemical properties of all zeolites were ana-
lyzed to understand the chemical composition, acid prop- ZSM-12
erties, crystalline structure and textural properties. The
employment of zeolites with different crystalline phases MCM-22
and distinct porous properties allows to evaluate the
accessibility of active sites for the voluminous 5 10 15 20 25 30 35 40 45 50
polymeric chains. 2θ /°
XRD patterns in 5°–50° 2h range of all zeolites are
Fig. 2 Wide-angle XRD patterns of the calcined zeolites samples
shown in Fig. 2. The hierarchical Beta, Beta, Y, ZSM-5,
ZSM-12 and MCM-22 samples exhibited XRD patterns
with diffraction peaks coincident with BEA, BEA, FAU, topology show tetragonal symmetry based on two main
MFI, MTW and MWW zeolitic topology, respectively, diffraction peaks in 7.7° and 22.6° 2h, according to the
according to Database of Zeolite Structures [48]. All zeo- literature [41, 42]. Regarding zeolites with BEA topology,
lites demonstrated a significant degree of crystallinity, a reduction in the intensity of the diffraction peaks (XRD
evidencing crystalline particles and absence of patterns in Fig. 2) is observed for hierarchical Beta sample,
amorphous material. when compared to Beta zeolite, as consequence of the
The MCM-22 zeolite shows a layered structure with disturbance from crystals growth by the silanization pro-
hexagonal unit cell, as evidenced by the reflection of peak cess [51, 52].
(002) in 6.58 2h [46, 47]. The ZSM-5 and ZSM-12 zeolites The zeolitic channels systems are distributed in: one-
show channel systems of cylindrical pores with dimensional with 12-ring members for ZSM-12; two-di-
orthorhombic symmetry (signals at 2h ranged 7.8, 8.8 and mensional with 10-ring members for MCM-22; three-di-
23°–25° 2h) [44] and monoclinic symmetry (diffraction mensional with 10-ring members for ZSM-5 and three-
peaks at 7.5°, 8.8° and 21° 2h) [45], respectively. The Y dimensional with 12-ring members for hierarchical Beta,
zeolite displays cubic framework with openings and cavi- Beta and Y zeolites. In addition, these zeolitic channels
ties represented by the reflection peaks at 6.2°, 10.2°, 12.0° systems provide pores with different diameters, such as:
and 15.88 2h [49, 50]. Moreover, the zeolites with BEA FAU (7.4 9 7.4 Å); BEA (6.6 9 7.7 - 5.6 9 5.6 Å);
MTW (5.6 9 6.0 Å); MFI (5.1 9 5.5 - 5.3 9 5.6 Å); and
MWW (4.0 9 5.5 - 4.1 9 5.1 Å) [48]. In order to better
understand this porosity, gas sorption measurements
100 1073 were taken.
973 Figure 3 shows the N2 adsorption–desorption isotherms
80 at 77 K in linear and logarithmic scale. All zeolites
TG 873
exhibited type I adsorption isotherm (Fig. 3a), typical to
Temperature
Temperature/K

60 773 the microporous crystalline solids, according to IUPAC

TG/%

673
[53] and corroborating with XRD measurements. The iso-
therms’ profiles initially demonstrate the micropore filling
40
573 to low relative pressure and a significant volume adsorbed
473 to high relative pressure (p/p0 [ 0.9), corresponding to the
20 interstitial spaces due to the agglomerated particles. Fig-
373
ure 3b shows the monolayer filling of the zeolitic micro-
0 273 pores in low relative pressure, where the different adsorbed
0 25 365 370 375 380 385 390 volumes correspond to the crystalline phase of each zeolite.
Time/min
The three-dimensional crystalline structure and micropores
Fig. 1 Representation of the thermogravimetric analysis procedure with large size provide high adsorbed volumes in microp-
with the thermal homogenization step ores for Beta (BEA), h-Beta (BEA) and Y (FAU) zeolites.

123
1944 V. P. S. Caldeira et al.

160
400 Beta (a) (b)
h-Beta
140
Y Zeolite
350
ZSM-5
ZSM-12 120
Adsorbed volume/cm3 g–1

Adsorbed volume/cm3 g–1

300 MCM-22

100
250

80
200

60
150

100 40

50 20

0 0
0.0 0.2 0.4 0.6 0.8 1.0 1E–6 1E–5 1E–4 1E–3 0.01
Relative pressure/p/p0 Relative pressure/p/p0

Fig. 3 N2 adsorption–desorption isotherms at 77 K for all zeolites: a linear scale of relative pressure; b logarithmic scale of relative pressure

The textural properties of the zeolites, with values of hierarchical zeolite Beta (350 m2 g-1). However, among
area and volume obtained from N2 adsorption isotherms, these three zeolites with large pore diameters, the h-Beta
are summarized in Table 1. The larger specific area values showed superior external area to the micropores (SEXT—
(SBET—Table 1) were obtained for the zeolites with high 333 m2 g-1), due to the use of the bulky silanized agent in
adsorbed volume, which is clearly shown in Fig. 3a, b. the synthesis. The silanization process interrupts the micro-
Despite the MCM-22 exhibiting two-dimensional crys- porous crystalline growth, generating small crystalline
talline structure, this zeolite shows similar specific area to domains that agglomerate in little particles, providing
the ZSM-5 zeolite that has three-dimensional crystalline superior external area to the micropores [51]. The generation
structure, due to the elevated accessibility provided by the of small crystalline domains for the h-Beta, which corrobo-
distribution of its pillared particles. rates with XRD measurement, evidences the formation of an
Zeolites are known as crystalline materials with a superior additional secondary porosity to the zeolite micropores. This
area of ordered micropores. Thus, the micropore volume and secondary porosity, caused by the silanization process
area were calculated by the t-plot method, as given in employing a bulky silanized agent, promotes high external
Table 1. Beta and Y zeolites showed the larger microporous area in addition to the typical zeolitic phase. This fact reveals
areas (444 and 442 m2 g-1, respectively), followed by the presence of mesopores in a zeolite with only microporous
structure, proving that hierarchical zeolitic materials should
have at least two levels of pore sizes [28, 30].
Table 1 Textural properties of the zeolites by nitrogen adsorption– The molar composition is of great interest to understand
desorption at 77 K the chemical structure of the zeolites and thus probably
Samples SaBET/ SbMIC/ VbMIC/ ScEXT/ identify the number of active sites. Table 2 shows the alu-
m2 g-1 m2 g-1 cm3 g-1 m2 g-1 minum content and Si/Al molar ratio values for the different
Beta 621 444 0.20 177
synthesized zeolites. According to the Al content, each
h-Beta 683 350 0.16 333
zeolite showed a significant insertion of this metal relative to
its stoichiometric chemical composition, which proves the
Y zeolite 530 442 0.20 88
effectiveness of synthesis gel obtainment. The high Al
ZSM-5 398 230 0.11 167
content for Y zeolite is characteristic of its chemical com-
ZSM-12 239 149 0.07 90
position, with lower Si/Al molar ratio, for its crystalline
MCM-22 368 217 0.12 151
structure [49]. The Si/Al molar ratio values for synthesized
a
Applied BET method zeolites are slightly lower than the theoretical Si/Al molar
b
Applied t-plot method ratio (Table 2), but this did not make it difficult to compare
c
SEXT = SBET - SMIC the stoichiometric ratio of zeolites each other.

123
Polyethylene catalytic cracking by thermogravimetric analysis 1945

Table 2 Acid properties and chemical composition of the zeolites zeolites with BEA phase, the hierarchical zeolite (h-Beta)
samples exhibited a somewhat lower acid strength and number of
Samples Ala/ Si/Al Theoretical Maximum Acidityb/ acid sites (563 K and 0.449 meqNH3 g-1, respectively),
mass% ratioa/ Si/Al ratio/ temperatureb/ meqNH3 compared to the Beta sample (585 K and
a.u. a.u. K g-1 0.478 meqNH3 g-1, respectively). It could be related to a
Beta 7.0 13.3 20 585 0.478 change in the nature of acid sites associated with the
h-Beta 7.7 12.0 20 563 0.449 increase in the external surface area, crystalline domains of
Y zeolite 23.5 3.3 – 541 0.429 lower dimensions and a higher proportion of Al atoms
ZSM-5 4.6 20.7 25 657 0.359 located in a less ordered environment. On the other hand,
ZSM-12 5.5 17.2 25 498 0.073
an elevated Al content does not imply greater acidity (as in
MCM-22 8.5 10.8 15 539 0.383
the case of Y zeolite—Table 2) because it depends on how
the aluminum is located in the framework.
a
Calculated using the XRF measurements Despite its two-dimensional structure, the MCM-22
b
Calculated using the NH3-TPD measurements zeolite showed higher acidity than the ZSM-5 and similar
acid strength to the Y zeolite (Table 2), both with three-
dimensional structure. This fact evidences a remarkable
capacity of accessibility to active sites due to the presence
Aluminum content determines the acidity and influences of lamellar layers pillared in a disorderly form [46]. The
the catalytic performance of zeolitic materials. Ammonia maximum temperature value for the ZSM-5 was the larger
TPD is a widely applied method for characterizing the among the zeolites analyzed, probably revealing a high
acidic properties of zeolites as it provides information on number of Brönsted acid sites in its structure. For this
both, the total number of acid sites (calculated from the reason, the MFI zeolitic phase is widely used to obtain light
NH3 detected during desorption) and their acid strength hydrocarbons in catalytic cracking processes, according to
(related to the temperature of the maximum peak in the the literature [54]. Moreover, the one-dimensional structure
desorption curve). and low micropore volume were made with which the
Figure 4 shows the NH3-TPD profiles of the zeolite ZSM-12 zeolite had the lowest acidity between
samples, even as Table 2 shows the values of acidity (total the samples.
number of acid sites) and maximum temperature (acid
strength). All of the zeolite samples exhibited a typical Polyethylene catalytic cracking
NH3-TPD behavior for microporous solids with two des-
orption peaks, the main peak corresponding to the weak All of the zeolite samples were tested in cracking reactions
acid sites and the other to strong acid sites. Regarding the of low-density polyethylene (LDPE). In this case, the

Fig. 4 NH3-TPD 0.18 873

measurements of the zeolite
samples 0.16 823

0.14 773

Beta
0.12 723
h-Beta
Temperature/K
Signal/a.u.

0.10 Y Zeolite 673

ZSM-5
0.08 623
ZSM-12
MCM-22
0.06 573

0.04 523

0.02 473

0.00 423

0 10 20 30 40 50 60
Time/min

123
1946 V. P. S. Caldeira et al.

polymeric macromolecules mainly react in the external The thermogravimetric curves for catalytic degradation
surface of the catalysts, due to the several diffusional of low-density polyethylene under heating rate of
limitations imposed, reducing their access to the zeolitic 10 K min-1 are shown in Fig. 5; as well the thermo-
micropores. gravimetric values obtained of these curves are given in
However, the textural properties of the catalysts must be Table 3.
evaluated carefully so that they supply the accurate Thermogravimetric curves show events of mass loss
accessibility to desired products in a catalytic cracking corresponding to the cracking of the polymer, associated
reaction. Therefore, the techniques of thermal analysis, with the evaporation or volatilization of lighter products. It
such as thermogravimetry (TG) and derivative thermo- is interesting to note that the addition of the catalyst
gravimetry (DTG), can be successfully employed to decreases the polymer degradation temperature, making it
determine the physicochemical properties of the catalysts. possible to expose even more than one mass loss event,

100
(a) (b)
Rate of 10 K min–1
80 LDPE
LDPE + Beta

Normalized DTG/% K–1

LDPE + hBeta
LDPE + Zeolite Y
60
LDPE + ZSM-5
TG/%

LDPE + ZSM-12
LDPE + MCM-22
40

20

0
473 573 673 773 873 973 473 523 573 623 673 723 773
Temperature/K Temperature/K

Fig. 5 TG (a) and DTG (b) curves obtained in the degradation of LDPE with zeolites, under heating rate of 10 K min-1

Table 3 Thermogravimetric values obtained in the degradation of LDPE with zeolites, under heating rate of 10 K min-1
Samples Ta/
InitialK TaFinal/K Temperature of degradationa/K Mass lossb/mass% Residual massc/mass% Coked/mass%
1st 2nd

LDPE 611 774 745 – 98.7 0.3 1.0

Beta 443 756 625 – 80.3 17.7 2.0
h-Beta 443 738 632 – 83.0 15.9 1.1
Y zeolite 491 770 590 713 77.5 20.2 2.3
ZSM-5 496 770 645 700 82.6 15.6 1.8
ZSM-12 498 784 590 745 77.8 19.4 2.8
MCM-22 496 741 691 – 79.2 20.2 0.6
a
Obtained in DTG curve
b
Until the temperature of 823 K
c
In the final temperature of 1073 K
d
In the range of 823–1073 K

123
Polyethylene catalytic cracking by thermogravimetric analysis 1947

according to the catalyst properties. In thermal degradation, noticeable separation between the mass loss events. Since
only one reaction mechanism occurs, while the presence of the catalytic cracking process consists of scission of long
active sites on catalyst surface provides broad possibilities chain hydrocarbons bonds, the lower molecular mass
of reaction mechanisms [33]. In this present work, it can be molecules will be volatilized at lower temperatures,
noted that the addition of the catalyst reduced the initial depending on their respective boiling points.
temperature (Tinitial) of LDPE degradation by about 433 K A detailed analysis of the DTG curves for the LDPE
(Table 3). All zeolites used as catalysts caused effects of catalytic cracking (Fig. 5b) exhibits distinct behaviors for
decomposition, reducing considerably the initial tempera- the zeolitic catalysts employed where volatilized com-
tures of LDPE degradation (Table 3). pounds with close boiling points overlap in one only mass
However, to compare the zeolites to each other, it is loss event and compounds having different physical prop-
observed that the zeolitic structures with larger pore erties are volatilized in more than one event. The lower the
diameter and three-dimensional channel systems (Beta, degradation temperature values of the events, the higher
h-Beta and Y zeolite) supplied the lowest values of ini- the possibility of light hydrocarbons formation, such as
tial temperature. Despite the ZSM-5 zeolite demonstrat- olefins and paraffins of low molecular mass, which are of
ing three-dimensional channel systems, the diameter of great interest to the petrochemical industry.
its pores did not allow a similar decrease in Tinitial. This The MFI, ZSM-12 and Y zeolites showed two mass loss
fact can be explained by the accessibility of the active events, while the other zeolites, just a single event. The
sites of the catalyst, because the polymeric macro- degradation temperatures (Tdegrad) of each mass loss event
molecules will go a more accessible way to react, thus are given in Table 3. Among the zeolites with two mass
reducing the diffusional pathway of the formed products. loss events, the ZSM-5 demonstrated the first event
The BEA zeolitic phase revealed the most significant (Tdegrad = 645 K) as the main event with greater selectivity
reduction of Tinitial, about 433 K lower when compared to lighter compounds. This fact can be explained by the
to thermal cracking, indicating that this zeolitic phase is high acid strength belonging to this zeolite, where an
very promising for cracking reactions of bulky interaction with strong Brönsted acid sites probably occurs
molecules. through protons transfer reactions. For the ZSM-12 and Y
It may be noted that the values of residual mass, zeolites, the first mass loss event (Tdegrad = 590 K, simi-
obtained in the temperature of 1073 K, are equivalent to larly) occurs in small proportions when compared to the
real proportion of catalyst in the mixture, except for the second event, indicating the predominance of higher
pure LDPE. These results showed a variation of about molecular mass compounds.
4 mass% between the zeolites (Table 3), and this fact is To compare all zeolites to each other, it is observed that
due to the solid–solid method employed to the homoge- the degradation temperature for the main mass loss events
nization process. However, this variation in percentage varied significantly, obtaining temperatures up to 393 K
does not interfere in the evaluation of the catalytic prop- lower than the temperature of the thermal cracking. The
erties during the LDPE decomposition reaction. selectivity for lighter compounds follows the order:
When the thermogravimetric curves in Fig. 5a are Beta [ h-Beta [ MFI [ MCM-22 [ Y zeolite [ ZSM-
carefully observed, it can be noted that, after the LDPE 12. This selectivity denotes the possibility of distinct
degradation reaction (before 773 K), a mass loss event in a mechanisms reactions in the process, which strongly
range 823–1073 K was identified. Such event may be depends on a combination of properties to acidity and
defined as a decomposition of coke formed during the active sites accessibility. For example, the zeolites with
cracking process, which requires high temperatures to BEA phase showed the highest values of acidity and
decompose the hydrocarbons of high molecular mass. The external area (Tables 1, 2), thereby obtaining the lowest
presence of zeolitic catalysts in the cracking process pro- values of the initial and degradation temperatures
motes a coke deposition on external surface and pore (Table 3). Then, the ZSM-5 and MCM-22 zeolites pre-
opening, thus blocking the diffusional pathway of mole- sented significant values of acidity (0.359 and
cules inside the pores. The Y and ZSM-12 catalysts showed 0.383 meqNH3 g-1, respectively) and external area (167
higher coke formation, evidencing lower efficiency in the and 151 m2 g-1, respectively), which overcomes in selec-
LDPE decomposition, corroborating with the mass loss tivity the Y zeolite, that, despite displaying higher acidity
values (Table 3). (0.429 meqNH3 g-1), has lower external area (88 m2 g-1).
During the LDPE degradation, the physicochemical This behavior among the zeolites with two- and three-di-
properties of zeolitic catalysts contribute to the formation mensional channel systems proves the importance of
of products with different reaction mechanisms. Thus, accessibility to active sites of the catalyst, reducing the
through the thermogravimetric analysis it is possible to diffusional pathway of products. The ZSM-12 zeolite had
distinguish the reaction mechanisms when there is a the lowest value of degradation temperature, similar even

123
1948 V. P. S. Caldeira et al.

to the thermal cracking, due to low values of acidity and As noted earlier, the BEA zeolitic phase exhibited the
external area (Tables 1, 2). lowest values of initial temperature, due to their structural
To better understand the catalytic activity of zeolites in properties. The ZSM-12 showed the initial temperature
function of its properties of acidity and accessibility, an value much higher when compared to the process at
analysis of the LDPE catalytic cracking was performed, 10 K min-1, indicating that the thermal homogenization
with an additional step of thermal homogenization. In order for this zeolite did not contribute to a more efficient cat-
to overcome the limitations of contact surface between a alytic activity.
solid–solid system, an isotherm at 393 K during 6 h was The residual mass values for thermogravimetric analysis
carried out, according to Fig. 1. Thus, a thermal homoge- with a heating rate of 30 K min-1 exhibited a variation of
nization occurs between the catalyst particles and the about 3 mass% for all catalytic cracking (Table 4). This
polymer liquid phase. After this homogenization proce- variation does not impair the comparison between the
dure, the samples were heated to 1073 K under a high zeolite catalysts during the LDPE decomposition reaction,
heating rate (30 K min-1) to complete the LDPE similar to the thermogravimetric experiments previously
degradation. applied.
The thermogravimetric curves for catalytic degradation The procedures of thermal homogenization and high
of low-density polyethylene under heating rate of heating rate provided lower coke formation during the
30 K min-1 are shown in Fig. 6; as well the thermo- LDPE decomposition reaction, except for the MCM-22
gravimetric values obtained of these curves are listed in sample. There was a coke reduction of 100% for the h-Beta
Table 4. and ZSM-5 zeolites, and values equal or superior to 50%
The LDPE thermal cracking under heating rate of for Beta, ZSM-12 and Y zeolites, when compared to the
30 K min-1 showed higher values of initial, final and procedure of 10 K min-1. This fact reveals that the thermal
degradation temperatures, when compared to the same homogenization leads to a better accommodation of the
process under 10 K min-1. This fact can be explained by molecules on the catalyst surface, favoring the bond scis-
the increased amount of energy supplied in heat form, for sion and production of lower molecular mass compounds.
the same increment of time, similar to that reported in the When both zeolitic catalysts with BEA phase are com-
literature [24]. As it was to be expected, similar behavior pared, the elevated external area (333 m2 g-1) and addi-
for the catalytic cracking process employing all zeolites tional porosity of h-Beta zeolite continue to provide an
was observed. enhancement in diffusional pathway for the compounds,
According to the thermogravimetric data obtained from which react in their active sites, justified by the improve-
the curves TG/DTG (Fig. 6), the presence of the catalyst ment in accessibility.
promoted a reduction in the initial temperature up to To investigate the behavior of DTG curves for all zeo-
423 K, when comparing the thermal and catalytic cracking. lites (Fig. 6b), it can be observed that ZSM-5, ZSM-12 and

100
(a) (b)
Rate of 30 K min–1
LDPE
80 LDPE + Beta
Normalized DTG/% K–1

LDPE + hBeta
LDPE + Zeolite Y
LDPE + ZSM-5
60
LDPE + ZSM-12
TG/%

LDPE + MCM-22

40

20

0
473 573 673 773 873 973 473 523 573 623 673 723 773 823
Temperature/K Temperature/K

Fig. 6 TG (a) and DTG (b) curves obtained in the degradation of LDPE with zeolites, under heating rate of 30 K min-1

123
Polyethylene catalytic cracking by thermogravimetric analysis 1949

Table 4 Thermogravimetric values obtained in the degradation of LDPE with zeolites, under heating rate of 30 K min-1
Samples TaInitial/K TaFinal/K Temperature of degradationa/K Mass lossb/mass% Residual massc/mass% Coked/mass%
1st 2nd

LDPE 629 797 765 – 99.9 0.1 –

Beta 482 701 605 649 80.3 18.7 1.0
h-Beta 482 688 599 655 82.3 17.7 0.0
Y zeolite 507 721 704 – 80.3 19.2 0.5
ZSM-5 507 721 677 – 80.3 19.7 0.0
ZSM-12 586 797 765 – 80.3 19.2 0.5
MCM-22 507 731 693 – 82.3 16.6 1.1
a
Obtained in DTG curve
b
Until the temperature of 823 K
c
In the final temperature of 1073 K
d
In the range of 823–1073 K

Y zeolites exhibited only one mass loss event; on the other and superposed on only one mass loss event with Tdegrad
hand, h-Beta and Beta zeolites showed two mass loss equal to 677 K, for the ZSM-5 zeolite. However, for the
events. Opposite behavior was observed to the previous MCM-22 zeolite, it was noticed that the temperature
thermogravimetric procedure for all zeolites, except for the degradation was almost similar (691–693 K), showing that
MCM-22 zeolite, which remained with only a single mass its two-dimensional structure promotes a high contact sur-
loss event. This fact indicates that the thermal homoge- face even without the thermal homogenization procedure.
nization effectively contributed for the modification of And with great interest, it was observed that the degradation
reaction mechanisms in the LDPE degradation. temperature values in two mass loss events for the zeolite
It was possible to note that the degradation temperature to h-Beta and Beta (Table 4) promoted very similar reaction
main mass loss events demonstrated a variation of up to mechanisms, but with different proportions. Both zeolites
433 K (superior to the found value of 393 K for procedure at exhibited Tdegrad values lower than the procedure of
10 K min-1) when compared to thermal cracking. This fact 10 K min-1 for the first mass loss event, emphasizing that
contributed to the statement that the thermal homogenization the h-Beta showed higher proportion. This behavior cor-
supplies different reaction mechanisms and that lower roborates with the elevated textural properties in function of
molecular mass products are preferred. The selectivity for external area and secondary porosity, according to results of
lighter compounds followed an order practically similar to N2 adsorption and desorption.
the previous process: h-Beta [ Beta [ MFI [ MCM-
22 [ Y zeolite [ ZSM-12, except for the superiority of
H-Beta compared to the Beta. This selectivity order corre- Conclusions
lates with the acidity and accessibility properties relevant of
each zeolite, as discussed above. The catalytic cracking of low-density polyethylene over
Due to the rise of heating rate from 10 to 30 K min-1, the different zeolites was evaluated through two distinct pro-
degradation temperature increases in 293 K (Tables 3, 4) for cedures by thermogravimetric analyses, in order to better
the LDPE thermal cracking. From this assumption, it would understand the interactions of contact surfaces between the
be expected a similar behavior for the LDPE catalytic catalyst and the polymer macromolecules. The zeolites
cracking. This occurred to employ the ZSM-12 zeolite, employed in this proposal showed different physicochem-
where the degradation temperature increased from 745 to ical properties, such as chemical composition, acid prop-
765 K, which is characterized as a zeolite with one-dimen- erties, crystalline structure and textural properties.
sional channel systems and has low specific area and acidity. The characterization techniques denoted that all zeolites
However, due to thermal homogenization procedure, the showed a significant degree of crystallinity with distinct
contact surface of the liquid–solid mixture enhanced the zeolitic channels systems, and singular microporous area
interactions of the polymer molecules with the active sites of and volume, where the highest values were to zeolites with
the catalysts. So, the degradation temperature value showed three-dimensional channels systems. Additionally, among
a decrease for the Y zeolite (713–704 K), related to the main the zeolites with large pore diameters, the hierarchical Beta
event. As well, the reaction mechanisms became uniform (h-Beta) showed superior external area due to the use of

123
1950 V. P. S. Caldeira et al.

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