Accepted Manuscript

Synthesis and characterization of Y zeolites from alternative silicon and aluminium

sources

Larissa B. Bortolatto, Rozineide A.A. Boca Santa, Jarina C. Moreira, Diego B.

Machado, Maria Ana P.M. Martins, Márcio A. Fiori, Nivaldo C. Kuhnen, Humberto G.
Riella
PII: S1387-1811(17)30270-6
DOI: 10.1016/j.micromeso.2017.04.030
Reference: MICMAT 8281

To appear in: Microporous and Mesoporous Materials

Received Date: 21 February 2017

Revised Date: 13 April 2017
Accepted Date: 15 April 2017

Please cite this article as: L.B. Bortolatto, R.A.A. Boca Santa, J.C. Moreira, D.B. Machado, M.A.P.M.
Martins, Má.A. Fiori, N.C. Kuhnen, H.G. Riella, Synthesis and characterization of Y zeolites from
alternative silicon and aluminium sources, Microporous and Mesoporous Materials (2017), doi: 10.1016/
j.micromeso.2017.04.030.

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 ACCEPTED MANUSCRIPT
Graphic abstract

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1 Synthesis and characterization of Y zeolites from alternative silicon and aluminium
2 sources
3
a
4 Larissa B. Bortolatto, aRozineide A. A. Boca Santa, aJarina C. Moreira, aDiego B. Machado,
b
5 Maria Ana P. M. Martins, aMárcio A. Fiori, aNivaldo C. Kuhnen, aHumberto G. Riella
6

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a
7 Departamento de Engenharia Química e Engenharia de Alimentos, Universidade Federal de
8 Santa Catarina, 88040-900, Florianópolis – SC, Brasil
b
9 Departamento de Química, Universidade do Sul de Santa Catarina, 88704-090,

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10 Tubarão –SC, Brasil.
11

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12 Abstract. The synthesis of zeolites from alternative sources of silicon and aluminium are
13 promising routes to obtaining zeolitic materials. Such materials are typically applied in

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14 catalytic and adsorptive processes, to obtain new products and at separation and purification
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15 processes. In order to obtain a material with environmentally friendly features, this research
16 was focused on the study of an effective and viable route for the synthesis of Y zeolite from
17 different sources of silicon and aluminium. In this research two types of metakaolin were used:
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18 metakaolin residue (MKR) and metakaolin (MK). An experimental design was carried out as a
19 tool to evaluate the effects of time and temperature parameters and they influence on the
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20 crystallization of zeolites with analytical reagents. The raw materials and the products obtained
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21 were characterized by a series of techniques: X-Ray Fluorescence (XRF), X-Ray Diffraction

22 Spectroscopy (XRD), Fourier Transform Infrared (FTIR), Thermogravimetric Analysis (TG /
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23 DTG), BET surface area analysis, Scanning Electron Microscopy (SEM), Scanning Electron
24 Microscopy with field emission (SEM / FEG) and Transmission Electron Microscopy (TEM).
25 The results obtained from the analysis and characterization showed that the route developed
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26 through hydrothermal reaction for the synthesis of Y zeolite is significantly efficient. The
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27 synthesized zeolites were compared with a commercial zeolite and yielded promising results,
28 thus proving the efficiency of the proposed method. As a result of the experimental planning,
29 time was verified to be a key factor in the crystallinity of the zeolitic material.
30 Keywords. synthesis zeolite Y, waste purification, kaolin, metakaolin.
31
32 1. Introduction
33 The concern with the environment is fundamental nowadays, and thus the presence of
34 environment preservation methods has been increasing significantly. Numerous researches
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1 have been carried out aiming to develop new materials, such as zeolites, which are also known
2 as molecular sieves. Zeolites, due to their physical-chemical and morphological properties, are
3 promising materials which can be applied for the development of highly efficient technologies
4 and contribute for the preservation of the environment [1]. Since, the synthetic zeolites can be
5 produced with different sizes of pores according to the industrial needs of application.
6 In the zeolite's channels and cavities of interconnected molecular dimensions,

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7 compensation ions, water molecules or other adsorbates and salts can be found. The structure
8 of the zeolites imparts the same properties of great importance to the industrial processes [2,3].

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9 Currently more than 119 types of zeolitic structures are known, such as the type Y zeolites,
10 from the class of faujasites, which are of great industrial importance [4].

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11 Y zeolites (ZEO-Y) are formed by aluminosilicate crystals with the aspect of fine
12 powder and characterized by the presence of small micropores in their crystals [5]. The
13 material is employed in several processes, e.g. as selective adsorbents in separation processes
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and in the purification of hydrocarbons, and, in their acid form, are the main component of
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15 catalysts utilized in petrol cracking.
16 The environmental friendly matters related to the production of zeolites also include the
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17 integral or partial reuse of industrial waste, lowering the extraction of raw material and the
18 environmental liability deposited. Among the residues with an economic and technological
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19 potential are the ones derived from the paper sludge, which, depending on the processing,
20 contain cellulose, calcium carbonate and a high concentration of kaolin in their structure [6].
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21 In this context, this research has been elaborated in order to evaluate the best processing
22 conditions for the attainment of ZEO-Y using different materials as the raw material for the
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23 synthesis. The zeolite Y was considered for the study because it presents numerous important
24 applications and an important role in the chemical industry, since it has a highly stable
crystalline structure, a large pore cavity and also large pore surface area [7]. Therefore, a (32)
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26 experimental design was conducted and nine samples of ZEO-Y were synthetized from
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27 analytic reagents (ZEO-Y-AR) with the goal of testing the best temperature and reaction times.
28 From the best results obtained in th e synthesis of ZEO-Y-AR other two synthesis were carried
29 out employing two different kaolins as the source of aluminosilicates, in order to test
30 alternative raw materials for the attainment of ZEO-Y.
31 The kaolins utilized were a natural kaolin (NK) and one derived from paper sludge.
32 Kaolin is a mineral with good properties for zeolite production and has been used in a large
33 number of works [8]. Its microstructure has favorable SiO2 and Al2O3 concentrations for the
34 process, as can be seen in Table 4. Other minerals such as fly ash or mixtures of materials have
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1 been used [8]. However, the choice of the raw material used for the synthesis must consider the
2 future application of the produced zeolite. The kaolins were prepared and submitted to a heat
3 treatment, turning into natural metakaolin (ZEO-Y-NM) and purified metakaolin from
4 industrial white paper residues (ZEO-Y-WM).
5 The research has scientific merit since no other studies including the formulation and
6 synthesis of ZEO-Y from three alternative processes, including the evaluation of metakaolin

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7 derived from residues of the paper sludge , were found in the literature.
8

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9 2. Methodology
10 2.1. Materials

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11 The analytical reagents employed as a source of silicate and aluminium were sodium
12 silicate, Na2SiO3 (28,7% of SiO2, 8,09% of Na2O), produced by Manchester Chemistry, and
13 sodium aluminate, Na2Al2O4, from Sigma-Aldrich, respectively. Sodium hydroxide (NaOH) in
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the form of micropearls, from Vetec, was utilized as a mineralizing agent and as a source of
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15 alkaline metal added to the process, and deionized water was used as a solvent.
16 A sample of commercial Y zeolite, provided by Petrobras' Research and Development
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17 Ceter (CENPES), will be used as a comparison pattern (in a few essays) for the synthetized
18 zeolites.
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19 The natural kaolin and the kaolin-rich industrial residues derived from paper sludge
20 were obtained from companies situated in the southern region of Brazil. Hydrochloric acid
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21 (HCl) was also utilized for the purification of residual kaolin. The methodology used to purify
22 the kaolin obtained from the paper residue was prepared according to the studies of Boca Santa
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23 et al. [9].
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26 2.2. Experimental Design
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27 Based on the International Zeolite Association (IZA) [4] and in the works of Karami
28 and Rohani (2009) [7], a study of the best formulations for the attainment of ZEO-Y was
29 carried out. In order to obtain the best parameters and determine the main variations in
30 temperature and time for the synthesis of ZEO-Y, a three-level and two-variable experimental
31 design (32) totalizing 9 experiments was carried out (as shown in Table 1). The temperature
32 parameters tested for the reaction were from 80 to 120ºC and the reaction time intervals were
33 from 5 to 7 h (Table 1).
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1 The response surfaces and statistical models were computationally obtained with the
2 help of the software STATISTICA 6.0.
3 The responses to evaluate the crystallinity percentage of synthetized ZEO-Y were
4 attained by integrating the area of the crystalline peaks (software Origin) in the X-ray
5 diffractograms (XRD) and subtracting the area regarding the amorphous halo according to the
6 results of each sample. A similar study was carried out by Boca Santa (2016) [8].

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7
8

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9 2.3. Method for the synthesis of ZEO-Y- AR
10 The zeolites were obtained through the hydrothermal synthesis in steel cylindrical

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11 reactors internally coated with polytetraurethane, projected with a storage volume of 35 mL.
12 Initially, 4.07 g of NaOH were dissolved in 19.95 mL of water and kept under stirring.
13 Subsequently, 2.09 g of Na2Al2O4 (sodium aluminate) and 22.72 g of a Na2SiO3 solution
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(28,7% of SiO2, 8,09% of Na2O) were added. The resulting solution was then stirred and left to
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15 stand for 24 h at 25 ºC. In a second stage 0.14 g of NaOH and 13.09 g of Na2Al2O4 were
16 dissolved in 130.97 g of deionized water, with a subsequent addition of 142.43 g of a Na2SiO3
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17 solution (28,7% of SiO2, 8,09% of Na2O). At the end of this stage 16.50 g of the solution
18 prepared in the first stage were added, resulting in a gel which was left to stand for 24 h (a
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19 mandatory ageing step for the formation of ZEO-Y-AR). After this period the gel was
20 transferred to the reactor and heated (hydrothermal treatment). After the predetermined time
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21 frames the solidified product was cooled and rinsed with water until reaching a pH close to 9.
22 The resulting material was then centrifuged and oven-dried at 60 ºC for 24 h.
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23 The methodology described was carried out for the synthesis of the nine samples of
24 ZEO-Y-AR, with respective time spans and temperatures according to the experimental design
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25 described in Table 1.
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27 2.4. Methods for the synthesis of ZEO-Y-NM and ZEO-Y-WM

28 The residue obtained from pumping industries, from white paper sludge , contain in
29 their formulation calcium carbonate, kaolin and cellulose. For the utilization of the kaolin
30 present in the residue a separation of the three components was carried out. The material was
31 first subjected to combustion in a muffle oven at, approximately, 400 ºC for 2h, for the
32 removal of cellulose, then rinsed in hydrochloric acid (HCl). The methodology adopted was
33 similar to the procedures employed by Boca Santa et al. (2013) [6], in which 1.8 M of HCl
34 were utilized for each 150 g of in natura residual material. After the acidic rinse, the material
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1 was rinsed with water and filtered in a vacuum pump. The remaining kaolin was oven-dried at
2 100 ºC for 24 h.
3 The kaolin obtained from the residue and the natural kaolin were both subjected to
4 calcination in a muffle at 850 ºC for 2 h for the transformation of crystalline kaolin into
5 amorphous metakaolin through desidroxilation [9]. According to Boca Santa et al. [9], in
6 temperatures of 800, 850 and 900 °C there is no significant variation in the process.

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7 Temperatures above 900 ° C can cause formation of crystalline structures in the material.
8 The methodology employed for the synthesis of ZEO-Y-NM and ZEO-Y-WM

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9 consisted in the following procedures: 10 g of metakaolin and 15 g of sodium hydroxide were
10 dispersed in 100 g of deionized water and kept under stirring for 30 min, with a

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11 metakaolin/NaOH ratio of 1/1.5 in mass units, according to a test performed by Htay et al.
12 (2008) [10]; to adjust the Si/Al ratio to 2.5 [11] approximately 14 g of sodium silicate
13 (Na2SiO3) were dispersed in 50 g of deionized water and the mixture was stirred for 30 minutes
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for gel formation; the material was left to stand for 24 h and, subsequently, was transferred to
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15 the steel reactor and stored in an oven at 100 ºC for 6 h (best temperature and time obtained
16 with ZEO-Y-AR). After this period the material was first rinsed with water to lower its Ph,
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17 then centrifuged, and the reaction product was oven-dried at 60 ºC for 24 h.

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19 2.5. Characterization of the materials

20 In the present study both the kaolin and the zeolite were characterized by X-Ray
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21 Diffraction (XRD) technique in a Philips diffractometer (model X’pert) and X-Ray

22 Fluorescence (XRF) technique in a Philips spectrophotometer (model PW 2400). The
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23 identification of functional groups was attained by Fourier Transform Infrared Spectroscopy

24 (FTIR) in a Shimadzu FTIR Spectrophotometer (model IR Prestige-21) and, to evaluate the
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25 microstructure of the materials, some samples underwent Scanning Electron Microscopy

26 (SEM), which was carried out in two devices: one from Philips (model XL30) and one from
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27 Jeol (model JSM-6390LV). The specific area of the synthetized zeolites was determined by the
28 Brunauer, Emmet and Teller (BET) method in a Quantachrome Autosorb-1 device, employing
29 the multipoint method with data from nitrogen adsorption isotherms at 77K in vapor pressures
30 ranging between 0.01 and 0.99.
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32 3. Results and discussion
33
34 3.1. Characterization of ZEO-Y-AR
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1 3.1.1. XRD of ZEO-Y-AR
2 The samples synthesized from the analytical reagents (ZEO-Y-AR) in temperatures
3 from 80 to 120 ºC in time intervals from 5 to 7 h were analysed by XRD technique. The results
4 are described in Figure 1.
5 Synthesized ZEO-Y-AR (Figure 1 (9), identified with the inscription (Y)) presents
6 peaks corresponding to the criteria of commercial Y zeolite, with intense diffraction peaks at

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7 2θ = 6.20o; 10.30o; 11.80o; 15.80o; 18.60o; 20.0o; 23.56o; 26.93o; 31.20o; 34.00o and 37.60o.
8 According to the pattern obtained by IZA (2014) [4] with the JCPDS 43-0168 form, such

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9 peaks are typical of sodium Y zeolite.
10 The results indicated that at certain temperatures and heating times some samples did

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11 not present the characteristics required for being considered a type Y zeolite, while others did
12 not react, or reacted in small proportions, resulting in the non-formation of the crystalline
13 peaks pertaining to the type Y zeolite.
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15 3.1.2. Evaluation of the factorial 3² design
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17 The XRD results from all samples were subjected to integral calculations through the
18 software Origin to evaluate de crystallinity percentage. The percentage was attained by
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19 subtracting the area of the peaks pertaining to ZEO-Y and dividing by the total area. According
20 to the zealotical standards it was possible to observe the samples with the greatest conversion
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21 percentage of the reagents into a crystalline material (ZEO-Y-AR).

22 The percentages obtained in each sample, which are described in Table 2, were utilized
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23 as response factor for the 3² factorial design presented in Table 1.

24 The crystallinity exhibited dispersion in the results, with values between 42.72 and
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25 94.25%. Table 3 shows the variance analysis, ANOVA, which aimed to verify significant
26 differences between the averages and the factors that may influence a dependant variable over
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27 crystallinity. It is possible to observe that the F values are significant (considering p < 0.5).
28 Furthermore, it can be inferred that the interaction between the variables temperature and time
29 (linear terms) has a large influence on the model composition, as is confirmed by the quadratic
30 sum (QS). Thus, the time factor (linear term) and temperature factor (linear term) are defined
31 as more interactive factors to the model. The model obtained demonstrated a good correlation
32 with its data, since the value of R2 is 0.93.
33 The Pareto Diagram, illustrated in Figure 2, shows the variables’ effect values.
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1 Zhang et al. (2014) [12] observed in their study that time is the most significant
2 variable for the crystallinity in the synthesis of the zeolite. Melo et al. (2012) [13] highlight
3 that time is an important parameter to be considered, since, generally, crystallinity increases
4 over time.
5 The response surface of the model applied to crystallinity is presented in Figure 3.
6 The point of greatest crystallinity for ZEO-Y is close to the central point from the

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7 planning (time of 6 hours and temperature of 100 ºC), confirming the Y zeolite’s synthesis
8 conditions presented by IZA.

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9 Thus, for the synthesis of ZEO-Y-IR and ZEO-Y-WM a temperature of 100 ºC and a
10 period of 6 hours were selected.

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12 3.2. Characterization of Waste (WM) and Natural Metakaolin (NM) and synthetized
13 ZEO-Y
14 3.2.1. FTIR spectres of WM and NM
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15 Figure 4 presents the infrared absorption spectres in the WM (a) and NM (b) samples.
16 The bands observed near 3459 cm-1 represent the OH group. These molecules are able to
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17 vibrate in different ways and involve symmetrical and asymmetrical stretching or flexion
18 combinations. The band at 2350 cm-1 is attributed to carbon dioxide [14]. For the metakaolin
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19 obtained from the waste the sample should, ideally, contain a few traces of cellulose, due to the
20 band at 1636 cm-1, which represents the OH group present in cellulose. The bands at 1083
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21 cm−1, 801 cm−1and 464 cm−1 represent the modifications of kaolin into metakaolin. The
22 absorptions occurring at 1083 and 1084 cm-1 correspond to the Si-O-Si interactions, while the
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23 bands at 800 and 801 cm−1 correspond to the Al-O interactions, and the ones at 465 and 464
24 cm−1 are related to a O-Si-O coupling, characteristic of kaolins [15]. The width of the three last
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25 bands suggests that the structure is disorderly [16].

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27 3.2.2. Results of XRD analysis of WM and NM

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29 Through the diffractograms in Figure 5 (a) natural kaolin and (c) paper sludge kaolin it
30 is possible to verify that the kaolins present crystalline phases corresponding to calcite (C),
31 kaolinite (K), cellulose (P) and quartz (Q). After the heat treatment, a transformation of kaolin
32 into metakaolin (Fig.5 (b) natural and (d) paper sludge) is observed.. The corresponding peaks
33 disappear, due to the rupture of the crystalline structure, resulting in amorphous metakaolinite,
34 which is fundamental for the synthesis of zeolites [11].
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1 The diffractograms in Fig. 5 (c and d) correspond to the metakaolin derived from the
2 waste of paper pulping, in which it is possible to observe that the acid rinse with HCl and the
3 calcination for the combustion of cellulose were effective to obtain purified kaolin, as was
4 confirmed by the results in oxide presented in Table 3.
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6 3.2.3. Results in oxides obtained from the samples of WM, NM and synthesised

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7 ZEO-Y.
8 Table 4 reports the results of the chemical analysis conducted by XRD in natural

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9 metakaolin (NM), metakaolin derived from the waste of white paper pulping (WM) and
10 samples of ZEO-Y-IR, ZEO-Y-IM and ZEO-Y-WM.

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11 From the results of chemical analysis, presented on Table 4 (a and b), it is possible to
12 observe that, for both metakaolin samples, silicone oxide (SiO2) and aluminium oxide (Al2O3)
13 are the major components, corresponding to 90% of the material. Iron oxide (Fe2O3) and
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calcium oxide (CaO) present greater concentration in the paper sludge metakaolin. The
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15 SiO2/Al2O3 ratio is observed to be close to 1.0 and, since for the synthesis of Y zeolite the most
16 favorable ratio is 2.0, an adjustment was necessary in silicon concentration.
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17 Table 4 (c) presents the result of a chemical analysis conducted in a standard

18 (commercial) sample (ZEO-Y-S), while the data described in Table 4 (d) correspond to the
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19 oxides obtained from the sample synthesized for experiment nine (ZEO-Y-IR). The oxide
20 percentages observed in ZEO-Y-IR are close to the percentage values of the commercial
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21 zeolite. The stoichiometric Si/Al ratios are of 4.21 for ZEO-Y-S and 3.10 for ZEO-Y-IR. The
22 values are in accordance with the literature for ZEO-Y [1]. According to Breck (1984) [2], for
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23 ZEO-Y the Si/Al ratio is bigger than 1.5, whereas Meier and Olson (1992) [17] found this ratio
24 to vary from, approximately, 2.0 to 8.0.
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25 The XRF results in Table 4 (e and f) were collected form the ZEO-Y-WM and ZEO-Y-
26 NM samples, respectively. In the WM sample a significant increase in titanium and iron
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27 concentrations stands out. According to Hildebrando (2012) [18], the presence of impurities in
28 the starting materials, such as those previously mentioned and, specially, iron-based
29 substances, are prone to causing disruptions during the synthesis reactions. The latter tend to
30 remain insoluble during the crystallization stage, leading to a precipitation of undesired
31 species, such as insoluble silicates, thus interfering in the zeolites’ formation process.
32 The Si/Al ratio was of 2.43 for ZEO-Y-WM and 2.26 for ZEO-Y-NM. These
33 composition ratios are characteristic of ZEO-Y [19].
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1 The zeolites produced are essentially composed of silicon and aluminium, with a
2 smaller amount of sodium, characteristic of NaY zeolites.
3
4 3.2.4. Diffractograms of ZEO-Y-WM and ZEO-Y-NM.
5 Through the crystalline peaks in the diffractograms presented in Figure 6 the formation
6 of ZEO-Y can be observed, as listed on the JCPDS 43-0168 sheet. In the diffractogram

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7 pertaining to ZEO-Y-WM (Figure 6a) it is also possible to observe the presence of crystalline
8 peaks corresponding to type P zeolite (ZEO-P). According to Huo et al. (2013) [20] the

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9 formation of ZEO-P can occur in more prolonged synthesis. Farzanet et al. (1989) [21] state
10 that the formation of ZEO-Y might vary depending on the composition of the gel formed in the

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11 beginning of the process and, mostly, due to a temperature variation in the synthesis and the
12 crystallization time. Freitas et al. (2011) [22] add that the P phase is more stable than the Y
13 phase, and can occur in synthesis stemming from metakaolin. According to Liu et al. (2003)
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[23] the control of reaction temperature is an important factor for obtaining ZEO-Y with a high
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15 purity level, since crystallization at lower temperatures favors the synthesis of metastable
16 zeolitic materials, i.e. faujasites, while high temperatures tend to form more
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17 thermodynamically stable phases. Thus, this study initially prioritized the knowledge of the
18 best temperature and time for the synthesis, in order to obtain ZEO-Y of commercial quality.
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19 An increase in crystallization temperature can affect the properties of the reactional gel and
20 influence particle size and, in some cases, reduce the dimensions and accelerate the diffusion
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21 between particles.
22 Through the calculation of the areas of the XRD peaks a crystallinity of 75 and 78%
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23 was detected for ZEO-Y-WM (Fig. 6a) and ZEO-Y-NM (Fig. 6b), respectively. These values
24 were considered significant for the production of ZEO-Y from matakaolin, especially if
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25 derived from industrial waste.

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27 3.2.5. FTIR spectres of ZEO-Y-WM and ZEO-Y-NM

28 The spectres of Figure 7a (ZEO-Y-AR) present bands close to the regions of 3472 cm-1
29 and 1640 cm-1, corresponding to the vibrations in the water molecules contained in the
30 zeolites’ cavities (KULPRATHIPANJA, 2010) [24]. The presence of a zeolitic material was
31 confirmed through the band 1005 cm-1, which is located near a band (1000 cm-1) characteristic
32 of the Si-O-Al bonding of the tetrahedral structure TO4 (T = S or Al) of primary construction
33 units [25]. The main vibrational characteristics regarding the crystallization of the zeolites can
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1 be identified by the bands in the region of 710, 570 and 457 cm-1, and characterize the
2 crystallinity of the zeolites.
3 According to Huo et al. (2013) [20], frequencies observed near 1005 cm-1 are attributed
4 to the asymmetrical narrowing of the Si-O or Al-O bondings, while vibrations at 457 and 460
5 cm-1are related to the deflection mode of these same bondings, and vibrations from 570 to 710
6 cm-1 are attributed to the symmetrical narrowing of the internal tetrahedrons of ZEO-Y.

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7 In the FTIR spectres of the samples synthesized from metakaolins, presented in Figure
8 7 (b – c), vibrational bands can be observed in the wavelengths of 3470 and 1640 cm-1

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9 regarding the functional groups OH, which are attributed to water molecules [19].
10 Furthermore, vibrational frequencies around 1005, 1000, 565, 563, 467 and 461 cm-1 suggest

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11 that a formation of zeolitic materials occurred in the ZEO-Y-WM and ZEO-Y-NM samples,
12 involving structural changes that can be observed by a change in length when compared to the
13 matakaolin samples (Figure 4), especially in a shift of the regions close to 1083 cm-1 to 1005
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cm-1. These changes can be related to the formation of zeolitic structures, with similar
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15 characteristics reported by Htay and Oo (2008) [10].
16 The occurrence of the referred vibrations can also be observed in the spectre of Figure
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17 7d, regarding the commercial zeolite employed as standard.

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19 3.2.6. Results of the SEM analysis

20 The image in Figure 8 (a) concerns a ZEO-Y-S sample, which was employed in this
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21 study as a comparison to the ZEO-Y produced from different materials. An agglomeration of

22 the ZEO-Y-AR particles can be observed (Fig. 8b) due to the simultaneous growth of the
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23 nuclei. The synthesized zeolites present smaller crystallite sizes and greater dispersion in
24 particle size when compared to ZEO-Y-S. This can also explain the increase in the surface area
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25 obtained through BET technique.

26 ZEO-Y-NM (Fig. 8c) presented more isolated crystals than ZEO-Y-WM (Fig. 8d),
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27 probably due to an impurity in the waste material. . The micrographs of ZEO-Y presented an
28 octahedral morphology similar to those present in the study conducted by Breck (1984) [2] and
29 Kovo et al. (2009) [26]. Htay and Oo (2008) [10] also obtained ZEO-Y with the same
30 characteristics in their studies.
31
32 3.2.7. Results of the specific area essays by the BET method
33 In Table 5 are presented the values of specific area determined by the BET method in
34 the synthesized zeolites and in the standard sample.
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1 Zeolites show distinct superficial areas, indicating a variation in the density of
2 micropores. According to Yates (1968) [27], the increase in specific area contributes to the ion
3 exchange capacity, high adsorption and catalysis efficiency, due to the presence of spacious
4 cavities in the crystalline structure. ZEO-Y-AR (sample 9), synthesized from analytic reagents,
5 presented a surface area similar to ZEO-Y-S. The results of the specific areas obtained in the
6 essay are according to the results found in the literature for type Y zeolite (RAHMAN et al.,

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7 2012) [28].
8 ZEO-Y-NM was the sample which presented the largest surface area in relation to the

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9 ZEO-Y-WM sample, indicating the presence of bigger proportions of micropores. The
10 increased area indicates that there was a good crystallinity of this material, as well as a larger

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11 quantity of zeolitic structure formed through the synthesis. This value of BET area, around
12 554.9 m2. g-1, is superior to the 246.7 m2.g-1 obtained by Liu et al. (2003) [23], who synthesized
13 Y zeolite with 75% crystallinity from metakaolin. Furthermore, the zeolite from metakaolin
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derived from industrial waste presented the smallest specific area, possibly due to the
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15 impurities contained in the material.
16 The results obtained by the BET essay are according to those of the morphology
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17 obtained by the SEM technique.

18
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19 4. Conclusion
20 From the synthesis of ZEO-Y employing analytical reagents as a silicon and aluminium
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21 source, it was possible to verify that the synthesis method based on IZA standart was
22 extremely adequate to the attainment of the faujisite phase (Y zeolite). The XRD analysis
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23 showed the formation of a ZEO-Y-AR from analytical reagents with an elevated crystallinity
24 degree, which is according to the standards found for Y zeolite. The experimental design
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25 permitted the evaluation of the importance of the variables time and temperature in the process,
26 as well as the attainment of parameters to perform the substitution of the analytical reagents by
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27 alternative materials for the synthesis of ZEO-Y, including natural metakaolin and metakaolin
28 derived from paper sludge..
29 The SEM allowed the observation of the growth of crystals obtained in the synthesized
30 samples from analytical reagents and from two kaolins, and the crystals were quite similar to
31 those of the standard sample used as a reference.
32 The production of ZEO-Y in industrial scale from Brazilian kaolins can benefit several
33 different sectors. The reproduction through different materials led to the conclusion that ZEO-
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1 Y, in the synthesis conditions employed, can be produced according to the necessities from
2 other raw materials as a source of aluminosilicates.
3
4 Acknowledgments
5 The authors wish to thank CAPES, LCME and UFSC for the support to this research.
6

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7 5. References
8

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9 [1] G.G. Pace, A.R. Montes, G.F. Rodrigues. Zeolitas: características, propriedades y
10 aplicaciones industriales. Editorial Innovacín Tecnológica. Facultad de Ingeniería UCV.
11 Madri. 2000.

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13 [2] D.W. Breck. Zeolite molecular sieves. John Wiley & Sons. Inc. New York. 1984.
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15 [3] A.B Luz, A.R. Campos, E.A. Carvalho, L.C. Bertolino. Caulim. Rio de Janeiro:

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16 CETEM/ Rochas e Minerais Industriais: Usos e Especificações. (2005) 231-262.
17
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18 [4] IZA. Iza synthesis commission – fau linde type y. D. M. Ginter. A. T. Bell. C. J.
19 Radke. 2016.
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21 [5] J.R. Scheiber. L.A. Lima. P.H.L. Quintela. E.L. Silva. M.G.F. Rodrigues. Síntese da
22 zeólita e sua utilização como adsorvente para remoção de contaminantes orgânicos em
23 efluentes líquidos. in: X Encontro Brasileiro sobre Adsorção. EBA. Guarujá – SP. 2014.
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25 [6] R.A.A. Boca Santa, A.M. Bernardin, H.G. Riella, N.C. Kuhnen. Geopolymer Synthetized
26 from Bottom Coal Ash and Calcined Paper Sludge. J. Clean. Prod. 57 (2013) 302-307.
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27
28 [7] D. KARAMI, S. ROHANI. Synthesis of pure zeolite Y using soluble silicate, a two-
29 level factorial experimental design. Chem. Eng. Process. 48 (2009) 1288–1292. atualizada
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30
31 [8] R.A.A. Boca Santa, C. Soares, H.G. Riella. Geopolymers with a high percentage of
32 bottom ash for solidification/immobilization of different toxic metals. J. Hazard. Mater. 318
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33 (2016) 145–153.atualizada
34
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35 [9] R. A. A. Boca Santa, J. C. Moreira, L. L. Coelho, N. C. Kuhnen, H. G. Riella.

36 Recovery techniques of industrial waste stemmed from white paper pulping process to obtain
37 metakaolin. Int. J. Miner Process 161 (2017) 59–64.
38 [10] M.M. Htay, M.M. Oo. Preparation of zeolite Y catalyst for petroleum cracking.
39 World Academy of Sci. Eng. and Technology. 24 (2008) 108-114.
40
41 [11] E.A. Hildebrando, R.S. Angelica, F.R. Neves, F.R. Valenzuela-Diaz. Síntese de
42 zeólita do tipo Faujasita a partir de um rejeito de caulim. Cerâmica. 58 (2012) 453-458.
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44 [12] X. Zhang, D. Tong, W. Jia, D. Tang, X. Li, R. Yang. Studies on room-temperature
45 synthesis of zeolite NaA. Mater Res Bull. 52 (2014) 96 – 102.
46
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1 [13] C.R. Melo, H.G. Riella, N.C. Kuhnen, E. Angioletto, A.R. Melo, A.M. Bernardin.
2 M. R. Rocha, L. Silva. Synthesis of 4A zeolites from kaolin for obtaining 5A zeolites through
3 ionic exchange for adsorption of arsenic. Mater. Sci. Eng. B. 177 (2012) 345–349.
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5 [14] B.C. Smith. Fundamentals of Fourier Transform Infrared spectroscopy. Flórida -
6 USA: CRC press, 1996.
7
8 [15] J.C. Moreira. Síntese e caracterização da zeólita 5A por troca iônica a partir de um
9 resíduo da indústria de papel. Master Thesis. Department of Chemical Engineering and Food

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10 Engineering. Federal University of Santa Catarina. Florianópolis- SC. 2013.
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12 [16] A.G. San Cristóbal, R. Castelló, M.A.M. Luengo, C. Vizcayno. Zeolites prepared

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13 from calcined and mechanically modified kaolins: A comparative study. Appl. Clay Sci. 49
14 (2010) 239-246.
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16 [17] W.M. Meier, D.H. Olson, Atlas of Zeolite Structure Types 3ed. rev. London,
17 Butterworth; Heinemann, 1992.
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19 [18] E.A. HILDEBRANDO, Síntese de zeólita do tipo faujasita utilizando rejeito de

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20 caulim da Amazônia como fonte de silício e alumínio: Aplicação como adsorvente. Thesis.
21 University of São Paulo. São Paulo - SP. 2013.
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23 [19] Q. Li, Y. Zhang, Z. Cao, W. Gao, L. Cui. Inuence of synthesis parameters on the
24 crystallinity and Si/Al ratio of NaY zeolite synthesized from kaolin. Pet. Sci. China University
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25 of Petroleum (Beijing). 7 (2010) 403-409.

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27 [20] Z. Huo, X. Xu, Z. Lv, J. Song, M. He, Z. Li, Q. Wang, L. Yan, Y. Li. Thermal study of
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28 NaP zeolite with different morphologies. J. Therm. Anal. Calorim. 111 (2013) 365-369.
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30 [21] F. Farzanet, M.K. Oskooie, M.M.A. Nejad. The synthesis of zeolites A, X and HS
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31 from natural iranian kaolinite and the study of the transformation of zeolites X to HS and
32 zeolites Y to P, by x-ray diffraction and scanning electron microscopy. J. Sci. Islamic Replubic
33 Iran. 1 (1989) 23-28.
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35 [22] V.A.A. Freitas, J.S.V. Lima, P.R.C. Couceiro. Caracterização e análise estrutural
36 da Hidroxisodalita sintetizada a partir de amostras de solo amazônico. Cerâmica. 57 (2011)
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37 281-287.
38
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39 [23] X. Liu, Z. Yan, H. Wang, Y. Luo. In situ synthesis of NaY zeolite with coal based
40 kaolin. J. Nat. Gas Chem. 12 (2003) 63-70.
41
42 [24] S. Kulprathipanja. Zeolites in Industrial Separation and Catalysis. Germany:
43 Wiley-VCH, 2010.
44
45 [25] N. Taufiqurrahmi, A. R. Mohamed, S. Bhatia. Nanocrystalline Zeolite Y.
46 Synthesis and Characterization. Mat. Sci Engineering, 17 (2011) 1-6.
47
48 [26] A.S. Kovo, O. Hernandez, S. M. Holmes. Synthesis and characterization of zeolite
49 Y and ZSM-5 from nigerian ahoko kaolin using a novel, lower temperature, metakaolinization
50 technique. J. Mater. Chem. 19 (2009) 6207-6212.
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1
2 [27] D.J.C. Yates, Studies on the surface area of zeolites, as determined by physical
3 adsorption and x-ray crystallography. Can. J. Chemistry. 46 (1968) 1695-1701.
4
5 [28] M.M. Rahman, M.B. Awang, A.N.M. Yusof. Preparation, characterization and
6 application of zeolite-Y (Na-Y) for water fitration. Aust. J. Basic Appl. Sci. 6 (2012) 50-55.
7
8 Table 1. Factorial planning 3².

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9 Table 2. Percentages obtained by integrating the area of the crystalline peaks for the 9
10 samples of synthesized ZEO-Y-AR.

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11 Table 3. Analysis of variance values (ANOVA), model with quadratic correlation (R2)
12 of 0.93.

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13 Table 4. Composition in oxides of WM (a), NM (b), a standard sample (ZEO-Y-S) (c)
14 and synthesized (d) ZEO-Y-AR (sample 9), (e) ZEO-Y-WM and (f) ZEO-Y-NM.
15 Table 5. Specific surface area of synthesized ZEO-Y and standard sample.
16
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17 Figure 1. Diffractograms of the nine samples synthesized with analytical reagents
18 Figure 2. Pareto Diagram of the effects for the crystallinity model.
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19 Figure 3. Graph of response surface for the crystallinity of ZEO-Y-AR

20 Figure 4. FTIR of the samples WM and NM.
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21 Figure 5. XRD of (a) natural kaolin and (b) metakaolin from natural kaolin, and kaolin
22 from paper sludge (c) and metakaolin from paper sludge (d). .
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23 Figure 6. Spectres of DRX of synthesized ZEO-Y-WN (a) and ZEO-Y-NM (b).

24 Figure 7. FTIR of the samples of ZEO-Y-AR (a); ZEO-Y-WM (b); ZEO-Y-NM (c) and
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25 ZEO-Y-S.
26 Figure 8. Micrographies obtained in SEM of the following materials: natural kaolin (a);
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27 NM (b); ZEO-Y-S (c); ZEO-Y-AR (sample 9) (d); ZEO-Y-WN (e) and ZEO-Y-NM (f).
28
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29
30
31
32
33
34
35
36
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1 Synthesis and characterization of Y zeolites from alternative silicon and aluminium
2 sources
3
a
4 Larissa B. Bortolatto, aRozineide A. A. Boca Santa, aJarina C. Moreira, aDiego B. Machado,
b
5 Maria Ana P. M. Martins, aMárcio A. Fiori, aNivaldo C. Kuhnen, aHumberto G. Riella
6

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a
7 Departamento de Engenharia Química e Engenharia de Alimentos, Universidade Federal de
8 Santa Catarina, 88040-900, Florianópolis – SC, Brasil
b
9 Departamento de Química, Universidade do Sul de Santa Catarina, 88704-090,

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10 Tubarão –SC, Brasil.
11

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12 Abstract. The synthesis of zeolites from alternative sources of silicon and aluminium are
13 promising routes to obtaining zeolitic materials. Such materials are typically applied in

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14 catalytic and adsorptive processes, to obtain new products and at separation and purification
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15 processes. In order to obtain a material with environmentally friendly features, this research
16 was focused on the study of an effective and viable route for the synthesis of Y zeolite from
17 different sources of silicon and aluminium. In this research two types of metakaolin were used:
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18 metakaolin residue (MKR) and metakaolin (MK). An experimental design was carried out as a
19 tool to evaluate the effects of time and temperature parameters and they influence on the
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20 crystallization of zeolites with analytical reagents. The raw materials and the products obtained
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21 were characterized by a series of techniques: X-Ray Fluorescence (XRF), X-Ray Diffraction

22 Spectroscopy (XRD), Fourier Transform Infrared (FTIR), Thermogravimetric Analysis (TG /
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23 DTG), BET surface area analysis, Scanning Electron Microscopy (SEM), Scanning Electron
24 Microscopy with field emission (SEM / FEG) and Transmission Electron Microscopy (TEM).
25 The results obtained from the analysis and characterization showed that the route developed
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26 through hydrothermal reaction for the synthesis of Y zeolite is significantly efficient. The
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27 synthesized zeolites were compared with a commercial zeolite and yielded promising results,
28 thus proving the efficiency of the proposed method. As a result of the experimental planning,
29 time was verified to be a key factor in the crystallinity of the zeolitic material.
30 Keywords. synthesis zeolite Y, waste purification, kaolin, metakaolin.
31
32 5. Introduction
33 The concern with the environment is fundamental nowadays, and thus the presence of
34 environment preservation methods has been increasing significantly. Numerous researches
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1 have been carried out aiming to develop new materials, such as zeolites, which are also known
2 as molecular sieves. Zeolites, due to their physical-chemical and morphological properties, are
3 promising materials which can be applied for the development of highly efficient technologies
4 and contribute for the preservation of the environment [1]. Since, the synthetic zeolites can be
5 produced with different sizes of pores according to the industrial needs of application.
6 In the zeolite's channels and cavities of interconnected molecular dimensions,

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7 compensation ions, water molecules or other adsorbates and salts can be found. The structure
8 of the zeolites imparts the same properties of great importance to the industrial processes [2,3].

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9 Currently more than 119 types of zeolitic structures are known, such as the type Y zeolites,
10 from the class of faujasites, which are of great industrial importance [4].

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11 Y zeolites (ZEO-Y) are formed by aluminosilicate crystals with the aspect of fine
12 powder and characterized by the presence of small micropores in their crystals [5]. The
13 material is employed in several processes, e.g. as selective adsorbents in separation processes
14
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and in the purification of hydrocarbons, and, in their acid form, are the main component of
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15 catalysts utilized in petrol cracking.
16 The environmental friendly matters related to the production of zeolites also include the
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17 integral or partial reuse of industrial waste, lowering the extraction of raw material and the
18 environmental liability deposited. Among the residues with an economic and technological
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19 potential are the ones derived from the paper sludge, which, depending on the processing,
20 contain cellulose, calcium carbonate and a high concentration of kaolin in their structure [6].
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21 In this context, this research has been elaborated in order to evaluate the best processing
22 conditions for the attainment of ZEO-Y using different materials as the raw material for the
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23 synthesis. The zeolite Y was considered for the study because it presents numerous important
24 applications and an important role in the chemical industry, since it has a highly stable
crystalline structure, a large pore cavity and also large pore surface area [7]. Therefore, a (32)
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25
26 experimental design was conducted and nine samples of ZEO-Y were synthetized from
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27 analytic reagents (ZEO-Y-AR) with the goal of testing the best temperature and reaction times.
28 From the best results obtained in th e synthesis of ZEO-Y-AR other two synthesis were carried
29 out employing two different kaolins as the source of aluminosilicates, in order to test
30 alternative raw materials for the attainment of ZEO-Y.
31 The kaolins utilized were a natural kaolin (NK) and one derived from paper sludge.
32 Kaolin is a mineral with good properties for zeolite production and has been used in a large
33 number of works [8]. Its microstructure has favorable SiO2 and Al2O3 concentrations for the
34 process, as can be seen in Table 4. Other minerals such as fly ash or mixtures of materials have
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1 been used [8]. However, the choice of the raw material used for the synthesis must consider the
2 future application of the produced zeolite. The kaolins were prepared and submitted to a heat
3 treatment, turning into natural metakaolin (ZEO-Y-NM) and purified metakaolin from
4 industrial white paper residues (ZEO-Y-WM).
5 The research has scientific merit since no other studies including the formulation and
6 synthesis of ZEO-Y from three alternative processes, including the evaluation of metakaolin

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7 derived from residues of the paper sludge , were found in the literature.
8

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9 6. Methodology
10 6.1. Materials

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11 The analytical reagents employed as a source of silicate and aluminium were sodium
12 silicate, Na2SiO3 (28,7% of SiO2, 8,09% of Na2O), produced by Manchester Chemistry, and
13 sodium aluminate, Na2Al2O4, from Sigma-Aldrich, respectively. Sodium hydroxide (NaOH) in
14
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the form of micropearls, from Vetec, was utilized as a mineralizing agent and as a source of
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15 alkaline metal added to the process, and deionized water was used as a solvent.
16 A sample of commercial Y zeolite, provided by Petrobras' Research and Development
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17 Ceter (CENPES), will be used as a comparison pattern (in a few essays) for the synthetized
18 zeolites.
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19 The natural kaolin and the kaolin-rich industrial residues derived from paper sludge
20 were obtained from companies situated in the southern region of Brazil. Hydrochloric acid
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21 (HCl) was also utilized for the purification of residual kaolin. The methodology used to purify
22 the kaolin obtained from the paper residue was prepared according to the studies of Boca Santa
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23 et al. [9].
24
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25
26 6.2. Experimental Design
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27 Based on the International Zeolite Association (IZA) [4] and in the works of Karami
28 and Rohani (2009) [7], a study of the best formulations for the attainment of ZEO-Y was
29 carried out. In order to obtain the best parameters and determine the main variations in
30 temperature and time for the synthesis of ZEO-Y, a three-level and two-variable experimental
31 design (32) totalizing 9 experiments was carried out (as shown in Table 1). The temperature
32 parameters tested for the reaction were from 80 to 120ºC and the reaction time intervals were
33 from 5 to 7 h (Table 1).
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1 The response surfaces and statistical models were computationally obtained with the
2 help of the software STATISTICA 6.0.
3 The responses to evaluate the crystallinity percentage of synthetized ZEO-Y were
4 attained by integrating the area of the crystalline peaks (software Origin) in the X-ray
5 diffractograms (XRD) and subtracting the area regarding the amorphous halo according to the
6 results of each sample. A similar study was carried out by Boca Santa (2016) [8].

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7
8

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9 6.3. Method for the synthesis of ZEO-Y- AR
10 The zeolites were obtained through the hydrothermal synthesis in steel cylindrical

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11 reactors internally coated with polytetraurethane, projected with a storage volume of 35 mL.
12 Initially, 4.07 g of NaOH were dissolved in 19.95 mL of water and kept under stirring.
13 Subsequently, 2.09 g of Na2Al2O4 (sodium aluminate) and 22.72 g of a Na2SiO3 solution
14
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(28,7% of SiO2, 8,09% of Na2O) were added. The resulting solution was then stirred and left to
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15 stand for 24 h at 25 ºC. In a second stage 0.14 g of NaOH and 13.09 g of Na2Al2O4 were
16 dissolved in 130.97 g of deionized water, with a subsequent addition of 142.43 g of a Na2SiO3
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17 solution (28,7% of SiO2, 8,09% of Na2O). At the end of this stage 16.50 g of the solution
18 prepared in the first stage were added, resulting in a gel which was left to stand for 24 h (a
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19 mandatory ageing step for the formation of ZEO-Y-AR). After this period the gel was
20 transferred to the reactor and heated (hydrothermal treatment). After the predetermined time
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21 frames the solidified product was cooled and rinsed with water until reaching a pH close to 9.
22 The resulting material was then centrifuged and oven-dried at 60 ºC for 24 h.
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23 The methodology described was carried out for the synthesis of the nine samples of
24 ZEO-Y-AR, with respective time spans and temperatures according to the experimental design
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25 described in Table 1.
26
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27 6.4. Methods for the synthesis of ZEO-Y-NM and ZEO-Y-WM

28 The residue obtained from pumping industries, from white paper sludge , contain in
29 their formulation calcium carbonate, kaolin and cellulose. For the utilization of the kaolin
30 present in the residue a separation of the three components was carried out. The material was
31 first subjected to combustion in a muffle oven at, approximately, 400 ºC for 2h, for the
32 removal of cellulose, then rinsed in hydrochloric acid (HCl). The methodology adopted was
33 similar to the procedures employed by Boca Santa et al. (2013) [6], in which 1.8 M of HCl
34 were utilized for each 150 g of in natura residual material. After the acidic rinse, the material
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1 was rinsed with water and filtered in a vacuum pump. The remaining kaolin was oven-dried at
2 100 ºC for 24 h.
3 The kaolin obtained from the residue and the natural kaolin were both subjected to
4 calcination in a muffle at 850 ºC for 2 h for the transformation of crystalline kaolin into
5 amorphous metakaolin through desidroxilation [9]. According to Boca Santa et al. [9], in
6 temperatures of 800, 850 and 900 °C there is no significant variation in the process.

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7 Temperatures above 900 ° C can cause formation of crystalline structures in the material.
8 The methodology employed for the synthesis of ZEO-Y-NM and ZEO-Y-WM

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9 consisted in the following procedures: 10 g of metakaolin and 15 g of sodium hydroxide were
10 dispersed in 100 g of deionized water and kept under stirring for 30 min, with a

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11 metakaolin/NaOH ratio of 1/1.5 in mass units, according to a test performed by Htay et al.
12 (2008) [10]; to adjust the Si/Al ratio to 2.5 [11] approximately 14 g of sodium silicate
13 (Na2SiO3) were dispersed in 50 g of deionized water and the mixture was stirred for 30 minutes
14
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for gel formation; the material was left to stand for 24 h and, subsequently, was transferred to
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15 the steel reactor and stored in an oven at 100 ºC for 6 h (best temperature and time obtained
16 with ZEO-Y-AR). After this period the material was first rinsed with water to lower its Ph,
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17 then centrifuged, and the reaction product was oven-dried at 60 ºC for 24 h.

18
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19 6.5. Characterization of the materials

20 In the present study both the kaolin and the zeolite were characterized by X-Ray
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21 Diffraction (XRD) technique in a Philips diffractometer (model X’pert) and X-Ray

22 Fluorescence (XRF) technique in a Philips spectrophotometer (model PW 2400). The
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23 identification of functional groups was attained by Fourier Transform Infrared Spectroscopy

24 (FTIR) in a Shimadzu FTIR Spectrophotometer (model IR Prestige-21) and, to evaluate the
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25 microstructure of the materials, some samples underwent Scanning Electron Microscopy

26 (SEM), which was carried out in two devices: one from Philips (model XL30) and one from
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27 Jeol (model JSM-6390LV). The specific area of the synthetized zeolites was determined by the
28 Brunauer, Emmet and Teller (BET) method in a Quantachrome Autosorb-1 device, employing
29 the multipoint method with data from nitrogen adsorption isotherms at 77K in vapor pressures
30 ranging between 0.01 and 0.99.
31
32 7. Results and discussion
33
34 7.1. Characterization of ZEO-Y-AR
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1 7.1.1. XRD of ZEO-Y-AR
2 The samples synthesized from the analytical reagents (ZEO-Y-AR) in temperatures
3 from 80 to 120 ºC in time intervals from 5 to 7 h were analysed by XRD technique. The results
4 are described in Figure 1.
5 Synthesized ZEO-Y-AR (Figure 1 (9), identified with the inscription (Y)) presents
6 peaks corresponding to the criteria of commercial Y zeolite, with intense diffraction peaks at

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7 2θ = 6.20o; 10.30o; 11.80o; 15.80o; 18.60o; 20.0o; 23.56o; 26.93o; 31.20o; 34.00o and 37.60o.
8 According to the pattern obtained by IZA (2014) [4] with the JCPDS 43-0168 form, such

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9 peaks are typical of sodium Y zeolite.
10 The results indicated that at certain temperatures and heating times some samples did

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11 not present the characteristics required for being considered a type Y zeolite, while others did
12 not react, or reacted in small proportions, resulting in the non-formation of the crystalline
13 peaks pertaining to the type Y zeolite.
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15 7.1.2. Evaluation of the factorial 3² design
16
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17 The XRD results from all samples were subjected to integral calculations through the
18 software Origin to evaluate de crystallinity percentage. The percentage was attained by
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19 subtracting the area of the peaks pertaining to ZEO-Y and dividing by the total area. According
20 to the zealotical standards it was possible to observe the samples with the greatest conversion
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21 percentage of the reagents into a crystalline material (ZEO-Y-AR).

22 The percentages obtained in each sample, which are described in Table 2, were utilized
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23 as response factor for the 3² factorial design presented in Table 1.

24 The crystallinity exhibited dispersion in the results, with values between 42.72 and
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25 94.25%. Table 3 shows the variance analysis, ANOVA, which aimed to verify significant
26 differences between the averages and the factors that may influence a dependant variable over
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27 crystallinity. It is possible to observe that the F values are significant (considering p < 0.5).
28 Furthermore, it can be inferred that the interaction between the variables temperature and time
29 (linear terms) has a large influence on the model composition, as is confirmed by the quadratic
30 sum (QS). Thus, the time factor (linear term) and temperature factor (linear term) are defined
31 as more interactive factors to the model. The model obtained demonstrated a good correlation
32 with its data, since the value of R2 is 0.93.
33 The Pareto Diagram, illustrated in Figure 2, shows the variables’ effect values.
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1 Zhang et al. (2014) [12] observed in their study that time is the most significant
2 variable for the crystallinity in the synthesis of the zeolite. Melo et al. (2012) [13] highlight
3 that time is an important parameter to be considered, since, generally, crystallinity increases
4 over time.
5 The response surface of the model applied to crystallinity is presented in Figure 3.
6 The point of greatest crystallinity for ZEO-Y is close to the central point from the

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7 planning (time of 6 hours and temperature of 100 ºC), confirming the Y zeolite’s synthesis
8 conditions presented by IZA.

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9 Thus, for the synthesis of ZEO-Y-IR and ZEO-Y-WM a temperature of 100 ºC and a
10 period of 6 hours were selected.

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11
12 7.2. Characterization of Waste (WM) and Natural Metakaolin (NM) and synthetized
13 ZEO-Y
14 7.2.1. FTIR spectres of WM and NM
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15 Figure 4 presents the infrared absorption spectres in the WM (a) and NM (b) samples.
16 The bands observed near 3459 cm-1 represent the OH group. These molecules are able to
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17 vibrate in different ways and involve symmetrical and asymmetrical stretching or flexion
18 combinations. The band at 2350 cm-1 is attributed to carbon dioxide [14]. For the metakaolin
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19 obtained from the waste the sample should, ideally, contain a few traces of cellulose, due to the
20 band at 1636 cm-1, which represents the OH group present in cellulose. The bands at 1083
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21 cm−1, 801 cm−1and 464 cm−1 represent the modifications of kaolin into metakaolin. The
22 absorptions occurring at 1083 and 1084 cm-1 correspond to the Si-O-Si interactions, while the
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23 bands at 800 and 801 cm−1 correspond to the Al-O interactions, and the ones at 465 and 464
24 cm−1 are related to a O-Si-O coupling, characteristic of kaolins [15]. The width of the three last
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25 bands suggests that the structure is disorderly [16].

26
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27 7.2.2. Results of XRD analysis of WM and NM

28
29 Through the diffractograms in Figure 5 (a) natural kaolin and (c) paper sludge kaolin it
30 is possible to verify that the kaolins present crystalline phases corresponding to calcite (C),
31 kaolinite (K), cellulose (P) and quartz (Q). After the heat treatment, a transformation of kaolin
32 into metakaolin (Fig.5 (b) natural and (d) paper sludge) is observed.. The corresponding peaks
33 disappear, due to the rupture of the crystalline structure, resulting in amorphous metakaolinite,
34 which is fundamental for the synthesis of zeolites [11].
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1 The diffractograms in Fig. 5 (c and d) correspond to the metakaolin derived from the
2 waste of paper pulping, in which it is possible to observe that the acid rinse with HCl and the
3 calcination for the combustion of cellulose were effective to obtain purified kaolin, as was
4 confirmed by the results in oxide presented in Table 3.
5
6 7.2.3. Results in oxides obtained from the samples of WM, NM and synthesised

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7 ZEO-Y.
8 Table 4 reports the results of the chemical analysis conducted by XRD in natural

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9 metakaolin (NM), metakaolin derived from the waste of white paper pulping (WM) and
10 samples of ZEO-Y-IR, ZEO-Y-IM and ZEO-Y-WM.

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11 From the results of chemical analysis, presented on Table 4 (a and b), it is possible to
12 observe that, for both metakaolin samples, silicone oxide (SiO2) and aluminium oxide (Al2O3)
13 are the major components, corresponding to 90% of the material. Iron oxide (Fe2O3) and
14
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calcium oxide (CaO) present greater concentration in the paper sludge metakaolin. The
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15 SiO2/Al2O3 ratio is observed to be close to 1.0 and, since for the synthesis of Y zeolite the most
16 favorable ratio is 2.0, an adjustment was necessary in silicon concentration.
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17 Table 4 (c) presents the result of a chemical analysis conducted in a standard

18 (commercial) sample (ZEO-Y-S), while the data described in Table 4 (d) correspond to the
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19 oxides obtained from the sample synthesized for experiment nine (ZEO-Y-IR). The oxide
20 percentages observed in ZEO-Y-IR are close to the percentage values of the commercial
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21 zeolite. The stoichiometric Si/Al ratios are of 4.21 for ZEO-Y-S and 3.10 for ZEO-Y-IR. The
22 values are in accordance with the literature for ZEO-Y [1]. According to Breck (1984) [2], for
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23 ZEO-Y the Si/Al ratio is bigger than 1.5, whereas Meier and Olson (1992) [17] found this ratio
24 to vary from, approximately, 2.0 to 8.0.
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25 The XRF results in Table 4 (e and f) were collected form the ZEO-Y-WM and ZEO-Y-
26 NM samples, respectively. In the WM sample a significant increase in titanium and iron
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27 concentrations stands out. According to Hildebrando (2012) [18], the presence of impurities in
28 the starting materials, such as those previously mentioned and, specially, iron-based
29 substances, are prone to causing disruptions during the synthesis reactions. The latter tend to
30 remain insoluble during the crystallization stage, leading to a precipitation of undesired
31 species, such as insoluble silicates, thus interfering in the zeolites’ formation process.
32 The Si/Al ratio was of 2.43 for ZEO-Y-WM and 2.26 for ZEO-Y-NM. These
33 composition ratios are characteristic of ZEO-Y [19].
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1 The zeolites produced are essentially composed of silicon and aluminium, with a
2 smaller amount of sodium, characteristic of NaY zeolites.
3
4 7.2.4. Diffractograms of ZEO-Y-WM and ZEO-Y-NM.
5 Through the crystalline peaks in the diffractograms presented in Figure 6 the formation
6 of ZEO-Y can be observed, as listed on the JCPDS 43-0168 sheet. In the diffractogram

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7 pertaining to ZEO-Y-WM (Figure 6a) it is also possible to observe the presence of crystalline
8 peaks corresponding to type P zeolite (ZEO-P). According to Huo et al. (2013) [20] the

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9 formation of ZEO-P can occur in more prolonged synthesis. Farzanet et al. (1989) [21] state
10 that the formation of ZEO-Y might vary depending on the composition of the gel formed in the

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11 beginning of the process and, mostly, due to a temperature variation in the synthesis and the
12 crystallization time. Freitas et al. (2011) [22] add that the P phase is more stable than the Y
13 phase, and can occur in synthesis stemming from metakaolin. According to Liu et al. (2003)
14
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[23] the control of reaction temperature is an important factor for obtaining ZEO-Y with a high
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15 purity level, since crystallization at lower temperatures favors the synthesis of metastable
16 zeolitic materials, i.e. faujasites, while high temperatures tend to form more
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17 thermodynamically stable phases. Thus, this study initially prioritized the knowledge of the
18 best temperature and time for the synthesis, in order to obtain ZEO-Y of commercial quality.
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19 An increase in crystallization temperature can affect the properties of the reactional gel and
20 influence particle size and, in some cases, reduce the dimensions and accelerate the diffusion
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21 between particles.
22 Through the calculation of the areas of the XRD peaks a crystallinity of 75 and 78%
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23 was detected for ZEO-Y-WM (Fig. 6a) and ZEO-Y-NM (Fig. 6b), respectively. These values
24 were considered significant for the production of ZEO-Y from matakaolin, especially if
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25 derived from industrial waste.

26
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27 7.2.5. FTIR spectres of ZEO-Y-WM and ZEO-Y-NM

28 The spectres of Figure 7a (ZEO-Y-AR) present bands close to the regions of 3472 cm-1
29 and 1640 cm-1, corresponding to the vibrations in the water molecules contained in the
30 zeolites’ cavities (KULPRATHIPANJA, 2010) [24]. The presence of a zeolitic material was
31 confirmed through the band 1005 cm-1, which is located near a band (1000 cm-1) characteristic
32 of the Si-O-Al bonding of the tetrahedral structure TO4 (T = S or Al) of primary construction
33 units [25]. The main vibrational characteristics regarding the crystallization of the zeolites can
 24
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1 be identified by the bands in the region of 710, 570 and 457 cm-1, and characterize the
2 crystallinity of the zeolites.
3 According to Huo et al. (2013) [20], frequencies observed near 1005 cm-1 are attributed
4 to the asymmetrical narrowing of the Si-O or Al-O bondings, while vibrations at 457 and 460
5 cm-1are related to the deflection mode of these same bondings, and vibrations from 570 to 710
6 cm-1 are attributed to the symmetrical narrowing of the internal tetrahedrons of ZEO-Y.

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7 In the FTIR spectres of the samples synthesized from metakaolins, presented in Figure
8 7 (b – c), vibrational bands can be observed in the wavelengths of 3470 and 1640 cm-1

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9 regarding the functional groups OH, which are attributed to water molecules [19].
10 Furthermore, vibrational frequencies around 1005, 1000, 565, 563, 467 and 461 cm-1 suggest

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11 that a formation of zeolitic materials occurred in the ZEO-Y-WM and ZEO-Y-NM samples,
12 involving structural changes that can be observed by a change in length when compared to the
13 matakaolin samples (Figure 4), especially in a shift of the regions close to 1083 cm-1 to 1005
14
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cm-1. These changes can be related to the formation of zeolitic structures, with similar
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15 characteristics reported by Htay and Oo (2008) [10].
16 The occurrence of the referred vibrations can also be observed in the spectre of Figure
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17 7d, regarding the commercial zeolite employed as standard.

18
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19 7.2.6. Results of the SEM analysis

20 The image in Figure 8 (a) concerns a ZEO-Y-S sample, which was employed in this
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21 study as a comparison to the ZEO-Y produced from different materials. An agglomeration of

22 the ZEO-Y-AR particles can be observed (Fig. 8b) due to the simultaneous growth of the
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23 nuclei. The synthesized zeolites present smaller crystallite sizes and greater dispersion in
24 particle size when compared to ZEO-Y-S. This can also explain the increase in the surface area
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25 obtained through BET technique.

26 ZEO-Y-NM (Fig. 8c) presented more isolated crystals than ZEO-Y-WM (Fig. 8d),
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27 probably due to an impurity in the waste material. . The micrographs of ZEO-Y presented an
28 octahedral morphology similar to those present in the study conducted by Breck (1984) [2] and
29 Kovo et al. (2009) [26]. Htay and Oo (2008) [10] also obtained ZEO-Y with the same
30 characteristics in their studies.
31
32 7.2.7. Results of the specific area essays by the BET method
33 In Table 5 are presented the values of specific area determined by the BET method in
34 the synthesized zeolites and in the standard sample.
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1 Zeolites show distinct superficial areas, indicating a variation in the density of
2 micropores. According to Yates (1968) [27], the increase in specific area contributes to the ion
3 exchange capacity, high adsorption and catalysis efficiency, due to the presence of spacious
4 cavities in the crystalline structure. ZEO-Y-AR (sample 9), synthesized from analytic reagents,
5 presented a surface area similar to ZEO-Y-S. The results of the specific areas obtained in the
6 essay are according to the results found in the literature for type Y zeolite (RAHMAN et al.,

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7 2012) [28].
8 ZEO-Y-NM was the sample which presented the largest surface area in relation to the

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9 ZEO-Y-WM sample, indicating the presence of bigger proportions of micropores. The
10 increased area indicates that there was a good crystallinity of this material, as well as a larger

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11 quantity of zeolitic structure formed through the synthesis. This value of BET area, around
12 554.9 m2. g-1, is superior to the 246.7 m2.g-1 obtained by Liu et al. (2003) [23], who synthesized
13 Y zeolite with 75% crystallinity from metakaolin. Furthermore, the zeolite from metakaolin
14
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derived from industrial waste presented the smallest specific area, possibly due to the
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15 impurities contained in the material.
16 The results obtained by the BET essay are according to those of the morphology
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17 obtained by the SEM technique.

18
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19 8. Conclusion
20 From the synthesis of ZEO-Y employing analytical reagents as a silicon and aluminium
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21 source, it was possible to verify that the synthesis method based on IZA standart was
22 extremely adequate to the attainment of the faujisite phase (Y zeolite). The XRD analysis
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23 showed the formation of a ZEO-Y-AR from analytical reagents with an elevated crystallinity
24 degree, which is according to the standards found for Y zeolite. The experimental design
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25 permitted the evaluation of the importance of the variables time and temperature in the process,
26 as well as the attainment of parameters to perform the substitution of the analytical reagents by
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27 alternative materials for the synthesis of ZEO-Y, including natural metakaolin and metakaolin
28 derived from paper sludge.
29 The SEM allowed the observation of the growth of crystals obtained in the synthesized
30 samples from analytical reagents and from two kaolins, and the crystals were quite similar to
31 those of the standard sample used as a reference.
32 The production of ZEO-Y in industrial scale from Brazilian kaolins can benefit several
33 different sectors. The reproduction through different materials led to the conclusion that ZEO-
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1 Y, in the synthesis conditions employed, can be produced according to the necessities from
2 other raw materials as a source of aluminosilicates.
3
4 Acknowledgments
5 The authors wish to thank CAPES, LCME and UFSC for the support to this research.
6

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7 6. References
8

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9 [1] G.G. Pace, A.R. Montes, G.F. Rodrigues. Zeolitas: características, propriedades y
10 aplicaciones industriales. Editorial Innovacín Tecnológica. Facultad de Ingeniería UCV.
11 Madri. 2000.

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12
13 [2] D.W. Breck. Zeolite molecular sieves. John Wiley & Sons. Inc. New York. 1984.
14
15 [3] A.B Luz, A.R. Campos, E.A. Carvalho, L.C. Bertolino. Caulim. Rio de Janeiro:

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16 CETEM/ Rochas e Minerais Industriais: Usos e Especificações. (2005) 231-262.
17
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18 [4] IZA. Iza synthesis commission – fau linde type y. D. M. Ginter. A. T. Bell. C. J.
19 Radke. 2016.
20
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21 [5] J.R. Scheiber. L.A. Lima. P.H.L. Quintela. E.L. Silva. M.G.F. Rodrigues. Síntese da
22 zeólita e sua utilização como adsorvente para remoção de contaminantes orgânicos em
23 efluentes líquidos. in: X Encontro Brasileiro sobre Adsorção. EBA. Guarujá – SP. 2014.
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25 [6] R.A.A. Boca Santa, A.M. Bernardin, H.G. Riella, N.C. Kuhnen. Geopolymer
26 Synthetized from Bottom Coal Ash and Calcined Paper Sludge. J. Clean. Prod. 57 (2013)
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27 302-307.
28 [7] D. KARAMI, S. ROHANI. Synthesis of pure zeolite Y using soluble silicate, a two-
29 level factorial experimental design. Chem. Eng. Process. 48 (2009) 1288–1292.
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30
31 [8] R.A.A. Boca Santa, C. Soares, H.G. Riella. Geopolymers with a high percentage of
32 bottom ash for solidification/immobilization of different toxic metals. J. Hazard. Mater. 318
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33 (2016) 145–153.
34
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35 [9] R. A. A. Boca Santa, J. C. Moreira, L. L. Coelho, N. C. Kuhnen, H. G. Riella.

36 Recovery techniques of industrial waste stemmed from white paper pulping process to obtain
37 metakaolin. Int. J. Miner Process 161 (2017) 59–64.
38
39 [10] M.M. Htay, M.M. Oo. Preparation of zeolite Y catalyst for petroleum cracking.
40 World Academy of Sci. Eng. and Technology. 24 (2008) 108-114.
41
42 [11] E.A. Hildebrando, R.S. Angelica, F.R. Neves, F.R. Valenzuela-Diaz. Síntese de
43 zeólita do tipo Faujasita a partir de um rejeito de caulim. Cerâmica. 58 (2012) 453-458.
44
45 [12] X. Zhang, D. Tong, W. Jia, D. Tang, X. Li, R. Yang. Studies on room-temperature
46 synthesis of zeolite NaA. Mater Res Bull. 52 (2014) 96 – 102.
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1
2 [13] C.R. Melo, H.G. Riella, N.C. Kuhnen, E. Angioletto, A.R. Melo, A.M. Bernardin.
3 M. R. Rocha, L. Silva. Synthesis of 4A zeolites from kaolin for obtaining 5A zeolites through
4 ionic exchange for adsorption of arsenic. Mater. Sci. Eng. B. 177 (2012) 345–349.
5
6 [14] B.C. Smith. Fundamentals of Fourier Transform Infrared spectroscopy. Flórida -
7 USA: CRC press, 1996.
8
9 [15] J.C. Moreira. Síntese e caracterização da zeólita 5A por troca iônica a partir de um

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10 resíduo da indústria de papel. Master Thesis. Department of Chemical Engineering and Food
11 Engineering. Federal University of Santa Catarina. Florianópolis- SC. 2013.
12

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13 [16] A.G. San Cristóbal, R. Castelló, M.A.M. Luengo, C. Vizcayno. Zeolites prepared
14 from calcined and mechanically modified kaolins: A comparative study. Appl. Clay Sci. 49
15 (2010) 239-246.

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16
17 [17] W.M. Meier, D.H. Olson, Atlas of Zeolite Structure Types 3ed. rev. London,
18 Butterworth; Heinemann, 1992.
19

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20 [18] E.A. HILDEBRANDO, Síntese de zeólita do tipo faujasita utilizando rejeito de
21 caulim da Amazônia como fonte de silício e alumínio: Aplicação como adsorvente. Thesis.
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22 University of São Paulo. São Paulo - SP. 2013.
23
24 [19] Q. Li, Y. Zhang, Z. Cao, W. Gao, L. Cui. Inuence of synthesis parameters on the
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25 crystallinity and Si/Al ratio of NaY zeolite synthesized from kaolin. Pet. Sci. China University
26 of Petroleum (Beijing). 7 (2010) 403-409.
27
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28 [20] Z. Huo, X. Xu, Z. Lv, J. Song, M. He, Z. Li, Q. Wang, L. Yan, Y. Li. Thermal
29 study of NaP zeolite with different morphologies. J. Therm. Anal. Calorim. 111 (2013) 365-
30 369.
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31
32 [21] F. Farzanet, M.K. Oskooie, M.M.A. Nejad. The synthesis of zeolites A, X and HS
33 from natural iranian kaolinite and the study of the transformation of zeolites X to HS and
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34 zeolites Y to P, by x-ray diffraction and scanning electron microscopy. J. Sci. Islamic Replubic
35 Iran. 1 (1989) 23-28.
36
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37 [22] V.A.A. Freitas, J.S.V. Lima, P.R.C. Couceiro. Caracterização e análise estrutural
38 da Hidroxisodalita sintetizada a partir de amostras de solo amazônico. Cerâmica. 57 (2011)
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39 281-287.
40
41 [23] X. Liu, Z. Yan, H. Wang, Y. Luo. In situ synthesis of NaY zeolite with coal based
42 kaolin. J. Nat. Gas Chem. 12 (2003) 63-70.
43
44 [24] S. Kulprathipanja. Zeolites in Industrial Separation and Catalysis. Germany:
45 Wiley-VCH, 2010.
46
47 [25] N. Taufiqurrahmi, A. R. Mohamed, S. Bhatia. Nanocrystalline Zeolite Y.
48 Synthesis and Characterization. Mat. Sci Engineering, 17 (2011) 1-6.
49
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1 [26] A.S. Kovo, O. Hernandez, S. M. Holmes. Synthesis and characterization of zeolite
2 Y and ZSM-5 from nigerian ahoko kaolin using a novel, lower temperature, metakaolinization
3 technique. J. Mater. Chem. 19 (2009) 6207-6212.
4
5 [27] D.J.C. Yates, Studies on the surface area of zeolites, as determined by physical
6 adsorption and x-ray crystallography. Can. J. Chemistry. 46 (1968) 1695-1701.
7
8 [28] M.M. Rahman, M.B. Awang, A.N.M. Yusof. Preparation, characterization and
9 application of zeolite-Y (Na-Y) for water fitration. Aust. J. Basic Appl. Sci. 6 (2012) 50-55.

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10
11 Table 1. Factorial planning 3².

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12 Table 2. Percentages obtained by integrating the area of the crystalline peaks for the 9
13 samples of synthesized ZEO-Y-AR.

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14 Table 3. Analysis of variance values (ANOVA), model with quadratic correlation (R2)
15 of 0.93.
16 Table 4. Composition in oxides of WM (a), NM (b), a standard sample (ZEO-Y-S) (c)
17
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and synthesized (d) ZEO-Y-AR (sample 9), (e) ZEO-Y-WM and (f) ZEO-Y-NM.
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18 Table 5. Specific surface area of synthesized ZEO-Y and standard sample.
19
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20 Figure 1. Diffractograms of the nine samples synthesized with analytical reagents

21 Figure 2. Pareto Diagram of the effects for the crystallinity model.
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22 Figure 3. Graph of response surface for the crystallinity of ZEO-Y-AR

23 Figure 4. FTIR of the samples WM and NM.
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24 Figure 5. XRD of (a) natural kaolin and (b) metakaolin from natural kaolin, and kaolin
25 from paper sludge (c) and metakaolin from paper sludge (d). .
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26 Figure 6. Spectres of DRX of synthesized ZEO-Y-WN (a) and ZEO-Y-NM (b).

27 Figure 7. FTIR of the samples of ZEO-Y-AR (a); ZEO-Y-WM (b); ZEO-Y-NM (c) and
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28 ZEO-Y-S.
29 Figure 8. Micrographies obtained in SEM of the following materials: natural kaolin (a);
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30 NM (b); ZEO-Y-S (c); ZEO-Y-AR (sample 9) (d); ZEO-Y-WN (e) and ZEO-Y-NM (f).
31
32
33
34
35
36
37
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Table 1

Variables -1 0 +1
A – reaction time (h) 5 6 7
o
B – Temperature ( C) 80 100 120
Experiments Blocks A B
1 1 6 120
2 1 7 100

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3 1 5 80
4 2 5 100

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5 2 7 120
6 2 6 80
7 3 7 80

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8 3 5 120
9 3 6 100

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Table 2

Samples 1 2 3 4 5 6 7 8 9
(%) Crystallinity 80,33 90,80 42,72 62,73 76,01 72,41 88,52 85,95 94,25

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Table 3

Factors SS df MS F p
Time (h) L 680,96 1 680,96 14,0817 0,03306
Time (h) Q 124,08 1 124,08 2,56596 0,20751
Temperature (°C) (L) 248,84 1 248,84 5,14586 0,10808
Temperature (°C) (Q) 136,67 1 136,67 2,82635 0,19132

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1L by 2L 776,74 1 776,74 16,0623 0,02787
Error 145,07 3 48,36

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SS total 2112,4 8

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Table 4

(a) (b) (c) (d) (e) (f)

Oxide (%) WM NM ZEO-Y- S ZEO-Y-AR ZEO-Y-WM ZEO-Y-NM
SiO2 53,61 53,49 54,86 48,34 40,13 41,43
Al2O3 37,32 44,13 19,51 23,36 24,77 27,45
TiO2 1,84 < 0,05 0,07 < 0,05 0,99 0,08

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Fe2O3 1,64 0,42 < 0,05 < 0,05 0,92 0,29
CaO 2,03 0,06 < 0,05 < 0,05 0,75 <0,05
MgO 1,63 < 0,05 0,05 0,06 0,95 0,09

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K 2O 0,48 0,93 0,06 < 0,05 0,23 0,54
Na2O 0,34 0,18 11,71 14,67 14,88 16,42

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MnO < 0,05 < 0,05 < 0,05 < 0,05 <0,05 <0.05
P2O5 0,16 0,07 < 0,05 < 0,05 <0,05 <0,05

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LoI 0,60 0,35 13,68
AN 13,43 16,38 13,63
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Table 5

Zeolitic materials Surface area BET (m2/g)

(a) ZEO-Y-S 690,8
(b) ZEO-Y-AR (sample 9) 758,1
(c) ZEO-Y-WM 456,0

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(d) ZEO-Y-NM 554,9

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Figure 1

3000 Y
Y Y Y YY Y Y Y Y (9)
Y
0

2000

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(8)
0
2000
(7)

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0
1000
(6)

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Intensity (cps)

2000
0

1000
(5)

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280
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(4)

500
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(3)
2500

(2)
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(1)
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10 20 30 40 50
2 θ (°)
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Figure 2

Pareto Chart of Standardized Effects; Variable: Cristaliinity (%)

2 3-level factors, 1 Blocks, 9 Runs; MS Residual=48,35767
DV: Cristallinity (%)

1Lby2L -4,00778

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(1)Time (h)(L) 3,752567

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(2)Temperature (ºC)(L) 2,268448

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Temperature (ºC)(Q) 1,681174

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Time (h)(Q) 1,601861
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p=,1
Standardized Effect Estimate (Absolute Value)
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Figure 3

Response Surface
Crystallinity (%)

100

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90

80

70

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Cristallinity (%)

60

50

40

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30

20

10
5
12

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5

7,
11

2
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0
11

6,
> 90

8
5

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10
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6
6,
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m

10 < 82
4
6,
pe

95 2
6,
ra

h)
0

e( < 72
tu

5,

90
re

Tim
5,
(ºC

85
6

< 62
5,
4
)

80
5,
2

< 52
5,

75
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4,

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< 32
< 22
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Figure 4

2350
80 (a)

1636
3450
40

801

464
Transmitance (%)

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1083
0

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80

2350

465
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3450

800
60

1084
40
U (b)
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4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
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Figure 5

800
K
K
(a)
Q
600

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Q (b)
Intensity (cps)

400

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C
(c)
K P K C C C

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(d)

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Figure 6

2500
Y
2000

1500
(a) ZEO-Y-WM

1000
Y Y Y Y
Intensity (cps)

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500 P Y Y Y YY
YY Y Y
0
2500 10 20 30 40 50
Y

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2000

1500
(b)ZEO-Y-NM

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Y Y Y Y
500 Y Y Y YY
Y Y
Y Y

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2 Theta (°)
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Figure 7

60 60

(a) ZEO-Y-AR (b) ZEO-Y-WM

1640
50

457 570
40 40

710

1640
30

1005

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3472

563
20
20

467
3470

1000
Transmittance (%)

10

0
04000

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3500 3000 2500 2000 1500 1000 50080 2000 1500 1000 500
(c) ZEO-Y-NM 1640 (d) ZEO-Y-S
60
60

1640
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40
40
565
1005

570
3470

1005

690
461

20 20

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3470

460
0
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4000 3000 2000 1000 4000 3000 2000 1000

Wavernumber (%)
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Highlights
• Synthesis of Y zeolite from analytical reagents, natural kaolin, and kaolin from
paper sludge
• Experimental design to evaluate the time and temperature on the crystallization
• Time was verified to be a key factor in the crystallinity of the Y zeolitic.
• Hydrothermal reaction for the synthesis of Y zeolite is significantly efficient.

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