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Article

Determining the Role of Water Molecules in Sodalite Formation Using the Vapor Phase Crystallization Method

by
Claudia Belviso
Istituto di Metodologie per l’Analisi Ambientale (CNR–IMAA), 85050 Potenza, Italy
Processes 2024, 12(3), 486; https://doi.org/10.3390/pr12030486
Submission received: 2 February 2024 / Revised: 19 February 2024 / Accepted: 25 February 2024 / Published: 27 February 2024
(This article belongs to the Section Chemical Processes and Systems)
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Abstract

:
The efficiency of the vapor phase crystallization (VPC) process in zeolite formation using mixtures of a natural source (obsidian) and common waste materials (red mud and fly ash) was analyzed. The aim was to demonstrate that water molecules available during this treatment control mainly the synthesis of sodalite, regardless of the raw material used, as long as it is rich in amorphous silica and alumina pre-fused with NaOH. The data indicate that increasing the temperature to generate steam from distilled water during the VPC process results in the continuous transformation of amorphous material into sodalite and, subordinately, cancrinite. The formation of the newly formed phases was monitored by powder XRD and SEM.

Graphical Abstract

1. Introduction

Different methods have been described for zeolite synthesis using many raw materials.
The conversion of fly ash (FA) into zeolites was performed for the first time by the pioneers Holler and Wirsching [1] who used this waste, resulting from coal combustion in power plants, as an innovative Al and Si source. Mondragon et al. [2] published the first paper on the coal fly ash zeolitization by an alkaline hydrothermal process, whereas Shigemoto et al. [3] introduced alkaline pre-fusion treatment before the hydrothermal method. Data from other literature have documented the successful application of these two methods to form zeolite from coal fly ash [4,5,6,7,8,9,10,11,12], other wastes [13,14,15,16,17], including red mud (RM) [18,19,20,21], or using natural sources such as obsidian (OS) [22,23,24,25]. A-, X-, Y-, P-type zeolite and sodalite formation was documented after the alkaline hydrothermal process of fly ash in the temperature range between 45 °C and 90 °C [26,27,28], whereas in our previous papers, the synthesis of a GIS zeolite with a cactus-like and wool ball-like shape was performed at 40 and 90 °C using red mud [29]. According to Xie and co-workers [30], conventional hydrothermal treatment of red mud determined the formation of 4A-zeolite, whereas Cheng et al. [31] formed a NaP1 zeolite at different temperatures (90–130 °C). The use of RM in combination with FA was carried out to form A-, X-, and ZK-5-type zeolites with magnetic properties at low temperatures (25–40 °C) [32]. The mixture of red mud and coal gangue determined the crystallization of zeolite A after a calcination process, followed by the hydrothermal method from 60 °C to 90 °C [33]. EMT-type zeolite (a hexagonal polytype of cubic faujasite) formed, instead, after NaOH pre-fusion treatment and hydrothermal process from 35 °C to 60 °C of an obsidian sample [34].
However, the presence of unreacted material in the final product and the high cost due to the temperature necessary for the pre-fusion treatment (<500 °C) constitute the main disadvantages of conventional and pre-fusion hydrothermal process, respectively, regardless of the source used [35]. In addition, the significant amount of water required should not be overlooked, as well as its evolution into liquid waste at the end of the synthesis process.
In the last few years, many papers have also described successful zeolite formation using sonication treatment. FA was converted to sodalite, Na-P-, A- or X-type zeolite via an ultrasound process carried out as the only treatment or applied before and after the hydrothermal process [35,36,37,38,39,40], whereas in our previous paper, the formation of a zeolite-layered double-hydroxide composite (LTA-LDH) was documented using red mud treated by sonication [21]. However, although the ultrasonic treatment shows numerous advantages mainly related the low temperature and short time, this method also requires a significant amount of water that becomes a waste product after the synthesis process.
Another treatment which has been widely used for zeolite synthesis from different raw materials is microwave heating, including microwave-assisted ionothermal synthesis, microwave-assisted hydrothermal synthesis, and microwave-assisted aging synthesis [35,41,42,43]. Querol et al. [44] transformed fly ash into zeolite A by both hydrothermal and microwave energy with NaOH and KOH alkaline agents, and this result was confirmed by many recent papers [45,46]. Liu et al. [47] documented NaP zeolite formation using the microwave–ultrasonic–hydrothermal method, whereas Wang et al. [48] synthesized zeolite X via microwave extraction combined with hydrothermal processes [48]. To our knowledge, the microwave process has not been applied to form zeolite from red mud, but some literature data have documented the use of this treatment to remove silica and iron oxides from the low-iron bauxite residue (Fe ~24%) [49] and to modify red mud-based adsorption material, thus improving its adsorption phosphorus capacity in solutions [50]. The main advantage of microwave treatment is the high amorphous silica and alumina dissolution within a short time. However, the process is performed at high temperatures, thus limiting the formation of zeolites stable at lower ones. Moreover, regarding previous methods, microwave treatment requires a considerable amount of water.
To address the above-mentioned problems with respect to the large amount of water and liquid waste production using the more diffused treatments for zeolite synthesis, the efficiency of vapor phase crystallization (VPC) method to form zeolite from a waste material [51] or natural source [52] was tested. The VPC process is based on the use of vapor molecules produced by heating distilled water at low temperatures (≤90 °C). During the synthesis, raw material is in contact only with vapor from the liquid. Xu et al. [53] applied the vapor-phase transport method (VPT) to synthesize an MFI zeolite from amorphous dry gel in the early 1990s. This green process has not been widely applied until now, and to our knowledge, it has not been used to form zeolite from red mud or obsidian and their mixtures.
In this paper, new experiments were performed using mixtures of fly ash, red mud, and obsidian, with the dual objectives as follows: (i) to demonstrate that the water available during the VPC method controls the sodalite formation regardless of the type of source used, as long as it is rich in silica and amorphous aluminum; (ii) and exploit the chemical and mineralogical composition of two most widespread wastes (fly ash and red mud), and the high silica content of a natural source (obsidian).
The choice to use mixtures of wastes is aimed to improve the application of these materials according to the concept of industrial symbiosis. It is in fact well known that fly ash and red mud are only partially used, and more than half is disposed of in landfills since they find no other application, thus contributing to environmental pollution [35,54]. The use of obsidian is driven by the easy availability of amorphous silica in a natural, widespread, and economical source. Literature data have documented its combination with other phases to form a new raw material available for the synthesis of zeolites [55,56].

2. Material and Experimental Design

2.1. Resources

The experiments were performed using mixtures of two industrial waste materials and one natural source. In detail, one sample of fly ash (FA) collected from the ENEL thermoelectric power plants of Cerano (Brindisi, Italy) was mixed with a sample of red mud (RM) from the aluminum extraction in an area close to the city of Podgorica (Montenegro) (80:20). The mixture was labeled FARM. FA was also mixed with a sample of one natural rhyolitic obsidian (OS) collected from Aeolian islands (Italy) (50:50). The new mixture was labeled FAOS. Finally, OS was mixed with RM (50:50) to form the OSRM sample.
The flow diagram for mixture preparation is shown in Figure 1a.

2.2. Experimental Procedure

The three mixtures were treated with NaOH (1:1.2) and heated at 600 °C. The resulting fused materials were cooled, grounded with a mortar and pestle, and finally placed in a ceramic raised holder inside a water bath. As already performed in our previous experiments [51,52], deionized water was poured into the bottom of the water bath to produce vapor molecules at 45, 60, and 90 °C for 4 days under environmental pressure. The flow diagram for the synthesis process is shown in Figure 1b.
The synthetic products were finally dried at 80 °C overnight.

2.3. Raw Material and Final Product Characterization

Chemical analysis of the sources as investigated by X-ray fluorescence (XRF) (Philips PW 1480, Burladingen, Germany) is shown in Table 1.
The mineralogical composition of both raw materials and synthetic products was determined by powder X-ray diffraction (XRDP), using a Rigaku Rint 2200 (Tokyo, Japan) powder diffractometer with Cu-Ka radiation and a graphite monochromator. X-ray diffraction patterns were collected in a θ–θ geometry, within the angular range of 2–70° of 2θ, step size of 0.02°, scan step time of 3 s and working conditions of 30 kV–40 mA. A scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS) was used to analyze the zeolite morphology. The investigation was carried out using a Zeiss Supra 40 instrument (Oberkochen, Germany) equipped with Oxford INCA Energy micro analysis system and x-act Silicon Drift Detector. To avoid charging the surface, the samples were carbon-coated (10 nm thick).

3. Results

3.1. Raw Material and Pre-Fused Products

The XRD patterns of each raw material before and after NaOH pre-fusion treatment are displayed in Figure 2. The results indicate that FA is mainly characterized by the presence of amorphous together with crystalline phases such as mullite and quartz. Magnetite was also present in traces. The peaks detectable on the X-ray profile after NaOH pre-fusion are mainly attributable to sodium silicate and sodium aluminosilicate (Figure 2a). This mineralogical composition also characterizes the other two samples after pre-fusion treatment (OS_NaOH and RM_NaOH), although OS is originally composed of only amorphous material (Figure 2b), and RM pattern shows the presence of gibbsite, boehmite, calcite, and large amount of hematite (Figure 2c).

3.2. VPC Treatment at 45 °C

XRD pattern of the FARM sample after VPC treatment at 45 °C indicates the presence of sodalite as the main newly formed phase; lower amount of thermonatrite and trona are also detectable together with andradite (Figure 3a). Quartz is a residual mineral, as well as mullite and iron oxides/hydroxides. Amorphous material is also present, and it is not excluded the presence of cancrinite/nosean and gmelinite at trace levels. These results are confirmed by SEM images in Figure 4a showing the rose-type morphology of sodalite together with the chopsticks of trona (Figure 4a). The described mineralogical composition also characterizes the OSFA sample, although both the X-ray profile and SEM pictures indicate the slightly greater presence of trona (Figure 3b and Figure 4b, respectively). Finally, the XRD data of OSRM at 45 °C mainly show the presence of sodalite (Figure 3c), of which the typical rose-shape morphology is displayed in Figure 4c.

3.3. VPC Treatment at 60 °C

Figure 5 shows the XRD pattern of the three samples after VPC treatment at 60 °C. The results indicate that FARM, OSFA, and OSRM are mainly characterized by the presence of sodalite as a crystalline phase. The peaks attributable to gmelinite and cancrinite are faintly detectable. Residual quartz and iron oxide/hydroxides are still present in different amounts among the samples. However, beyond these common newly formed phases, there are some minor differences in the profiles of each sample. Figure 5a, in fact, shows the presence of thermonatrite in FARM, whereas the XRD pattern of OSFA displays weaker peaks of this phase (Figure 5b) that are not detectable in the OSRM X-ray profile (Figure 5c). This last sample is instead characterized by the presence of a large amount of calcite, and gmelinite is detectable in trace amounts. The SEM images in Figure 6 confirm the XRD results showing well-defined sodalite crystals mainly in the OSRM sample (Figure 6c).

3.4. VPC Treatment at 90 °C

The mineralogy of all the samples after the VPC process at 90 °C is displayed in Figure 7, indicating the presence of a large amount of well-crystalized sodalite. Moreover, the XRD patterns of FARM and OSRM show the presence of well-detectable peaks of cancrinite (Figure 7a,c), whereas the sodalite-to-cancrinite evolution is shown in the SEM image in Figure 8.

4. Discussion

This study intends to continue the investigation on the mechanism controlling zeolite crystallization using the VPC method, as already started in our previous studies [51,52]. In these new experiments, attention is focused on the role of raw material chemical composition with respect to the final synthetic products when water is available in the form of vapor molecules. The results indicate that sodalite formed in all the samples starting at 45 °C (Figure 3, Figure 4, Figure 5, Figure 6, Figure 7 and Figure 8), thus confirming that during the VPC treatment, sodium silicate and sodium aluminosilicate resulting from the pre-fusion process of all raw materials (Figure 2) are directly involved in the dissolution process controlled by steam generated during distilled water heating.
The silicate–aluminosilicate dissolution process followed by nano-zeolite crystallization has been well documented during zeolite formation via the conventional process [57,58,59,60] and already detected by the VPC treatment of pre-fused bauxites and fly ash [51,52]. In both cases, amorphous geopolymer and its progressive re-arrangement into the crystalline phase with the increase in temperature during the synthesis process play a decisive role in zeolite formation. However, the role of water and temperature during this process is different according to whether the hydrothermal or VPC method is used.
Hydrothermal incubation after the alkaline fusion of raw material determines the fast dissolution of Na2SiO3 and NaAlSiO4 phases after dispersion in a distilled water solution. The following steps are characterized by geopolymer material precipitation because of the saturated state of the solution and its progressive crystallization into different type of zeolites [61]. However, the newly formed zeolites are metastable and tend to dissolve and/or re-crystallize during the process. In our previous study [61], we demonstrated that the concentration of the elements in the solutions does not change significantly, and a continuous ion transfer from solid to solution takes place. When local chemical conditions are favorable for different and specific types of zeolites (such as A-type and/or X-type zeolites), they grow within the geopolymer material or on its surfaces [61]. This mechanism is favored or even accelerated, increasing the incubation temperature. The process occurs in a closed system with a liquid solution, of which the amount does not change during the synthesis process.
According to literature data, the mechanism controlling zeolite formation during the VPC method can be approximated according to an intermediate process between the solid-state transformation and hydrothermal synthesis [62]. The absence of a liquid solution controls the fast crystallization of the more-stable zeolite at 45 °C (Figure 3) since the typical step of the metastable phase dissolution followed by re-crystallization with continuous element transfer from a solid to solution and vice versa is denied. This also explains the sodalite formation in all the samples, regardless of the source used, as long as it is rich in amorphous material, as well as silica and alumina phases. The results of the experiments performed using different mixtures of wastes or natural-source wastes confirm, in fact, that the increasing availability of water vapor molecules determines the progressive transformation of amorphous material into sodalite [51,52,63] (Figure 5). The crystallinity improves under higher-temperature steam conditions (90 °C) (Figure 7) when a well-detectable evolution to cancrinite also takes place (Figure 7 and Figure 8). According to the literature, the transformation of a sodalite to a cancrinite requires water in some form [64], and the presence of a larger amount of vapor water molecules at higher temperatures guarantees conditions approximating the presence of a liquid medium, thus permitting a sort of water vapor-mediated solid-phase transformation [64]. However, the sodalite-to-cancrinite/gmelinite transformation is already weakly detectable in the OSRM mixture at 60 °C, as indicated in Figure 9, showing detail of an XRD hump at low angles of cancrinite (Figure 9a) and SEM image displaying a benning of the morphology of cancrinite/gmelinite in that typical of sodalite (Figure 9b).
The formation of trona (Na3(CO3)(HCO3)·2H2O), mainly in the samples after the VPC method at 45 °C (Figure 3), is due to the progressive dissolution process of pre-fused raw material and increasing availability of Na+. The presence of these newly formed minerals seems to be competitive with thermonatrite (Na2CO3·H2O), of which the amount increases slightly at 60 °C VPC (Figure 5 and Figure 6). Although the conditions determined during the VPC process at different temperatures are fast from the complex phase relationships between the coexisting Na carbonate−bicarbonate minerals described by the literature data [65,66,67], Na2CO3·H2O formation takes place via the transformation of trona with the temperature increase [68].

5. Concluding Remarks

The results of these new experiments indicate that the low amount of water molecules by the vapor phase crystallization process performed at temperatures ranging from 45 to 90 °C is enough to form sodalite and control its evolution into cancrinite, regardless of the raw material used, as long as it is rich in amorphous silica and alumina pre-fused with NaOH.
According to the literature, the mechanism controlling zeolite formation by the VPC method in all the investigated raw material mixtures is intermediate between a solid state transformation and hydrothermal process [62]. Precisely, the low quantity of available water in the form of vapor molecules controls the fast crystallization of the more stable sodalite also due to the absence of a continuous dissolution and recrystallization activity taking place in the presence of a liquid solution, and thus during the conventional hydrothermal process. A hint of this process occurs only at VPC 90°, when a higher percentage of vapor molecules determines the slow dissolution of sodalite and crystallization of cancrinite.
Although this paper adds to information dealing with the repeatability of the process regardless of the sources, the mechanism controlling zeolite formation by the VPC method still is not well understood and needs more in-depth analyses.

Funding

This research received no external funding.

Data Availability Statement

Data are contained within the article.

Acknowledgments

The author thanks colleague Antonio Lettino for assistance with SEM analysis.

Conflicts of Interest

The author declares no conflicts of interest.

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Figure 1. Experimental flow chart of the zeolite synthesis process. (a) mixture preparation; (b) process.
Figure 1. Experimental flow chart of the zeolite synthesis process. (a) mixture preparation; (b) process.
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Figure 2. XRD patterns of (a) FA; (b) OS; and (c) RM samples before and after NaOH pre-fusion treatment. Mul = mullite; Qz = quartz; Bhm = boehmite; Gbs = gibbsite; Hem = hematite.
Figure 2. XRD patterns of (a) FA; (b) OS; and (c) RM samples before and after NaOH pre-fusion treatment. Mul = mullite; Qz = quartz; Bhm = boehmite; Gbs = gibbsite; Hem = hematite.
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Figure 3. XRD patterns of (a) FARM; (b) OSFA; and (c) OSRM after the vapor-phase crystallization (VPC) process at 45 °C. Sdl = sodalite; Tnat = thermonatrite; Tn = trona; Qz = quartz.
Figure 3. XRD patterns of (a) FARM; (b) OSFA; and (c) OSRM after the vapor-phase crystallization (VPC) process at 45 °C. Sdl = sodalite; Tnat = thermonatrite; Tn = trona; Qz = quartz.
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Figure 4. SEM images of (a) FARM; (b) OSFA; and (c) OSRM after the VPC process at 45 °C. Sdl = sodalite; Tn = trona.
Figure 4. SEM images of (a) FARM; (b) OSFA; and (c) OSRM after the VPC process at 45 °C. Sdl = sodalite; Tn = trona.
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Figure 5. XRD patterns of (a) FARM; (b) OSFA; and (c) OSRM after the vapor-phase crystallization (VPC) process at 60 °C. Sdl = sodalite; Tnat = thermonatrite; Qz = quartz.
Figure 5. XRD patterns of (a) FARM; (b) OSFA; and (c) OSRM after the vapor-phase crystallization (VPC) process at 60 °C. Sdl = sodalite; Tnat = thermonatrite; Qz = quartz.
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Figure 6. SEM images of (a) FARM; (b) OSFA; and (c) OSRM after the VPC process at 60 °C. Sdl = sodalite; Tn = trona.
Figure 6. SEM images of (a) FARM; (b) OSFA; and (c) OSRM after the VPC process at 60 °C. Sdl = sodalite; Tn = trona.
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Figure 7. XRD patterns of (a) FARM; (b) OSFA; and (c) OSRM after the vapor-phase crystallization (VPC) process at 90 °C. Sdl = sodalite; Tnat = thermonatrite; Ccn = cancrinite; Qz = quartz.
Figure 7. XRD patterns of (a) FARM; (b) OSFA; and (c) OSRM after the vapor-phase crystallization (VPC) process at 90 °C. Sdl = sodalite; Tnat = thermonatrite; Ccn = cancrinite; Qz = quartz.
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Figure 8. Representative SEM image of sodalite/cancrinite in the FARM sample after the VPC process at 90 °C. Sdl = sodalite; Tn = trona.
Figure 8. Representative SEM image of sodalite/cancrinite in the FARM sample after the VPC process at 90 °C. Sdl = sodalite; Tn = trona.
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Figure 9. Zoom of (a) the XRD pattern; and (b) SEM image of the OSRM sample after the VPC process at 60 °C showing the starting sodalite/cancrinite transformation.
Figure 9. Zoom of (a) the XRD pattern; and (b) SEM image of the OSRM sample after the VPC process at 60 °C showing the starting sodalite/cancrinite transformation.
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Table 1. Chemical composition (wt %) of fly ash (FA), obsidian (OS), and red mud (RM).
Table 1. Chemical composition (wt %) of fly ash (FA), obsidian (OS), and red mud (RM).
ElementFAOSRM
Na2O 0.544.314.03
MgO 1.430.150.21
Al2O3 28.2113.2011.46
SiO2 46.874.207.89
P2O5 0.780.020.09
K2O 1.264.940.45
CaO 5.570.963.53
TiO2 1.490.094.82
MnO 0.060.080.21
Fe2O3 5.231.7636.8
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Belviso, C. Determining the Role of Water Molecules in Sodalite Formation Using the Vapor Phase Crystallization Method. Processes 2024, 12, 486. https://doi.org/10.3390/pr12030486

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Belviso C. Determining the Role of Water Molecules in Sodalite Formation Using the Vapor Phase Crystallization Method. Processes. 2024; 12(3):486. https://doi.org/10.3390/pr12030486

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Belviso, Claudia. 2024. "Determining the Role of Water Molecules in Sodalite Formation Using the Vapor Phase Crystallization Method" Processes 12, no. 3: 486. https://doi.org/10.3390/pr12030486

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