Thermal stability of sodalite synthetized from zeolite 4A

Dipartimento di Chimica, Materiali e Ingegneria Chimica “G.Natta”

Politecnico di Milano
Piazza Leonardo da Vinci 32, 20133 Milano - Italy

A. C. TITO (1), F. BIANCO (2), C. MAZZOCCHIA (3)

♦ (2)Politecnico di Milano Piazza Leonardo da Vinci 32, 20133 Milano – Italy

atito@chem.polimi.it

♦ (1)Politecnico di Milano Piazza Leonardo da Vinci 32, 20133 Milano – Italy

biancof@polimi.it

♦ (3)Politecnico di Milano Piazza Leonardo da Vinci 32, 20133 Milano – Italy

Carlo.mazzocchia@polimi.it

Abstract
This work is focused on the evolution of the mixture of zeolite 4A and sodium chloride increasing the
temperature. One of the most important goal in the nuclear waste management is to develop a method to
stabilize the High Level radioactive Waste (HLW) using a suitable matrix with a strong leaching resistance,
a good thermal stability and a marked mechanical resistance. Material issues are important during the entire
process of nuclear-waste management and the performance of the materials used in nuclear waste
management determines its safety/hazard. Since the safety of nuclear waste management relies mainly on
the immobilization of radioactive constituents and long-term isolation of these from the biosphere,
materials issues with the immobilization and long-term isolation of nuclear waste are particularly
important. An interesting matrix is sodalite. In order to verify its thermal stability, it is studied the solid
state reactions of a mixture of zeolite 4A and sodium chloride. Zeolite 4A was treated, in presence of NaCl,
from 500°C to 900°C, in a traditional oven and in a microwaves oven in order to compare these two heating
systems.
Comparing the microwave assisted reaction with the one made in the traditional tubular oven it’s possible
to remark the microwaves effects on the reaction. In fact the synthesis made with traditional heating
usually requires longer reaction times. The microwaves- assited process produces a pure sodalite in 5 hours
keeping constant the temperature of the reaction and making, in succession, 1 hour and a half heating to
reach 900°C.
The reactions in the conventional oven, instead, didn’t produce a pure sodalite not even after 10 hours of
reaction. This effect is due to microwaves action: the presence of NaCl (a polar compound on which
microwave irradiation can act) allows to reach high temperatures in the reaction mixture. Because of the
equally distribution of the salt into the mixture, homogenous hot spots are created in which the temperature
locally goes over 900°C and this phenomenon highly increases the reaction rate.

Keywords. sodalite, zeolite, microwaves, radioactive waste, sodium chloride

INTRODUCTION
Sodalite is a volcanogenic mineral belonging to the silicate class. The silicates are divided into many
subclasses and sodalite is classified in the feldspathoid group that belongs to the same subclass of the

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zeolites: the tectosilicates. This subclass is often called framework silicates because their structures are
tridimensional lattices made by polyhedrons [(Si,T)On] binding among them by oxygen bridges. Usually T
= Aluminium and n = 4, so the polyhedrons are silico-aluminate tetrahedron [SiAlO 4]. Sodalites have this
generic formula:
Mmq+ [ (AlnSi12-nO24)n- ] Xxr- · a Z where qm–rx=n
The sodalite lattice is made by [AlO4]5- and [SiO4]4- tetrahedrons which provide a total negative charge.
Some positive cations Mmq+ are able to coordinate themselves with active oxygen and other negative species
Xxr- which are in the lattice, balancing the tetrahedron negative charge. In this way the sodalite structure
could contain different cations (generally alkali and alkaline-heart metals) and different anions.
Furthermore it could be possible to find a neutral molecule (Z) as, for example, water. The ideal formula of
natural sodalite is Na8 [ (Al6Si6O24) ] Cl2 and this kind of sodalite has been the object of this work.
As it was described before, different sodalites could be made with different compositions depending on the
cations, the anions and the neutral molecules they contain in the structure, but all of them have the same
tridimensional lattice usually called ‘sodalite-cage’ or ‘β-cage’. This elementary geometric structure is a
basic unit of many other silico-aluminates, in particular many zeolites (figure 1).

Figure 1. Zeolites made by sodalite cages

Sodalite can undergo a ionic exchange as many zeolites, so it’s possible to synthesize sodalites with
different compositions. Derek Taylor [1] produced many kinds of sodalite by ionic exchange (figure 2)
method. Sodalite is a crystalline compound which is able to include into its lattice different cations and
anions, in particular halides. Therefore it has been studied as a possible silico-aluminate matrix that might
trap the radioactive waste, in form of halide, coming from the nuclear waste electrorefining treatment [2, 3,
4]. So it’s very important to find out a simple synthesis method which could produce the leach resistant
sodalite with a good yield for immobilizing waste chloride salts containing radionuclides and hazardous
nuclide material for permanent geological disposal.

Na8 [(Al6Si6O24)]Cl2
Li4.4Na3.6 [(Al6Si6O24)]Cl2
Li8 [(Al6Si6O24)]Br
Li8 [(Al6Si6O24)]Cl2
Na5.5K2.5 [(Al6Si6O24)]Cl2
Na8 [(Al6Si6O24)]I2
Na0.3K2Rb6.3 [(Al6Si6O24)]Cl2
Figure 2. Sodalites produced by Derek Taylor [1]

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The sodalite synthesis has already been the object of many researches. Different methods with different
starting reactants have been studied by many authors, but there are only two synthesis classes: the solid
state reactions [2, 3] and the hydrothermal reactions [5].
This work is focused on the solid state synthesis of sodalite from zeolite 4A and NaCl.
EXPERIMENTAL SECTION
The use of zeolite A as reactant for sodalite synthesis derives from different reasons related to the chemical
and physical zeolite properties and, above all, its lattice geometry:
• Zeolite A shows a Si: Al ratio equal to 1, exactly the same of that of the sodalite, so it isn’t
necessary to correct that ratio.
• A very important aspect is that related to zeolite A structure: this is very similar to natural
sodalite fundamental structure. In fact, zeolite A is formed by 8 sodalitic lattices, placed at the
vertexes of an imaginary cube, joined through 4 O2 bridges (fig. 3).
• Zeolite A is thermally stable below 600°C. At a higher temperature, it collapses. On the contrary,
the sodalite has a thermal stability more high.
• Sodalite thermodynamically represents a zeolite evolution at high temperature.
Becauseof its properties zeolite can be considered an optimal sodalite precursor.
The zeolite A solid state reaction is made either in a traditional oven or in a microwave oven in order to
compare these two heating systems.
Sodalitic lattice

Figure 3. Representation of the zeolite A fundamental lattice unity

Microwave-assisted synthesis of sodalite

The microwave-assisted reaction is made in a Milestone Ethos 1600 microwave oven (with a temperature-
control program, operating at a constant output power of 300 W) at 900°C to assure the complete zeolite A
decomposition and to obtain melted NaCl with a higher reaction rate (T m NaCl=801°C). Salt quantity is
higher than stoichometric value because of the aim of this research is to verify sodalite formation, without
focusing on material balance and optimal reaction conditions. Many tests are made varying time in order to
carry out a kinetic study of the synthesis process. At the end of the reaction the product is washed with hot
water, in presence of mechanical agitation for 1 hour with the purpose of melting the excess of unreacted
salt. At last, the powder is recovered by vacuum filtration.
Before starting the experimentation, a test (called ZEOCAL) is made. In this test, zeolite A is thermally
treated at 900°C for 5 hours in a microwaves oven in NaCl absence, for evaluating the salt influence in the
reaction. It’s possible to conclude that a zeolite A thermal treatment at 900°C produces nepheline
(NaAlSiO4) (fig. 4). This compound seems the more stable phase obtainable under these conditions.
Thermodynamically, under the above mentioned operative conditions, on the contrary, it shall be obtained
either the sodalite, if chloride ions are present in the reaction ambient, or the hydroxyapatite (or basic
sodalite, in that OH- ions substitute the Cl- ones), as more stable phases.
During the ZEOCAL test, the two possible sodalite don’t show an aggregate of chloride ions and the
hydroxylic ions (in absence of water into the reaction ambient).

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 Figure 4. ZEOCAL test sample XRD pattern. The stripes marked in the upper section of the pattern show the presence of nepheline

In the table 1 the experiments made to obtain sodalite are reported. The 4 tests are made using the same
amount of reactants, but with different run time (t).

Sample Zeolite A NaCl T t* product

[g] [g] [°C] [g]
zos01 2 3 900 1h30' R 1,91
(uop 7007) (+) 1h40'
zos02 2,02 3,02 900 1h R 2,02
(uop 7007) (+) 2h
zos03 2,1 3,02 900 1h30' R 2,1764
(uop 7007) (+) 3h
zos04 2,045 3 900 1h30' R 2,26
(uop 7007) (+) 5h
*the reaction time is related to a step, R, in that the oven reached the set temperature and to a second step in that the temperature is
constant
Table 1. Solid state synthesis tests of natural sodalite

zeolite A
zos01
zos02
zos03
Tempo

zos04

10 20 30 40 50 60 70
2θ

Figure 5. XRD patterns comparison of the tests reported in table 1

Observing figures 5 and 6 it can be noted that, in all the tests, the starting zeolite peaks are not present: these
data confirm the zeolitic structure instability at high temperatures (X-ray diffraction (XRD) patterns is
recorded using a X Philips Analytical generator with a difractometer PW1710 BASED type (λ = 1.542)).
Moreover only zos04 test sample shows the zeolite spectrum, indicating that the reaction is ended in a
reaction heating rate of 1h30’.

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 Sodalite di riferimento
Zos04

10 20 30 40 50 60 70
2θ

Figure 6. Comparison between zos04 test and the sodalite spectrum of reference

The patterns of samples prepared in presence of reaction times lower than those of zos04 test are analyzed
with the aim of comprising the intermediate phase nature. The figure 7 shows that test zos04 sample
spectrum presents the sodalite peaks and the nepheline peaks. It is possible to conclude that the zeolite A
and NaCl starting reaction brings to sodalite production, yet the reaction advances through the formation of
nepheline, like intermediate phase. This aspect confirms the metastable nature of zeolite A and nepheline ,
compounds that, in a suitable reaction ambient, tend to transform themselves into the more stable phase: the
sodalite. It just is the sodalite stability at high temperatures that makes this compound very interesting for
the nuclear waste inertization operation, because of the nuclear decadence reactions show a very high
energetic release, that can deteriorate the containing material resistance. This resistance could be the higher
possible.

Zeolite calcinata
Zos01
Sodalite

10 20 30 40 50 60 70
2θ

Figure 7. Comparison between zos04 test sample and thermally treated zeolite and sodalite

In the zos02 and zos03 tests samples spectra, the nepheline peaks tend to disappear leaving space to
sodalite, that, on the other hand, is in crystallization step (figure 5).
The zos04 test is the one that produces pure and crystalline sodalite. The ideal reaction is
Na 12 Al 12 Si 12 O48 + 4 NaCl →2 Na 8 Al 6 Si 6 O24 Cl 2 .
On the basis of this stoichometric ideal equation, the total yield of product is calculated and it is equal to
97.1%. The reaction can be considered complete. Comparing the solid state reaction yield with the
hydrothermal synthesis yield (typically 80%) it can be observed that this is higher of 17 points percent [6].

At last the zos04 test product is analyzed with Scanning Electron Microscopy (Zeiss EVO 50 EP electron
microscope operating at an acceleration tension between 200V and 30 kV) (figures 8 and 9).

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 Figure 8 and Figure 9. zos04 sample SEM images

Figures 8 and 9 show sodalite crystals without a well defined geometric shape (with the average dimensions
of 40- 70 nm) like that of the samples produced during a typical hydrothermal synthesis (with the average
dimensions of 200 nm). This is probably due to the different reaction system: into an aqueous ambient
mechanism there is a germination and a next uniform crystals growth, in a solid state reaction, on the
contrary, a reactive act probably occurs at the interface between the different phases, that constitute the
mixture, and involves the formation of non uniform and without a well defined geometry crystals. Either
way it is possible to notice some regular geometric shapes, even if crystals present many sink marks
probably caused to the excess of unreacted salt, washed after the reaction.

Tests made in a traditional tubular oven

To make a comparison between the conventional heating method and the microwaves one, some tests
inside a tubular traditional oven (Carbolite® tubular oven MTF series) are made. In this case the reaction is
conducted at 900°C and in presence of an excess of NaCl. The tests are made varying their duration time in
order to verify the kinetic profile of the process (the set temperature is reached in a time frame of 15-20
minutes).

Sample Zeolite A NaCl T t product

[g] [g] [°C] [h] [g]
zost02 1,01 1,514 900 5 0,99
zost03 1,03 1,52 900 8 1,08
zost04 1 1,51 900 10 1,0424
Table 2. Tests made to obtain sodalite from zeolite made in a tubular oven

The figure 10 shows the XRD spectra of the 3 prepared samples.

Rising the reaction time, keeping all other conditions unchanged, the reaction evolves to form sodalite ,
even if in spite of the 10 hours of reaction of the zost04 test, the desired purity of the product is not reached.
The peaks not attributable to sodalite, present in the XRD pattern, decrease in intensity when the reaction
time increases and they represent an intermediate phase between starting zeolite A and sodalite.

ZOST02
ZOST03
ZOST04

10 20 30 40 50 60 70
2θ

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 Figure 10. XRD patterns of the 3 samples made in the tubular oven

Zeolite calcinata
ZOST03
Sodalite di riferimento

10 20 30 40 50 60 70
2θ

Figure 11. Comparison between zost03 test, thermally treated zeolite and sodalite of reference

In the figure 11 the zost03 test is compared with the sodalite of reference and calcinated zeolite. This figure
shows that, even heating in the traditional tubular oven, the reaction proceeds through the formation of
nepheline before the sodalite.
Comparing the microwave assisted reaction with the one made by the conventional heating it’s possible to
remark again the microwave effects on the reaction. In fact the reaction made by the traditional oven
usually requires longer reaction times. zos04 test produces pure sodalite in a reaction time of 5 hours
working at a constant temperature operative step followed by a 1 hour and a half heating to reach 900°C.
On the contrary the reactions in the tubular oven don’t produce a pure sodalite not even after 10 hours of
reaction. This effect is due to microwaves action: probably NaCl in the reaction mixture, being a polar
compound, picks up the microwaves and it allows to reach high temperatures into the reactant system.
Because of the salt being uniformly distributed into the mixture, different zones are created in which the
temperature locally is more than 900°C and these phenomena highly increase the reaction rate.
References
1) Taylor, D.: Cell Parameter correlations in the aluminosilicate sodalites. Contrib. Mineral.
Petrol. 51, 39-47 (1975).
2) Koyama, T.: Method to synthesize dense crystallized sodalite pellet for immobilizing halide salt
radioactive waste. U.S. Patent n. 5,340,506 (1994).
3) Pereira, C.: Method of preparing sodalite from chloride salt occluded zeolite. U.S. Patent n.5,613,240
(1997).
4) Laidler, J.J., Battles J.E., Miller, W.E., Ackerman, P., Carls, E.L.: Development of Pyroprocessing
Technology. Progress in Nuclear Energy 31, 131-140 (1997).
[5] Barrer, R. M., Cole, J. F., Sticher, H: Chemistry of soil mineralspart V: Low Temperature Hydrotermal
Transformations of Kaolinite, Chem. Soc. (A), 2475 (1968).
[6] De Angelis, G. Nannicini, R. Martini, F. Mazzocchia, C. Modica, G.: Different methods to synthesize
sodalite, as a matrix for conditioning chloride spent salts from pyroprocesses, Radiochim. Acta, 96, 303-310
(2008).