Journal

J. Am. Ceram. Soc., 80 [9] 244953 (1997)

Zeolites Synthesized from Class F Fly Ash and Sodium Aluminate Slurry
Michael W. Grutzeck*
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802

Darryl D. Siemer
Lockheed Idaho Technology Company, Idaho Falls, Idaho 83415

A Class F fly ash was combined with a sodium aluminate slurry (3:1 Na:Al) in an attempt to synthesize zeolites from a highly alkaline waste stream. The reaction was studied as a function of composition (3:2, 1:1, and 1:2 fly ash:slurry), time (1, 3, and 7 days), and temperature (80, 130, and 180C). X-ray diffraction analyses of the products indicated that the fly ash and sodium aluminate had combined to form Zeolite A at 80C, and NaP1 (a gismondene-type) and an unnamed hydroxysodalite-type at 130 and 180C. The fact that the pH of the reactants decreased from initial values in excess of 13 to near neutral (79) after reaction signifies that the bulk of the sodium had been incorporated into zeolitic phases. Because of the unique adsorptive and cation exchange capabilities of zeolites and the fact that some samples formed reasonably hard monoliths, zeolitic materials formed in this way might make excellent waste forms for mixed wastes which contain both radioactive and hazardous chemical species. I. Introduction

are known host phases for heavy-metal and radioactive waste ions. Zeolites can accommodate species such as cesium and strontium either through in situ incorporation during the synthesis process or through subsequent cation exchange. In their dried state zeolites are exceptional desiccants able to adsorb as much as their own weight of various aqueous and organic liquids. Zeolites are a family of complex aluminosilicates having a three-dimensional network structure.1,2 By definition, they are tectosilicates; however, unlike quartz and feldspar, zeolites form very open structures containing relatively large channels and cavities. As a result, zeolites have densities in the range of 2.02.2 g/cm3 compared to the more compact structures of quartz and feldspar, which have densities in the 2.6 g/cm3 range. The structural openings in zeolites are normally occupied by alkali and alkaline-earth cations and loosely held water molecules. If the channels and cavities are continuous (i.e., not isolated) the cations are said to be exchangeable, and both the water molecules and cations can be desorbed/sorbed reversibly.3 Because of these structural and chemical characteristics, the zeolites have unique and well-known properties such as ion exchange, selective adsorption, and catalysis.4 Naturally occurring zeolites and their synthetic counterparts
EOLITES

C. M. Jantzencontributing editor

Manuscript No. 191289. Received January 9, 1997; approved June 2, 1997. Supported by the Department of Energy, Office of Basic Energy Science, under Grant No. DE-FG02-91ER45456, and by the Department of Energy, Pittsburgh Energy Technology Center, under Grant No. DE-FG22-96PC96210. *Member, American Ceramic Society.

are an extremely important class of materials. The majority of naturally occurring zeolites are products of reactions between glassy volcanic ashes (tuffs) and the alkaline solutions associated with certain types of rock strata. In nature, the rate of zeolite formation is limited by the fact that reaction temperatures/pressures are quite low and soil solutions are only slightly alkaline.1,2 However, the use of hydrothermal vessels, more concentrated solutions, and templating agents have shortened synthesis times to a few hours.5 For example, see Table I, which contains a compilation of data taken from the literature. Finally, in an extremely comprehensive study, BarthWirsching and Ho ller13 were able to synthesize a variety of zeolites from ground alkali-containing basaltic and rhyolitic glasses (see Table II for the composition of these two glasses) using a series of different sodium and potassium hydroxide solutions. Phase data were collected at 8 and 80 days and reaction temperatures ranged from 50 to 250C. These researchers were able to synthesize chabazite, phillipsite, analcime, merlinoite, NaP, and X. Clearly, the synthesis procedure described in this paper is not novel, but the discovery that zeolites could be made to form in situ from a mixture of alkali hydroxides and Class F fly ash, and that zeolites could nucleate and grow in equilibrium with a calcium silicate hydrate (C-S-H) matrix, is.1416 These findings were an outgrowth of previous research with cementbased waste forms which started much earlier. By monitoring leach and pore solution compositions, Hoyle and Grutzeck1719 were able to demonstrate that aluminosilicate-enriched blends of cement and silica fume made much better waste forms for cesium than did portland cement because the fly ash-containing cements were forming cesium-containing zeolites. Based on this finding, Hoyle and Grutzeck synthesized Glasses 8 and 9 (Table II), which they ground and subsequently mixed with saturated CsOH solutions. By monitoring the progress of the reaction with X-ray diffraction and SEM they documented a correlation between zeolite formation (cesium retention) and both glass composition and temperature. At 90C Glass 8 formed the Cs-substituted zeolite herschelite (Cs4Al4Si8O24 12H2O) while Glass 9 formed pollucite (Cs2Al2Si4O12H2O). In addition, the zeolites were observed to be cemented by a reticulated calcium silicate hydrate (C-S-H) which imparted strength to the material.17 Bozich20 reported the formation of gobbinsite (Na5Al5S11O3211H2O) when she hydrated two glasses having compositions similar to Glass 9 in 1M NaOH solution at 70 and 90C. Finally, LaRosa et al.14 generated zeolites NaP1 (Na3Al3Si5O166H2O) and Y (Na2Al2Si4.5O13 xH2O) when she mixed Class F fly ash with 2.85M NaOH and KOH solutions (see Table II for the composition of the fly ash B92). LaRosa et al.15 also synthesized the same zeolites plus chabazite (Ca2Al4Si8O2412H2O) from mixtures of B92 fly ash (80%) and portland cement (20%) having a w/s ratio of 0.4. In this instance she reported that the zeolite-containing samples made with a 5M NaOH solution were significantly stronger than companion samples made with water. Since these papers were published, others either have confirmed the zeolitization of waste glasses (fiber glass21 and fly ash2227) or have begun
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Communications of the American Ceramic Society Table I. Zeolite Synthesis from Glasses
Alkali type Time (days) Temp (C)

Vol. 80, No. 9

Researcher(s)

Starting materials

Product

Ottana et al.6 Burriesci et al.7

Lipari pumice Sardinian perlite, Sicilian tuff Shirasu volcanic ash Volcanic ash Na-metasilicate, Al-phosphate Aluminosilicate gels Aluminates, silicic acid, glassy quartz wool, silica sol

NaOH, NaCl NaOH

<1 <1

95 8595

ZK-19, hydroxysodalite, phillipsite Na-P, hydroxysodalite, phillipsite, faujasite-type Faujasite-type, P, phillipsite, analcime Clinoptilolite ZK-14, ZK-19, Y Chabazite

Yoshida and Inoue8 Hawkins et al.9 Kuhl10 Barrer11 Fiedler

12

NaOH NaK(CO3) NaOH, KOH NaOH NaOH

07 315 121

90 130150 90100

17

60150

A, faujasite

Table II.
SiO2 Al2O3

Chemical Composition of Natural and Synthetic Glasses

Fe2O3 FeO MgO Composition (wt%) CaO Na2O K2O P2O5 SO3 Totals

Basalt Rhyolite Glass 8 Glass 9 Fly ash (B92)

46.33 72.78 51 66 53.2

19.21 11.89 23 16 26.0

4.00 0.55 7.95

4.78 0.99

2.48 0.22 0.97

6.65 0.55 26 18 3.57

8.20 3.03 0.29

4.05 5.31 2.59

0.90 0.01 0.59

96.6 95.3 100 100 95.2

As analyzed from Steinberg near Feldbach, Styria, Austria. As analyzed from Lake Tecopa, Inyo County, CA. As-formulated compositions synthesized from reagent-grade oxides and hydroxides. As analyzed from PP&L Montour Unit #1, Montoursville, PA. Other components include TiO2, elemental carbon, CO32 and OH.

to identify zeolites in cementitious materials.2830 and DOE waste sludges.21,31 The objective of the research described in this paper was to demonstrate that a typical DOE mixed waste could readily be converted to a zeolite-containing waste form. The waste in question is the as-yet-uncalcined 5700 m3 (1.5 106 gal) of liquid sodium-rich reprocessing waste at the Idaho Chemical Processing Plant (ICPP). Chemically, the waste is a rather simple aqueous solution containing 1.5M sodium nitrate, 0.5M aluminum nitrate, and 1.5M nitric acid. Also present are trace amounts (ppm) of fission product elements, actinides, and toxic metals (primarily chromium, lead, cadmium, and mercury). From a regulatory standpoint, it is a complicated waste because it is simultaneously mixed waste as well as transuranic (TRU), greater than class-C and listed. If it were to be processed by ICPPs existing calciner, it could be converted to 450 m3 of a mixture of sodium oxide and sodium aluminate powders, materials perfectly suited to the zeolitization process discussed earlier. II. Experimental Procedure

A simulant emulating a water-based slurry of calcined ICPP sodium bearing waste was made by stirring a low-fired

Mixed waste contains source, special nuclear, or byproduct material subject to regulation under the Atomic Energy Act and hazardous waste subject to regulation under the Resource Conservation and Recovery Act. [U.S. Code Title 42., Section 2011]. This and the following definitions have been taken from a working draft of ASTM standard definitions originating in ASTM Committee C26.07. Transuranic waste is any waste material measured or assumed to contain more than a specified concentration (e.g., presently 10 nCi of transuranic activity per gram of waste) of transuranic elements. Greater than class-C waste contains radionuclides in concentrations exceeding the limits for Class C wastes as defined in 10 CFR 61 and is generally not suitable for disposal in shallow land burial facilities. Listed waste is one which appears on the U.S. Environmental Protection Agencys list of hazardous wastes. It is highly probable that radiolytic/chemical reactions have long since destroyed these compounds (most of the waste has been in underground tanks for over 20 years and the compounds cannot be detected by modern analytical methods). Calcination of this waste was successfully demonstrated in ICPP pilot plants more than 30 years ago.

alumina (Rho ne-Poulenc flash calcined Al2O3) in a solution of reagent-grade sodium hydroxide. The proportions used were 0.5 mol of alumina and 3 mol of sodium hydroxide plus enough deionized water to make 1 L. This slurry was stirred for 3 months in a sealed flask before use. Residual material present in the slurry was determined to be the stable aluminum hydroxide phase (gibbsite). The resulting slurry had a specific gravity of 1.16 g/cm3. The slurry was mixed with varying amounts of the same Class F fly ash used by LaRosa et al.14,15 (Table II) in her experiments. The fly ash was mixed with the slurry in various weight proportions (fly ash:slurry 3:2, 1:1, 1:2) and allowed to react in Teflon-lined pressure vessels at 80, 130, and 180C for 1, 3, and 7 days. The vessels were quenched by immersing them in cold water. When cool, the samples were transferred to filter-paper-lined funnels and rinsed with DI water. After drying in air, the samples were examined using X-ray diffraction (Phillips APD 3600) and SEM (ISI DS-130). Some samples contained residual liquids which were tested using pH indicator paper. Generally there was a dramatic drop in the pH of the slurry from an initial >13 before the reaction to 7 to 9 after the reaction. This suggests that the majority of the sodium ions in the slurry were incorporated in the zeolite network during the zeolitization process. Composites of X-ray patterns illustrating the time dependency of the reactions for the fly ash/slurry combinations studied at 80 and 180C are given in Figs. 1 and 2, respectively. At 80C, Zeolite A forms most readily at 1 day in the 3:2 and 1:1 fly ash:slurry mixtures. Because Zeolite A is metastable, the amount present in the samples seems to decrease with length of reaction, presumably changing into a more stable but X-ray amorphous material. Although it is absent in the 1:2 mixture, this does not automatically preclude its formation and rapid alteration. The quartz and mullite which coexist with Zeolite A and other zeolites mentioned later are residual phases originally present in the fly ash. The 130 and 180C mixtures are essentially carbon copies of each other, except for the

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Fig. 1. 80C X-ray diffraction patterns of mixtures of fly ash plus sodium aluminate slurry (fly ash: slurry 3:2, 1:1, 1:2) plotted as a function of time (1, 3, 7 days): () Zeolite A, (M) mullite, (Q) quartz, and (U) unknown.

Fig. 2. 180C X-ray diffraction patterns of mixtures of fly ash plus sodium aluminate slurry (fly ash: slurry 3:2, 1:1, 1:2) plotted as a function of time (1, 3, 7 days): () Zeolite NaP1, (), hydroxysodalite-type (JCPDF No. 31-1270), (M) mullite, (Q) quartz, and (U) unknown.

greater degree of reaction one might expect at the higher temperature. These samples contain two zeolites: a gismondinetype (NaP1), and increasing amounts of a hydroxysodalite-type (similar to unnamed JCPDS No. 31-1270) as the proportion of slurry in the mixtures is increased. Unlike the 80C mixture, the zeolites that form initially continue to form with time as increasingly larger amounts of the fly ash react with the slurry (amorphous hump decreases with time). Note that gibbsite is not detectable in any of the mixtures, indicating extremely favorable reactivities. Finally, a small amount of an unknown phase was detected in all mixtures. The microstructure of the samples is decidedly temperature dependent. The micrographs taken at 1 day (Fig. 3) illustrate the greater reactivity of the glassy fly ash spheres at higher temperatures. At 80C many spheres remain, whereas at 180C they are essentially absent. In some instances crystals can be seen adhering to the surfaces of the fly ash spheres (Figs. 3(A) and (B), sphere with hole, respectively). Presumably these overgrowths represent early stages in the dissolution/growth process. Zeolite A (Fig(A), 80C) is cubic and seems to coexist

with occasional assemblages of needlelike crystals. NaP1 (massive to clusters of radiating crystals) and hydroxysodalitetype (intersecting disks) zeolite crystals (Figs. 3(B,C)) are found in the 130 and 180C runs. Published data suggest that the zeolite phases grow from solution. In this instance the zeolites seem to nucleate and grow outward from the surface of the fly ash spheres, sometimes retaining the overall spherical shape of the fly ash. The reticulated honeycomb phases that form with the zeolites have the appearance of calcium silicate hydrate (C-S-H), the phase which gives portland cement its strength. As more zeolites form, they tend to intergrow with each other and with the C-S-H forming more massive material (Fig. 3(C)). It is this intergrowth which seems to be giving the samples their strength. III. Results and Discussion

This work suggests that low-cost cementitious technologies could be used to convert properly calcined U.S. defense-type reprocessing radwaste to mineral assemblages that would constitute superior waste forms in likely ultimate repository set-

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Fig. 3. Representative SEM micrographs of phases present in the 1:1 mixture after 1 day at 80C (A), and in the 1:2 mixtures after 1 day at 130C (B) and 180C (C). The bar at the bottom of each figure is 5 m in length. Zeolite A is cubic in appearance and easily differentiated from residual spherical mullite clusters seen in view (A). Views (B) and (C) contain spheres assembled from intersecting disks (not mullite, more likely hydroxysodalite), more massive crystals (NaP1) and traces of hydrates having a C-S-H like reticulated honeycomb structure.

tings (e.g., in DOEs proposed Yucca Mountain facility or DOE-Nevadas Greater Confinement Disposal system). The reason for this is that, in surroundings consisting largely of zeolitized tuff, zeolitic materials would be much closer to thermodynamic equilibrium than glass would be. Calcination is necessary because the alkali metal salts that constitute the bulk of these radwastes must be converted to caustics capable of quantitative reaction with pozzolans such as fly ash. The intrinsic radioactivities of U.S. defense-type reprocessing radwaste are simultaneously too low to damage cementitious materials and sufficiently high to promote hydrothermal curing reactions in an insulated interim storage system. The zeolites A, NaP1, and sodium hydroxysodalite formed in these reactions are capable of incorporating ions of various types in

their cavities. The fact that the same zeolites formed from various proportions of fly ash and sodium aluminate slurry above and below 100C suggests that the process could accommodate minor changes in waste stream composition and temperature without compromising the waste forms properties. The fact that some formulations produced rather hard monolithic samples (usually the 1:2 fly ash:slurry samples) further suggests that mechanical properties might also be optimized if needed. IV. Summary and Conclusions

E. J. Bonano et al., The Disposal of Orphan Wastes Using the Greater Confinement Disposal Facility; pp. 86168 in Waste Management 91, Vol. 1. Edited by R. G. Post and M. E. Wacks. Arizona Board of Regents, 1991. The radioactive heat generation rates of DOEs high level reprocessing radwastes range from about 7 W/m3 for Hanford sludge up to about 60 W/m3 for Savannah River Plant sludge. U.S. high level radwaste is 24 orders of magnitude less radioactive than are the materials being vitrified at modern British and French reprocessing facilities. After calcination, the waste addressed by this project would generate roughly 12 W/m3. Most of DOEs low level radwaste is less radioactive. L. R. Dole et al., Cement-Based Radioactive Waste Hosts Formed under Elevated Temperatures and Pressures (FUETAP Concretes) for Savannah River Plant, High-Level Defense Waste, Doc. No. ORNL/TM-8579, pp. 5064 (1983)

Although the study was exploratory, the fact that zeolites can be formed from mixtures of fly ash and sodium aluminate solutions with only moderate heating of the sample is encouraging in as much as a zeolitic waste form could be ideally suited to dealing with mixed waste which contains radioactive cesium, strontium, and heavy-metal elements. References
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4 F. A. Mumpton, Utilization of Natural Zeolites; pp. 172204 in Reviews in Mineralogy, Vol. 4, Mineralogy and Geology of Natural Zeolites. Edited by F. A. Mumpton. Mineralogical Society of America, Washington, DC, 1977. 5 P. A. Jacobs and J. A. Martens, Synthesis of High-Silica Aluminosilicate Zeolites. Elsevier, New York, 1987. 6 R. Ottana, L. M. Saija, N. Burriesci, and N. Giordano, Hydrothermal Synthesis of Zeolites from Pumice in Alkaline and Saline Environment, Zeolites, 2, 29598 (1982). 7 N. Burriesci, M. L. Crisafulli, N. Giordano, J. C. J. Bart, and G. Polizzotti, Hydrothermal Synthesis of Zeolites from Low-Cost Natural SilicaAlumina Sources, Zeolites, 4, 38488 (1984). 8 A. Yoshida and K. Inoue, Formation of Faujasite-type Zeolite from Ground Shirasu Volcanic Glass, Zeolites, 6, 46773 (1986). 9 D. B. Hawkins, R. A. Sheppard, and A. J. Gude, Hydrothermal Synthesis of Clinoptilolite and Comments on the Assemblage of Phillipsite ClinoptiloliteMordenite; pp. 33743 in Natural Zeolites, Occurrence, Properties, Use. Edited by L. B. Sand and F. A. Mumpton. Pergamon Press, Oxford, U.K., 1978. 10 G. H. Kuhl, Influence of Phosphate and Other Complexing Agents on the Crystallization of Zeolites; pp. 8591 in Molecular Sieves, Proceedings of a Conference held at the University of London, April 46, 1967. Soc. Chemical Industry, London, U.K., 1968. 11 R. M. Barrer, Hydrothermal Chemistry of Zeolites. Academic Press, London, U.K., 1982. 12 F. J. Fiedler, H. H. Lohse, and K. Schurmann, Synthesis of Zeolites in the System Na2OAl2O3SiO2H2O, Neues Jahrb. Mineral. Monatsh., 35864 (1983). 13 U. Barth-Wirsching and H. Ho ller, Experimental Studies on Zeolite Formation Conditions, Eur. J. Mineral. 1, 489506 (1989). 14 J. LaRosa, S. Kwan, and M. W. Grutzeck, Zeolite Formation in Class F Fly Ash Blended Cement Pasters, J. Am. Ceram. Soc. 75, 157480 (1992). 15 J. LaRosa, S. Kwan and M. W. Grutzeck, Self-Generating Zeolite Cement Composites, Mater. Res. Soc. Symp. Proc., 245, 21116 (1991). 16 M. W. Grutzeck, ZeoliteCement Composites; pp. 36895 in Mineral Admixtures in Cement and Concrete, Vol. 4. Edited by S. Sarkar. ABI Books (P) Ltd., New Delhi, India, 1993. 17 S. L. Hoyle and M. W. Grutzeck, Incorporation of Cesium by Hydrating Calcium Aluminosilicates, J. Am. Ceram. Soc., 72, 193847 (1989). 18 S. Hoyle and M. W. Grutzeck, Effect of Pore Solution Composition on Cesium Leachability of Cement-Based Waste Forms, Mater. Res. Soc. Symp. Proc., 84, 30917 (1987).

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