NATURAL ZEOLITES: INDUSTRIAL AND ENVIRONMENTAL APPLICATIONS

VASSILIS J. INGLEZAKIS1, ANTONIS ZORPAS National Technical University of Athens School of Chemical Engineering Unit of Environmental Science and Technology (UEST) GR- 157 80, Zografou Campus Athens, Greece e-mail: v_inglezakis@yahoo.com Abstract Natural zeolites are the least-known treasures for industrial applications, environmental pollution control, separation science and technology. Natural zeolites are volcanic minerals with unique characteristics. Their chemical structure classifies them as hydrated aluminosilicates, comprised of hydrogen, oxygen, aluminum, and silicon, arranged in an interconnecting lattice structure. The arrangement of these elements in a zeolite crystal gives rise to a honeycomb framework with consistent diameter connecting channels that vary in size from 2.5 to 5.0 angstroms, depending on the type of zeolite mineral. This unique structure makes zeolites different from "other" aluminosilicates (kaolin, bentonite, etc.) due to the following special properties: the ability to selectively adsorb molecules of gases and vapors, the ability to reversibly absorb/desorb water without any chemical or physical change in the zeolite matrix and the ability to exchange inherent cations for other cations on a basis of ion selectivity. The present paper reviews the critical properties of natural zeolites and important uses in industry and environmental-related applications. Key words: natural zeolites, wastewater, adsorption, ion exchnage 1. INTRODUCTION Zeolites are hydrated aluminosilicates of the alkaline and alkaline-earth metals. About 40 natural zeolites have been identified during the past 200 years; the most common are analcime, chabazite, clinoptilolite, erionite, ferrierite, heulandite, laumontite, mordenite, and phillipsite. The most commonly mined varieties of natural zeolites are chabazite and clinoptilolite. More than 150 zeolites have been synthesized; the most common are zeolites A, X, Y, and ZMS-5. Natural and synthetic zeolites are used commercially because of their unique adsorption, catalytic, ion exchange, and molecular sieve properties [1]. As the synthetic zeolite (molecular sieve) business began to take hold in the late 1950s, huge beds of zeolite-rich sediments, formed by the alteration of volcanic ash (glass) in lake and marine waters, were discovered in the western United States and elsewhere in the world. These beds were found to contain as much as 95% of a single zeolite; they were generally flat-lying and easily mined by surface methods. The properties of these low-cost natural materials mimicked those of many of their synthetic counterparts, and considerable effort has made since that time to develop applications for them based on their unique adsorption, cation-exchange, dehydration-rehydration, and catalytic properties. Natural zeolites (i.e., those found in volcanogenic sedimentary rocks) have been and are being used as building stone, as lightweight aggregate and pozzolans in cements and concretes, as filler in paper, in the take-up of Cs and Sr from nuclear waste and fallout, as soil amendments in agronomy and horticulture, in the removal of ammonia from municipal, industrial, and agricultural waste and drinking waters, as energy exchangers in solar refrigerators, as dietary supplements in animal diets, as consumer deodorizers, in pet litters, in taking up ammonia from animal manures, and as ammonia filters in kidney-dialysis units. From their use in construction during Roman times, to their role as hydroponic (zeoponic) substrate for growing plants on space missions, to their recent success in the healing of cuts and wounds, natural zeolites are now considered to be full-fledged mineral commodities, the use of which promise to expand even more in the future [3]. Zeolites can be compared to a sponge. The molecules absorbed by the zeolite are in part determined by the size of each molecule. A molecule can only be absorbed if it can fit through the microscopic holes in the zeolite. If a molecule is too large, then it is not absorbed because it cannot fit through the gap. Ammonia, hydrogen sulfide, carbon monoxide, carbon dioxide, sulfur dioxide, steam, oxygen, nitrogen dioxide and formaldehyde can all be absorbed by passing through the microscopic holes. Zeolite can be thought of as a molecular sieve. Apart from adsorption, another major mechanism of adsorption by zeolites was found to be ion-exchange. In the three dimensional structure there are large channels containing negatively charged sites resulting from Al 3+ replacement of Si4+ in the O4 tetrahedrallinked by sharing oxygen atoms in rings and cagescavities occupied by cations which are weakly held in the structure to compensate the charge imbalance. Zeolites contain various types of cationic sites.

The overall negative charge of the anions is balanced by cations that occupy the channels within the structure, and can be replaced with heavy metal ions. Zeolite has a natural porosity because it has a crystal structure with windows, cages, and supercages. The natural zeolites are limited in their window size (pore size) and are all hydrophilic (having an affinity for water). Some synthetic zeolites are similar to an absorbent carbon, since both can be considered hydrophobic (having an affinity for organics, with lack of or a decreased affinity for water), and can adsorb organic vapors with molecules smaller than their pore size. With both carbon and zeolite you can adsorb water and organic molecules; however, that for which it has affinity will displace the other molecules. Zeolite has a uniform pore size which leads to it being referred to as a molecular sieve, while carbons appear to have pores leading to smaller pores leading to still smaller pores ad infinitum. 2. OCCURRENCE, PRODUCTION AND MARKET World production of natural zeolite was estimated to be between 2.5 million metric tons (Mt) and 3 Mt based on reported production by some countries and production estimates published in trade journals [1]. Estimates for individual countries were China, 1.5 Mt to 2.0 Mt; Japan, 140,000 t to 160,000 t; the Republic of South Korea, 150,000 t; the United States, 45,400 t; Cuba, 37,500 t; Hungary and Turkey, 30,000 t each; Bulgaria, Slovakia, and South Africa, 15,000 t each; Australia, 7,000 t; Georgia, 6,000 t; New Zealand, 5,000 t; Canada, Greece, Italy, and other republics of the Commonwealth of Independent States, 4,000 t each. Small amounts of natural zeolite also probably were produced in Indonesia. In general, countries mining large tonnages of zeolite often have substituted zeolite for other materials. Natural zeolites were used in large quantities for such applications as dimension stone (as an altered volcanic tuff), lightweight aggregate, pozzolanic cement, soil conditioners, etc. In these cases, the ready availability of zeolite-rich rock at low cost and the shortage of competing minerals and rocks are probably the most important factors for its large-scale use. Also, it is likely that a significant percentage of the material sold as zeolite in some countries is probably ground or sawn volcanic tuff containing only a small amount of zeolite [1]. Prices for natural zeolite vary with zeolite content and processing. Unit values, obtained through the U.S. Geological Survey canvass of domestic zeolite producers, ranged from $85 per metric ton to $320 per metric ton. Most unit values were between $85 per metric ton and $140 per metric ton. Holmes [2] reported that prices for industrial or agricultural applications ranged from $30 per metric ton to $70 per metric ton for granular products down to 40 mesh and from $50 per metric ton to $120 per metric ton for finer (-40 to +325 mesh) ground material. For such products as pet litter, fish tank media, or odor control applications, prices ranged from $0.50 per kilogram to $4.50 per kilogram. Prices for Asian and European zeolite (mainly clinoptilolite) were between $75 per metric ton and $172 per metric ton. Quoted prices should be used only as a guideline because actual prices depend on the terms of the contract between seller and buyer [1]. Sales of natural zeolite have rebounded from their sharp decline in 1996. Growth since 1996 has averaged 5.7% per year. Increased sales for animal feed supplements, wastewater cleanup, and water purification account for much of this growth. Horticultural and pet litter applications also have contributed to the growth, but to a lesser extent. As in the past few years, many companies continue to focus on the development of more value-added products. Given the limitations in growth and the returns of several zeolite markets, the focus on value-added products should allow companies to optimize their returns. Production of natural zeolites should be in the range of 45,000 t/yr and 50,000 t/yr, and sales of natural zeolite probably will reach 40,000 t/yr within a few years [1]. 3. INDUSTRIAL APPLICATIONS 3.1. ADSORPTION AND CATALYSIS Two principal uses of synthetic molecular sieves are the purification of gaseous hydrocarbons and the preparation of catalysts for petroleum refining. In general, natural zeolites do not compete with their synthetic counterparts in adsorption or catalytic applications because of their inherent lower adsorption capacities and, to some extent, to the presence of traces of Fe and other catalyst "poisons." Most natural materials have smaller pore openings than the synthetics. Despite the low cost of the natural materials (a few cents per kilogram), the economics of hardware construction, activation, and regeneration favor the more expensive synthetics, even at $2.00/kg, for most adsorption applications [3]. By using certain natural zeolites, however, researchers have made headway in the drying and purification of acid gases. Mordenite and chabazite, for example, can withstand the rigors of continuous cycling in acid environments and have been used to remove water and carbon dioxide from sour natural gas. Union Carbide Corporation (now

UOP Corporation, Tarrytown, NY) marketed an AW-500 product (natural chabazite-rich tuff from Bowie, AZ) for removing HCl from reformed H2 streams (pH < 2), H2O from Cl2, and CO2 from stack gas emissions [8]. Modifying the surface of clinoptilolite with long-chain quaternary amines allowed it to adsorb benzene, toluene, and xylene in the presence of water, a process that shows promise in the clean up of gasoline and other petroleum spills [3]. These hydrophilic products can be treated further with additional amine to produce anion exchangers capable of taking up chromate, arsenate, selenate, and other metal oxyanions from aqueous solutions. Applications in catalysis include (i) a selective-forming catalyst developed by Mobil Corporation using natural erionite-clinoptilolite [9]; (ii) a hydrocarbon conversion catalyst for the disproportionation of toluene to benzene and xylene, employing a hydrogen-exchanged natural mordenite [10]; (iii) a catalyst using cation-exchanged clinoptilolite from Tokaj, Hungary, for the hydromethylation of toluene [11]; and (iv) clinoptilolite catalysts for the isomerization of n-butene, the dehydration of methanol to dimethyl ether, and the hydration of acetylene to acetaldehyde [12]. 3.2 CONSTRUCTION MATERIALS Their low bulk density, high porosity, and homogeneous, close-knit texture have contributed to their being easily sawed or cut into inexpensive building blocks. For example, many Zapotec buildings near Oaxaca, Mexico, were constructed of blocks of massive, clinoptilolite tuff [4], which is still used for public buildings in the region. The easily cut and fabricated chabazite- and phillipsite-rich tuffo giallo napolitano in central Italy has also been used since Roman times in construction, and the entire city of Naples seems to be built out of it [3]. Numerous cathedrals and public buildings in central Europe were built from zeolitic tuff quarried in the Laacher See area of Germany. Early ranch houses in the American West were built with blocks of locally quarried erionite; they were cool and did not crumble in the arid climate. Similar structures made of zeolitic tuff blocks have been noted near almost every zeolitic tuff deposit in Europe and Japan [5]. The high silica content of the zeolites neutralizes excess lime produced by setting concrete, much like finely powdered pumice or fly ash. In the U.S., nearly $1 million was saved in 1912 during the construction of the 240mile-long Los Angeles aqueduct by replacing 25% of the required portland cement with an inexpensive clinoptilolite-rich tuff mined near Tehachapi, CA [6, 7]. 3.3 FILLERS Zeolites are used extensively in Japan as fillers in the manufacture of paper. These filler grades of zeolite have a large potential for utilization in the paint and plastics industries. Many deposits of natural zeolites contain highbrightness reserves and the potential for benefaction is increasing with improved technology for magnetic separation and bleaching of zeolite. 3.4 GAS PURIFICATION AND SEPARATION Because zeolites possess the ability to act as molecular sieves, they are used to purify or sweeten natural gases through the removal of impurities such as carbon dioxide, sulfur dioxide and water. In addition to upgrading natural gas, zeolites are used to separate oxygen and nitrogen in pressure swing adsorption columns. These utilizations of natural zeolites are most common in Japan, as most domestic gas purification and separation is done with high-cost synthetic zeolite molecular sieves. The removal of nitrogen from methane gas to meet the pipeline quality of greater than 90% is becoming important in the field of natural gas and enhanced oil recovery processes. The typical US pipeline specifications for natural gas is 950 BTU/ft3 of < 4% inert contaminants. Methane removed from coal mines, natural gas reserves, and aging gas wells have a naturally occurring concentration of nitrogen; and the process of nitrogen injection for the removal of the methane further increases the level of nitrogen contamination. Nitrogen is typically removed in an adsorption process. Most known sorbents, such as activated carbon, large pore zeolites and molecular sieves, silica gel, and activated alumina have an equilibrium selectivity that favors methane over nitrogen [21]. 3.4 HEAT STORAGE AND SOLAR REFRIGERATION The high heat of adsorption and ability to hydrate and dehydrate while maintaining structural stability have been found to be useful in various heat storage and solar refrigeration systems. A hydroscopic nature coupled with an inherent exothermic reaction when taken from a dehydrated to a hydrated form (heat of adsorption), make natural zeolites effective in the storage of solar and waste heat energy. 3.5 HYDROGEN ENERGY

It has been recognized many decades now that there it is very necessary to find an alternative resource to fossil ones. Such kind of fuel must be improvable, friendly with natural and found with huge amounts. The production, storage and usage of the fuel are also important points when choosing the fuel. It must be easy reachable, carriage of it must not be dangerous. The most powerful alternative is hydrogen energy. The storage and material become very important. In that view, natural zeolite is one of the fuel resources which have been experienced. The encapsulation of hydrogen gas in zeolite, which is used in industry and in different branches of technology, has been examined and some offers are made depending on literature searches. The adsorption of hydrogen in natural zeolites is anticipated to be large, due to its small size relative to channel or pore dimensions. Another reason is the relatively weak interaction energy with the cations or the framework. It remains to be tested, however, if the adsorption of hydrogen is not structure sensitive. Furthermore, reasonable values of adsorption constants are critical to model several processes occuring in zeolitic membranes, e.g. hydrogen removal. Macroscopic measurements concerning hydrogen in zeolites are not available so far [19]. Furthermore, natural zeolites can adsorb H 2S in large amounts. That way the gas is stored into the zeolite and could be desorbed, if required. In view of this, H2S, released either as a consequence of anaerobic defect or in geothermal waters, can be stored in natural zeolites and with the aid of solar energy, hydrogen can be produced with photocatalitic methods. Thus, at least theoretically, hydrogen can be produced from H 2S, which is released as a consequence anaerobic defect (in biogas plants), exist in geothermal waters or it is a by-product of several industrial and other processes. 4. ENVIRONMENTAL APPLICATIONS 4.1 WASTEWATER TREATMENT Many industries such as mining, refining, plating, and metals processing are challenged with managing the integrity of process materials and process waste. Sewage disposal is extremely costly, with the main emphasis on purifying the effluent so it can be discharged into the environment without causing pollution. Since large amounts of nutrients go to waste, the question is how to turn this waste into a product with value [18]. Traditional sewage treatment methods include passing the sludge trough a gravel or charcoal filtration bed. The gravel or charcoal becomes virtually useless, and creates a second disposal problem. Zeolite is an alternative and is being developed as a sewage filter aid. The basic premise would see the zeolite use to absorb the waste material, and then used as slow-release fertilizer. Costs concerns is the main barrier to this application as zeolites are more expensive materials than gravel and charcoal. However, its advantage is the environmental benefits [18]. Because of their ion-exchange properties, adsorption capabilities, mechanical, chemical and thermal resistance and surface charge density, zeolites can be an effective treatment for the capture of deleterious materials in wastewater and in industrial treatment processes. Ammonia is a major issue for the treatment of municipal wastewater. Ammonia levels in municipal wastewaters can be reduced to 10-15 ppm through traditional primary and secondary treatment facilities. Final circulation in the tertiary treatment stage is accomplished with polishing filters containing clinoptilolite, a popular form of natural zeolite. The zeolites lower the level of ammonium to non-toxic, acceptable levels. The zeolite beds can be regenerated and recycled indefinitely. Zeolites are highly selective scavengers of a variety of metal cations that can be removed from liquid effluents through the process of ion-exchange. These cations include lead, silver, cadmium, cobalt, zinc, copper, mercury, magnesium, iron, aluminum, chromium and others. Clinoptilolite water polishing treatment systems are applicable in industries such as mining, electroplating and electronics. Giant industrial houses, like IBM, have deployed this application for treatment of wastewater containing heavy metals. 4.2 RADIOACTIVE WASTE TREATMENT Natural zeolites have superior selectivity for certain radionuclides (e.g., 90Sr, 137Cs, 60Co, 45Ca, and 51Cr) compared with organoresins and are cheaper and much more resistant to nuclear degradation [3]. Process effluents bearing radioactive isotopes can be treated through columns packed with natural zeolites. The zeolites selectively remove cesium and Strontium isotopes through the process of ion-exchange. Effluent liquids are purified to acceptable limits for discharge as the radioactive isotopes are held within the zeolite cage structure. One outstanding example of the application is the British Nuclear Fuels, Ltd. Site Ion Exchange Efficient Plant (SIXEO) at Sellifield, England. The other large application is for the treatment of low level liquid effluents at the DOE West Valley, NY site, where Phillipsite was used to selectively remove 137Cs and 90Sr isotopes. The permanent storage or disposal of the waste is facilitated by the inorganic and stable structure of the zeolite which can be encapsulated in cement or glass.

Permeable barriers incorporate sorbent materials, including zeolite, to selectively contain contaminants that are percolating from shallow land burial sites of low-level radioactive waste. The zeolites are combined with clays and other materials that retard the migration of leachate for a period long enough to allow exchange and/or decay of radioactive ions. The same selectivities for Cs and Sr by zeolites permit treatment of radioactive fallout from nuclear tests and accidents. Several zeolite processes have been developed to counteract the fallout from the 1986 Chernobyl disaster. Shenbar and Johanson [13] found that 137Cs in soils was not taken up by plants after treating the soil with a zeolite, and Forberg et al. [14] showed that a zeolite supplement to the diets of Swedish reindeer accelerated the excretion of 137Cs ingested with food contaminated by Chernobyl fallout. Zeolites added to soils reduced the uptake of 137Cs by pasture plants in the vicinity of Chernobyl [15], and dietary zeolite reduced sorption of radiocesium by sheep fed fallout-contaminated rations in Scotland [16]. In Bulgaria, zeolite pills and cookies were prepared for human consumption to counteract Chernobyl fallout [17]. The zeolite apparently exchanges 137Cs and 90Sr in the gastrointestinal tract and is excreted by normal processes, thereby minimizing assimilation into the body. 4.3 GASEOUS EMISSIONS TRETAMENT Natural zeolites are an adsorbent of choice for many cost effective air pollution control technologies treating the hazardous air pollutants (HAP) and listed volatile organic compounds (VOC). The need for technologically improved air purification systems has been indicated by keen client interest in the use of zeolites in controlling indoor air pollutants or "sick building syndrome". Existing filtration systems typically contain activated carbon as the adsorbent media. Because most grades of activated carbon contain large internal pores, they tend to trap a wide variety of larger molecules. Zeolites, on the other hand, contain a very small internal pores, in all cases from 3 to 5 angstroms. For this reason zeolite is a highly selective adsorbent of specific gas-phase molecules and elements. Many of the identified indoor air pollutants, including formaldehyde, chloroform, ammonia and carbon monoxide, are in a size range that is most effectively sieved by zeolite. Many promising zeolite and zeolite/carbon air purification and odor controlling systems are being developed to meet the need. Ammonia and urea are the distinctive smelling fumes which are given off from urine. Zeolite can be used in livestock rearing areas, zoos, kennels, pet shops, and pet litter trays to remove these gases and the distress caused to the throat and nose. These natural minerals have also been used very effectively in the control of odours coming from waste disposal areas, public toilets, garbage bins, refrigerators, pantries and some industrial processes. Clintoptilolite has been used to control ammonia from urine in both kitty litter and horse stables. It is also used to adsorb VOC that cause odors from mildew, foot fungus, and carpets [20].

Figure 1: Typical pore diameter distributions of porous solids. For comparison, the kinetic diameters of water, methane and neopentane are also indicated. 4.4 REMEDIATION OF SOIL CONTAMINATED BY PETROLEUM HYDROCARBONS One of the modern approaches to remediation of soil and groundwater contaminated by petroleum hydrocarbons (HC) is considered to be combined sorption/biodegradation cleaning assisted by natural sorbents. Recently a number of modern methods were proposed for modifying of mineral sorbent surfaces by cationic surfactants to make sorbents more hydrophobic. The application of cheap zeolite-containing materials (ZCMs) could be promising for ecological purposes. Such sorbents simultaneously are characterized by high cation exchange capacities (due to the presence of zeolites) and high specific surface areas (due to clay minerals) [22].

5. CONCLUSIONS

REFERENCES [1] Virta R.L., Zeolites, U.S. Geological Survey Minerals Yearbook, 2003. [2] Holmes, D.A., Zeolites, in Carr, D.D., ed., Industrial minerals and rocks (4th ed.): Littleton, CO, Society for Mining, Metallurgy, and Exploration, Inc., p. 1129-1158, 1994. [3] Frederick A. Mumpton, La roca magica: Uses of natural zeolites in agriculture and industry, Proceedings of the National Academy of Sciences of the United States of America (PNAS), Vol. 96, Issue 7, 3463-3470, March 30, 1999. [4] Mumpton F. A., Am. Miner. 68, 287-289, 1973. [5] Mumpton F. A., Ind. Miner. (London) 73, 30-45, 1973. [6] Mielenz, R. C., Green, K. T. & Schlette, N. C., Econ. Geol. 46, 311-328, 1951. [7] Drury, F. W., Calif. Miner. Inf. Serv. 7(10), 1-6, 1954. [8] Union Carbide Corporation, Linde Molecular Sieve Bulletin F-1617 (Union Carbide), 1962. [9]. Chen, N. Y. (1971) U.S. Patent 3,630,066, 1971. [10]. Ohtani, S., Iwamura, T., Sando, K. & Matsumura, K., Japanese Patent 72 046,667, 1972. [11]. Papp, J., Kall, D. & Schay, G., J. Catal. 23, 168-182, 1971. [12]. Kall, D., in Occurrence, Properties & Utilization of Natural Zeolites, eds. Kall, D. & Sherry, H. S. (Akademiai Kiado, Budapest), pp. 601-624, 1988. [13] Shenbar, M. A. & Johanson, K. J., Sci. Total Environ. 113, 287-295, 1992. [14] Forberg, S., Jones, B. & Westermark, T., Sci. Total Environ. 79, 37-41, 1989. [15] Firsakova, S. K., Grebenchchikova, N. V., Timofeev, S. F. & Novik, A. A., Dokl. Vses. Akad. Skh. Nauk im. V. I. Lenina 3, 25-27, 1992. [16] Phillippo, M., Gvozdanovic, S., Gvozdanovic, D., Chesters, J. K., Paterson, E. & Mills, C. F., Vet. Rec. 122, 560-563, 1988. [17] Filizova, L., Program & Abstracts: Zeolite '93: 4th International Conference on the Occurrence, Properties, and Utilization of Natural Zeolites, Boise, Idaho (Int. Comm. Natl. Zeolites, Brockport, NY), pp. 88-90, 1993. [18] Crossley P., Swell times for adsorbent minerals, Industrial Minerals, 34-41, May 2002. [19] Delman, B., Yates J. T., (Advisory Editors), Chan, H., Woo, S. I., Pank S. E., (Editors), Recent Advanced and New Horizons in Zeolite Science and Technology, Korea, 1996. [20] EPA, Zeolite: A Versatile Air Pollutant Adsorber, US, EPA-456/F-98-004, July 1998. [21] Deng S., Reiersen D., Viswanathan V., Modification of natural clinoptilolite for nitrogen and methane separation, in: R. S. Bowman and S. E. Delap (Eds.), Zeolite 067th International Conference on the Occurrence, Properties, and Utilization of Natural Zeolites, Socorro, New Mexico USA, 1621 July, 2006. [22] Mishchenko A., Krivosheeva A., Breus V., Neckludov S., Breus I., The investigation of zeolitecontaining material as a potential sorbent for petroleum hydrocarbons, R. S. Bowman and S. E. Delap (Eds.), Zeolite 067th International Conference on the Occurrence, Properties, and Utilization of Natural Zeolites, Socorro, New Mexico USA, 1621 July, 2006.