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PNAS 1999 Mumpton 3463 70 PDF
PNAS 1999 Mumpton 3463 70 PDF
USA
Vol. 96, pp. 34633470, March 1999
Colloquium Paper
ABSTRACT
For nearly 200 years since their discovery in
1756, geologists considered the zeolite minerals to occur as
fairly large crystals in the vugs and cavities of basalts and
other traprock formations. Here, they were prized by mineral
collectors, but their small abundance and polymineralic nature defied commercial exploitation. 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 f lat-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, dehydrationrehydration, 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-f ledged mineral commodities, the
use of which promise to expand even more in the future.
PROPERTIES
A zeolite is a crystalline, hydrated aluminosilicate of alkali and
alkaline earth cations having an infinite, open, threedimensional structure. It is further able to lose and gain water
reversibly and to exchange extraframework cations, both without change of crystal structure. The large structural cavities
and the entry channels leading into them contain water
molecules, which form hydration spheres around exchangeable
cations. On removal of water by heating at 350400C, small
molecules can pass through entry channels, but larger molecules are excludedthe so called molecular sieve property
of crystalline zeolites. The uniform size and shape of the rings
of oxygen in zeolites contrasts with the relatively wide range of
pore sizes in silica gel, activated alumina, and activated carbon,
and the Langmuir shape of their adsorption isotherms allows
zeolites to remove the last trace of a particular gas from a
system (e.g., H2O from refrigerator Freon lines). Furthermore,
zeolites adsorb polar molecules with high selectivity. Thus,
polar CO2 is adsorbed preferentially by certain zeolites, allowing impure methane or natural gas streams to be upgraded.
The quadrupole moment of N2 contributes to its selective
adsorption by zeolites from air, thereby producing O2-enriched
products. The adsorption selectivity for H2O, however, is
greater than for any other molecule, leading to uses in drying
and solar heating and cooling.
The weakly bonded extraframework cations can be removed
or exchanged readily by washing with a strong solution of
another cation. The CEC of a zeolite is basically a function of
the amount of Al that substitutes for Si in the framework
tetrahedra; the greater the Al content, the more extraframework cations needed to balance the charge. Natural zeolites
have CECs from 2 to 4 milliequivalentsyg (meqyg), about twice
the CEC of bentonite clay. Unlike most noncrystalline ion
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This preference for larger cations, including NH41, was exploited for removing NH4-N from municipal sewage effluent
and has been extended to agricultural and aquacultural applications (1, 2). Clinoptilolite and natural chabazite have also
been used to extract Cs and Sr from nuclear wastes and fallout.
Most zeolites in volcanogenic sedimentary rocks were
formed by the dissolution of volcanic glass (ash) and later
precipitation of micrometer-size crystals, which mimic the
shape and morphology of their basalt counterparts (Fig. 1; ref.
3). Sedimentary zeolitic tuffs are generally soft, friable, and
lightweight and commonly contain 5095% of a single zeolite;
Table 1.
APPLICATIONS
Construction
Dimension Stone. Devitrified volcanic ash and altered tuff
have been used for 2,000 years as lightweight dimension stone.
Only since the 1950s, however, has their zeolitic nature been
recognized. 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 (Fig. 2). Numerous cathedrals and public buildings in
central Europe were built from zeolitic tuff quarried in the
Laacher See area of Germany. Early ranch houses (Fig. 3) 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).
Cement and Concrete. The most important pozzolanic raw
material used by the ancient Romans was obtained from the
tuffo napolitano giallo near Pozzuoli, Italy (6, 7). Similar
Zeolite
Representative unit-cell
formula
Void volume,
%
Channel dimensions,
Analcime
Chabazite
Clinoptilolite
Erionite
Faujasite
Ferrierite
Heulandite
Na10(Al16Si32O96)z16H2O
(Na2Ca)6(Al12Si24O72)z40H2O
(Na3K3)(Al6Si30O72)z24H2O
(NaCa0.5K)9(Al9Si27O72)z27H2O
(Na58)(Al58Si134O384)z240H2O
(Na2Mg2)(Al6Si30O72)z18H2O
(Ca4)(Al8Si28O72)z24H2O
18
47
34
35
47
28
39
Laumonitte
Mordenite
(Ca4)(Al8Si16O48)z16H2O
(Na8)(Al8Si40O96)z24H2O
34
28
Phillipsite
(NaK)5(Al5Si11O32)z20H2O
31
Linde A
Linde X
(Na12)(Al12Si12O48)z27H2O
(Na86)(Al86Si106O384)z264H2O
47
50
2.6
3.7 3 4.2
3.9 3 5.4
3.6 3 5.2
7.4
4.3 3 5.5
4.0 3 5.5
4.4 3 7.2
4.1 3 4.7
4.6 3 6.3
2.9 3 5.7
6.7 3 7.0
4.2 3 4.4
2.8 3 4.8
3.3
4.2
7.4
*Modified from refs. 103 and 104. Void volume determined from water content.
Thermal stability
(relative)
CEC, meq/g
High
High
High
High
High
High
Low
4.54
3.84
2.16
3.12
3.39
2.33
2.91
Low
High
4.25
2.29
Medium
3.31
High
High
5.48
4.73
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FIG. 4. Clinoptilolite-filled columns at a Denver, CO, waterpurification plant [Reproduced with permission from ref. 106 (Copyright 1997, AIMAT)].
clinoptilolite for extracting NH41 from municipal and agricultural waste streams. The clinoptilolite exchange process at the
TahoeTruckee (Truckee, CA) sewage treatment plant removes .97% of the NH41 from tertiary effluent (15). Hundreds of papers have dealt with wastewater treatment by
natural zeolites. Adding powdered clinoptilolite to sewage
before aeration increased O2-consumption and sedimentation,
resulting in a sludge that can be more easily dewatered and,
hence, used as a fertilizer (16). Nitrification of sludge is
accelerated by the use of clinoptilolite, which selectively
exchanges NH41 from wastewater and provides an ideal
growth medium for nitrifying bacteria, which then oxidize
NH41 to nitrate (1719). Liberti et al. (19) described a
nutrient-removal process called RIM-NUT that uses the selective exchange by clinoptilolite and an organic resin to
remove N2 and P from sewage effluent.
Drinking Water. In the late 1970s, a 1-MGD (million gallons
per day) water-reuse process that used clinoptilolite cationexchange columns went on stream in Denver, CO, (Fig. 4) and
brought the NH41 content of sewage effluent down to potable
standards (,1 ppm; refs. 2022). Based on Sims and coworkers (23, 24) earlier finding that nitrification of sewage sludge
was enhanced by the presence of clinoptilolite, a clinoptiloliteamended slow-sand filtration process for drinking water for the
city of Logan, UT, was evaluated. By adding a layer of crushed
zeolite, the filtration rate tripled, with no deleterious effects.
At Buki Island, upstream from Budapest, clinoptilolite filtration reduced the NH3 content of drinking water from 1522
ppm to ,2 ppm (25, 26). Clinoptilolite beds are used regularly
to upgrade river water to potable standards at Ryazan and
other localities in Russia and at Uzhgorod, Ukraine (27, 28).
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Agriculture
Animal Nutrition and Health. Since 1965, studies in Japan
using #10% clinoptilolite and mordenite as dietary supplements for swine and poultry showed that test animals generally
grew faster than control groups, with simultaneous decrease in
the amount and cost of the feed. Young and mature pigs fed
rations containing 5% clinoptilolite gained 16% more weight
than animals fed a normal diet (58, 59). The animals excrement was less odoriferous because of the take up of NH41 by
the zeolite, and the number and severity of intestinal diseases
decreased. To reduce the toxic effect of high NH41 in ruminal
fluids when nonprotein-nitrogens, such as urea and biuret, are
added to animal diets, White and Ohlrogge (60) introduced
both synthetic and natural zeolites into the rumen of test
animals. NH41 formed by the enzyme decomposition of the
nonprotein-nitrogen was exchanged immediately by the zeolite
and held for several hours until released by Na1 entering the
rumen in saliva. This gradual release of the excess nitrogen
allowed rumen organisms to synthesize cellular protein for
assimilation into the animals digestive systems. Several hundred studies of the effect of zeolites in animal diets have been
made in the U.S. and elsewhere (61). The results are mixed, but
in countries in which the level of animal productivity is not as
high as in the U.S. and the sanitary conditions of feed lots and
production facilities are much worse, substantial increases in
productivity and mortality have been achieved (62). Weight
gain may be caused by the zeolite acting as an ammonium
reservoir in the gastrointestinal tract, thereby allowing the
animal to use ingested nitrogen more efficiently. The prevention or minimization of scours and other intestinal diseases,
however, is more baffling. An NH41-containing zeolite may
support the growth of nitrogen-loving bacteria that contribute
to the health of the animals; the zeolite may take up deleterious heavy metals, or it may simply regulate pH in the gut
system, resulting in fewer or less severe stomach ailments.
FIG. 6.
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Tomatoes grown zeoponically in Havana, Cuba [Reproduced with permission from ref. 106 (Copyright 1997, AIMAT)].
FIG. 7. Wheat grown zeoponically for use in space flights and stations, Johnson Space Center, Houston, TX [Reproduced with permission from
ref. 106 (Copyright 1997, AIMAT)]. Photograph by D. W. Ming.
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FIG. 8.
Zeolite deodorization products from Itaya, Japan [Reproduced with permission from ref. 106 (Copyright 1997, AIMAT)].
FIG. 9.
Footwear and garbage-can zeolite deodorization products [Reproduced with permission from ref. 106 (Copyright 1997, AIMAT)].
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