A MICROWAVE-ASSISTED METHOD FOR THE RAPID

REMOVAL OF K FROM PHLOGOPITE

Stephen A. Stout and Sridhar Komarneni*

Department of Crop and Soil Sciences and Materials Research Institute, The Pennsylvania State University,
University Park, Pennsylvania 16802, USA

*
E-mail address of corresponding author: komarneni@psu.edu

The ability to remove K rapidly with a solution containing sodium tetraphenylborate (NaTPB)
from the interlayers of naturally-occurring phlogopite using a microwave-assisted technique
has been examined. Samples were equilibrated with a 1.0 N sodium chloride (NaCl) – 0.2 N
NaTPB – 0.01 M disodium ethylenediaminetetraacetic acid (EDTA) solution at 60, 80 and 100°C
under both conventional and microwave-assisted heating methods and for periods of
time ranging from 1 to 3 h. The samples also underwent treatments of either continuous time
periods or for successive treatments of 1 h with a washing step between each treatment.
Following sample treatment, the expansion of the c-axis value (d001) from 10.0 to 12.2 Å
indicated the presence of hydrated Na ions in the phlogopite structure. Under most treatment
conditions the 10.0 Å peak remained even after treatment due to incomplete K removal.
Chemical analysis and X-ray diffraction (XRD) revealedthat samples heated using microwave
radiation exchanged their interlayer K for Na much more rapidly than under conventional heating
for all treatment times and temperatures. The successive treatments also degraded the mica more
rapidly than the continuous treatments. The greatest amount of K (95%) was removed when the
mica was treated three times for 1 h at 60°C. The results suggest that successive treatments of
phlogopite mica heated under microwave radiation will rapidly remove K from the
mica. Decreasing the amount of time required to prepare K-depleted phlogopite micas will make
these materials more appealing as ion exchangers for separation of Cs from nuclear wastes.

Key Words: Ion Exchange • K-depleted Phlogopite • Mica • Microwave • Radioactive Waste
Disposal
SYNTHESIS OF KAOLINITE FROM MICAS AND K-
DEPLETED MICAS
Yunchul Cho and Sridhar Komarneni*

Department of Crop and Soil Sciences and Materials Research Institute, The Pennsylvania State University,
University Park, Pennsylvania 16802, USA

*
E-mail address of corresponding author: komarneni@psu.edu

The weathering stages of K-depleted biotite, K-depleted phlogopite, and natural biotite were
investigated using hydrothermal treatment with AlCl3 solution at 200°C for 12 to 72 h. Although
there were some differences in the degree of weathering of the two K-depleted micas, both first
transformed to hydroxy-Al interlayered vermiculite (HIV), which then altered to kaolinite. In
case of the natural biotite, the biotite first transformed to a K-depleted mica-like phase, which
then altered to kaolinite. The natural biotite had resisted weathering to kaolinite more than did
the K-depleted biotite, as expected. The K-depleted phlogopite had less resistance in weathering
to kaolinite than the K-depleted biotite. The transformation process changed the color of
the micas. The K-depleted biotite changed from greenish-black through yellow to pale gray
whereas the natural biotite changed from greenish-black through beige to yellow. However, in
the case of K-depleted phlogopite, there was no significant color change during the
transformation process. The presence of the interlayer K+ ions and the structural Fe2+ ions in
mica appear to have contributed to the differences in the degree of weathering to kaolinite among
the micas investigated.

Key Words: Hydrothermal Treatment • Hydroxy Al-interlayered Vermiculite (HIV) • Kaolinite

• K-depleted Biotite • K-depleted Phlogopite • Transformation • Weathering
MICROWAVE EXFOLIATION OF VERMICULITE AND
PHLOGOPITE
Abdullah Obut1, Ismail Girgin1,* and Abdülkerim Yörüko lu2
1
Hacettepe University, Mining Engineering Department, 06532, Beytepe, Ankara, Turkey
2
Mineral Research and Exploration General Directorate, 06520 Ankara, Turkey

*
E-mail address of corresponding author: girgin@hacettepe.edu.tr

Vermiculites and phlogopites can be exfoliated by chemical and thermal treatment methods to
obtain chemically inert, adsorbent, fire-resistant, low-density materials with excellent
thermal and acoustic insulation properties. The water content of the clay generally determines the
extent of exfoliation and the presence of interstratification is claimed to increase the rate of
exfoliation. Considering the strong interaction between water and microwaves, the effect of
microwave power on exfoliationcharacteristics of vermiculites and phlogopites after
treatment with water and hydrogen peroxide solution were studied at 600, 950 and 1300 W for
microwave exposure times of 10, 20, 30, 60, 120 and 300 s. It was observed that the water
molecules in the interlayers of the individual flakes were driven off quickly by microwave
treatment causing layer separation in the samples. The vermiculite sample showed 2.8 and 5.6
times, respectively, the exfoliation ratio of the phlogopite samples, in accord with their water
contents.

Key Words: Exfoliation • Microwave Energy • Phlogopite • Vermiculite

Infra-red studies of ammoniation of pillared
montmorillonites
S. WITKOWSKI1, Z. SOJKA1, K. DYREK1,2,*, J. FIJAL3, S. OLKIEWICZ3, P.
FINK4 and H. HOBERT4
1
Faculty of Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Cracow, 2 Regional Laboratory of
Physicochemical Analyses and Structural Research, ul. Ingardena 3, 30–060 Cracow, 3 Department of Mineralogy
and Geochemistry, Academy of Mining and Metallurgy, al. Mickiewicza 30, 30–059 Cracow, Poland, and 4 Institute
of Physical Chemistry, Friedrich Schiller University, Lessingstrasse 10, 07–743 Jena, Germany

*
E-mail: dyrek@trurl.ch.uj.edu.pl

(Received 20 November 1998; revised 16 August 1999)

Ammoniation of montmorillonites pillared with polyhydroxo-complexes of Al was performed in

flow conditions at 773–1073 K and monitored by IR spectroscopy. Interaction of the clay with
ammonia revealed exchange of terminal and bridging -OH groups by NH2-, NH- and N-species
depending on the reaction temperature. Amination begins at 773 K while formation of NH
groups starts at 873 K. Transformation of NH- into N-species occurs at 973 K. A mechanism for
the ammoniation reaction is proposed and the series of the relative reactivity of OH groups
was established: Si–OH > Mg–OH–Mg > Al–OH–Mg > Al–OH–Al. This series was rationalized
in terms of accessibility of the OH groups.

KEYWORDS: IR, ammoniation, pillared montmorillonite, polyhydroxo complexes

Photochemical Studies of Zeolites
Abstract
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STEVEN L. SUIB, OVIDIU G. BORDEIANU, KERRY C. McMAHON, DIMITRIOS PSARAS

University of Connecticut, Department of Chemistry and Institute of Materials Science, Storrs, CT 06268

Inorganic Reactions in Organized Media

Chapter 14, pp 225–238

Chapter DOI: 10.1021/bk-1982-0177.ch014

ACS Symposium Series, Vol. 177

ISBN13: 9780841206700eISBN: 9780841208643

Publication Date (Print): February 12, 1982

Copyright © 1982 AMERICAN CHEMICAL SOCIETY

Abstract
The following paper reviews recent results in the field of zeolite photochemistry and describes
preliminary results of photochemical studies of uranyl-exchanged zeolites. The areas of water
splitting by metal-exchanged zeolites and luminescence quenching are discussed as well as
some of the properties of zeolites that make them excellent media for organizing chemical
reactions. Some preliminary results of the photochemistry of uranyl ions exchanged
into zeolites A, X, Y, mordenite and ZSM-5 are then presented. Quenching of the
uranyl zeolites with isopropanol and bulk analyses of the products of this quenching are
reported. Factors affecting the luminescence of uranyl ions in zeolites and their reactivity are
described at the end of this paper. Results of these studies indicate that uranyl-exchanged X, Y
and ZSM-5 zeolites are the most active in the photochemical conversion of isopropanol into
acetone.
Redox Catalysis in Zeolites
Abstract
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J. A. Dumesic1, W. S. Millman2

1
Laboratory for Surface Studies, University of Wisconsin, P.O. Box 413, Milwaukee, WI 53201

2
Department of Chemical Engineering, University of Wisconsin, 1415 Johnson Drive, Madison, WI 53706

Novel Materials in Heterogeneous Catalysis

Chapter 6, pp 66–74

Chapter DOI: 10.1021/bk-1990-0437.ch006

ACS Symposium Series, Vol. 437

ISBN13: 9780841218635eISBN: 9780841212930

Publication Date (Print): September 21, 1990

Copyright © 1990 American Chemical Society

Abstract
The active sites for redox reactions carried out using zeolitic catalysts are the exchangeable
cations introduced into the zeolite matrix. These cations may occupy a number of different
exchange sites, and in general, the catalytic activity of a cation depends upon its site location.
This leads to the possibility of altering the catalytic activity by changing the site population of
the exchangeable cations. We discuss two methods which have been used to alter the sites
occupied by Fe2+/Fe3+ cations in Y zeolite structures: increasing the silicon-to-aluminum ratio via
silicon-substitution and co-exchanging Fe together with a second cation (Eu).

The effect on the catalytic activity for N2O decomposition on increased silicon content of the
zeolite is to provide nearly 2 orders of magnitude increase in the turn-over-frequency (TOF) of
the Fe cations. The increased TOF is accompanied by a change in the Mössbauer spectra of the
Fe2+ cations. These cations exhibit spectra which are indicative of cations moving from sites of
high coordination (Site I) tQ sites of lower coordination (Sites I'/II' and/or II). In addition, the
rate of oxidation of the cations decreases with increasing Si content of the lattice. When Eu and
Fe are coexchanged into a Y zeolite, which hasn't had its silicon-to-aluminum ratio increased,
the Fe2+ Mössbauer spectrum is intermediate between those of the Fe exchanged Y-
zeolites having silicon-to-aluminum ratios of 4.5 and 6.2 as determined by 29Si NMR. The
catalytic activity for N2O decomposition, while greater than normal Fe-Y, is less than expected
from correlation with Mössbauer spectra. This observation is discussed in terms of interaction
between Eu and Fe. When Eu is present alone it does not undergo redox until the temperature is
increased to 873 K. When both cations are present Eu can undergo redox half reactions at 723 K.
EPR spectra show that different sites may be involved when both cations are present as opposed
to when Eu is present alone.
Zeolites Offer Variety as Ligands
Abstract
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J. N. Armor, Brian H. Toby1

Air Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, PA 18195

Current address: Reactor Radiation Division, National Institute of Standards and Technology, Gaithersburg,
MD, 20899.

Electron Transfer Reactions

Chapter 6, pp 91–98

Advances in Chemistry, Vol. 253

ISBN13: 9780841234567eISBN: 9780841224384

Publication Date (Print): May 05, 1997

Copyright © 1997 American Chemical Society

Abstract
This chapter presents some general observations that extend the concepts that govern the use
of zeolites as catalysts. Traditionally, zeolites are used for the production of petrochemicals,
and their reactivity is associated with either their acidity or their shape
selectivity. Zeolites also offer unusual chemical environments for transition metal ions. Cations
exchanged into zeolites often site at defects or at positions of high coordinative unsaturation.
Such effects have been previously demonstrated with type A, X, and Yzeolites. Each zeolite
structure type offers a different ligating environment to the cation. This variation is illustrated
by the use of computer graphics to show the various cation environments of cobalt, copper, and
nickel ions in ZSM-5 vs. faujasite and type A zeolites.
Acidic and Catalytic Properties of Zeolites
Abstract
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DENISE BARTHOMEUF

Laboratoire de Catalyse Organique, L.A. CNRS n° 231, Ecole Supérieure de Chimie Industrielle de Lyon, 43,
boulevard du 11 novembre 1918, 69621 Villeurbanne, France

Molecular Sieves—II

Chapter 38, pp 453–472

Chapter DOI: 10.1021/bk-1977-0040.ch038

ACS Symposium Series, Vol. 40

ISBN13: 9780841203624eISBN: 9780841203266

Publication Date (Print): June 01, 1977

Copyright © 1977 American Chemical Society

Abstract
ABSTRACT

In the first part a review of zeolite acidity is presented. The concepts of proton and cation
mobilities which become more widely considered these last years, are emphasized. The
dynamics of zeolite systems appears also in the second part related to correlations between
catalytic and acidic properties. A model based on the comparison of zeolites with polyacids in
solution is presented.

Recent reviews in the field of catalysis with zeolites have been published (1-5). They point out
that the major applications of zeolites in catalytic systems are related to their acidic
properties.
Shape-Selective Catalysis with Zeolites and Molecular Sieves
Abstract
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Charles B. Khouw, Mark E. Davis

Department of Chemical Engineering, California Institute of Technology, Pasadena, CA 91125

Selectivity in Catalysis

Chapter 14, pp 206–221

Chapter DOI: 10.1021/bk-1993-0517.ch014

ACS Symposium Series, Vol. 517

ISBN13: 9780841225190eISBN: 9780841213739

Publication Date (Print): May 05, 1993

Copyright © 1993 American Chemical Society

Abstract
The types of shape selective catalysis that occur in zeolites and molecular sieves are reviewed.
Specifically, primary and secondary acid catalyzed shape selectivity and encapsulated metal ion
and zero valent metal particle catalyzed shape selectivity are discussed. Future trends in shape
selective catalysis, such as the use of large pore zeolitesand electro- and photo-chemically
driven reactions, are outlined. Finally, the possibility of using zeolites as chiral shape selective
catalysts is discussed.