Copyright © 1990 Published by Elsevier Inc.

Paper

Reactions of alcohols with hydrogen sulfide over zeolites: IV. The role
of acidity in the hydrosulfurization of ethanol over X-type zeolite
catalysts

M. Zió k*H. G. Karge and W. Nieβen

Faculty of Chemistry, A. Mickiewicz University, Pozna , Poland

Fritz-Haber-Institut der Max-Planck-Gesellschaft, West Berlin, Germany

Received 24 April 1989;

accepted 29 January 1990.
Available online 7 September 2004.

Abstract

The reaction of ethanol with hydrogen sulfide was studied on divalent cation-exchanged X-type zeolites at 523 K.
The decomposition of ethanol to hydrocarbons is competitive with the hydrosulfurization process, i.e., the reaction
between EtOH and H2S. Brönsted acid sites together with divalent cations are involved in the hydrosulfurization of
ethanol. Cation sites take part in the formation of ethanethiol. The increase of the strength of Brönsted acid sites
causes the increase of the selectivity towards diethyl sulfide.

Author Keywords: X-type zeolites ; temperature-programmed desorption of ammonia from MeII---NaX;

II
temperature-programmed desorption of pyridine from Me ---NaX; hydrosulfurization of ethanol; hydrosulfurization
over X-type zeolites ; hydrosulfurization, effect of acidity

Article Outline

• References

*
On leave at the Fritz-Haber-Institut, West Berlin.
Copyright © 1990 Published by Elsevier Inc.

Paper

Reactions of alcohols with hydrogen sulfide over zeolites: III. The role
of divalent cations in the reaction of C 2 and C3 alcohols with H2S over X-
type zeolite catalysts

M. Zió k and J. Kujawa

Faculty of Chemistry, A. Mickiewicz University, Pozna , Poland

Received 24 April 1989;

accepted 29 January 1990.
Available online 7 September 2004.

Abstract

The activity and selectivity of the Me2+ = NaX zeolites (Me = Cd, Zn, Ni, Co, Mn) in the hydrosulfurization of
ethanol and n-propanol at 623 and 523 K are presented. The formation of sulfur-organic compounds is observed
mainly at 523 K using an excess of H2S. The influence of the chemisorption of H2S on the selectivity of the
hydrosulfurization process is discussed. No simple correlation between the Coulomb potential, e/r, of cations or the
electronegativity of zeolite catalysts and their selectivity toward sulfur-organic products was found. The
mechanism of the formation of thiols and sulfides is considered.

2+
Author Keywords: Hydrosulfurization; hydrosulfurization of alcohols over Me = NaX zeolites ; hydrosulfurization
of (C2, C3) alcohols
Copyright © 1991 Published by Elsevier Inc.

Paper

Kinetics of zeolite dissolution: Part 1. Dissolution of zeolite A in hot

sodium hydroxide

,a a a b b
Ankica Čimek , Ljepša Komunjer , Boris Subotić , Marija Široki and Sanda Rončević

a
“Ruder Bošković” Institute, Zagreb, Croatia, Yugoslavia

b
Department of Analytical Chemistry, Faculty of Science, The University of Zagreb, Zagreb, Croatia, Yugoslavia

Received 19 April 1990;

accepted 20 August 1990.
Available online 6 April 2005.

Kinetics of dissolution of zeolite A in 1 M and 2 M NaOH solutions, at 338, 343, 348, and 353 K, were studied by (i)
measuring the change in concentration of Si and Al in the liquid phase, (ii) determining of the stage of
polycondensation of silicate anions in the liquid phase, (iii) following the change in particulate characteristics of the
suspended zeolite A, and (iv) phase analysis of the solid during the dissolution. The results obtained were
analyzed and discussed in accordance with known theories of dissolution, taking into account the chemical and
structural characteristics of zeolites.

Keywords: Zeolite A; dissolution; mechanism; kinetics

Copyright © 1992 Published by Elsevier Inc.

Paper

Reactions of alcohols with hydrogen sulfide over zeolites: Part V. The

role of Brönsted acid sites in thiols formation — A comparative study
of zeolites and heteropoly acids

M. Zió ek , K. Nowi ska and K. Leksowska

Faculty of Chemistry, A. Mickiewicz University, Pozna , Poland

Received 16 September 1991;

accepted 17 February 1992.
Available online 7 September 2004.

Abstract

The activity and selectivity of Me2+ NaX zeolites (Me = Cd, Zn, Ni, Co) and free and supported heteropoly acids
(HPA) for hydrosulfurization of n- and i-PrOH have been investigated. The influence of concentration and strength of
Brönsted acid centers on the yield of thiols is discussed on the basis of comparative measurements carried out on
zeolites and HPA. The effect of H2S chemisorption on the selectivity of hydrosulfurization process is considered.

Author Keywords: Hydrosulfurization of alcohols; zeolites ; heteropoly acids

Copyright © 1989 Published by Elsevier Inc.

Paper

Leached asbestos materials: precursors of zeolites

R. Le Van Mao , P. Kipkemboi, P. LévesqueA. Vaillancourt and G. Dénès

Department of Chemistry and Laboratories for Inorganic Materials, Laboratory of Catalysis, Concordia University,
Montréal, Québec, Canada

Laboratory of Solid State Chemistry and Mössbauer Spectroscopy, Department of Chemistry and Laboratories for
Inorganic Materials, Concordia University, Montreal, Quebec, Canada

Received 21 September 1987;

Revised 3 February 1989;
accepted 3 February 1989.
Available online 23 August 2004.

Abstract

Zeolites have been synthesized from the Alix materials obtained by acid leaching of chrysotile asbestos having a
magnesium leaching degree (MLD) larger than 60%. Above removal of 60% of Mg, acid-leaching results in a rapid
morphological degradation of the asbestos fibers leading to a more porous and noncrystalline solid, comparable,
when the MLD approaches 100%, to the highly siliceous zeolites or silicalite in terms of surface area, density, and
hydrophobicity. Such microporous silica materials constitute excellent matrices for the growth of submicron zeolite
particles. The rate of water uptake of the resulting zeolite A is much faster than that of commercial zeolite
A, which can be used in applications for soil conditioning. The presence of Mg in the zeolites results in improved
catalytic conversion of methanol to light olefins.

Author Keywords: Crystotile asbestos; ZSM-5 zeolite ; leaching, synthesis, catalysts

Copyright © 1990 Published by Elsevier Inc.

Paper

The state of iron in natural zeolites: A Mössbauer study

Rolando Roque-Malherbe , Carlos Diaz-Aguila, Edilso Reguera-RuizJuan Fundora-Lliteras, Lazaro López-

Colado and Manuel Hernández-Vélez

National Center for Scientific Research, Havana, Cuba

Physical Faculty, Higher Pedagogical Institute of Havana, Ciudad Libertad, Havana, Cuba

Received 17 July 1989;

accepted 5 February 1990.
Available online 7 September 2004.

Abstract

The state of iron in natural zeolites is an important feature for the practical applications of these materials. A
Mössbauer study, complemented with other methods, of iron-containing zeolitic rocks from several countries (Mexico,
Cuba, Czechoslovakia, and the USSR) was developed. It has been determined that iron is located as high spin
Fe3+ in framework tetrahedral sites, in extraframework octahedral sites as free Fe(H 2O)63+, and as high spin Fe2+ in
octahedral coordination in extraframework sites or in another aluminosilicate associated with the zeolite. Iron is
also located in magnetite contained in the zeolite rocks.

Author Keywords: Iron; natural zeolite ; Mössbauer spectroscopy; tetrahedral site; octahedral site; magnetite
Copyright © 1991 Published by Elsevier Inc.

Paper

Identification of the volatile products resulting from the thermal

decomposition of tetra-, tri-, di-, and mono-n-propylammonium cations
occluded in MFI-type zeolites

S. Bilger , M. Soulard, H. Kessler and J.L. Guth

Laboratoire de Matériaux Minéraux, URA CNRS 428, Ecole Nationale Supérieure de Chimie de Mulhouse, Mulhouse,
France

Received 27 March 1991;

accepted 13 April 1991.
Available online 7 March 2005.

The volatile thermal decomposition products of Pr4N+, Pr3NH+, P2NH2+, and PrNH3+ (Pr = n-propyl), occurring as
templates in MFI-type zeolites prepared in various media (presence of F− or OH− anions and TIII substituents for
Si), were analyzed by using differential thermal analysis (d.t.a.)-coupled mass spectrometry. In a second type of
experiment, the products released during the d.t.a. were separated in a preliminary stage, using gas chromatography.
The data from these combined techniques prompted a main decomposition scheme involving a Hofmann elimination,
followed by β-eliminations. In addition to propene and its oligomers, a variety of other molecules are evolved. Their
nature and proportions depend on the type of PrxNHy+ template, on the kind of anion (OH− or F−) accompanying the
organic cation in the ion pairs, and on the acidity of the zeolite, which is related to the substitution of Si by a
III +
T element. The thermal decomposition products of a common template Pr 4N were compared when T = Al, B, Fe,
and Ga. A marked difference was observed when the in situ conversion of propene to aromatic or aliphatic
hydrocarbons takes place. The extent of the catalytic side reactions in the thermal decomposition increases in the
following sequence: mono- < di- < tri- < tetrapropylammonium.

Keywords: Gas chromatography; mass spectrometry; propylammonium templates; thermal decomposition; MFI-
type zeolites
Copyright © 1988 Published by Elsevier Inc.

Paper

Catalytic and acid properties of pentasil zeolites: Isomerization of o-

xylene and alkylation of toluene

J. Datka, Z. Piwowarska, J. Rakoczy and B. Sulikowski

Faculty of Chemistry, Jagiellonian University, Karasia 3, 30-060, Krakow, Poland

Institute of Organic Chemistry and Technology, Technical University, Warszawska 24, 31-155 Krakow, Poland

Received 15 June 1987.

Available online 12 September 2005.

Acid and catalytic properties of H,NaZSM-5 (Si/Al = 47) zeolites of various exchange degrees (0–98%) were
studied. H,NaZSM-5 zeolites contain Lewis acid sites and two kinds of Brönsted sites (strong sites: 3609 cm −1OH
groups, and weak sites: not being those OH groups). The concentration of all these sites was determined. Weak
Brönsted sites are inactive in all the reactions studied. In the zeolites of exchange degrees higher than 11%, the
conversion increases linearly with the number of 3609 cm −1 OH groups.

Keywords: ZSM-5 zeolite ; acidity; i.r. spectroscopy; toluene alkylation; o-xylene isomerization
Copyright © 1991 Published by Elsevier Inc.

Paper

Asbestos-derived zeolites as water-retaining materials in soils

*, * †
Raymond Le Van Mao , Bernard Sjiariel and Jacques Dunnigan

*
Catalysis Research Laboratory and Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry,
Concordia University, 1455 de Maisonneuve Blvd. West, Montreal, Quebec H3G 1M8, Canada

†
Asbestos Institute, Pavilion Marie-Victorin, Bureau 336, University of Sherbrooke, Sherbrooke, Quebec J1K 2R1,
Canada

Received 5 December 1990;

revised 24 February 1991;
accepted 3 April 1991.
Available online 7 March 2005.

Asbestos-derived zeolites, when added to soil, are found to be capable of retaining water for longer periods of
time. Textural properties (micropore diameter and percent of “larger” pores) are probably important factors because
they may determine the level of water storage within the zeolite particles during the wetting phase. These
zeolite materials do not exhibit any in vitro cytotoxicity.

Keywords: Asbestos-derived zeolite ; Na and CaA zeolites ; water-retention capacity in soil; toxicity tests
Copyright © 1988 Published by Elsevier Inc.

Paper

Reactions of alcohols with hydrogen sulphide over zeolites: II. Activity

of faujasite-type and ZSM-5 zeolites in the reaction of C2 and
C3alcohols with H2S

M. Ziółek, J. Kujawa and P. Decyk

Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznań, Poland

Received 23 April 1987;

revised 10 June 1987.
Available online 7 March 2005.

The reactions of ethanol and propanol with H2S were studied over different types of zeolites at 523 and 623 K.
The most active of all investigated zeolites is Na-X at 623 K. The first step of the hydrosulphurization of C2 and
C3 alcohols is the dehydration of alcohols toward olefins, which react with chemisorbed H 2S, giving thiols and other
organic sulphur compounds. The role of sodium cations as active sites is stressed. The dehydration of alcohols
increases in the presence of H2S.

Keywords: Zeolites ; C2 and C3 alcohols; dehydration; hydrosulphurization

Copyright © 1983 Published by Elsevier Inc.

Paper

Conversion of alkylbenzenes over zeolite catalysts II.

Disproportionation of ethylbenzene over faujasite-type zeolites

* † †
H. G. Karge, K. Hatada , Y. Zhang and R. Fiedorow

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin-Dahlem, Federal Republic of Germany

Received 12 March 1982.

Available online 23 August 2004.

Abstract

Selective disproportionation of ethylbenzene, yielding benzene and diethylbenzenes in the ratio 1 : 1, was carried out
in a micro flow reactor over various faujasite-type zeolites, hydrogen L zeolite and hydrogen ZSM-5.
Ethylbenzene disproportionation occurs without any catalyst deactivation. The reaction rate depends on the Brönsted
acidity of the zeolite catalysts as measured by i.r. spectroscopy. It is concluded from the acid strength distribution
of HNa-Y, BeNa-Y, MgNa-Y, CaNa-Y, SrNa-Y and BaNa-Y, which was determined via butylamine titration, that only
very strong Brönsted acid sites (H0 −8.2, HR −13.3) are capable of catalysing the disproportionation of
ethylbenzene.

Author Keywords: X-and Y-type zeolite ; ZSM-5; acidity; alkylbenzenes; transalkylation; i.r. spectroscopy;
butylamine titration