Zeolites and Zeolite-Like Materials

459 Pages·2016·42.28 MB·English

by  Bert Sels, Leonid Kustov

Zeolites and Zeolite-like
Materials
Zeolites and Zeolite-like
Materials
Edited by
Bert F. Sels
Centre for Surface Chemistry and Catalysis, Leuven, Belgium
Leonid M. Kustov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences; Moscow State
University, Moscow, Russia
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Contributors
J. Aguilhon Refining & Base Chemicals, Total Research & Technology Feluy, Seneffe, Belgium
Ph. Bodart Refining & Base Chemicals, Total Research & Technology Feluy, Seneffe, Belgium
J. Caro Leibniz University Hannover, Hannover, Germany
J.-P. Dath Refining & Base Chemicals, Total Research & Technology Feluy, Seneffe, Belgium
J. Dijkmans Centre for Surface Chemistry and Catalysis, Leuven, Belgium
M. Dusselier Centre for Surface Chemistry and Catalysis, Leuven, Belgium
T. Ennaert Centre for Surface Chemistry and Catalysis, Leuven, Belgium
E.J.M. Hensen Eindhoven University of Technology, Eindhoven, The Netherlands
V.I. Isaeva N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
Moscow, Russia
A. Kuperman Chevron Corporation, Richmond, United States
L.M. Kustov N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences;
Moscow State University, Moscow, Russia
A. Kustov N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences;
Moscow State University, Moscow, Russia
J. Liu Jilin University, Changchun, PR China
D. Minoux Refining & Base Chemicals, Total Research & Technology Feluy, Seneffe, Belgium
N. Nesterenko Refining & Base Chemicals, Total Research & Technology Feluy, Seneffe, Belgium
R. Oord Utrecht University, Utrecht, The Netherlands
E.A. Pidko Eindhoven University of Technology, Eindhoven, The Netherlands
W. Schutyser Centre for Surface Chemistry and Catalysis, Leuven, Belgium
B.F. Sels Centre for Surface Chemistry and Catalysis, Leuven, Belgium
E.F. Sousa-Aguiar Petrobras Research Centre (CENPES); Federal University of Rio de Janeiro
(UFRJ), Rio de Janeiro, Brazil
A.G. Stepanov Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
B.M. Weckhuysen Utrecht University, Utrecht, The Netherlands
J. Yu Jilin University, Changchun, PR China
xi
Preface
Zeolites have been known for about 250 years, though their active life in science and
industry started in late 1960s. The definition of zeolites experienced a few attacks from
aluminophosphates (AlPOs, SAPOs, MeAPOs etc.), and metallosilicates (Fe-silicate,
B-silicate, Ti-silicate, and others) in the 1980s, then from mesoporous oxide materials
(silicate families MCM-41, SBA-15, mesoporous TiO , ZrO and the like), and now from
2 2,
the organic-inorganic hybrid materials (metal-organic frameworks, MOFs, covalent organic
frameworks, COFs, and porous coordination polymers, PCPs), though the hybrid materials
may contain no traces of silicon or aluminum. All these new materials should be classified as
zeolite-like materials. They are not true silica-alumina compositions and cannot be included
in the family of zeolites. On the other hand, they do exhibit a clear molecular sieve effect
and extended micro/meso porosity. In some aspects, these new materials are better or richer
in properties and structures than the classical zeolites, and provide more opportunities for
variation of the structure and composition. The new zeolite-like materials are not “boiling
stones” anymore. Moreover, some of them are hydrophobic materials with preference for
adsorption of non-polar molecules rather than water. But, the zeolite nature, or character,
of these newcomers in the zeolite world can be easily recognized by the shape-selectivity
effects, huge specific surface areas and pore volumes, and typical zeolite architecture.
The new wave of materials looks like a dangerous avalanche that can absorb the classical
zeolites. But this will not happen, because the Si-Al zeolites have already inscribed their
names (faujasites, mordenites, ZSM-5 zeolites, just to mention a few) in the history of
modern industry—oil refining, petrochemicals synthesis, air separation, detergents, and
other applications. Zeolites continue to be catalysts of choice in the conversion of light and
heavy oil hydrocarbons, and the last decade offered a number of challenges for the use of
zeolite-like materials. The conversion of biomass is another intriguing area where zeolites and
zeolite-like materials will definitely show promising results. There is still a very large domain
of fine chemicals synthesis, as well as other areas of potential applications, where zeolites
do not provide an ideal solution. Yet, the time has not come to judge whether or not the little
brothers of zeolites are better than their elder relatives.
This book is not a comprehensive handbook covering all the areas related to zeolites; it
has been prepared as a kind of an introduction to zeolites for the Pre-Conference School
xiii
xiv Preface
preceding the 17th International Zeolite Conference (Moscow, July 2013). Also, the book is
a contribution of the catalysis commission of the International Zeolite Association (IZA).
The incentive was to show the progress in the key aspects of the zeolite arena. The lecturers
of the Pre-Conference School were asked to prepare their chapters for this book, and they
responded positively to this initiative. It was a difficult task to prepare chapters that should
be, on the one hand, tutorial and understandable to the young generation of zeolite chemists
(especially to those who just started the journey in this wonderful world) and, on the other
hand, reflective of the modern state of the art, showcasing the hot spots in zeolite research.
We intend to show that we are just in the middle of the road and the perception of the current
state of the art will help to trace the path to new, yet undiscovered structures and functions of
zeolite-like materials.
We hope that this book will be considered as a modest extension of the comprehensive
encyclopedia of zeolites—Introduction to Zeolite Science and Practice, 2001. On the other
hand, we were not going to be a shadow of this great book, and tried to identify those areas
that are hot and need to be analyzed and updated after twelve years since 2001.
Every new material brings a new knowledge, not necessarily the promise of a new
application, but this knowledge will serve as the foundation for the forthcoming applications
of new generations of materials.
Bert F. Sels
Centre for Surface Chemistry and Catalysis, Leuven, Belgium
Leonid M. Kustov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences; Moscow State
University, Moscow, Russia
CHAPTER 1
Toward Greener and Designed Synthesis
of Zeolite Materials
J. Liu, J. Yu
Jilin University, Changchun, PR China
1 Introduction
Zeolites are crystalline nanoporous inorganic materials formed by TO tetrahedra (T = Si, Al,
4
P, etc.), which show widespread applications in many industrial processes such as catalysis,
adsorption, and separation [1–3]. In the 1940s, Barrer and Milton opened up the avenue to the
synthesis of zeolites. Since then, there have been considerable efforts in the synthesis of new
zeolite materials. Up to Jun. 2013, 206 types of zeolite materials have been identified by the
Structure Commission of the International Zeolite Association (IZA), each of which has been
named with a three-letter code [4]. Table 1 presents the new framework types approved since
the 16th International Zeolite Conference (IZC-16) in 2010.
Zeolites are typically synthesized in a gel under hydrothermal/solvothermal conditions with
alkali metal cations or organic amines/ammonium cations as the templates or structure-
directing agents (SDAs). The reactive reagents usually include tetrahedral atom (Al, Si, P,
etc.) sources, the SDA, the mineralizer (OH− or F−), the solvent, and so on. The mixture is
then heated in a polytetrafluoroethylene-lined stainless-steel autoclave under autogenous
pressure at temperature below 250°C for a period of time. Many synthetic factors influence
the formation of zeolites, such as the source materials, solvent, SDA, gel composition, pH
value, and crystallization temperature and time. So far, there is insufficient understanding
of the formation mechanism of zeolite materials. Such hydrothermal/solvothermal synthesis
process coupled with the unclear formation mechanism makes the synthesis of zeolites not in
an environmentally friendly and rational way. Despite this, in recent decades, many research
efforts have been made toward the greener and designed synthesis of zeolites. Traditionally,
green chemistry is defined as the utilization of a set of principles that reduces or eliminates
the use or generation of hazardous substances in the design, manufacture, and application of
chemical products [17]. It emphasizes the economy of resource and energy, minimizing waste
and cost, reducing chemical hazards, ensuring process safety, and the like [18]. In the aspect
of zeolite synthesis, various approaches have been exploited toward greener synthesis by
Zeolites and Zeolite-like Materials. http://dx.doi.org/10.1016/B978-0-444-63506-8.00001-X
Copyright © 2016 Elsevier B.V. All rights reserved. 1
2 Chapter 1
Table 1: New framework types approved by the IZA Structure Commission since IZC-16
Date Approved Framework Type Type Material Tetrahedral Elements Refs.
04/03/2011 -ITV ITQ-37 Ge, Si [5]
IRR ITQ-44 Ge, Si [6]
UWY IM-20 Ge, Si [7]
15/10/2011 JST GaGeO-CJ63 Ga, Ge [8]
LTJ Linde Type J Si, Al [9]
NPT Oxonitridophosphate-2 Ba, P [10]
*SFV SSZ-57 Si [11]
07/10/2012 BOZ Be-10 Be, As(P) [12]
JOZ LSJ-10 Be, Si [13]
JSN MAPO-CJ69 Co(Zn), Al, P [14]
JSW MAPO-CJ62 Co(Zn), Al, P [15]
PCR IPC-4 Si [16]
considering the green chemistry principles such as cost and environmental impact reduction,
waste reusing, energy efficiency, process safety, and more. Consequently, some greener
synthesis methods have been developed, such as organic-template-free synthesis, solvent-free
synthesis, cheap or low-toxic organic-template-directed synthesis, waste reused synthesis,
microwave-assisted synthesis, ionothermal synthesis, and more. Meanwhile, many attempts
have been devoted to the rational synthesis of zeolites with specific framework structures and
functions by novel SDA design, charge density mismatch (CDM), heteroatom substitution,
and topotactic conversion [19,20]. In this chapter, we highlight some recent progress toward
greener and rational synthesis of zeolite materials.
2 Green Synthesis
Currently, with increasing attention being paid to environmental and resource issues, green
chemistry has been in the spotlight as a topic of research and has become one of the main
objectives of by synthetic chemists. Anastas and Warner summarize 12 principles to guide
the green chemical synthesis [17]. Many relevant factors should be taken into account in the
process of green synthesis, including the concepts of the use and generation of safe and low
or no-toxic substances, the design of energy-efficient processes, the best disposal of waste
filtrate, and the like [18].
However, for zeolite synthesis, the traditional synthesis strategies more or less violate the
principles of green chemistry. The hydrothermal or solvothermal synthesis method is usually
conducted at high temperature and high pressure, undoubtedly increasing the hidden danger
factors and causing energy consumption; the organic templates and organic solvents are
usually toxic and expensive, thus increasing the synthesis costs; the discarded filtrates contain
abundant inorganic/organic species that can be reused; and the resultant products need to
be calcined at high temperature to remove the occluded organic templates, further causing
Toward Greener and Designed Synthesis of Zeolite Materials 3
environmental pollution. Chemists have therefore been making great efforts toward greener
synthesis of zeolite materials. Herein, we will introduce the recent representative works
toward greener synthesis of zeolites from the aspects of reduced cost and environmental
impact, waste reused, energy efficiency, and process safety.
2.1 Synthesis for Reduced Cost and Environmental Impact
2.1.1 Organic-template-free synthesis
In the early time, zeolites are synthesized mainly in the basic M O/MOSiO − Al O − H O
2 2 2 3 2
(M = Li+, Na+, K+, Ca2+, Ba2+, etc.) systems with metal cations as templates. These cations
play the role of directing the formation of structures and balancing the negative framework
charges. Since Barrer and Denny first introduced organic templates into the synthesis system
in 1961 [21], many novel zeolite structures have been prepared by using various types of
organic amines/ammonium cations as templates. However, using organic templates also
has disadvantages in zeolite synthesis. On the one hand, most organic amines/ammonium
cations are toxic and expensive. The synthesis process will produce more or less poisonous
vapor with a hazard to human health and the environment. And the posttreatment process
requires a lot of water to wash reaction products and remove excessive raw materials,
resulting in much toxic wastewater. On the other hand, the subsequent process of calcination
to remove the organic amines/ammonium cations for opening up the channel system will be
accompanied with the release of CO , NO, and other waste gases. Both aspects are against
2 x
the environmentally friendly principles. To this end, the organic-template-free synthesis
of zeolites becomes an effective strategy to avoid the environmental hazard, save sources,
and reduce costs. To exclude organic templates from the synthesis, some crucial factors are
needed to be considered [22]: (1) Metal cations. In replace of organic templates, inorganic
metal cations (eg, Na+) become an important factor in the formation of zeolites acting as the
templates and framework charge balancers. (2) Molar ratio of the reactant gel. Because of
the absence of organic templates, the phase regions of zeolite formation may be narrowed
and different from the ordinary ones. So, careful exploration of the reactant gel molar ratio is
needed. (3) Seeds. The addition of seeds may help to accelerate the growth of zeolite crystals.
(4) Potential building units. The seed solution containing the potential building units of
targeted zeolite products may direct the growth of zeolite crystals.
2.1.1.1 Metal-cation-directed synthesis
To overcome the disadvantages caused by organic templates, researchers attempted to
directly omit the organic templates by carefully controlling the gel molar ratio in the
synthesis. The aluminosilicate zeolite ZSM-5 (MFI) can be traditionally synthesized with
the tetrapropylammonium cation as the organic template [23]. ZSM-5 with high crystallinity
was first synthesized in the system of Na OSiO Al O H O in the 1970s [24,25]. Several
2 2 2 3 2
years later, Clearfield and coworkers [26] further studied the organic-template-free synthesis
4 Chapter 1
of ZSM-5 by systematically adjusting the molar composition of the reaction gel. They found
that the Si/Al ratio and Na/Al ratio were the most important factors affecting the synthesis.
Only when the Si/Al ratio was 20 and Na/Al ratio was 2.25–3, pure ZSM-5 was crystallized;
when the Si/Al ratio was lower (<15), the resulting product was mainly aluminosilicate
zeolite mordenite (MOR) along with traces of ZSM-5; when the Si/Al ratio increased
(>30), the amount of α-quartz increased coexisting with ZSM-5 and mordenite; when the
gel contains no alumina, almost pure α-quartz could be obtained. Similarly, the increase of
Na/Al ratio could also lead to the crystallization of mordenite and α-quartz along with
ZSM-5. N absorption data showed the as-synthesized materials possessed open channel
2
system before calcination, which provided the successful synthesis of ZSM-5 in the
organic-template-free system.
The aluminosilicate zeolite ECR-1 (EON) was first synthesized with the
bis-(2-hydroxyethyl)-dimethyl-ammonium cations as the organic template [27]. As
gallosilicate zeolite TNU-7 (EON) that has the same framework type as ECR-1 can be
hydrothermally synthesized in the organic-template-free system [28], the organic- template-
free synthesis of ECR-1 becomes possible. In 2006, Xiao and coworkers reported their work
on the synthesis of ECR-1 without organic templates [29]. Through mixing NaOH, NaAlO ,
2
and water glass by stirring and aging at room temperature, a precursor solution (SiO : Al O :
2 2 3
Na O: H O = 15: 1.0: 16: 320) was prepared. Then, the precursor solution was mixed with
2 2
H O, water glass, Al (SO ) , NaAlO , and HCl to give the final mixture with a molar ratio of
2 2 4 3 2
SiO : Al O : Na O: H O = 10: 1.0: 2.5: 200. After crystallization at 100°C for 2 weeks, ECR-1
2 2 3 2 2
was obtained. By systemically studying the synthetic factors, it was found that alkalinity,
temperature, and crystallization time played a pivotal role in the synthesis.
In 2012, Mintova and coworkers captured ultra-small EMT zeolite of 6–15 nm from the
organic-template-free system at low temperature [30]. Traditionally, pure EMT could only
be synthesized with an expensive organic template (18-crown-6 ether) [31]. The novel
organic-template-free synthesis of EMT zeolite is from Na-rich precursor suspensions.
Gel composition, nucleation temperature and time, and heating method are the key for the
formation of ultra-small EMT zeolite, avoiding the conversion of zeolite EMT into zeolite
FAU or SOD. The synthesis proceeded at near ambient temperature (30°C) with a very high
yield. The successful synthesis of EMT zeolite provides a good example of zeolite synthesis
by an energy-efficient and green route.
2.1.1.2 Seed-assisted synthesis
It is thought that the zeolite seed solution may contain the zeolite building units such
as secondary building units (SBUs), which play a potential structure-directing role in
the crystallization of zeolite crystals. The introduction of seed crystals into the starting
aluminosilicate gels is considered to be an efficient way to accelerate the crystallization rate
of zeolites. A typical example is shown by the aluminosilicate zeolite Beta (*BEA). In 2008,