Title of Invention

CATALYTIC MATERIALS AND METHOD FOR THE PREPARATION THEREOF

Abstract ABSTRACT CATALYTIC MATERIALS AND METHOD FOR THE PREPARATION THEREOF The invention discloses a catalytic material, characterized in that the catalytic material is a mesoporous molecular sieve embedded with a zeolite and the catalytic material is thermally stable at a temperature of at least 900°C. The invention is also for a method for manufacture of a mesoporous molecular sieve embedded with a zeolite catalyst as stated above.
Full Text

Field of the Invention
The invention is related to mesoporous catalysts and particularly to novel mesoporous
molecular sieves embedded with a zeolite, having high thermal stability, and to a
method for the preparation of the catalytic materials. Said catalytic materials are
suitable for applications in the field of hydrocarbon processing.
State of the Art
Mesoporous molecular sieves as catalytic materials have attracted the attention of
scientists because of their unique properties, such as large uniform pores having a
very high surface area, the size of which can be varied from 2 to 50 nm. However,
mesoporous molecular sieves known in the art are often thermally and
hydrothermally not very stable, the pore walls are amorphous and they have mild
acidic properties. Further more, during the regeneration of the spent catalyst after
hydrocarbon processing, the mesoporous molecular sieve structure may collapse.
Crystalline materials having pore size in the microporous area (d catalysts and as carriers of catalysts on an industrial scale. Zeolites are well-known
examples of such materials. Zeolites are widely used because of their special
properties, such as large surface area, high capacity of adsorption and possibility to
regulate adsorption capacity. It is possible to create active sites in the zeolite
structure, build up active sites and to regulate the strength and amount of the acid
sites. The pore size of zeolites is typically in the range of 0.4 - 1.2 nm and both the

thermal and chemical stability of zeolites are high. However, the ability of zeolites to
process molecules having larger molecular size than the pore size of the zeolites is
limited and further, zeolites are deactivated relatively rapidly in several reactions.
US 5,198,203 discloses a family of ordered, mesoporous molecular sieves, designated
as M41S and developed in the beginning of 90's. M41S is a group of mesoporous
molecular sieve materials formed in an aqueous solution with silica and alumina
precursors with CiH2i(CH3)N+- cations (i > 7) at hydrothermal conditions. The most
well known members of this group are hexagonal MCM-41, cubic MCM-48 and
plate-like structure MCM-50. The pore size of the mesoporous molecular sieve can be
regulated between 2 and 10 run and the composition may contain pure silica or
metallosilica (e.g. A1-, V- and Ti-substituted silica). The mesoporous molecular sieve materials of the M4IS group are amgrophous by nature and their pore system is
ordered.
A synthetic composition of a material comprising ultra-large pore crystalline phase is
disclosed in US 5,246,689 and US 5,334,368. This material is inorganic, porous and
non-layered having pore dimensions between 1.3 and 20 nm. The pore size
distribution within a single phase is to some extent regular. At least one peak in the
X-ray diffraction pattern at d-spacing is greater than 1.8 nm.
EP 0 748 652 discloses a group of mesoporous materials (MSA) having a narrow
pore size distribution. This material was amorphous and totally disordered. The BET
surface area of the material was in the range of672-837m2/g.
Synthetically produced mesoporous materials are not acidic or their acidity is limited.
The amount of acid sites in mesoporous materials has been increased by
incorporation of aluminium in the silica structure of the mesoporous material. The

strength of the acidity of the mesoporous materials described above is, however, less
than the strength of the acidity of the zeolites.
Various methods for the manufacture of mesoporous materials are known in the art.
have been made to increase thermal and hydrothermal stability and acidity
of mesoporous molecular sieves, for example by introducing catalytically active
species in the mesoporous structures. In principal, the methods of synthesis comprise
preparation of a silicon source solution with an organic agent or agents, adjusting the
pH of the solution to a value where precipitation occurs, followed by recovering and
calcination of the precipitate. An aluminium source is added to the solution in any
step prior to the starting of the synthesis at elevated temperature. Several surfactants
and templates (organic agents), compositions, solvents and reaction conditions have
been suggested,
US 5,942,208 describes a method for the preparation of mesoporous material having
improved hydrothermal stability when compared to MCM-41. Various salts were
used in the method and the pH of the solution was adjusted with mild acids.
EP 0 795 517 provides a method for the synthesis of mesoporous materials wherein a
mixture of a silicon source and organic template containing fluorine was used.
US 5,942,208 describes the preparation of a mesoporous molecular sieve having
thermal and hydrothermal stability superior to the ones of traditional mesoporous
molecular sieves. The material could be boiled in water for 12 hours without essential
changes in the structure.
An alternative approach for the manufacture of stable and active mesoporous
materials is to introduce zeolites into the walls of the mesopores. US 09/764,686

discloses the synthesis of mesoporous materials using Y-zeolite seed, MFT zeolite
seed and beta-zeolite seed.
CN 1349929 teaches the preparation of MSA-3 and MAS-8 using L-zeolite precursor
solutions.
Kloetstra et al Micropor. Mesopor. Mater. 6 (1996) 287 have reported in situ
formation of faujasite and MCM-41. Their approach was based on sequential
synthesis of zeolites and MCM-41.
Karlsson et al,. Micropor. Mesopor Mater. 27 (1999) 181 disclose the use of mixed
template approach for the simultaneous synthesis of zeolite/MCM-41 phases.
The materials may be mixtures of two or more phases, or loosely bonded zeolite and
mesoporous material in the case the synthesis approach is to grow and deposit MCM-
41 over zeolite, or zeolite seeds may be added to the gel.
Two different types of templates have been used in the synthesis of mesoporous
materials. The reproducibility of such manufacturing methods may be difficult.
Furthermore, in the absence of chemical interaction between the zeolite and
mesoporous molecular sieve, thermal and hydrothermal stability of the resulting
materials is likely to be low.
According to the state of the art, mesoporous molecular sieves have a wide range of
applications in catalysis as active phases or as supports. Several hydrocarbon
conversion reactions are acid catalysed. Based on their acid catalysed function,
zeolites are know to be active in double-bond and skeletal isomerization of olefins,
isomerization of paraffins, cracking, dimerization of olefins, oligomerization of
olefins, ring opening of naphthenes, alkylation, transalkylation of aromatics,

aromatization etc. Bifunctional catalyst having metal or metal-oxide or sulfide phases
are applicable in reactions such as reforming, isomerization of paraffins,
hydrocracking, catalytic dewaxing, dehydrosulfurization, dehydrooxygenation,
dehydronitrogenation and several hydrogenation reactions. The major drawbacks in
the use of the zeolites are their relative high ability for deactivation and limited
capacity of handling of bulky molecules.
Based on the above it can be seen that there exists a need for thermally and
hydrothermally stable catalytic materials based on mesoporous molecular sieves and
for a method for the preparation of such thermally and hydrotherrnally stable catalytic
materials. It is also obvious that there is a need for a catalyst having zeolite type
active site but also high accessibility of the active sites for reactants, short diffusion
path length of reactants and products limiting secondary reactions and coking.
Object of the Invention
An object of the invention is to provide a novel and active catalytic material having
mesoporous molecular sieve embedded with a zeolite structure, particularly for
hydrocarbon conversion reactions.
A further object of the invention is a mechanically, thermally and hydrotherrnally
stable mesoporous molecular sieve embedded with a zeolite, having zeolite type
acidity.
A still further object of the invention is a method for the manufacture of said catalytic
material having mesoporous molecular sieve embedded with a zeolite structure.

A still farther object of the invention is the use of said catalytic material having
mesoporous molecular sieve embedded with a zeolite structure in hydrocarbon
conversion reactions.
The characteristic features of the mesoporous molecular sieve embedded with a
zeolite, of the method for the manufacture thereof and of the use of the mesoporous
molecular sieve embedded with a zeolite are stated in the claims.
Summary of the Invention
Without wishing to be restricted by the following explanations and theoretical
considerations regarding the synthesis of the novel catalytic material having
mesoporous molecular sieve embedded with a zeolite structure,which is particularly
suitable for hydrocarbon conversion reactions, the essential features of the invention
are discussed as follows.
The present invention relates to a novel and active catalytic material having a
mesoporous molecular sieve embedded with a zeolite structure. The invention relates
also to a method for the preparation of the mesoporous molecular sieve embedded
with a zeolite whereby the synthesis is facilitated and reproducible and the product
exhibits high catalytic activity.
The catalytic material having mesoporous molecular sieve embedded with zeolite
structure is suitable for hydrocarbon conversion reactions and particularly for
processing of high molecular weight hydrocarbons. This novel catalytic material can
be used as a component of a catalyst in cracking, hydrocracking, ring opening,
hydrogenation of aromatics and especially multiaromatics, dimerization of olefins,
oligomerization, isomerization of olefins and paraffins, alkylation of aromatics,

etherification, hydrodesulphurization and reforming, or as such or with modifications
known from the state of art.
Detailed Description of the Invention
It has now been found that the problems relating to zeolite catalysts and mesoporous
catalysts according to the state of the art can be avoided or at least significantly
decreased by the novel catalytic material according to the invention, which is a
mesoporous molecular sieve embedded with zeolite, having high mechanical, thermal
and hydrothermal stability. The novel mesoporous molecular sieve embedded with a
zeolite is thermally stable at temperatures of at least 900 °C in the presence of air.
The present invention pxovidgs a group of novel mesoporous molecular sieves
embedded with zeolites, which are mechanically, thermally and hydrothermally
stable. The materials are very well reproducible as can be seen in the examples, and
they exhibit superior properties in several hydrocarbon conversion reactions. The
group of the novel mesoporous molecular sieves embedded with zeolites are named
mesoporous materials (MM). Mesoporous means here materials having pores of 2 -
15 nm and their pore system is regular.
The mesoporous molecular sieve embedded with a zeolite comprises a mesoporous
molecular sieve selected from M41S group, which is defined on page 2 and
comprises mesoporous materials with ordered pore system. Preferably the
mesoporous molecular sieve is selected from mesoporous alurnino-silicates known as
the MCM-41 group.
The mesoporous molecular sieve is embedded with a zeolite selected from medium
pore zeolites, which are 10-member ring zeolites like MFI, MTT, TON, AEF, MWW
and FER structures, and large pore zeolites, which are 12-member ring zeolites like

BEA, FAU and MOR structures. Examples of said zeolite groups are ZSM-5, ZSM-
23, ZSM-22, SAPO-11, MCM-22, ferrierite, beta, Y-and X-zeolites and mordenite.
Preferably the zeolite is MFI, MTT, AEF, MWW, MOR or BEA zeolite.
The catalytic material contains 0.01 - 10 wt-% of aluminium (Al).
A catalyst, which is particularly suitable for industrial and commercial use, comprises
the mesoporous molecular sieve embedded with a zeolite according to the invention
and also a carrier selected from alumina, silica, clay and any other carrier according
to the state of the art, and combinations thereof. Preferably the carrier comprises
alumina or silica. The amount of the carrier varies between 10-90 wt-%, calculated
on the total weight of the catalyst.
The novel group of catalytic materials having a mesoporous molecular sieve
embedded with a zeolite structure according to the invention exhibits high specific
surface area (BET) in the range of 1400 - 500 m2/g, preferably 1200-600 m2/g.
The X-ray powder diffraction pattern of the catalytic material according to the
invention demonstrates the mesoporous molecular sieve and zeolite structures. The
unit cell dimension of the zeolite varies with amount of Al in the catalytic material.
The unit cell size decreases with the amount of Al, from 1.982 nm in a catalytic
material containing 0.2 wt% of Al to 1.972 nm in a catalytic material containing 3.9
wt% of Al, when the zeolite type was MFI (the code of the material is MM5). The
change in the unit cell size is opposite to the changes observed in zeolites in general.
The unit cell sizes were 1.428 nm and 1.430 nm, when the zeolite type was BEA (the
code of the material is MMBE), the unit cell sizes were 1.406 nm and 1.436 nm,
when the zeolite type was MWW (the code of the material is MMMW22) and the unit

cell sizes were 1.800 ran and 1.806 run, when the zeolite type was MOR (the code of
the material is MMMO).
The d100 spacing in the mesoporous molecular sieve MCM-41 decreases with
increasing zeolite content. The d100 varies from 4.4 nm to 3.8 nm in MM5 and the d100
varies from 4.1 nm to 4.0 nm in MMBE and MMMO, and from 4.0 to 4.2 in
MMMW.
The unit cell dimension and the d100 values are the same in pure zeolite and MCM-41
phases as in their mechanical mixtures.
The changes in the d100 spacing and the unit cell dimension are a clear evidence of a
true chemical bonding between the mesoporous molecular sieve and the embedded
zeolite in the catalytic material according to the invention.
The characteristic features of the catalytic material according to the invention, the
mesoporous molecular sieve embedded with a zeolite, were measured by X-ray
powder diffraction, scanning electron microscopy, transmission electron microscopy,
specific surface area measurement using nitrogen absorption (BET) and acidity
measurements using ammonia-TPD and pyridine-FTIR..
The total number of acid sites can be measured by the capacity of the catalytic
material to bind strong base molecules, such as ammonia or pyridine. The total
acidity was measured by ammonia-temperature programmed desorption (TPD) and
Bronsted and Lewis acidity by pyridine-infrared spectroscopy (FTIR).

Brief Description of the Accompanying Drawings
Fig. la & lb - give co-relation between the acidity and aluminium content in the
catalytic materials according to the invention.
Fig.2 - N2-adsorption and desorption isotherm of MMBE are shown in this
figure.
Fig.3 - BJH description illustrating mesopore diameter distribution is MMBE
is shown in this figure.
Fig.4&5 - The XRD diffraction pattern of calcined MM5, before and after
thermal treatment are shown in these figures.
Fig.6a - HRTEM picture of mesoporous material, embedded with beta zeolite,
according to the invention.
Fig.6b - HRTEM picture of an ordered MCM-41 material.
Fig.7 - Catalyst of example 8 is compared with the comparative catalyst
(example 1) in isobutene dimerization.
i
The acidity of the catalytic material can be tailored by the amount of A1 introduced in
the structure and modifying the aluminium (Al) content in the zeolite, MCM-41 and
MM phases. In Figures la and lb the correlation between the acidity and aluminium

content in the catalytic materials according to the invention is presented. Figure la
shows the linearity of total acidity as a function of Al-content in the various MM
catalytic materials and Figure 1 b shows how the zeolitic and the MCM-41 catalytic
materials deviate in total acidity from the MM catalytic materials. The zeolites exhibit
larger amount of acid sites as a function of Al content than MM5, MMBE and
MMMW samples, MCM-41 is less acidic with similar aluminium content.
Since there are no international standard methods available for acidity determination,
the methods used here are described below.
Acidity determination was performed by NH3-TPD. The total acidity of catalytic
materials was measured by temperature-programmed desorption of ammonia (NH3-
TPD)using an Altamira AMI 100 instrument Sample size was 40 mg The total
acidity was measured by desorption of NH3 as a function of temperature. The acidity
of the samples was calculated from the amount of NH3 adsorbed at 200 °C and
desorbed between 100 °C and 500 °C. The NH3-TPD instrument was equipped with a
thermal conductivity detector (TCD) manufactured by company Gow Mac. A ramp
rate of 20 °C/min was applied and the temperature was linearly raised to 500 °C
where it was held for 30 min. The quantification was made using pulses of known
volume of 10 % NH3 in He.
Acidity determination was determined also by pyridine-FTIR. The acidity of samples
was measured by infrared spectroscopy (ATI Mattson FTIR.) by using pyridine (≥
99.5 %, a.r.) as a probe molecule for qualitative and quantitative determination of
both Bronsted and Lewis acid sites. The samples were pressed into thin self-
supported wafers (10-12 mg/cm2). Pyridine was first adsorbed for 30 min at 100 °C
and then desorbed by evacuation at different temperatures (250. 300, and 450 °C) to
obtain a distribution of acid site strengths. All spectra were recorded at 100 °C with a
spectral resolution equal to 2 cm-1. Spectral bands at 1545 cm-1 and 1450 cm-1,

respectively, were used for identifying Bronsted (BAS) and Lewis acid sites (LAS).
The amounts of BAS and LAS were calculated from the intensities of corresponding
spectral bands by using the molar extinction coefficients.
The acid sites are situated on the surface of the catalytic material. The total surface
area and pore volume were evaluated using N2-adsorption and desorption. The
average mesopore surface area and mesopore diameter were evaluated from the N2-
desorption utilizing the BJH (Barrer-Joyner-Halenda) equation. The pore diameter
has a size-limiting effect both on reactants and products. The size of micropores
depends on the structure of the zeolite. Pores with a diameter less than 2 nm are
defined as micropores and pores with a diameter between 2 and 50 nm are defined as
mesopores according to IUPAC.
The N2-absorption desorption isotherms of MMBE are shown in Figure 2. The
mesopore diameter remains similar, 2.4 - 2.7 nm, in the embedded material compared
to 2.6 nm in the mesoporous molecular sieve.
BJH desorption illustrating mesopore diameter distribution in MMBE is shown in
attached Figure 3.
The surface area and total pore volume decrease when the zeolite is embedded in the
mesoporous molecular sieve as can be seen from table 1 below, presenting surface
area, pore volume and pore diameter values for MM5, MMBE and MMMW, and for
comparison MCM-41, MFI and BEA data are enclosed.


The zeolite is identified by X-ray diffraction (XRD). From the XRD patterns the unit
cell dimensions of the zeolite as well as of the MCM-41 phase can be measured when
suitable internal standards are used. α-Al2O3 or TiO2 (rutile) was used as the internal
standard.
The unit cell size of MFI was measured by ASTMD 3942-97 method,.using α-Al2O3
as internal standard.


The unit cell of BEA was measured by a modified ASTM D 3942-97 method, using
TiO2 as internal standard and the [302] reflection at 22°2 theta.
The unit cell of MWW was measured by a modified ASTM D 3942-97 method, using
α-Al2O3 as internal standard and the [100] reflection at 7.2°2 theta.
The unit cell size of MMMO was estimated from the peak positions without internal
standard. The estimation was ao=2 * d[100]/V3.
The unit cell size of the mesoporous molecular sieve (MCM-41) was estimated by a
method described by IS. Becker etal, /. Am, Chem. Soc. 114 (1992) 10834.
The unit cell size of zeolites corresponds to the amount of A1 incorporated in the
zeolite framework. The A1 atom is larger than the Si atom, thus the unit cell size
typically increases with increasing amount of Al in most zeolites. On the contrary, in
the embedded zeolite the unit cell dimension decreases with increasing amount of Al
in the MM5 catalytic material, as can be seen from table 2 (MFI, BEA, MWW and
MOR a0 values). The change in unit cell dimension (UCD) of MCM-41 does not
correlate with the amount of Al, it rather decreases with increasing intensity of the
MFI phase. The changes in unit cell dimensions are clear evidences of true chemical
bonding between the mesoporous molecular sieve and the embedded zeolite.
Aluminium content and unit cell dimensions of MCM-41, as well as of MFI, BEA,
MWW and MOR zeolites embedded in mesoporous molecular sieve (MCM-41) are
presented in the following table 2.


Thermal stability of the catalytic material according to the invention was tested by
exposing the embedded material to a temperature of 1000°C in air. The XRD
diffraction pattern of calcined MM5 is shown in Figure 4. After thermal treatment at

1000 °C the same pattern is obtained, as shown in Figure 5. This observation provides
evidence that this catalytic material according to the invention is thermally stable to a
temperature of at least 1000°C.
The nanostructure of the catalytic materials according to the invention was studied by
high-resolution transmission electron microscopy using (HRTEM) (Philips CM-
200FEG transmission electron microscope with point resolution of 0.24 nm). The
composition was measured with EDS (NORAN Voyager energy dispersive X-ray
spectrometer). In Fig. 6a a HRTEM picture of the mesoporous material embedded
with beta zeolite according to the invention is illustrated. For comparison, in Fig 6b,
HRTEM picture of an ordered MCM-41 material is shown.
The method for the manufacture of the mesoporous molecular sieve embedded with a
zeolite is described in more detail in the following.
The method for the manufacture of the mesoporous molecular sieve embedded with a
zeolite comprises the steps:
a) preparing of zeolite nuclei from a silicon source and an aluminium source and
structure directing agent (template R), or a silicate or aluminosilicate
precursor for the zeolite nuclei, and optionally removing the template with a
step calcination procedure;
b) preparing of mesoporous molecular sieve gel mixture from a silicon source,
an optional aluminium source, and surfactant (S);
c) introducing the zeolite nuclei or the silicate or aluminosilicate precursor,
prepared in step a) as reagents to the mesoporous molecular sieve gel mixture
obtained in step b), and the zeolite nuclei or the silicate or aluminosilicate
precursor are homogenised and dispersed in the molecular sieve gel;.
d) performing gel ripening of the mixture of step c) under stirring;

e) carrying out hydrothermal synthesis of the mixture of step c) by maintaining
the mixture under sufficient conditions including a temperature of from about
100 °C to about 200 °C under static or dynamic mode of stirring until crystals
are formed;
f) recovering the crystals;
g) washing of the solid product;
h) drying of the solid product, and
i) removing the surfactant (S) partly or totally with a step calcination procedure
and optionally the template (R) if it was not removed in step a), whereby a
mesoporous molecular sieve embedded with a zeolite catalyst is obtained.
In step a) the zeolite nuclei are prepared from a silicon source and an aluminium
source and structure directing agent (template R). The silicon source is selected from
silicon oxides, preferably from colloidal silica, solid silica and fumed silica.
The aluminium source is selected from aluminium sulphate (Al2(SO4)3.18H2O),
hydrated aluminium hydroxides, aluminates, aluminium isoproxide and alumina.
A suitable template is selected in order to obtain the desired zeolite structure.
Examples of typically used templates are alkyl ammonium hydroxides, alkyl
ammonium halogenides, alkyl amine hydroxide and alkyl amine halogenides like
tetrapropylammonium bromide, tetramethylammonium hydroxide, tetramethyl-
ammonium bromide, tetraethylammonium bromide, tetraethylammonium hydroxide,
piperidine, pyrrolidine, octylamine, ethylenediamine, 1,6-diaminohexane and
hexamethyleneimine.
The temperature in step a) is between 40 - 200 °C and the preparation can take place
in static or in dynamic mode. Finally, in step a) the template is optionally removed by
a thermal treatment procedure known as step calcination procedure. The temperature

of the treatment is in the range of 350 - 900 °C removed. The template may
alternatively be removed in step i) if it was not removed in step a) but preferably the
template is removed in step a).
in step b) the mesoporous molecular sieve gel is prepared from silicon sources,
optional aluminium sources, and surfactant (S). The silicon sources are selected from
silicon compounds having an organic group and from inorganic silicon sources.
Those silicon sources having an organic group are tetraethoxy silane (TEOS),
tetramethylarnmonium silicate, tetraethylammonium silicate etc. The inorganic
silicon sources are sodium silicate, water glass, colloidial silica, solid silica and
fumed silica. The aluminium source is selected from aluminium sulphate
(Al2(SO4)3.18H2O), hydrated aluminium hydroxides, aluminates, aluminium
isoproxide and alumina. The surfactant is selected in order to obtain the desired
mesoporous phases. Suitable surfactants used are alkyltrimethyl ammonium halide
compounds with the general formula CnH2n+1 (CH3)3NX, where n = 12 to 18, X= CI,
Br. Preferably the surfactant is selected from the group consisting of n-
hexadecyltrimethyl ammonium bromide, n-hexadecyltrimethyl ammonium chloride,
cetyltrimethyl ammonium bromide and cetyltriethylammonium bromide. The
temperature in step b) ranges between 20 and 100 °C and the preparation takes place
under stirring.
In step c) the zeolite nuclei or the silicate or aluminosilicate precursor prepared in
step a) are introduced to the molecular sieve gel under stirring. The formed mixture is
homogenised and the zeolite nuclei or the silicate or aluminosilicate precursor are
dispersed. For adjusting the acidity of the product, additional aluminium source may
be added. This additional aluminium source is an aluminium source having an
organic ligand selected from aluminium alkoxides, preferably aluminium
isopropoxide. The stirring rate in step c) ranges between 50 and 1000 rpm. The
treatment time is between 10 - 500 minutes.

In step d) the gel is ripened under stirring. The stirring rate is 200 - 1000 rpm and the
time of the gel ripening is between 30 - 1800 minutes.
In step e) the hydrothermal synthesis is performed at a temperature between 100-200
°C. The time for the hydrothermal synthesis can vary between 10 h - 300 h depending
the material desired. The hydrothermal synthesis is performed in dynamic mode
under continuous stirring of the mixture until crystals are formed.
In step f) the crystals from step e) are recovered, for example by filtration or by
another method known to be state of the art. If necessary, the pH of the mixture is
adjusted to 6 - 8 before the recovery, such as filtration.
-In-step-g.)-the-solid-product obtained in step f) is thoroughly washed using for
example water as the washing liquid. The temperature 'of the water is from room
temperature to 60 °C. The washing is finished when all undesired, soluble materials
are removed from the solid product.
In step h) the solid product is dried for removal of solvent by the methods known to
be state of art.
In step i) the surfactant (S) is partly or totally removed by a thermal treatment
procedure known as step calcination procedure. The templetate (R) may optionally be
removed in step i) simultaneously with the removal of the surfactant. The temperature
of the treatment is in the range of 350 - 900 °C. The heating rate ranges between 0.2
and 10 °C/min. The atmosphere in the treatment is oxidising and in the final step the
material is typically treated in air. A mesoporous molecular sieve embedded with a
zeolite catalyst is obtained.

In the manufacturing method a gel solution is prepared of the mesoporous molecular
sieve, then the zeolite nucleating agent is added at suitable synthesis conditions and
an aluminium source is substituted with zeolite nucleating agent. Suitably the
aluminium source is an aluminium alkoxide and preferably aluminium isopropoxide.
Preferably the surfactant is n-hexadecyltrimethylammonium bromide, n-
hexadecyltrimethyl ammonium chloride, cetyltrimethylammonium bromide or
cetyltriethylammonium bromide.
Preferably distilled water or deionized water is used as a solvent and in washing of
the material.
Zeolite nuclei are aluminosilicate precursors free of structure directing agents, and
they may be partially or fully crystalline. Because of the variation in crystal size they
may be or may not be detected by XRD. However, their morphology can be observed
by scanning electron microscopy. The zeolite nuclei have a meta-stable phase, which
in the presence of a surfactant, during the synthesis of the catalytic material according
to the invention accomplishes chemical bonding with the walls of the mesoporous
molecular sieve.
After the intensive dispersion of the aluminosilicate nuclei to the mesoporous
molecular sieve gel solution, in the presence of a surfactant and during the gel
ripening period, a nuclei-surfactant mesophase complex is formed, which strengthens
and enhances the chemical bonding and crystallinity of the walls of the mesoporous
material.
The aluminosilicate precursor for the zeolite nuclei can be prepared for zeolite
structure types such as MFI, BEA, TON, MOR, MWW, AEF and FAU from known
state of the art (EP 23089, US Patent 3308069, EP 102716, EP 23089). Two

examples of the preparation of aluminosilicate precursors for zeolite nuclei of
structures MFI and BEA are given here. It is however obvious that the other
mentioned zeolites are equally suitable.
The zeolite nuclei, prepared from an aluminosilicate precursor, are suitably used in
the gel preparation. During the gel ripening period chemical interactions and bonding
via process of nucleation take place. Gel ripening accelerates the nucleation process
and secondary nucleation may also occur on the zeolite nuclei forming thereby a
complex "zeolite nuclei-surfactant mesophase", which enhances the chemical nature
of bonding between the micro and mesophases. Microphases are responsible for the
formation of the zeolite structure, and mesophases for the formation of the
mesoporous structure.
Formation of "zeolite nuclei-surfactant mesophase" is favoured when the zeolite
nuclei is introduced after the addition of the surfactant in alkaline media or soaking
the zeolite nuclei in an aqueous solution of the surfactant prior to its addition,
followed by gel ripening period.
The order of introducing the reagents, specially the surfactant and zeolite nuclei, pre-
treatment of the zeolite nuclei and gel ripening process are important for the creation
of the chemical nature of bonding between the microporous and mesoporous
molecular sieve material. In order to obtain the high acidity novel mesoporous
molecular sieve embedded with a zeolite materials, an aluminium source is
introduced after the addition of zeolite nuclei but prior to gel ripening period.
Vigorous stirring after introducing of the zeolite nuclei during the gel preparation is
significant in order to increase the homogenity and dispersion of zeolite nuclei in the
gel solution.

The obtained catalytic materials may optionally be transformed to the corresponding
proton forms via ammonium ion-exchange and calcination. A suitable source material
for ammonium ion-exchange is an ammonium salt like ammonium nitrate or
ammmonium chloride. The catalytic materials are treated in an aqueous solution of
the ammonium salt at temperatures between 25 - 80 °C for a suitable time interval
like 1 to 6 hours. The ammonium cations replace the alkali or alkaline cations of the
materials during the treatment. The degree of the ion-exchange can be varied by
changing the time of the treatment, concentration of ammonium solution and
temperature. After the ion-exchange treatment, the obtained material is dried and
calcined for decomposing the ammonium ions to proton and ammonia.
Modifications of catalytic material according to the invention, the novel mesoporous
molecular sieve embedded with a zeolite, can be carrier out by methods selected from
a group consisting of precipitation, deposition, encapsulation, and selective removal.
Both impregnation and ion exchange are deposition methods. In impregnation, the
deposition is carried out from liquid phase and adsorption, ion exchange and selective
reaction may take place on or with the surface of the support. During the removal of
the liquid, crystallites rather than monolayers are formed on the surfaces. In ion
exchange diluted solutions are used, and the desired metal cation is exchanged from
the solution to the material replacing the cation or proton of the solid material. The
procedures and choice of method for modification depend on the target reactions.
Generally, ion exchange method is preferred when lower loading and higher
dispersion of metal is needed.
The removal of surfactant after the completion of the synthesis is necessary to obtain
the mesoprous molecular sieves embedded with a zeolite with high surface area and
acidity. The calcination temperature, heating rate and duration may influence the
surface area, pore size distribution and location of aluminium in the framework. Very
large surface area, determined by nitrogen adsorption and varying strong acidity,

determined by TPD of ammonia, of the synthesized novel mesoporous molecular
sieve embedded with a zeolite confirms that the step calcination procedure is a very
suitable method for surfactant removal.
The removal of template from the mesoporous molecular sieves embedded with a
zeolite is also performed by step calcination procedure.
The synthesis of the mesoporous material may be carried out with or without
additional aluminium sources. Only one template is needed in the synthesis of the
catalytic material.
The catalytic material may be incorporated in or on a carrier using any methods
known in the art.
The method of synthesis results in increased crystallinity of the pore walls by
chemically bonding the zeolite material in the mesoporous material and thereby
introducing the desired zeolite properties and simultaneously maintaining the
mesoporous structure intact. In this method only one type of template in the gel
solution for the synthesis of the product is needed.
Small crystals of a zeolite are used as "nuclei" in the synthesis of the mesoporous
material and it is possible to vary the concentration of the "nuclei" and the size of the
zeolite crystals. This results in the increase of the concentration of zeolite nuclei and
in embedding of large amount of the microporous structure in the mesoporous
molecular sieve and increased crystallinity of the mesoporous wall. It also influences
the thermal and hydrothermal stability and acidic properties of the material. Variation
in the size of the zeolite nuclei may influence the shape selective property of the
material.

The X-ray powder diffraction patterns, scanning electron microscopy and nitrogen
adsorption characterization results confirm the high thermal and hydrothermal
stability of the mesoporous molecular sieve embedded with a zeolite according to the
invention, such as MFI, BEA, MWW and MOR. structures.
Further, the complete or almost complete regeneration of the used catalysts from
different hydrocarbon conversion reactions, like n-butane and 1 -butene isomerization
and 1-decene oligomerization, and retaining of the catalytic activities also indicates
the stability of catalytic material.
The manufacturing method makes it possible to design intrinsic acidic properties in
the mesoporous molecular sieve. The intrinsic acidic properties of the mesoporous
molecular sieve materials can be designed using a source of aluminium and varying
the Si/Al ratio of the gel solution and different zeolite nuclei. Characterization results
of H-MM5, H-MMBE and H-MMMW catalysts by TPD of ammonia and different
test reactions like n-butane isomerization confirm the success in designing these
materials exhibiting varying acidities.
The pore walls of the mesoporous material are amorphous in MCM-41, but with the
introduction of zeolite they exhibit increased crystallinity. The zeolite unit cell in the
product according to the invention is different from the one in a mechanical mixture
of a zeolite and a mesoporous molecular sieve, and the mesoporous molecular sieve
unit cell is larger than that in a mechanical mixture.
A further essential feature of the product is that the majority of the zeolite phase is
chemically bonded to the mesoporous molecular sieve. The product is thermally
stable at a temperature of at least 900°C in the presence of air.

The mesoporous molecular sieve embedded with a zeolite according to the invention
and the method for the manufacture of such material are significantly different from
the ones disclosed in the state of the art and exhibit several advantages.
The new MM5 mesoporous molecular sieve embedded with MFI structure is
thermally stable up to at least 1000 °C and MMBE to at least 900 °C, as can be seen
from XRD and SEM figures and surface area measurements.
The transformation of the cationic forms of MM5, MMBE, MMMW and MMMO,
such as the Na-forms presented in the examples, to the corresponding proton forms of
MM5, MMBE, MMMW and MMMO by ion-exchange with aqueous solution of
ammonium nitrate, followed by drying at 100 °C and calcination at 500 °C did not change the structure as was. shown by XRD patterns, indicating the hydrothermal
stability of the novel material. It is known that the structure of MCM-41 collapses
after bringing it in contact with water at high temperatures.
Metal modifications of MM5, MMBE, MMMW and MMMO, such as noble metal
modifications and particularly platinum modifications of the examples, manufactured
using aqueous solutions of hexachloroplatinic acid at 80 °C for 24 hours, followed by
drying at 100 °C and calcination at 450 °C did not influence the structures of MM5
and MMBE as shown by XRD patterns. This indicates that the material is stable in an
acidic medium.
The proton form of the mesoporous molecular sieve embedded with MFI structure
showed very high activity in n-butane and 1-butene isomerization reactions. The H-
MM5 catalysts showed an increase in n-butane conversion with an increase in the
acidity.

The proton forms of the mesoporous molecular sieve embedded with MFI and BEA
structures showed very high activity in the dimerization of 1-olefins. The H-MM5
and H-MMBE catalysts showed an increase in 1-decene conversion, with an increase
in the acidity. The proton form of the mesoporous molecular sieve embedded with
MFI structure showed very high activity in the dimerization of isobutene and the
catalyst was not deactivated.
The H-MM5 and H-MMBE catalytic materials were fully regenerated in presence of
air. The regenerated materials showed almost the same catalytic activity in n-butane
and 1-butene isomerization and 1-decene oligomerization as the fresh catalyst. It is
well known that one of the major problems of MCM-41 catalyst is the regeneration
i.e. the mesoporous structure collapses after regeneration. The retaining of the
catalytic activity in the new mesoporous molecular sieve embedded with a zeolite
materials in both the reactions unequivocally shows that the structure after the
regeneration is stable.
Pt-MM5 showed very high conversion in n-butane isomerization and the catalytic
material after regeneration retained its catalytic activity.
Pt-MMBE showed a high selectivity to ring opening products.
Thus post-synthesis modification is not needed for the MM5 and MMBE mesoporous
materials to increase the thermal and hydrothermal stability. The high thermal and
hydrothermal stability of the novel materials are attributed to embedding of the
zeolite, such as MFI and BEA structure to the walls of mesoporous molecular sieves
by using method as described above.
This new group of mesoporous materials can be applied as catalysts in dimerization
of olefins, oligomerization of olefins, isomerization of olefins, cracking of

hydrocarbons, alkylation of aromatics, aromatization of light hydrocarbons,
etherification, dehydration and ring opening reactions without further modifications
of the active material. The metal modified material showed a high activity in the
isomerization of light paraffins. Similarly, the metal modified materials may also be
active in the isomorization of long chain paraffins, hydrogenation, hydrocracking,
hydrodesulfurization, hydrodeoxygenation, hydrodenitrogenation, dehydrogenarion,
reforming, Fisher-Tropsch and oxidation reactions when modified using the manners
known to be state of art. The metal in the catalyst can be in metallic, oxide or in
sulfide form or in any other form when modified with the manner known to be state
of art.
The material according to the invention can also be utilised in various separation
techniques like in adsorption, absorption or in selective removal.
The following illustrative examples provide better understanding of the invention and
its practical embodiments, however it is evident to a man skilled in the art that the
scope of the invention is not limited to these examples in any way.
EXAMPLES
Example 1 (Comparative)
Manufacture of ZSM-5 zeolite according to US 3,926,784
The starting materials were aluminium silicate, aluminium sulphate,
triisopropylamine bromide (TPABr), sodium chloride, sulphuric acid and water.
Solution A was prepared by mixing of 3.5 g of aluminium silicate with 4.4 1 water.
Solution B was prepared by mixing 107 g of aluminium sulphate, 438 g of TPABr,
1310"- of NaCl, 292 g of H2S04 and 6 1 water. The solutions were introduced to a

reactor under stirring with the stirring speed of 250 r/min. The temperature was
gradually increased to 100 °C and the pressure was increased to 8 bar. The reaction
was under stirring for 6 days. The reactor was cooled. The formed solid product
(ZSM-5) was filtered, washed with warm water and dried at 110 °C overnight. The
"roduct was calcined for the removal of the template, ion exchanged with ammonium
nitrate and calcined for preparing the proton form of the zeolite (H-ZSM-5).
Examples 2-4 (Comparative)
Manufacture of MSA type materials according to EP 0 784 652
The starting materials used in the synthesis of MSA type materials were aluminium
isopropoxide (Al-i-C3H7O)3, tetraethyl orthosilicate (Si(C2H5O)4) and aqueous
solution of tetrapropyl ammonium hydroxide (TPA-OH).
TPA-OH, (Al-i-C3H7O)3 and water were mixed at 60 °C for 40 minutes. The obtained
solution was heated to 85 °C and a clear solution was formed. Then liquid
Si(C2H5O)4 was added via a drop runnel. The obtained mixture was stirred for 3
hours. The reaction mixture was cooled under continuous stirring for 20 hours. After
cooling the formed alcohol and water was evaporated and the solid gel was dried at
100 °C. The dry solid was milled and calcined at 550 °C for 8 hours.
In the following table 3 the preparation and properties of the obtained MSA type
catalysts are provided.



Example 5(C omparative")
Manufacture of mesoporous molecular sieve H-MCM-41
The synthesis of Na-MCM-41 was carried out by preparing solutions A, B and C.
Solution A was prepared by mixing fumed silica with distilled water with continuous
stirring for 15 minutes. Solution B was prepared by adding tetramethylammonium
silicate to sodium silicate with continuous stirring and the mixture was stirred for 20
minutes. Solution C was prepared by dissolving tetradecyltrirnethyl ammonium
bromide in distilled water with stirring for 20 minutes. Solution B was added to
Solution A slowly (in 15 min) with stirring and after the addition Solution B the
mixture was stirred for further 20 minutes. Solution C was slowly (20 min) added to
the mixture of A and B with stirring and after the addition of solution C the mixture
was further stirred for 20 minutes. Then aluminium isopropoxide was added to the gel
solution (A -B -C) under stirring and the obtained mixture was gel ripened for two
hours with stirring. The pH was controlled and the gel was introduced in a teflon cup,
which was inserted in an autoclave. The synthesis was carried out for 48 h at 100 °C.

After completion of the synthesis, the reactor was quenched and the mesoporous
material was filtered and washed with distilled water. The obtained Na-MCM-41 was
dried at 110 aC and calcined at 550 °C for 10 h. The sodium form of Na-MCM-41
was ion-exchanged with aqueous 1 M ammonium nitrate solution for 2 h at 80 °C and
then the obtained NH4-MCM-41 was washed with distilled water, dried and calcined.
Examples 6-8
Mesoporous molecular sieve embedded with MFI zeolite structure
Preparation of the MFI zeolite nuclei
Three different solutions A, B and C were made for MFI zeolite nuclei preparation.
Solution A was prepared by adding 10.5 g of fumed silica to 81.2 ml of distilled
water. Solution B was prepared by dissolving 2.2 g of NaOH and 0.3 g of Al (OH)2 in
9.4 ml of distilled water. Solution B was added to Solution A and the obtained gel
mixture stirred for 20 minutes. Solution C was prepared by dissolving 3.7 g of
tetrapropyl ammonium bromide in 3.8 ml of water and stirring for 20 minutes.
Solution C was added to the gel mixture (A+B) and stirred for 15 minutes and 55 ml
of water was added. The obtained gel mixture was further stirred for 20 minutes.
Synthesis was carried out at 150 °C for 18 h. After the completion of synthesis the
product was filtered, washed with distilled water, dried and calcined and MFI zeolite
nuclei were obtained.
Example 6a
Synthesis of mesoporous molecular sieve embedded with MFI structure, Na-
MM5-96h-4ZS, without aluminium source
The synthesis of Na-MM5-96h-4ZS was carried out by preparing solutions A, B and
C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of distilled
water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared

by adding 18.1 g of tetramethyl ammonium silicate to 11.7 g of sodium silicate with
continuous stirring (r.m.p 180) and the mixture was stirred for 20 minutes. Solution C
was prepared by dissolving 26.3 g of tetradecyltrimethyl ammonium bromide in
174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution
B was added to Solution A slowly (in 15 min) with. vigorous stirring (r. m. p. 320)
and after the addition of solution B the mixture was stirred for further 20 min.
Solution C was added to the mixture (A + B) slowly (20 min) with vigorous stirring
(r. m. p. 336) and after the addition of solution C the mixture was further stirred for
20 minutes.
Then 4.2 g of MFI nuclei manufactured above were dispersed to the gel solution
(A+B+C) under vigorous stirring (r.m.p. 340) for 20 minutes. The homogem'sation of
the dispersed MFI was carried out by further vigorous stirring (340 r.m.p.) of the gel
for 35 minutes. Then the gel solution was ripened for three hours at ambient
temperature with stirring (r.m.p 180). pH of the gel was controlled and the gel was
. introduced in a teflon cup which was then inserted in an autoclave. The synthesis was
carried out for 96 h at 100 °C. After completion of the synthesis, the reactor was
cooled for 30 min and the obtained mesoporous molecular sieve material imbedded
with MFI structure was mixed with distilled water, filtered and washed thoroughly
with distilled with water for 3 h. The Na-MM5-96h-4ZS was dried and calcined at
450 °C using step calcination procedure for 10 h in a muffle oven.
Example 6b
Preparation of H-MM5-96h-4ZS, proton form of the above material
TO g "of Na"-MM5-96h^4ZS (sodium form; prepared~above) was ion-exchanged with
an aqueous solution of 1 M ammonium nitrate or ammonium chloride for 24 h at
ambient temperature. After ion-exchange the obtained NH4-MM5-96b-4ZS was

washed thoroughly with distilled water, dried and calcined using step calcination
procedure in a muffle oven at 450 °C.
The XRD pattern of the obtained H-MM5-96h-4ZS was similar to that of Na-MM-5-
96h-4ZS indicating that the aqueous treatment of the novel mesoporous material and
subsequent thermal treatment did not influence the stability of the structure.
Example 7
Synthesis of mesoporous molecular sieve embedded with MFI structure, Na-
MM5-96h-4ZS-2AI, using aluminium source
Example 7a
Synthesis of Na-MM5-96h-4ZS-2AI
The synthesis of Na-MM5-96h-4ZS-2AI was carried out by preparing solutions A, B
and C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of
distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was
prepared by adding 18.1 g of tetramethylammotiium silicate to 11.7 g of sodium
silicate with continuous stirring (r.m.p 180) and the obtained mixture was stirred for
20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecyl trimethyl
ammonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336)
for 20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) and after the addition of solution B the mixture was stirred for
further 20 min. Solution C was added to the mixture (A + B) slowly (20 min) with
vigorious stirring (r. m. p. 336) and after the addition of solution C it was further
stirred for 20 minutes.

Then 4.2 g of MFI nuclei was dispersed to the gel solutions (A +B +C) under
vigorous stirring (r.m.p. 340) for 20 minutes. The homogenisarion of the dispersed
MFI was carried out by further vigorous stirring (r. m. p. 340) of the gel for 35
minutes. Then 2.3 g of aluminium isopropoxide was added and stirred for 20 min.
The obtained gel was allowed to ripen for three hours with stirring (r.m.p 180). pH of
the gel was controlled and the gel was introduced in a teflon cup which was then
inserted in an autoclave. The synthesis was carried out for 96 h at 100 °C. After
completion of the synthesis, the reactor was quenched and the obtained mesoporous
material was filtered and washed thoroughly with distilled with water. The obtained
Na-MM5-96h-4ZS-2AI was dried and calcined using step calcination procedure in a
muffle oven.
Example 7b
Synthesis of H-MM5-96h-4ZS-2AI
10 g of Na-MM5-96h-4ZS-2AI (prepared above) was ion-exchanged with 1 M
ammonium nitrate aqueous solution for 24 h at room temperature. After the ion-
exchange the mesoporous material was washed thoroughly, dried at and calcined for
four hours using step calcinations procedure in a muffle oven at 450 aC. The XRD
pattern of the obtained H-MM5-96h-4ZS-2AI was similar to that of Na-MM-5-96h-
4ZS-2AI indicating that the aqueous treatment of the novel mesoporous material and
subsequent thermal treatment did not influence the stability of the structure.
Example 8
Synthesis of mesoporous molecular sieve embedded with MFI structure, Na-
MM5-96h-4ZS-2AI-35, using aluminium source

Example 8a
Synthesis of Na-MM5-96h-4ZS-2AI-35
The synthesis of Na-MM5-96h-4ZS-2AI-35 was carried out by preparing solutions A,
B and C. Solution A was prepared by mixing 4.5 g of fumed silica with 51.7 g of
distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was
prepared by adding 18.1 g of tetramethylammonium silicate to 11.7 g sodium silicate
with continuous stirring (r.m.p 180) and the obtained mixture was stirred for 20
minutes. Solution C was prepared by dissolving 26.3 g of tetradecyl trimethyl
ammonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336)
for 20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) and after the addition of Solution B the obtained mixture was
stirred for further 20 min. Solution C was added to the mixture (A + B) slowly (20
min) with vigorous stirring (r. m. p. 336) and after the addition of solution C the
mixture was further stirred for 20 minutes. Then 4.2 g of MFI nuclei, prepared in
example 6, were dispersed to the gel mixture (A -KB +C) under vigorous stirring
(r.m.p. 340) for 20 minutes. The homogenisation of the dispersed MFI was carried
out by further vigorous stirring (r. m. p. 340) of the gel for 35 minutes. Then 2.3 g of
aluminium isopropoxide was added to the mixture and stirred for 20 min. Then the
gel was allowed to ripen for three hours with stirring (r.m.p 180). pH of the gel was
controlled and the gel was introduced in a teflon cup which was then inserted in an
autoclave. The synthesis was carried out for 96 h at 100 °C. After completion of the
synthesis, the reactor was quenched and the obtained mesoporous material was
filtered and washed thoroughly with distilled with water. The obtained Na-MM5-96h-
4ZS-2AI-35 was dried and calcined using step calcination procedure in a muffle oven at 450°c.

Example 8b
Preparation of H-MM5-96 h-4ZS-2AI-35
10 g of Na-MM5-96h-4ZS-2AI-35 (manufactured above) was ion-exchanged with 1
M ammonium nitrate aqueous solution for 24 h at room temperature. After the ion-
exchange the mesoporous material was washed thoroughly, dried and calcined using
step calcination procedure in a muffle oven at 450 °C.
The XRD pattern of the H-MM5-96 h-4ZS-2AI-35 was similar to that of Na-MM-5-
96 h-4ZS-2AI-35 indicating that the aqueous treatment of the novel mesoporous
material and subsequent thermal treatment did not influence the stability of the
structure.
Example 9
Platinum modified MM5 material, Pt-H-MM5-96 h-4ZS-2AI
5 g of H-MM5-96h-ZS-2AI was loaded with 2 wt % of Pt using impregnation
method. 2 wt % Pt impregnation was performed in a rotary evaporator at 80 °C for 24
h using aqueous solution of hexachloroplatinic acid. The 2 wt % Pt impregnated MM-
5-96h-2AI was dried at 100 °C and calcined at 450 °C. The XRD pattern Pt-H-MM-
5-96h-4ZS-2AI presented in Figure 5 was similar to those of parent Na-MM-5-96h-
2AI indicating the hydrothermal stability of the novel mesoporous molecular sieve
embedded with a zeolite.
Example 10
Preparation of platinum modified MM5 material, Pt-H-MM5-96h-4ZS-2AI-35
5 g H-MM5-96h-4ZS-2AI-35 was loaded with 2 wt % Pt using impregnation method.
2 wt % Pt impregnation was performed in a rotary evaporator at 80 °C for 24 h using

aqueous solution of hexachloroplatinic acid. The 2 wt % Pt impregnated MM-5-96h-2
AI-35 was dried at 100 °C and calcined at 450 °C.
The XRD pattern Pt-H-MM-5-96h-4ZS-2AI-35 was similar to that of parent Na-MM-
5-96h-2AI-35 indicating the hydrothermal stability of the novel mesoporous
molecular sieve embedded with a zeolite.
Examples 11-13
Preparation of mesoporous materials embedded with BEA-structure
Preparation of BEA zeolite nuclei
7.8 g of NaA102 was mixed with 60 ml of distilled water under stirring for 10
minutes and to this solution 74 g of tetraethyl ammonium hydroxide (TEA-OH,40
%) was added and stirred for 20 minutes. 145.4 g of colloidal silica was added to the
above solution and stirred for 25 minutes.
The obtained gel was put in the autoclave and inserted in the teflon cups. The
synthesis was carried out at 150 °C for 65 h in static mode. After the completion of
synthesis the product was filtered, washed with distilled water, dried at 110 °C and
calcined at 550 °C for 7 hours and the BEA zeolite was obtained.
Example 11a
Synthesis of mesoporous molecular sieve embedded with BEA structure, Na-
MMBE-96h-4B, without aluminium source
The synthesis of Na-MMBE-96h-4B was carried out by preparing of solutions A, B
and C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of
distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was

prepared by adding 18.1 g of tetramethylammonium silicate to 11.7 g of sodium
silicate with continuous stirring (r.ra.p 180) and the mixture was stirred for 20
minutes. Solution C was prepared by dissolving 26.3 g of tetradecyltrimethyl
ammonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336)
for 20 minutes.Solution A Slowly (in 15 min) with vigorous
stirring (r. m. p. 320) and after the addition of solution B the obtained mixture was
stirred for further 20 min. Solution C was added to the mixture A + B slowly (20 min)
with vigorous stirring (r. m. p. 336) and after the addition of solution C the mixture
was further stirred for 20 minutes.
Then 3.7 g of BEA zeolite nuclei precursor, prepared above was added to the gel
mixture (A +B +C) under vigorous stirring (r.m.p. 350) and the gel was ripened for
three hours with stirring (r.m.p 180). pH of the gel was controlled and the gel was
introduced in a teflon cup which was then inserted in an autoclave.
The synthesis was carried out for 96 h at 100 °C. After completion of the synthesis,
the reactor was quenched and the obtained mesoporous material was filtered and
washed thoroughly with distilled with water. The obtained Na-MM-BE-96h-4B was
dried and calcined using step calcination procedure.
Example lib
Preparation of H-MMBE-96h-4B
10 g of Na-MMBE-96h-4B (manufactured above) was ion-exchanged with 1 M
ammonium nitrate solution for 24 h at room temperature. After the ion-exchange the
mesoporous material was washed thoroughly, dried and calcined using step
calcination procedure.

The XRD pattern of H-MMBE-96h-4B was similar to that of Na-MMBE-96h-4B
indicating that the aqueous treatment of the novel mesoporous material and
subsequent thermal treatment did not influence the stability of the structure.
Example 12
Synthesis of mesoporous molecular sieve embedded with BEA structure, Na-
MMBE-96h-4B-2AI, with aluminium source.
Example 12a
Synthesis of Na-MMBE-96h-4B-2AI
The synthesis of Na-MM-BE-96 h-4B-2AI was carried out by preparing of solutions
A, B and C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of
distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was
prepared by adding 18.1 g of tetramethyl ammonium silicate to 1.1.7 g sodium silicate
with continuous stirring (r.nxp 180) and the obtained mixture was stirred for 20
minutes. Solution C was prepared by dissolving 26.3 g of tetradecyl trimethyl
ammonium bromide in 174.3 g distilled water with vigorous stirring (r.m.p. 336) for
20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) and after the addition of solution B the mixture was stirred for
further 20 min. Solution C was added to the mixture (A + B) slowly (20 min) with
vigorous stirring (r. m. p. 336) and after the addition of solution C the mixture was
further stirred for 20 minutes.
Then 3.7 g of BEA zeolite nuclei precursor (prepared above) was added to the gel
mixture (A +B +C) under vigorous stirring (r.m.p. 350) and stirred for 25 min and
then 1.9 g of aluminium isopropoxide was added and stirred for 20 min. The obtained
gel was allowed to ripen for three hours with stirring (r.m.p 180). pH of the gel was
controlled and the gel was introduced in a teflon cup which was then inserted in an

autoclave. The synthesis was carried out for 96 h at 100 °C. After completion of the
synthesis, the reactor was quenched and the mesoporous material was filtered and
washed thoroughly with distilled with water. The obtained Na-MMBE-96h^-B-2AI
was dried and calcined using step calcination procedure for 10 h.
Example 12b
Preparation of H-MMBE-96 h-4B-2AI
10 g of Na-MMBE-96h-4B-2AI (manufactured above) was ion-exchanged with 1 M
ammonium nitrate aqueous solution for 24 h at ambient temperature. After the ion-
exchange the mesoporous molecular sieve material was washed thoroughly with
distilled water, dried and calcined in a muffle oven using step calcination procedure.
The XRD pattern of the H-MMBE-96h-4B-2AI was similar to that of Na-MMBE-96
h-4B-2AI indicating that the aqueous treatment of the novel mesoporous material and
subsequent thermal treatment did not influence the stability of the structure.
Example 13
Synthesis of mesoporous molecular sieve embedded with a BEA structure, Na-
MMBE-96h-4B-2AI35, with aluminium source
Example 13a
Synthesis of Na-MMBE-96 h-4B-2AI-35
The synthesis of Na-MMBE-96h-4B-2AI-35 was carried out by preparing of
solutions A, B and C. Solution A was prepared by mixing 4.4 g of fumed silica with
51.7 g of distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution
B was prepared by adding 18.1 g of tetramethyl ammonium silicate to 11.7 g of
sodium silicate with continuous stirring (r.m.p 180) and the mixture was stirred for 20

minutes. Solution C was prepared by dissolving 26.3 g of tetradecyl trimethyl
ammonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336)
for 20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) and after the addition of solution B the mixture was stirred for
further 20 min. Solution C was added to the mixture (A + B) slowly (20 min) with
vigorous stirring (r. m. p. 336) and after the addition of solution C the mixture was
further stirred for 20 minutes. Then 3.7 g of BEA zeolite nuclei precursor (prepared
above) was added to the gel mixture (A +B +C) under vigorous stirring (r.m.p. 350)
and the mixture was stirred for 25 min. Then 1.9 g of aluminium isopropoxide was
added and stirred for 20 min. The obtained gel was allowed to ripen for three hours
with stirring (r.m.p 180). pH of the gel was controlled and the gel was introduced in a
teflon cup which was then inserted in an autoclave. The synthesis was carried out for
96 h at 100 °C. After completion of the synthesis, the reactor was quenched and the
mesoporous material was filtered and washed thoroughly with distilled with water.
The obtained Na-MMBE-96h-4B-2AI-35 was dried and calcined using step
calcination procedure.
Example 13b
Preparation of H-MMBE-96h-4B-2AI-35
10 g of Na-MMBE-96h-4B-2AI-35 (prepared above) was ion-exchanged with 1 M
ammonium nitrate aqueous solution for 24 h at ambient temperature. After the ion-
exchange the mesoporous molecular sieve material was washed thoroughly with
distilled water, dried and calcined in a muffle oven using step calcination procedure.
The XRD pattern of H-MMBE-96h-4B-2AI-35 was similar to that of Na-MMBE-96
h-4B-2AI-35 indicating that the aqueous treatment of the novel mesoporous material
and subsequent thermal treatment did not influence the stability of the structure.

Example 14
Platinum modified MMBE material, Pt-H-MMBE-96h-4B-2AI
5 g of H-MMBE-96h-4B-2AI-35 (prepared above) was loaded with 2 wt % Pt using
impregnation method. 2 wt % Pt impregnation was carried out in a rotator evaporator
at 80 °C for 24 h using aqueous solution of hexachloroplatinic acid. The 2 wt % Pt
impregnated H-MMBE-96h-2AI was dried and calcined. The XR.D pattern of Pt-H-
MMBE-96h-4B-2AI was similar to the one of the parent Na-MM-BE-96h-4B-2AI
indicating the hydrothermal stability of the novel mesoporous molecular sieve.
Further more Pt modification of H-MMBE-96h-4B-2AI did not influence the parent
structure.
Ex am.p.le 15
Preparation of platinum modified MMBE material Pt-H-MMBE-96h-4B-2AI-35
5 g of H-MMBE-96hB-2AI-35 was loaded with 2 wt % Pt using impregnation
method. 2 wt % Pt impregnation was carried out in a rotator evaporator at 80 °C for
24 h using aqueous solution of hexachloroplatinic acid. The 2 wt % Pt impregnated
H-MMBE-96h-2Al-35 was dried and calcined. The XRD pattern of Pt-H-MMBE-
96h-4B-2AI-35 was similar to that of the parent Na-MMBE-96h-4B-2AI-35
indicating the hydrothermal stability of the novel mesoporous molecular sieve.
Further more Pt modification of H-MMBE-96h-4B-2AI-35 did not influence the
parent structure.
Examples 16-18
Preparation of Pt-H-MMBE with ion exchange
2 g of each H-MMBE materials: H-MMBE-96h-4B (example 16), H-MMBE-96h-
4B-2AI (example 17) and H-MMBE-96h-4B-2AI-35 (example 18), was weighed to 2

1 flasks. 1 1 of ion-exchanged water was added. Reflux condenser was placed on top of
the flask. The flask was placed in a water bath, temperature 70°C and shake 110.
Flask was kept in these conditions for one hour. Then the reflux condenser was
replaced with dropping funnel with an air exhaust port. 52 ml of 0.01 M Pt-solution
was measured to the dropping funnel. The Pt-solution was dropped slowly (about 15
drops per minute) to the flask, temperature 70°C, shake 110. The Pt-adding took 53
minutes. The dropping funnel was replaced with a reflux condenser and the flask was
left to these conditions for 24 hours.
The reaction mixture from the flask was filtered with suction using sintered glass
crucible. The obtained material was washed in the flask with one 1 of ion-exchanged
water and filtered again. This was done twice. After the second wash the sintered
glass crucible with ihe material was placed to an oven at a temperature of 8Q°C for 16
hours.
After 16 hours drying material was transferred to a crucible and calcined in an oven.
Temperature was elevated from 21°C to 300°C with rate 0.2°C/min.
Examples 19 - 28
Mesoporous molecular sieve embedded with MWW zeolite structure
Preparation of MWW zeolite nuclei
Two solutions A and B were made for MWW zeolite nuclei preparation. Solution A
was prepared by adding 87.58 g of sodium silicate to 42 ml of distilled water under
stirring for 15 minutes and to this solution was added 16.7 g-of-hexamethylene
dropwise over a period of 25 minutes and solution stirred for 20 minutes. Solution B
was prepared by adding 7.35 g of concentrated sulphuric acid to 224 ml of distilled
water and stirring for 10 minutes after which 8.9 g of alumnium sulphate was added

and stirred for 20 minutes. Solution B was added to Solution A slowly and with
vigorous stirring. The gel was introduced in Teflon cups and inserted in 300 ml
autoclaves. The synthesis was carried out at 150 °C for 96 h in rotation mode. After
the completion of synthesis the product was filtered, washed with distilled water,
dried at 110 °C and calcined at 550 °C for 8 hours and MWW zeolite nuclei precursor
was obtained.
Example 1.9a
Synthesis of mesoporous molecular sieve embedded with MWW structure, Na-
MM-4MW22, without aluminium source
The synthesis of Na-MM-4MW22 was carried out by preparing of solutions A, B and
C. Solution A was prepared by mixing 3.3 g fumed silica with 51.7 g distilled water
with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared by
adding 18.10 g of tetramethylammonium silicate to 11.7 g sodium silicate with
continuous stirring (r.m.p 180) and the mixture was stirred for 20 minutes. Solution C
was prepared by dissolving 26.3 g of tetradecyl trimethyl ammonium bromide in
174.3 g distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution 3
was added to Solution A slowly (in 15 min) with vigorous stirring (r. m. p. 320) after
the addition of all of solution B the mixture was stirred for further 20 min. Solution C
was added to mixture (A + B) slowly (20 min) with vigorous stirring (r. m. p. 336)
after addition of solution C the mixture was further stirred for 20 minutes.
After that 4.22 g of MWW zeolite nuclei precursor prepared above was added to the
gel solutions (A +B +C) under vigorous stirring (r.m.p. 340) for 20 min. The
homogenisarion of the dispersed MWW was carried out by further stirring (r.m.p.
340) of the gel for 35 minutes. After that gel was allowed to ripen for three hours
with stirring (r.m.p 180) at ambient temperature. pH of the gel was controlled and the

gel was introduced in Teflon cups which were then inserted in an autoclave. The
synthesis was carried out for 96 hat 100 0C.
After completion of the synthesis, the reactor was cooled for 30 min and mesoporous
molecular sieve material embedded with MWW structure was mixed with distilled
water, filtered and washed thoroughly with distilled water for 3 h. As synthesized Na-
MM-4MW22 was dried at 110 °C and calcined at 550 °C using step calcinations
procedure for 10 h in a muffle oven.
Example 19b
Preparation of H-MM-4MW22
10 g Na-MM-4MW22 (sodium form, prepared above) was ion-exchanged with 1 M
ammonium nitrate or ammonium chloride aqueous solution for 24 h at ambient
temperature. After ion-exchange the obtained NH4-MM-4MW22 mesoporous
molecular sieve material was washed thoroughly with distilled water, dried at 110 C
for 12 hours and calcined at 450 °C for four hours in a muffle oven using step
calcinations procedure.
Example 20
Synthesis of mesoporous molecular sieve embedded with MWW structure, Na-
MM-4MW22-2AI, using aluminium source
Example 20a
Synthesis of Na-MM-4MW22-2AI
The synthesis of Na-MM-4MW22-2AI was carried out by preparing solutions A, B
and C. Solution A was prepared by mixing 8.3 g fumed silica with 51.7 g distilled
water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared

by adding 18.10 g of tetramethylammonium silicate to 11.7 g sodium silicate with
continuous stirring (r.m.p 180) and the mixture was stirred for 20 minutes. Solution C
was prepared by dissolving 26.3 g of tetradecyl trimethyl ammonium bromide in
174.3 g distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B
was added to Solution A slowly (in 15 min) with vigorous stirring (r. m. p. 320) after
the addition of solution B the mixture was stirred for further 20 min. Solution C was
added to Solutions (A + B) slowly (20 min) with vigorous stirring (r. m. p. 336) and
after the addition of all of solution C it was further stirred for 20 minutes.
4.2 g of MWW zeolite nuclei prepared above was added to the gel solutions (A +B
+C) under vigorous stirring (r.m.p. 340) for 20 min. The homogenisation of the
dispersed MWW was carried out by further vigorous stirring (r.m.p. 340) of the gel
for 35 minutes. Then 2.3 g of aluminium isopropoxide was added and stirred for 20
min. After that gel was allowed to ripen for three hours with stirring (r.m.p 180) at
ambient temperature. pH of the gel was controlled and gel was introduced in teflon
cups which was then inserted in 300 ml autoclaves. The synthesis was carried out for
96 hat 100 °C.
After completion of the synthesis, the reactor was quenched and mesoporous
molecular sieve material embedded with MWW structure was filtered and washed
thoroughly with distilled water for 3 h. As synthesized Na-MM-4MW22-2AI was
dried at 110 °C and calcined at 550 °C using step calcinations procedure for 10 h.
Example 20b
Preparation of H-MM-4MW22-2AI
10 g Na-MM-4MW22-2AI (sodium form, prepared above) was ion-exchanged with 1
M ammonium nitrate or ammonium chloride aqueous solution for 24 h at ambient
temperature. After ion-exchange the obtained NH4-MM-4MW22-2AI mesoporous

molecular sieve material was washed thoroughly with distilled water, dried at 110 C
for 12 hours and calcined at 450 °C for four hours in a muffle oven using step
calcinations procedure.
The XHD pattern of the obtained H-MM-4MW22-2AI was similar to that of Na-MM-
4MW22-2AI indicating that the aqueous treatment of the novel mesoporous material
and subsequent thermal treatment did not influence the stability of the structure.
Example 21
Synthesis of mesoporous molecular sieve embedded with MWW structure, Na-
MM-4MW22-2AI-35, using aluminium source
Example-21a
Synthesis of Na-MM-4MW22-2AI-35
The synthesis of Na-MM-4MW22-2AI-35 was carried out by preparing of solutions
A, B and C. Solution A was prepared by mixing 4.5 g of fumed silica with 51.7 g
distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was
prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g sodium
silicate with continuous stirring (r.m.p 180) and the obtained mixture was stirred for
20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecyl trimethyl
ammonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336)
for 20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) after addition of all of solution B the mixture was stirred for further 20 min. Solution was added to Solutions (A + B) slowly (20 min) with
vigorous stirring (r. m. p. 336) after the addition of solution C the mixture was further
stirred for 20 minutes.

4;2 g of MWW zeolite nuclei prepared in example 19 was dispersed to the gel
mixture (A +B +C) under vigorous stirring (r.m.p. 340) for 20 min. The
homogenisation of the dispersed MWW was carried out by further stirring (r.m.p.
340) of the gel for 35 minutes. Then 2.3 g of aluminium isopropoxide was added to
the mixture and stirred for 20 min. After that gel was allowed to ripen for three hours
with stirring (r.m.p 180) at ambient temperature. pH of the gel was controlled and the
gel was introduced in teflon cups which were then inserted in 300 ml autoclaves. The
synthesis was carried out for 96 h at 100 °C.
After completion of the synthesis, the reactor was quenched and the obtained
mesoporous molecular sieve material embedded with MWW structure was mixed
with distilled water, filtered and washed thoroughly with distilled water for 3 h. As
-synthesized-Na-MM-4MW-22-2AI-33-was-dried-at 1100C and calcined at 5500C in a
muffle oven using step calcinations procedure for 10 h.
Example 21b
Preparation of H-MM-4MW22-2AI-35
10 g Na-MM-4MW22-2AI-35 (sodium form, prepared above) was ion-exchanged
with 1 M ammonium nitrate aqueous solution for 24 h at ambient temperature. After
ion-exchange the obtained NH4-MM-4MW22-2AI-35 mesoporous molecular sieve
material was washed thoroughly with distilled water, dried at 110 °C for 12 hours and
calcined at 450 °C for four hours in a muffle oven using step calcinations procedure.
The-XRD-pattern of the obtained H-MM-4MW22-2AI-35 was similar to that of Na-
MM-4MW22-2AI-35 indicating that the aqueous treatment of the novel mesoporous
material and subsequent thermal treatment did not influence the stability of the
structure.

Example 22
Preparation of platinum modified H-MM-4MW22-2AI
5 g of H-MM-4MW22-2AI was loaded with 2 wt % Pt using impregnation method. 2
wt % Pt impregnation was performed in a rotary evaporator at 80 C for 24 h using
aqueous solution of hexachloroplatinic acid. The 2 wt % impregnated H-MM-
4MW22-2AI was dried at 100 °C and calcined at 450 °C. The XRD pattern of Pt-H-
MM-4MW22-2AI presented was similar to those of parent Na-MM-4MW22-2AI
indicating hydrothermal stability of the novel mesoporous molecular sieve embedded
with MWW structure.
Example 23
Preparation of platinum modified H-MM-4MW22-2AI-35
5 g of H-MM-4MW22-2AI-35 was loaded with 2 wt % Pt using impregnation
method. 2 wt % Pt impregnation was performed in a rotary evaporator at 80 C for 24
h using aqueous solution of hexachloroplatinic acid. The 2 wt % impregnated H-MM-
4MW22-2AI-35 was dried at 100 °C and calcined at 450 °C. The XRD pattern of Pt-
H-MM-4MW22-2AI-35 was similar to that of parent Na-MM-4MW22-2AI-35
indicating the hydrothermal stability of the novel mesoporous molecular sieve
embedded with MWW structure.
Examples 24- 28
Mesoporous molecular sieve embedded with MOR zeolite structure
Preparation of MOR zeolite nuclei
Two solutions A and B were made for preparation of MOR zeolite nuclei precursor.
Solution A was prepared by adding 37.8 g of Ludox AS 30 to 6.7 g of piperidine and

stirred for 15 min. Solution B was prepared by adding 44 ml of distilled water to 4.6
g of sodium hydroxide and stirred for 10 minutes and then 5.9 g of aluminium
sulphate was added and further stirred for 15 minutes. Solution B was added to
Solution A slowly and with vigorous stirring for 15 minutes. The gel was introduced
in Teflon cups and inserted in 300 ml autoclave. The synthesis was carried out at 200
C for 48 h in rotation mode. After completion of the synthesis the product was
filtered, washed with distilled water, dried at 110 °C and calcined at 550 C for 10
hours and MOR zeolite nuclei precursor was obtained.
Example 24a
Synthesis of mesoporous molecular sieve embedded with MOR structure, Na-
MM-MO-4MO-96 h, without aluminium source
The synthesis of Na-MM-MO-4MO-96 h was carried out by preparing of solutions A,
B and C. Solution A was prepared by mixing 8.3 g fumed silica with 51.7 g distilled
water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared
by adding 18.10 g of tetramethylammonium silicate to 11.7 g sodium silicate with
continuous stirring (r.nxp 180) and the mixture was stirred for 20 minutes. Solution C
was prepared by dissolving 26.3 g of tetradecyl trimethyl ammonium bromide (Fluka)
in 174.3 g distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution
B was added to Solution A slowly (in 15 min) with vigorous stirring (r. m. p. 320)
after addition of all of solution B the mixture was stirred for further 20 min: Solution
C was added to the mixture A + B slowly (20 min) with vigorous stirring (r. m. p.
336) after addition of all of solution C the mixture was further stirred for 20 minutes.
After that 3.7 g of MOR zeolite nuclei precursor prepared above was added to the gel
mixture (A +B +C) under vigorous stirring (r.m.p. 350) for 20 min. The
homogenisation of the dispersed MOR structure was carried out by further stirring

(n.m.p. 350) of the gel for-30 minutes. After that gel was allowed to ripen for three
hours with stirring (r.m.p 180) at ambient temperature. pH of the gel was controlled
and gel was introduced in a teflon cup which was then inserted in a 300 autoclave.
The synthesis was carried out for 96 h at 100 °C.
After completion of the synthesis, the reactor was quenched and mesoporous
molecular sieve material embedded with MOR structure was mixed with distilled
water, filtered and washed thoroughly with distilled water for 3 h. As synthesized Na-
MM-MO-4MO-96 h was dried at 110 °C and calcined at 550 °C using step
calcinations procedure for 10 h.
Example 24b
-preparation of H-MM MO=4M-O=96 h
10 g Na-MM-MO-4MO-96 h (sodium form, prepared above) was ion-exchanged with
1 M ammonium nitrate or ammonium chloride aqueous solution for 24 h at ambient
temperature. After ion-exchange the obtained NH4-MM-MO-4MO-96 h mesoporous
molecular sieve material was washed thoroughly with distilled water, dried at 110 °C
for 12 hours and calcined at 450 °C for four hours in a muffle oven using step
calcinations procedure.
The XRD pattern of the obtained H-MM-MO-4MO-96 h was similar to that of Na-
MM-MO-4MO-96h indicating that the aqueous treatment of the novel mesoporous
material and subsequent thermal treatment did not influence the stability of the
structure.
Example 25
Synthesis of mesoporous molecular sieve embedded with MOR structure, Na-
MM-MO-4MO-96 h-2AI, using aluminium source

Example 25a
Synthesis of Na-MM-MO-4MO-2AI
The synthesis of Na-MM-MO-4MO-96 h-2AI was carried out by preparing of
solutions A, B and C. Solution A was prepared by mixing 8.3 g fumed silica with
51.7 g distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B
was prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g sodium
silicate with continuous stirring (r.m.p 180) and the obtained mixture was stirred for
20 minutes. Solution C was prepared by dissolving 26.34 g of tetradecyl trimethyl
ammonium bromide in 174.3 g distilled water with vigorous stirring (r.m.p. 336) for
20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) and after the addition of all of solution B the mixture was stirred
for further 20 min. Solution C. was added to mixture A + B slowly (20 min) with
vigorous stirring (r. m. p. 336) after addition of all of solution C it was further stirred
for 20 minutes.
3.7 g of MOR zeolite nuclei precursor prepared in example 23 was added to the gel
mixtures (A +B +C) under vigorous stirring (r.m.p. 350) for 25 min. and then 1.9 g of
aluminium isopropoxide was added to the gel under vigorous stirring (r.m.p. 350) and
the gel was stirred for 30 minutes. After that gel was allowed to ripen for three hours
with stirring (r.m.p 180) at ambient temperature. pH of the gel was controlled and gel
was introduced in teflon cups which were then inserted in 300 ml autoclaves. The
synthesis was carried out for 96 h at 100 C.
After completion of the synthesis, the reactor was quenched for 30 min and
mesoporous molecular sieve material embedded with MOR structure was mixed with
distilled water, filtered and washed thoroughly with distilled water for 3 h. As

synthesized Na-MM-MO-4MO-96h-2AI was dried at. 110 °C and calcined at 550 °C
using step calcinations procedure for 10 h.
Example 25b
Preparation of H-MM-MO-4MO-96h-2AI
10 g Na-MM-MO-4MO-96 h-2AI (sodium form, prepared above) was ion-exchanged
with 1 M ammonium nitrate or ammonium chloride aqueous solution for 24 h at
ambient temperature. After ion-exchange the obtained NH4-MM-MO-4MO-96h-2AI
mesoporous molecular sieve material was washed thoroughly with distilled water,
dried at 110 C for 12 hours and calcined at 450 C for four hours in a muffle oven
using step calcinations procedure.
The XRD pattern of the obtained H-MM-MO-4MO-96 h-2AI was similar to that of
Na-MM-4MO-96h-2AI indicating that the aqueous treatment of the novel
mesoporous material and subsequent thermal treatment did not influence the stability
of the structure.
Example 26
Synthesis of mesoporous molecular sieve embedded with MOR structure, Na-
MM-MO-4MO-2AI-35, using aluminium source
Example 26a
Synthesis of Na-MM-MO-4MO-2AI-35
The synthesis of Na-MM-MO-4MO-96 h-2AI-35 was carried out by preparing of
solutions A, B and C. Solution A was prepared by mixing 4.4 g of fumed silica with
51.7 g distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B

was prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g sodium
silicate with continuous stirring (r.m.p 180) and the mixture was stirred for 20
minutes. Solution C was prepared by dissolving 26.3 g of tetradecyl trimethyl
ammonium bromide in 174.3 g distilled water with vigorous stirring (r.m.p. 336) for
20 minutes. Solution B was added to Solution A slowly (in 15 min) with vigorous
stirring (r. m. p. 320) after addition of all of solution B the mixture was stirred for
further 20 min. Solution C was added to mixture (A + B) slowly (20 min) with
vigorous stirring (r. m. p. 336) and after addition of all of solution C the mixture was
further stirred for 20 minutes.
3.7 g of MOR zeolite nuclei precursor prepared in example 45 was added to the gel
mixture (A +B +C) under vigorous stirring (r.m.p. 320) for 25 min. Then 1.9 g of
aluminium isopropoxide was added and stirred for 20 min. After that gel was allowed
to ripen for three hours with stirring (r.m.p 180) at ambient temperature. pH of the gel
was controlled and the gel was introduced in teflon cups which were then inserted in
300 ml autoclave. The synthesis was carried out for 96 h at 100 C.
After completion of the synthesis, the reactor was quenched for 30 min and
mesoporous molecular sieve material embedded with MOR structure was mixed with
distilled water, filtered and washed thoroughly with distilled water for 3 h. As
synthesized Na-MM-MO-4MO-96 h-2AI-35 v/as dried at 110 °C and calcined at 550
°C using step calcinations procedure for 10 h.
Example 26b
Preparation of H-MM-MO-4MO-96h-2AI-35
10 g Na-MM-MO-4MO-2AI-35 (sodium form, prepared above) was ion-exchanged
with 1 M ammonium nitrate or ammonium chloride aqueous solution for 24 h at

. ambient temperature. After ion-exchange the obtained NH4-MM-MO-4MO-2AI-35
mesoporous molecular sieve material was washed thoroughly with distilled water,
dried at 110 °C for 12 hours and calcined at 450 °C for four hours in a muffle oven
using step calcinations procedure.
Example 27
Preparation of Platinum modified H-MM-MO-4MO-96 h-2Al-35
5 g of H-MM-MO-4MO-96 h-2AI-35 was loaded with 2 wt % Pt using impregnation
method. 2 wt % Pt impregnation was performed in a rotary evaporator at 80 C for 24
h using aqueous solution of hexachloroplatinic acid. The 2 wt % impregnated MM-
MO-4MO-96 h-2AI-35 was dried at 100 °C and calcined at 450 °C. The XRD
patterns of Pr-H-MM-MO-4MO-96 h-2AI were similar to those of parent Na-MM-
MO-4MO-96 h-2AI-35 indicating hydrothermal stability of the novel mesoporous
molecular sieve embedded with MOR structure.
Example 28
Preparation of platinum modified H-MM-MO-4MO-96 h-2AI-35
5 g of H-MM-MO-4MO-2AI-35 was loaded with 2 wt % Pt using impregnation
method. 2 wt % Pt impregnation was performed in a rotary evaporator at 80 °C for 24
h using aqueous solution of hexachloroplatinic acid. The 2 wt % impregnated HMM-
MO-4MO-2AI-35 was dried at 100 °C and calcined at 450 °C. The XRD patterns of
Pt-H-MM-MO-4MO-96 h-2AI-35 were similar to those of parent Na-MM-MO-4MO-
96 h-2AI-35 indicating hydrothermal stability of the novel mesoporous molecular
sieve embedded with MOR structure.

Example 29
Thermal stability test
The thermal stability test was performed by heating the materials according to the
invention at temperatures 700 °C, 800 °C, 900 °C, and 1000 °C in air for 24 hours.
After this treatment the materials were analysed by BET and XRD. An example for
XRD diagram at 1000 °C treated samples is given in Fig. 5. No differences in the
structure of the materials could be detected with BET or XRD.
Example 30
Mechanical stability test
Mechanical stab.ility test,o.f_the_roaterials_according to the invention was performed by
pressing the powder of the material with a pressure of 20 000 Newton. The tablets
formed were crushed and sieved in different particle sizes. The XRD and BET
measurements of different fractions of the sieved powder were analysed by XRD and
BET. No differences in the XRD diagrams or in BET surface areas and pore size
distributions could be observed. The results are presented in the following table 4,
giving examples of N2-adsorption measurement results of mechanical stability tests.


.Example .3.1
Reproducibility of the methods
The same procedure for the manufacture of the material according to the invention
(example 8) was repeated in different scales. The batches showed very similar
properties as shown in table 5, presenting results of reproducibility test.

Examples 32-41
Oligomerization of 1-decene with materials according to the invention as
catalysts
Oligomerization of 1-decene with materials according to the invention as catalysts
showed high activity, low deactivation and regenerability of the catalysts according to
the invention. Catalytic materials according to the invention and comparative
catalysts according to the state of the art were tested in oligomerization of 1-decene.
The tests were carried out in a batch reactor under stirring. Reaction temperature was
200 °C. Reaction time was 24 h. The pressure in the reactor was about 20 bar.
The reaction products were analyzed by GC and by GC-distillation, and the peaks
were identified based on the carbon number of molecule. The molecules with carbon
number above 20 were identified as lubricant components in GC-analysis. The

molecules boiled above 343 °C were identified as lubricant molecules in GC-
distillation.
The catalysts used in the tests were regenerated in a muffle oven in air at 540 °C
temperature.
The results from the 1-decene oligomerization reaction tests are summarized in
following table 6.

Examples 42 and 43 Isobutene reaction w.ith materials according to invention as catalysts
Isobutene reaction tests were performed with materials according to the invention as
catalysts, showing the high activity and low deactivation of the catalysts according to

the invention. The catalysts were; tested in a fixed bed reactor at a reaction
temperature of 100°C under 20 bar with WHSV 20. High activity and no deactivation
of the catalysts were observed. As example isobutene reaction the catalyst of example
8 is compared with the comparative catalyst (example 1) in Figure 7 in isobutene
dimerization
Examples 44-47
Paraffin isomerization tests with materials according to the invention as
catalysts
The purpose of n-butane isomerization test reaction was to confirm the chemical
nature of the interaction in the mesoporous molecular sieve embedded with MFI
structure according to the inveation, formation of strong Branstod acid sites and
hydrothermal stability of novel material. n-Butane isomerization was used as a test
reaction for the evaluation of acidity of catalysts. n-Butane isomerization was carried
out over the proton form of the novel mesoporous molecular sieve catalysts to
evaluate the acidic properties. It was observed that the H-form (H-MM5-96h~4ZS-
2AI-35) catalyst with lowest Si/Al ratio showed highest conversion of n-butane,
clearly indicating the formation of strong Bronstedt acid sites and formation of a
novel mesoporous molecular sieve embedded with a MFI structure with true chemical
bonding.
The regeneration of the H-form and Pt-H-MM5 catalysts was carried out in presence
of air at 450 °C for two hours. The purpose of the regeneration was to evaluate
whether it was possible to regain the catalytic activity, further more also to evaluate
" the" hy drothermal" stability of the catalyst during the regeneration of the-catalyst-since
water is produced during the regeneration process. It was verified that both the H-
form and Pt modified catalysts almost completely retained their catalytic activity,
confirming hydrothermal stability of the structure.

isomerization of n-butane to isobutane was investigated over the proton form catalyst
and 2 wt % Pt-H-MM5-96h-4ZS-2AI catalysts in a fixed-bed micro-reactor made of
quartz. The experiments were carried out near atmospheric pressure and the amounts
of the catalyst used were 0.3 - 1.0 g. The reactant n-butane was fed into the reactor
using hydrogen as a carrier gas. The product analysing was carried out on-line using a
gas chromatograph equipped with a FI detector and a capillary column. The results
from the n-butane isomerization test reactions are provided in Table 7, presenting n-
Butane isomerization at a temperature of 450 °C, WTISV 1.23 h4, n-butane /
hydrogen ratio 1:1.

Examples 48 and 49
1-Butcne isomerization tests with materials according to the invention as
catalysts
The purpose of 1-butene isomerization test reaction was to confirm the chemical
interaction in the mesoporous- molecular sieve embedded with a MFI structure
according to the invention, formation of the strong Bronsted acid sites and
hydrothermal stability of the novel material.
1-butene isomerization was also used as a test reaction for the investigation of
isomerization of 1-butene to iso-butene. Further more the aim was to study the

possibilityof regeneration of used catalyst, and to evaluate if the catalyst retains its
catalytic activity after regeneration. It was found that the used catalyst, after the 1-
butene isomerization could be regenerated. Further more the regenerated catalyst
exhibited almost the same conversion (97.2 mol %) of 1-butene as the corresponding
fresh catalyst (97 mol %), indicating also the hydrothermal stability of the catalyst.
The isomerization of 1-butene to isobutene was investigated over proton form H-
MM5-96h-4ZS-2AI catalyst in a fixed-bed micro-reactor made of quartz. The
experiments were carried out near atmospheric pressure at a temperature of 350 °C
with WHSV 10 h-1. The reactant 1-butene was fed into the reactor using nitrogen as a
carrier gas with a ratio 1:1. The product analysis was carried out on-line using a gas
chromatograph equipped with a FT detector and a capillary column. A condenser was
placed after the GC in order to facilitate liquid product sampling of the heavier
compounds. The first sample was taken after 10 minutes on stream (TOS). The first
10 samples were taken at 1 h intervals and the subsequent samples every 3 h.
Example 50
Ring Opening test with material according to the invention as catalyst
The activity and selectivity of the catalyst according to the invention in decalin ring
opening reaction was tested in a 50 ml autoclave at 250 °C in 20 bar hydrogen
pressure. Decalin (10 ml ~9.0 g) was added to the reactor containing 1 g of at 250 °C
reduced catalyst in room temperature. The pressure was increased with hydrogen to
10 bar. Then the reactor was placed in an oil bath at 250 °C. When the temperature of
the reactor reached 250 °C, the hydrogen pressure was adjusted to 20 bar. The
reaction time was five hours. Then the reactor was cooled rapidly to -10 °C. The
reactor was weighted after the cooling. The pressure in autoclave was released. The
product containing the catalyst was taken to a sample vessel and a GC-sample was

taken thrqugha needle with a filter. The conversion of decalin was 81 % and the
selectivity to ring opening products 32 % with the catalyst according to the invention,
prepared according to example 16.
Examples 51 and 52
Hydrocracking tests with material according to the invention as catalyst
The activity and selectivity of the catalyst according to the invention (catalyst of
example 17) in hydrocracking reaction was tested in an autoclave at 300°C (example
51) and 350°C (example 52) under 30 bar hydrogen pressure. Paraffin mixture (about
80 g) was added to the reactor containing 2 g of at 400 °C reduced catalyst at room
temperature. The pressure was increased with hydrogen to 30 bar. When the temperature of the reactor reached 3000C(-example 51)or 3500C (example 52),the
hydrogen pressure was adjusted to 30 bar. The reaction time was 65 hours. The
reactor was weighted after the cooling. The pressure in autoclave was released. The
products were analysed by GC. The conversion of paraffins was 60 % (example 51)
and 65% (example 52) and the selectivity to the cracking products in both cases was
100%.

WE CLAIM:
1. A catalytic material, characterized in that the catalytic material is a mesoporous
molecular sieve embedded with a zeolite and the catalytic material is thermally stable at a
temperature of at least 900°C.
2. The catalytic material as claimed in claim 1, wherein the catalytic material has specific
surface area in the range of 1400 - 500 m2/g.
3. The catalytic material as claimed in claim 1 or 2, wherein the catalytic material
comprises a mesoporous molecular sieve selected from M41S group.
4. The catalytic material as claimed in any one of claims 1-3, wherein the catalytic
material comprises a medium pore zeolite selected from MFI, MTT, TON, AEF, MWW and
FER zeolites or a large pore zeolite selected from BEA, FAU, MOR zeolites. .
5. The catalytic material as claimed in any one of claims 1 - 4, wherein the mesoporous
molecular sieve is MCM-41 or MCM-48 and the zeolite is MFI or BEA or MWW or MOR
zeolite.
6. The catalytic material as claimed in any one of claims 1 -5, wherein the catalyst is in
proton form, cationic form or modified with metal.
7. A catalyst, characterized in that the catalyst comprises 90-10 wt-% of the catalytic
material as claimed in any one of claims 1 - 6 and 10-90 wt-% of a carrier.
8. A method for the manufacture of a mesoporous molecular sieve embedded with a
zeolite, characterized in that the method comprises the steps:
a) preparing of zeolite nuclei from a silicon source and an aluminium source and
structure directing agent, or a silicate or aluminosilicate precursor for the zeolite
nuclei, and optionally removing the structure directing agent with a step calcination
procedure;
b) preparing of mesoporous molecular sieve gel mixture from a silicon source, an
optional aluminium source, and surfactant;
c) introducing the zeolite nuclei or the silicate or aluminosilicate precursor prepared in
step a) to the mesoporous molecular sieve gel mixture obtained in step b), and

homogenising and dispersing in the molecular sieve gel the zeolite nuclei or the
silicate or aluminosilicate precursor;.
d) performing gel ripening of the mixture of step c) under stirring;
e) carrying out hydrothermal synthesis of the mixture of step d) by maintaining the
mixture under sufficient conditions including a temperature of from about 100 °C to
about 200 °C under static or dynamic mode of stirring until crystals are formed;
f) recovering the crystals;
g) washing of the solid product;
h) drying of the solid product, and
i) removing the surfactant (S) partly or totally with a step calcination procedure and
optionally the structure directing agent if it was not removed in step a), whereby a
mesoporous molecular sieve embedded with a zeolite catalyst is obtained.
9. The method as claimed in claim 8 for the manufacture of a mesoporous molecular
sieve embedded with a zeolite, wherein the silicon source in step a) is selected from
silicon oxides, .
10. The method as claimed in claim 8 or 9 for the manufacture of a mesoporous molecular
sieve embedded with a zeolite, wherein the silicon source or sources in step b) is selected
from silicon compounds having an organic group and from inorganic silicon sources..
11. The method as claimed in any one of claims 8 - 10 for the manufacture of a
mesoporous molecular sieve embedded with a zeolite, wherein the aluminium source is
selected from aluminium sulphate (Al2(SO4)3.18H2O), hydrated aluminium hydroxides,
aiuminates, aluminium isoproxide and alumina.
12. The method as claimed in any one of claims 8 - 11 for the manufacture of a
mesoporous molecular sieve embedded with a zeolite, wherein the surfactant is selected
from alkyltrimethyl ammonium halide compounds with the general formula CnH2n+1
(CH3)3-NX, where n = 12 to 18, X= CI, Br..
13. The method as claimed in any one of claims 8 - 12 for the manufacture of a
mesoporous molecular sieve embedded with a zeolite, wherein the additional aluminium
source is selected from aluminium alkoxidese.

14. The catalytic material as claimed in claim 2, wherein the catalytic material has specific
surface area in the range of 1200 - 600 m2/g.
15. The catalytic material as claimed in claim 3, wherein the catalytic material comprises a
mesoporous molecular sieve selected from MCM-41 or MCM-48.
16. The catalytic material as claimed in claim 4, wherein the catalytic material comprises a
medium or large pore zeolite selected from MFI, MTT, AEF, BEA, MWW or MOR zeolite.
17. The method as claimed in claim 8 for the manufacture of a mesoporous molecular
sieve embedded with a zeolite, wherein the silicon source in step a) is selected from
colloidal silica, solid silica and fumed silica.
18. The method as claimed in claim 10 for the manufacture of a mesoporous molecular
sieve embedded with a zeolite, wherein the silicon source or sources in step b) is selected
from silicon source having an organic group which is tetraethoxy silane,
tetramethylammonium silicate or tetraethylammonium silicate, or inorganic silicon source
which is sodium silicate, water glass, colloidal silica, solid silica or fumed silica.
19. The method as claimed in claim 12 for the manufacture of a mesoporous molecular
sieve embedded with a zeolite, wherein the surfactant is selected from n-
hexadecyltrimethyl ammonium bromide, n-hexadecyltrimethyl ammonium chloride,
cetyltrimethylammonium bromide and cetyltriethylammonium bromide.
20. The method as claimed in claim 13 for the manufacture of a mesoporous molecular
sieve embedded with a zeolite, wherein the additional aluminium source is aluminium
isopropoxide.


ABSTRACT
CATALYTIC MATERIALS AND METHOD FOR THE
PREPARATION THEREOF
The invention discloses a catalytic material, characterized in that the catalytic material is a
mesoporous molecular sieve embedded with a zeolite and the catalytic material is
thermally stable at a temperature of at least 900°C.
The invention is also for a method for manufacture of a mesoporous molecular sieve
embedded with a zeolite catalyst as stated above.

Documents:

02503-kolnp-2007-abstract.pdf

02503-kolnp-2007-claims.pdf

02503-kolnp-2007-correspondence others.pdf

02503-kolnp-2007-description complete.pdf

02503-kolnp-2007-drawings.pdf

02503-kolnp-2007-form 1.pdf

02503-kolnp-2007-form 3.pdf

02503-kolnp-2007-form 5.pdf

02503-kolnp-2007-gpa.pdf

02503-kolnp-2007-international publication.pdf

02503-kolnp-2007-international search report.pdf

02503-kolnp-2007-pct request form.pdf

02503-kolnp-2007-priority document.pdf

2503-KOLNP-2007-(06-01-2012)-ABSTRACT.pdf

2503-KOLNP-2007-(06-01-2012)-AMANDED CLAIMS.pdf

2503-KOLNP-2007-(06-01-2012)-AMANDED PAGES OF SPECIFICATION.pdf

2503-KOLNP-2007-(06-01-2012)-DESCRIPTION (COMPLETE).pdf

2503-KOLNP-2007-(06-01-2012)-DRAWINGS.pdf

2503-KOLNP-2007-(06-01-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

2503-KOLNP-2007-(06-01-2012)-FORM-1.pdf

2503-KOLNP-2007-(06-01-2012)-FORM-13.pdf

2503-KOLNP-2007-(06-01-2012)-FORM-2.pdf

2503-KOLNP-2007-(06-01-2012)-FORM-3.pdf

2503-KOLNP-2007-(06-01-2012)-OTHER PATENT DOCUMENT.pdf

2503-KOLNP-2007-(06-01-2012)-OTHERS.pdf

2503-KOLNP-2007-(17-10-2011)-CORRESPONDENCE.pdf

2503-KOLNP-2007-ASSIGNMENT 1.1.pdf

2503-KOLNP-2007-ASSIGNMENT.pdf

2503-KOLNP-2007-CORRESPONDENCE 1.1.pdf

2503-KOLNP-2007-CORRESPONDENCE 1.2.pdf

2503-KOLNP-2007-EXAMINATION REPORT.pdf

2503-KOLNP-2007-FORM 13.pdf

2503-KOLNP-2007-FORM 18 1.1.pdf

2503-kolnp-2007-form 18.pdf

2503-KOLNP-2007-FORM 3-1.1.pdf

2503-KOLNP-2007-FORM 3.pdf

2503-KOLNP-2007-FORM 5.pdf

2503-KOLNP-2007-GPA.pdf

2503-KOLNP-2007-GRANTED-ABSTRACT.pdf

2503-KOLNP-2007-GRANTED-CLAIMS.pdf

2503-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

2503-KOLNP-2007-GRANTED-DRAWINGS.pdf

2503-KOLNP-2007-GRANTED-FORM 1.pdf

2503-KOLNP-2007-GRANTED-FORM 2.pdf

2503-KOLNP-2007-GRANTED-SPECIFICATION.pdf

2503-KOLNP-2007-OTHERS.pdf

2503-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf


Patent Number 252411
Indian Patent Application Number 2503/KOLNP/2007
PG Journal Number 20/2012
Publication Date 18-May-2012
Grant Date 14-May-2012
Date of Filing 05-Jul-2007
Name of Patentee NESTE OIL OYJ
Applicant Address KEILARANTA 8, FI-02150 ESPOO, FINLAND
Inventors:
# Inventor's Name Inventor's Address
1 KUMAR NARENDRA OSTJAKINKATU 5 F 28, FI-20750 TURKU, FINLAND
2 SALMI TAPIO RAKUUNATIE 28, FI-20720 TURKU, FINLAND
3 OSTERHOLM HEIDI ITAINENTIE 18, FI-06100 PORVOO, FINLAND
4 TIITTA MARJA VIIKINTIE 11C 102, FI-06150 PORVOO, FINLAND
PCT International Classification Number C01B 39/02
PCT International Application Number PCT/FI05/050484
PCT International Filing date 2005-12-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/639314 2004-12-28 Finland
2 20041675 2004-12-28 Finland