A Review Study Ability Zeolite Synthetis Combination for

Catalytic Cracking, and Adsorption Metals Ion.

Boby Royan, A.

Abstract. Zeolite is a chemical compound hydrated alumino-silicates which have a unique

sruktur melekular, wherein the silicon atom surrounded by four oxygen atoms to form a kind
of network with a regular pattern. Aluminum Atom only has 3+ charge, while the silicon itself
has a charge of 4+. The existence of Aluminium atom as a whole will menyebababkan
zeolites have a negative charge. The negative charge that causes the zeolite capable of
binding cations. So zeolites are widely used both as penjerap metals and catalysts that can
reduce the energy requirements of production but still be able to obtain maximum results as
in the process of cracking hydrocarbons.

Introduction

Natural zeolite is recently reported as excellent material to support metal in the preparation of
catalyst. Natural zeolite materials are easily found in USA, Japan, Cuba, Soviet Union, Italy,
Czechoslovakia, Hungary, Bulgaria, South Africa, Yugoslavia, Mexico, Korea, and
Indonesia. In Indonesia, natural zeolite reserves were discovered more than 205.82 million
tons. Zeolite deposits are most numerous in the Java island,i.e: Central Java (Wonosari,
Klaten), West Java (Bogor, Tasikmalaya, Sukabumi), and East Java (Bayah). Hydrocracking
of plastic waste has been widely studied in literatures. However, the Indonesia’s natural
zeolite especially from Sukabumi is rarely applied as a catalyst for hydrocracking. have
observed the natural zeolite from Sukabumi. It contains the most mordenite mineral that has
high thermal stability. Hence, this work would study the effect of temperature condition as
well. The activation through acid treatment and modification using supported metals could
increase its acidity, pore and surface area as well could produce the good catalyst for
hydrocracking processes. Furthermore, the natural zeolite is very abundant and cheap, hence
its use as a catalyst is valuable to lower the cost of production.

Supports provide the cracking functions, where the cracking takes place on strong acid sites
in the supports. The most important function of support is maintenance of high surface area
for the active component and acidity for hydrocracking reactions. A support material is
chosen for given application on the basis of the several important characteristics including its
inertness to undesired side reactions, appropriate mechanical properties (attrition resistance,
strength, etc), stability under reaction conditions, a surface area and pore size distribution
appropriate for the desired reaction, and its cost [6]. Zeolites are widely used as catalyst
support and play an important role in the catalysts used in hydrocracking process because
they improve catalytic activity, selectivity, or stability by imparting shape selectivity.
Zeolites are defined as crystalline aluminosilicates, have been investigated and extensively
used in industry. Zeolites have been successful because of their crystallinity, high surface
area, adsorption capacity, and uniform size distribution which enable shape selectivity. The
elementary building units of zeolites are SiO4 and AlO4 tetrahedra. Among the properties
which are affected by the framework alumina content are the density of negative framework
charges, cation-exchange capacity, the density of Bronsted acid sites, their strength and
thermal stability [8]. For the majority of catalytic applications, medium or large pore zeolites
will usually be preferred. In the processes which work under hydrogen pressure, such as
hydrocracking of heavy petroleum distillates, the catalytic activity stems from the Bronsted
acid sites rather than the Lewis acid sites. It is well known, due to the higher electron
egativity of silicon compared to alumina, the strongest Bronsted acid sites in zeolites will
occur on completely isolated Al/O tetrahedra. This is the reason why, upon dealumination of
Yzeolites with typical Si/Al ratio of 2.5, the catalytic activity generally increase up to Si/Al
ratio of 10. In this region, the gain in acid strength over compensate the decrease in the
density of Bronsted acid sites.

Adsorption & Recovery Heavy Metas ion.

Before any uses or applications of zeolites to the recovery of heavy metals from mining or
metallurgical effluents can be seriously considered it is necessary to characterize the zeolite
minerals. Characterization makes it possible to match the physical and chemical properties of
the zeolite mineral to the environment of the application in which it must operate.

Characterization begins at the zeolite deposit. This means that a zeolite deposit must be
thoroughly explored to determine its extent, continuity and quality. Both the mined and
processed product must be carefully sampled to insure the purchaser a dependable supply of
zeolites which are of a consistent quality. The specifications which are used for grade or
quality control must match the specifications required for the intended use or application.

The characterization of zeolite minerals initially requires careful screening techniques to

identify the zeolite and gangue minerals and to determine the percentage of each present in
the product. Next the elemental composition of the product should be determined. Both the
mineralogy and the elemental composition must be known before the zeolite can be
considered for any ion exchange applications. If the zeolite product contains a high
percentage of usable zeolite minerals usually chabazite, clinoptilolite or mordenite and does
not contain significant quantities of the minerals smectite (montmorillonite), calcite or
dolomite or the elements potassium, magnesium or calcium then the product should undergo
additional testing.

The additional testing will determine other properties such as the ammonia exchange
capacity, pH stability, exchange selectivities, and exchange capacities for selected heavy
metal ions. These are some of the properties which must be matched to the specific
application if the product is to perform successfully. In the past zeolite products have been
introduced into effluent streams and expected to perform Without any information on the
composition of either the effluent stream or the zeolite product. Clearly this hit or miss
approach has seldom ever been.

Hydrocracking Process

Oil is nowadays the main energy source and this prevalent position most probably will
continue in the next decades. This situation is largely due to the degree of maturity that has
been achieved in oil refining and petrochemistry as a consequence of the large effort in
research and innovation. The remarkable efficiency of oil refining is largely based on the use
of zeolites as catalysts. The use of zeolites as catalysts in refining and petrochemistry has
been considered as one of the major accomplishments in the chemistry of the XXth century.
In this tutorial review, the introductory part describes the main features of zeolites in
connection with their use as solid acids. The main body of the review describes important
refining processes in which zeolites are used including light naphtha isomerization, olefin
alkylation, reforming, cracking and hydrocracking. The final section contains our view on
future developments in the field such as the increase in the quality of the transportation fuels
and the coprocessing of increasing percentage of biofuels together with oil streams. This
review is intended to provide the rudiments of zeolite science applied to refining catalysis.
Hydrocracking catalyst is a bi-functional catalyst and has a cracking function and
hydrogenation dehydrogenation function. The former is provided by an acidic support
whereas the latter is imparted by metals. Acid sites (Crystalline zeolite, amorphous silica
alumina, mixture of crystalline zeolite and amorphous oxides) provide cracking activity.
Metals [Noble metal (Pd, Pt) or non noble metal sulphides (Mo, Wo or Co, Ni)] provide
hydrogenation dehydrogenation activity. These metals catalyze the hydrogenation of
feedstocks making them more reactive for cracking and hetero-atom removal as well
reducing the coke rate Zeolite based hydrocracking catalysts have following advantages of
greater acidity resulting in greater cracking activity; better thermal/hydrothermal stability;
better naphtha selectivity; better resistance to nitrogen and sulphur compounds; low coke
forming tendency, and easy regenerability.

Hydrocracking process is a catalytic cracking process which takes place in the presence of an
elevated partial pressure of hydrogen and is facilitated by bio-functional catalyst having
acidic sites and metallic sites. During hydrocracking process hydrotreating reactions and
hydrocracking reactions are two major reactions which take place.

A typical hydrocracking reaction is as follows.

C22 H46 + H2  C16H34 + C6H14

Various hydrotreating reactions are hydrodesulphurization, denitrogenation, hydro

deoxygenation, hydro metallization, olefin hydrogenation partial aromatics
saturation.Various hydrocracking reactions are splitting of C-C bond and or C-C
rearrangement reaction (hydrisomerisation process) Hydrogenation and
dehydrogenation catalyst.

Conclusion

Hydrocracking of saturated hydrocarbons can proceed by means of four distinctly different

mechanisms. On bifunctional catalysts comprising hydrogenation/dehydrogenation and
Brønsted acid sites alkenes and carbocations occur as intermediates. The current mechanistic
views of bifunctional hydrocracking of long-chain n-alkanes are discussed in detail with
emphasis on the now widely accepted concept of ideal hydrocracking. Other mechanisms are
hydrogenolysis and Haag–Dessau hydrocracking which proceed, respectively, on
monofunctional metallic and acidic catalysts. Even without a catalyst, thermal hydrocracking
occurs in chain reactions via radicals. The chemistry of hydrocracking naphthenes on
bifunctional catalysts resembles that of alkanes. A peculiarity, however, is the pronounced
reluctance of cyclic carbenium ions to undergo endocyclic β-scissions. The effect manifests
itself in the so-called pairing reaction, which, in turn, forms the basis for measuring the
Spaciousness Index for characterizing the effective pore width of zeolitic catalysts.
Hydrocracking on bifunctional catalysts is among the very important processes in modern
petroleum refining. It is primarily used for converting heavy oils into diesel and jet fuel.
Besides, hydrocracking is appreciated for its pronounced versatility: numerous process
variants exist which help to meet specific requirements in refineries or petrochemical plants.
Two recent developments are briefly discussed in this review, viz. the conversion of surplus
aromatics, e.g., in pyrolysis gasoline, into a synthetic feedstock for steam crackers, and
quality enhancement of diesel fuel by selective ring opening of polynuclear aromatics.

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