3/20/18

CHEM 4471 – Industrial Inorganic Chemistry

Sultan Qaboos University

College of Science
Department of Chemistry

Spring semester 2018

Massimiliano Valentini, PhD

room 2026

valentini@squ.edu.om

Topics
Unit/Chapter Topics Section Weeks

Hydrogen (H2) and

1 Industrial gases 1
hydrogen peroxide (H2O2)
(a) Ammonia
2 Nitrogen and its compouds 2-3
(b) Nitric acid
(a) Ammonia salts
3 Mineral fertilizers (b) P containing fertilizers 4-5
(c) K containing fertilizers
Midterm exam 6

4 Sulphur and sulphuric acid 7

Phosphorus and
5 8
Phosphoric acid

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Topics
Unit/Chapter Topics Section Weeks

(a) Silicates
6 Inorganic solids
(b) zeolites

7 Ceramics 9-11

8 Cement industry

9 Glass industry 12

Midterm exam 13

10 Inorganic pigment 14

11 Portable water production 15

Final exam 16

Topics
Unit/Chapter Topics Section Weeks

(a) Silicates
6 Inorganic solids
(b) zeolites

7 Ceramics 9-11

8 Cement industry

9 Glass industry 12

Midterm exam 13

10 Inorganic pigment 14

11 Portable water production 15

Final exam 16

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Inorganic solids: zeolites

Zeolites are three-dimensional, microporous, crystalline solids with well-defined
structures that contain aluminium, silicon, and oxygen in their regular framework;
cations and water are located in the pores.
The general formula is:
[(M+, M2+0.5)AlO2]x[SiO2]y . [H2O]z

The silicon and aluminium atoms are tetrahedrally coordinated with each other
through shared oxygen atoms. Compositionally, zeolites are similar to clay minerals.
More specifically, both are alumino-silicates. They differ, however, in their crystalline
structure.

Zeolites
Many types of clay have a layered crystalline structure and are subject to
shrinking and swelling as water is absorbed and removed between the layers. In
contrast, zeolites have a rigid, 3-dimensional crystalline structure consisting of a
network of interconnected tunnels and cages.
Water moves freely in and out of these pores but the zeolites framework
remains rigid. Another special aspect of this structure is that the pore and
channel sizes are nearly uniform, allowing the crystal to act as a molecular sieve.

The porous zeolite is host to water molecules and ions of potassium and calcium,
as well as a variety of other positively charged ions, but only those of
appropriate molecular size to fit into the pores are admitted creating the
"sieving" property. Because of their regular and reproducible structure, they
behave in a predictable fashion.

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Types of zeolite
Zeolites are natural minerals that are mined in many parts of the world; most
zeolites used commercially are produced synthetically. When developing
applications for zeolites, it is important to remember that not all of these minerals
are the same.

There are nearly 50 different types of natural zeolites (clinoptilolite, chabazite,

phillipsite, mordenite, etc.), which differ for Si/Al ratio and with varying physical
and chemical properties. Crystal structure and chemical composition account for
the primary differences. Particle density, cation selectivity, molecular pore size,
and strength are only some of the properties that can differ depending on the
zeolite in question. It is important to know the specific type of zeolite one is using
in order to assure that it is appropriate for one's needs.

There are numerous naturally occurring and synthetic zeolites, each with a unique
structure. The pore sizes commercially available range from approximately 3 Å to
approximately 8 Å.

Some of the commercial materials are: A, X, Y, mordenite, ZSM-5.

Types of zeolite
The biggest differences between natural and synthetic zeolites are:
1. synthetics are manufactured from energy consuming chemicals and naturals
are processed from natural ore bodies.
2. synthetic zeolites have a silica to alumina ratio of 1 to 1 and clinoptotilite
(clino) zeolites have a 5 to 1 ratio.
3. Clino natural zeolites do not break down in a mildly acid environment, where
synthetic zeolites do. The natural zeolite structure has more acid resistant
silica to hold it’s structure together. The clino natural zeolite is broadly
accepted for use in the agricultural industry as a soil amendment and as a
feed additive.

In 1948, Richard Barrer first produced a synthetic zeolite that did not have a
natural counterpart. At approximately the same time, Milton made the first
materials that had no natural counterpart such as zeolite A. New natural zeolites
are still being discovered, and new synthetic zeolites are being invented in many
laboratories around the world.

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Zeolite structure
Zeolites occur in many different structures.
The basic units are always SiO4- and Al04-tetrahedra, linked to one another by
common oxygen atoms. These zeolites are built up of cubo-octahedra (“b-cages”)
with SiO4- and Al04-tetrahedra at their corners.

Zeolite A Zeolite X and Y

The zeolite A structure is produced by linking the b-cages via their quadratic
surfaces (over cubes). Linking over the six-corned surfaces with hexagonal prisms
leads to zeolite X and Y, which correspond to the mineral faujasite.

Zeolite structure

Theta-1 SUZ-4 ZSM-5

MFS ZSM-12 CIT-1

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Zeolites applications

Natural zeolite is a new and very good natural filter medium available for
the filtration of water. It offers superior performance to sand and carbon
filters, giving purer water and higher throughput rates with less
maintenance required. It has many advantages over sand and can be used
to directly replace sand in a normal sand filter. There are three main uses of
zeolites in industry:

1. catalysis;
2. gas separation;
3. ion exchange.

Catalysis
Zeolites are extremely useful as catalysts for several important reactions
involving organic molecules. The most important are cracking, isomerisation
and hydrocarbon synthesis. Zeolites can promote a diverse range of catalytic
reactions including acid-base and metal induced reactions. Zeolites can also
be acid catalysts and can be used as supports for active metals or reagents.

Zeolites can be shape-selective catalysts either by transition state selectivity

or by exclusion of competing reactants on the basis of molecular diameter.
They have also been used as oxidation catalysts. The reactions can take
place within the pores of the zeolite, which allows a greater degree of
product control.
The main industrial application areas are: petroleum refining, synfuels
production, and petrochemical production. Synthetic zeolites are the most
important catalysts in petrochemical refineries.

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Gas separation
Zeolites are used to adsorb a variety of materials. This includes
applications in drying, purification, and separation. They can remove
water to very low partial pressures and are very effective desiccants, with
a capacity of up to more than 25% of their weight in water. They can
remove volatile organic chemicals from air streams, separate isomers and
mixtures of gases. A widely used property of zeolites is that of gas
separation.
The porous structure of zeolites can be used to "sieve" molecules having
certain dimensions and allow them to enter the pores. This property can
be fine tuned by variating the structure by changing the size and number
of cations around the pores. Other applications that can take place within
the pore include polymerisation of semi conducting materials and
conducting polymers to produce materials having unusual physical and
electrical attributes.

Ion exchange

Hydrated cations within the zeolite pores are bound loosely to the
zeolite framework, and can readily exchange with other cations when
in aqueous media. Applications of this can be seen in water softening
devices, and the use of zeolites in detergents and soaps.
The largest volume use for zeolites is in detergent formulations where
they have replaced phosphates as water-softening agents. They do this
by exchanging the sodium in the zeolite for the calcium and
magnesium present in the water. It is even possible to remove
radioactive ions from contaminated water.

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Synthesis: introduction
The chemistry of zeolite synthesis is subject to perturbations caused by
impurities present in the source materials. Such contaminants may remain
insoluble during the crystallization and cause undesired species to nucleate.

They may be soluble and result in formation of different silicate or

metallosiicate species in solution, or they may cause an insoluble silicate
species to precipitate. Therefore, it is desirable to apply pure chemicals as
starting materials.

Depending on the zeolite to be synthesized and the application intended for

the product, less pure source materials are frequently employed, in order to
reduce the cost. If the materials are not pure, they may vary from batch to
batch and from different suppliers. It is of utmost importance to know the
source materials for zeolite synthesis, and technical grade materials need to
be assayed and analyzed for impurities. A few frequently used chemicals are
discussed below.

Synthesis: water content

Clearly, when commercially available solutions of chemicals are employed, such as
aqueous NaOH, H2F2, or silicate, the water content of the solution has to be taken into
account when the composition of the reaction mixture is established. Most other source
materials contain more or less water, while the water content of fume silica may be only
3% wt, that of aluminum nitrate, Al(NO3)3⋅ 9 H2O, is about 43% wt. Moreover, aluminum
nitrate is deliquescent, and the water content will change once the jar has been opened
and the chemical exposed to moist air. On the other hand, aluminum sulfate, Al2(SO4)3⋅
18H2O (48.6% wt. H2O), weathers by losing water upon exposure to the atmosphere.
Technical grade aluminum sulfate usually contains about 14 H2O.

Since the composition of a reaction mixture is given as ratio of oxides, any hydroxides
employed are to be considered as oxides plus water, for example, NaOH = 1/2Na2O +
1/2H2O (22.5 wt.% H2O). Additionally, a small percentage of free water may be present,
for example, sodium hydroxide pellets may contain about 97 or 98% NaOH. Similarly, an
85% H3PO4 contains 61.6 wt.% P2O5 and 38.4 wt.% H2O. The water content of source
materials may or may not constitute an important fraction of the total water content,
and it is recommended that the water contained in these chemicals always be
considered when the amount of water to be added in the preparation of the reaction
mixture is calculated.

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Synthesis: sources of Al
A disadvantage of using salts is that, after pH adjustment or addition of alkali silicate
solutions, alkali salts are formed which have a strong electrolytic effect on gel formation.
For example, such salts may cause sodalite to be crystallized instead of zeolite A type
materials. For this reason, it is advantageous, particularly for reaction mixtures of low
SiO2/Al2O3 ratios, to introduce aluminum in the anionic form, that is, as sodium aluminate.
Sodium aluminate tent to form aluminum oxide hydrates upon exposure to CO2 or upon
storage. It is not a widely used chemical, and, when obtained it is frequently aged to an
extent that makes it unsuitable for zeolite synthesis. Sodium aluminate should dissolve
completely with stirring in water room T in few minutes. If it does not, the precipitate or
cloudiness usually can not be dissolved by adding small quantities of alkali hydroxide, and
the chemical is not suitable. It is advisable to transfer the chemical with as little exposure
to moisture and CO2 as possible into small jars which should be sealed tightly and stored
below room T. The composition of such technical sodium aluminate varies widely with
Na/Al ratios from near 1.0 to 1.2. A small iron content manifests itself by the brownish
discoloration of the otherwise clear sodium aluminate solution. This iron hydroxide can be
removed by filtration.
In preparations containing phosphate, aluminum phosphate, AlPO4 2H2O, is a viable
alternative as it dissolves completely in alkaline phosphate or hydroxide solutions upon
mild heating with stirring.

Synthesis: sources of Si
A widely used silica source is aqueous sodium silicate, which contains about 8.9 wt.%
Na2O and 28.7 wt.% SiO2. It is sometimes slightly cloudy, so that filtration is
recommended. The precipitate can also be filtered off in the laboratory, but the
vacuum filtration is slow and the filtrate has a reduced water content and needs to be
reassayed. A small contamination with aluminum usually prevents zeolites with
SiO2/Al2O3 ratios above ~600 to be crystallized.

When a lower aluminum content in the product is desired, colloidal silica sol, such as
Ludox, can be used. This material is available in concentrations of 30 and 40 wt.%
SiO2 with different stabilizers employed. Without added aluminum, SiO2/Al2O3 ratios in
the range of 3000 to about 3500 can be obtained.

Zeolites of still lower aluminum content can be prepared with fume silica as the silica
source. Such materials are on the market as Cab-O-Sil (Cabot) or Aerosil (Degussa). The
water content of fume silica is very low, ~3 wt.%. Products obtained when using fume
silica as the silica source, without adding an alumina source, have SiO2/Al2O3 ratios
above 20,000.

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Synthesis: sources of Si
Precipitated silica is available in different qualities. Hi-Sil (PPG Industries, Pittsburgh, PA,
USA) contains about 90 wt.% of SiO2 as well as 1 wt.% of NaCl (it is recommended that
the percentage of SiO2 be determined; alternatively, the ash content minus 1% NaCl
should approximate the SiO2 content). The aluminum contamination prevents zeolites
with SiO2/Al2O3 ratios above ~220.

A somewhat purer material is Ultrasil (Degussa). The particle size of precipitated silica
may need to be considered. Whereas finely divided fume silica may yield a thick paste
of a reaction mixture, which is difficult to homogenize, a large-size precipitated silica,
for example, Ultrasil VN3SP, may react too slowly to provide the desired aluminosiicate
precursors in solution.

Tetramethyl- and tetraethylorthosilicate are available in high purity and yield the
highest SiO2/Al2O3 ratios. Any noticeable aluminum contamination is likely brought in
from other sources. The compounds are usually hydrolyzed, for example, in a stainless-
steel beaker, prior to incorporation in a reaction mixture. It is recommended that the
alcohol generated be removed by heating, although its effect on the crystallization of
high-silica materials is generally slight.

Synthesis: sources of Si

In order to prevent contamination, plastic containers such as polypropylene or Teflon,

are recommended for the preparation of all solutions, for the reaction mixture, and
for the crystallization.

Glass vessels should be avoided, as glass participates in the reaction, and silica,
alumina, and boron are known to be leached out of glass. For example, the catalytic
activity of a borosilicate or a ferrosilicate may be influenced by contamination with
traces of aluminum. When pressure vessels are used for the crystallization,
removable Teflon or stainless-steel liners are recommended. The reaction vessels
should be thoroughly cleaned prior to use by heating with aqueous sodium
hydroxide, if seeding is to be avoided. Teflon may also be cleaned with hydrofluoric
acid.

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Synthesis of A, X and Y
The manufacture of the industrially important zeolite types A, X and Y is generally
carried out by mixing sodium aluminate and sodium silicate solutions, whereupon
a sodium aluminosilicate gel is formed. In this gel SiO2- and Al203-containing
compounds pass into the liquid phase, from which the zeolites are formed by
crystallization. As the zeolite growth, components are removed from the solution.

The reaction mechanism for zeolite formation is presently not yet fully understood.
There is experimental evidence that, depending upon the reaction conditions,
different mechanisms are possible.

In zeolite synthesis the desired zeolite end-product is generally metastable with

respect to the byproducts associated with it, e.g. the byproduct sodalite is more
stable than zeolite A, and the byproduct phillipsite is more stable than zeolites X
and Y.

Variables in synthesis
Different variables must be controlled during zeolite syntheses to obtain a
material with optimum properties:
- the stoichiometry of the reaction mixture, which is not the same as that
of the zeolite formed;
- the respecting of particular concentration ranges;
- the respecting of particular temperatures or resulting temperature;
- the respecting of particular pH-values;
- the shear energy in stirring (explained by the degradation of oligomeric
structures upon stirring).

The above-mentioned variables do not play a role in all zeolite syntheses. In

the manufacture of different zeolites, aging of the gel at temperatures
below the crystallization is often useful. In many cases the synthesis can be
influenced or accelerated by the addition of small quantities of nuclei.

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Synthesis of A

In the synthesis of zeolite A for utilization in detergents, for which

small particles (< 5 µm) and a narrow particle size distribution are
necessary, the manufacturing economics have been improved in
recent years by optimizing all conditions. Continuous synthesis has
not yet been achieved industrially.

At the end of the crystallization, the zeolite formed is filtered off

(e.g. with the aid of filter presses o r continuous belt filters) and
washed. The mother liquor and filtrates from the washings have to
be recycled or processed, for ecological and economic reasons.

Zeolite Y: structure
Zeolite Y exhibits the FAU (faujasite) structure. It has a 3-dimensional pore
structure with pores running perpendicular to each other in the x, y, and z
planes, and is made of secondary building units 4, 6, and 6-6. The pore
diameter is large at 7.4 Å since the aperture is defined by a 12 member
oxygen ring, and leads into a larger cavity of diameter 12 Å.
The cavity is surrounded by ten sodalite cages (truncated octahedra)
connected on their hexagonal faces. The unit cell is cubic (a = 24.7Å) with Fd-
3m symmetry. Zeolite Y has a void volume fraction of 0.48, with a Si/Al ratio
of 2.43. It thermally decomposes at 793°C.

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Zeolite Y: synthesis and appplication

Zeolite Y, like zeolite A, is synthesized in a gelling process. Sources of alumina
(sodium aluminate) and silica (sodium silicate) are mixed in alkaline (NaOH)
aqueous solution to give a gel. The gel is then usually heated to 70-300°C to
crystallize the zeolite. The zeolite is present in Na+ form and must be converted to
acid form. To prevent disintegration of the structure from acid attack, it is first
converted to the NH4+ form before being converted to acidic form. If a
hydrogenation metal such as platinum is needed, it is deposited via impregnation
or ion exchange.

The most important use of zeolite Y is as a cracking catalyst. It is used in acidic

form in petroleum refinery catalytic cracking units to increase the yield of gasoline
and diesel fuel from crude oil feedstock by cracking heavy paraffins into gasoline
grade napthas. Zeolite Y has superseded zeolite X in this use because it is both
more active and more stable at high temperatures due to the higher Si/Al ratio. It
is also used in the hydrocracking units as a platinum/palladium support to increase
aromatic content of reformulated refinery products.

Ion exchange zeolite modification

Synthesized zeolites can be modified by ion exchange. Exchange of sodium by
potassium, anitnoniurn, calcium, barium, rare earth and transition metal elements is
industrially important.

The exchange equilibrium depends upon the cation and zeolite type. The Ag ion, for
example, is particularly strongly bound, whereas the Li ion is much more difficult to
incorporate. The extent of exchange is determined by the size of cation and also by
the structure of the zeolite.
Exchange of sodium by potassium and calcium in zeolite A and zeolite X is industrially
relevant.
Exchange of sodium by ammonium, rare earth ions and transition metal ions such as
nickel, cobalt, platinum, palladium etc. in wide pore and medium-sized pore zeolites
which are suitable for catalytic applications such as zeolite Y, Ieolite. mordenite,
zeolite L or ZSM 5, EU 1 , ZSM 22 is also relevant.

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Zeolite formation
Forming of zeolite powders is possible by:
• granulation on granulation dishes;
• drum granulation;
• extrusion;
• spray drying.

Zeolites can be produced by different processes, such as bead formation on dish

granulators and by drum granulators; extrusion of granules and by drum
granulators, extrusion or spray drying.
Clays are mainly used a s binders in the forming process, but SiOz-containing
materials and aluminosilicates are also used. When silica-containing binders are
used in the forming process, they can be subsequently converted into zeolite by
treatment with sodium aluminate solution at high temperatures. In this way
molded articles solely containing zeolite can be obtained. When kaolin is used as
a binder subsequent heating of the granules followed by treatment with sodium
hydroxide enables binder-free granules to be obtained.

Ion exchangers
In addition to the use of clinoptilolite for the removal of NH4+ ions from
municipal waste water and cesium 137 from process water, the ability
of zeolite A to exchange sodium ions for calcium and, to a lesser extent,
magnesium ions from aqueous solutions has acquired considerable
industrial importance in the detergent sector.
The replacement of ca. 50 to 100% of the tripolyphosphate in
detergents by zeolite A considerably reduces phosphate release into
mains drainage after passage of municipal waste water through sewage
plants. To achieve the same washing power other changes in the
composition of the detergent are required in addition to replacement of
the phosphate.

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Adsorption agent
Zeolites are capable of strongly binding molecules which are small enough to
penetrate their pore systems. This particularly holds for water and for other small
polar and polarizable molecules and is the basis of their utilization as drying- or
cleaning-agents for gases such as natural gas, cracked gases, hydrocarbons or air
prior to liquefaction.
Furthermore, they are utilized in closed liquid circuits, e.g. in refrigeration plants
and refrigerators, and for preventing condensation and bulging in double-glazed
windows by absorbing water and residual solvent in the space between the
panes. Utililation of zeolites for heat storage, in which water is absorbed from
moist air thereby heating up the zeolite and the air and the zeolite is regenerated
(dehydrated) with the help of lower temperature energy, such as waste heat or
solar energy, is under discussion and has been practically evaluated.
In addition to the removal of water, zeolites are industrially utilized for removal of
trace species, such as CO2, S-containing compounds, ammonia, etc. from different
gas mixtures.

Separation processes
Mixtures of n- and iso-alkanes can be separated with the help of calcium-
exchanged zeolite A (molecular sieve effect), since only n-alkanes can penetrate
into the zeolite cavities (known as Molex Process).
In the separation of mixtures of aromatic hydrocarbon isomers, the para-isomer
is generally preferentially absorbed and can be separated on the hasi\ of kinetic
effects. The most well-known example is the recovery of pxylene (Parex process).
The presence of cations i n the cavities of zeolites induce high electrostatic fields,
which can be used in the oxygen enrichment of air.
The nitrogen interacts with the cations (calcium exchanged zeolite A or X and
lithium exchanged zeolite X ) and is thereby more slightly adsorbed than oxygen.
By multistage adsorption-desorption cycles under reduced pressure (PSA
technology) i t is possible to produce up to 95% oxygen, which has widespread
uses.

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Catalysts
Important processes in which zeolites are utilized as catalysts are:
• catalytic cracking of crude oil distillate for fuel manufacture, so-called FCC-plants
(Fluid Catalytic Cracking) utilizing zeolite-containing catalysts and even zeolite Y in a
dealuminized or rare earth-exchanged form in a non-zeolite matrix. The catalyst is
utilized in fluidized beds. The activity of the catalyst is determined by the zeolite and
the matrix. H-ZSM-5 is often added to influence the product mix.
• alkylation of aromatic hydrocarbons, production of ethyl benzene, for which H-ZSM-5
is used.
• isomerization of n-paraffins to iso-paraffins for fuel purposes; noble metal-containing
zeolites are utilized, isomerization of xylenes utilizes ZSM 5.
• hydrocracking (conversion of crude oil fractions to petrol in the presence of
hydrogen).
• dewaxing, removal or decomposition of long-chain paraffins from crude oil fractions

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