PES Lecture 3

Raw Materials 1
Catalysts, Solvents, Oils
 Contents of Lecture
• Introduction
• Catalysts
• Diluents and solvents: - Petroleum based
hydrocarbon solvents, Acetone, Methanol, Ethanol,
Isopropanol, Benzene, Toluene, Xylene, n- Butanol,
Cyclohexanol, Cyclohexanone, MEK, MIBK, Di-acetone
alcohol, Isophorone, Ethyl acetate, Isopropyl acetate
• Oils
Introduction
 Polymer Engineering and Science
• This subject consists of two major
divisions: -
• Polymer Manufacturing
• Polymer processing or making the final
product from raw polymer.
 Polymer Manufacturing
• This involves catalysts, solvents or
diluents and monomers.
• Reactor design involves kinetics and other
engineering operations such as mixing,
fluid mechanics, heat transfer, material of
construction, process control etc.
 Polymer Processing
• This involves selection of material for a
given application, compounding of
additives and other ingredients and a
proper processing technique such as
extrusion, molding, calendaring etc.
• Polymer properties and product design
influence the selection of process.
• Decorative processes also play a role.
Catalysts
 Catalysts

• Two types of catalysts are used: -

Homogeneous and heterogeneous.
• Acid catalyst in ester formation can be
considered as an example of homogeneous
catalyst.
• In most cases the catalyst is heterogeneous.
• Heterogeneous catalyst is prepared in a very
careful way. The shape, size and size
distribution play an important role. The porous
catalyst have different characteristics as
compared to non porous catalysts.
• The surface area offered by catalyst is one of
the most important criterion of catalyst.
• Catalysts are many times deposited on
suitable inert support with desired size, shape
and functional groups.
• In polymerization process, Ziegler-Natta
catalysts have played a major role.
• These catalysts made it possible to make
Linear polyethylenes namely HDPE (High
Density Poly Ethylene) and LLDPE (Linear
Low Density Poly Ethylene) at lower
temperatures and pressures as compared
to those employed for the manufacture of
LDPE (Low Density Poly Ethylene) which
is branched.
• Ziegler Natta Catalysts
• These are made from salts of multivalent
metal elements such as Titanium,
Vanadium or Chromium.
• The catalysts are not porous and hence
the smaller size catalyst particles are
used.
• New generation catalysts are made by
depositing the titanium on active support
like Magnesium hydroxide.
• Ziegler Natta catalysts made the
manufacture of isotactic polypropylene
possible.
• Another type of catalysts are Metallocene
type.
• These two type of catalysts help to control
the stereo regularity and the molecular
weight distribution of PP and PE.
• The action of these two catalysts would be
discussed later in the manufacture of PP
and PE.
Solvents and Diluents
 Solvents and Diluents
• Solvents or diluents are used during
manufacturing of polymers.
• They may also be part of final formulations of
paints, inks or adhesives.
• The solubility of monomer, polymer, the reaction
conditions and health issues influence the
choice of solvents.
• Recovery of solvent during the manufacture of
polymer is very important factor in selecting the
solvent.
• Solvents dissolve the polymer / monomer
while diluents may only suspend the
polymer and reduce the viscosity of
medium.
• Viscosity of solution increases as the
polymer concentration increases or at a
given concentration it increases if
molecular weight is higher.
• In good solvents, the solubility of polymers
is better and the viscosity is also slightly
less.
• When ‘good’ solvents are used, viscosity
rise is minimal. However, the removal of
solvent by evaporation or by drying at
room temperature becomes difficult.
• It is a common practice to use mixture of
solvents to suit the needs.
• The vapor pressure of solvent and its
boiling point decide the use in a given
formulation.
• Some of the materials like benzene,
toluene or xylene are solvents as well as
starting materials for other monomers or
chemicals.
• Most hydrocarbon solvents are separated
during crude refining and are a mixture of
materials over a boiling point range.
• Some polymers precipitate if the molecular
weight increases beyond certain limit. The
solution polymerization can yield a control
over the molecular weight of a polymer
during the manufacturing.
• Low boiling white petroleum distillate
These are mixture of hydrocarbons
obtained as low boiling distillates. The
aromatic content of different grades can
change. The difference in the boiling
points of extreme constituents may not
differ by more than 20 – 25 0C.
• White Spirit is a traditionally used term.
The aromatic contents differ from 1 to 20
%. It is fast evaporating solvent used in
screen printing inks as well as a cleaning
solvent.
• CAS registry numbers for white spirit:
• [8052-41-3] (standard solvent)
[64742-82-1] (white spirit type 1)
[64741-92-0] (white spirit type 2)
[64742-48-9] (white spirit type 3)
[64742-88-7] (white spirit
type 0)
• Paraffin Oil (Kerosene)
• This is also a mixture obtained during
distillation of crude. Its boiling point range
is higher than that for white spirit. It
dissolves cyclic rubber and ester gum. It is
also used in letter press inks.
• The CAS registry number for kerosene is
[8008 – 20 – 6]
• High boiling petroleum distillate: - For
this solvent category, boiling point is in the
range of 250 0C. The aromatic contents
are in the range of 25 %. It dissolves ester
gums, rosins, phenolics etc.
• Naphthenic solvents: - The solvent action of
petroleum distillates is governed by its aromatic
contents which can impart some toxicity.
• Controlled hydrogenation of such distillates
yields more powerful solvents labeled as
naphthenic solvents which are low on the toxicity
of sulfur and olefinic contents.
• The solvents of this type are used in inks used
for printing on food wrappers due to lower
toxicity.
• CAS Registry Number is [64741 – 97 – 5]
• White spirit or kerosene etc are mixture of
many compounds. Many solvents are pure
chemicals. Some of these are discussed
now.
• Acetone: - O=CCH3CH3
• This is a powerful solvent. Its properties are
given below.
• CAS registry No [67 – 64 – 1]
• Chemical formula CH3COCH3
• Formula weight 58
• Boiling point 56.1 C
• Freezing point - 94.6 C
• Solubility soluble in water, ether,
alcohols and esters
• Manufacturing process for Acetone:
• Most of acetone is produced as a co product in
the manufacturing of phenol from cumene.
• Benzene, C6H6, is alkylated to cumene, C6H5CH
(CH3)2, which is oxidized to cumene hydro
peroxide, C6H5COOH(CH3)2 which is then
cleaved into phenol, C6H5OH, and acetone,
CH3COCH3. Details of this process are given
under phenol as a monomer.
 Hydrogenation H2

α Methyl Styrene
Acid
Cumene for Recycle

Cumene Acetone
Cleavage of cumene
Air Reactor Concentration Wash Distillation Phenol
hydroperoxide

Tar

Block diagram of cumene process for phenol (and

acetone) production
• Acetone … continued

• It can also be manufactured by catalytic

dehydrogenation of isopropyl alcohol.
• This reaction is endothermic and heat is
supplied by heating the reactants around
350 C.
• Catalyst is copper, silver, platinum or
sulfides of transition metals.
• The hydrogen is used as source of energy
or in other reactions.
• Acetone … continued

• The reaction products are cooled to

separate non condensable gasses and
acetone is purified by distillation.

• CH3CHOHCH3 → CH3COCH3 + H2
• Methanol, (Methyl Alcohol)
• The properties of methanol are given
below.
• CAS Registry NO [67 – 56 – 1]
• Chemical FormulaCH3OH
• Formula weight 32
• Boiling Point 64.70 C
• Freezing point - 97.10 C
• Solubility Soluble in water,
alcohols and esters
• Methanol … continued

• Methyl alcohol or methanol is a one of the largest

volume produced chemicals.
• It is used to be called as wood alcohol in earlier days
since it was produced by destructive distillation or wood.
• Methanol is a colorless liquid with boiling point of 64.7oc.
It has a density of 0.787 gm/cm3 and viscosity of 0.54
centipoises, at 25oc.
• Methanol … continued

• Methanol is one of the important solvents.

• It is also a chemical used in the manufacture of
many useful solvents / petrochemicals such as
Methyl tertiary butyl ether, MTBE – a fuel
additive, Formaldehyde, Methyl esters (Methyl
acrylates etc), Methyl amines etc.
• It also acts as antifreeze in natural gas
pipelines.
Patent Survey of Representative Types of Copper-Based Methanol Synthesis Catalysts
Sr. No. Company Catalyst System Typical Atomic Ratios
1 Lurgi Cu-Zn-V 61 : 30 : 9
Cu-Mn-V 48 : 30 : 22
2 ICI Cu-Zn-Al 61 : 30 : 9
Cu-Zn-Al 64 : 23 : 13
3 Haldor Topsoe Cu-Zn-Cr 37 : 15 : 48
4 DuPont Cu-Zn-Al 50 : 19 :31
5 BASF Cu-Zn-Al 32 : 42 : 26
Cu-Zn-Al-Cr-Mn 38 : 38 : 0.4 : 12 : 12
6 Mitsubishi Gas Chemical Cu-Zn-Mp* 55 : 43 : 2
Cu-Zn-Cr 55 : 43 : 2
Cu-Zn-B 61 : 38 : 1
7 Shell Cu-Zn-Ag 61 : 24 : 15
Cu-Zn-RE* 71 : 24 : 5
8 United Catalysts Cu-Zn-Al 62 : 21 : 17
9 Ammonia Casale Cu-Zn-Al-Cr 29 : 47 : 6 : 18

*Mp = Metal Phosphates, M = Li, Cu, Mg, Co, Zn, Mn, Fe 32

*RE = Rare earth oxides
• Manufacturing Process for Methanol:
• Catalytic reforming of methane (natural gas) or
similar feedstock produces methanol. The
feedstock is converted into syn gas (mixture of
carbon monoxide and hydrogen) and then
reformed into methane.
• CO + 2H2 → CH3OH
• CO2 + 3H2 → CH3OH + H2O
• The catalyst is specially designed copper – zinc –
aluminum system. Reaction pressure is ~ 50 to
100 atmospheres and temperature is 220 – 250
C.
 steam
feed
Partial oxidation
Process boiler Carbon recovery
oxygen

Removal of Carbon dioxide CO Shift reaction Sulfur recovery

Heat recovery Steam

Compressor and methanol synthesis

Block diagram for the manufacture of Methanol

• Ethanol, (Ethyl alcohol)
• This has been a well known solvent for more
than 100 years. It is normally mixed with 4 to 5 %
of methanol and is known as denatured spirit. Its
properties are given below. It is used in paints,
inks and cosmetics.
• CAS registry No [64 – 17 – 5]
• Chemical formula CH3CH2OH,
• Formula weight 46
• Boiling point 78.320 C
• Freezing point - 114.10 C
• Solubility soluble in water, other alcohols, esters
& organic solvents
• Manufacturing process for Ethanol:
• Industrially it can be produced from direct
or indirect hydration of ethylene. Indirect
hydration uses sulfuric acid. The reaction
is shown here.
• C2H4 + H2SO4 → CH3CH2OSO3H
• 2C2H4 + H2SO4 → (CH3CH2O)2SO4
• CH3CH2OSO3H + H2O → CH3CH2OH +
H2SO4
• (CH3CH2O)2SO4 + 2H2O → 2CH3CH2OH +
H2SO4
 Waste gases for recovery / disposal

Crude ethanol and

Ethylene Reactor Hydrolyser dilute acid for
recovery

water
Sulfuric acid

Block diagram for the manufacture of ethyl alcohol

• Ethanol … continued
• In direct hydration process, acidic catalyst is
used. Ether and acetaldehyde are produced as
by-products. The reaction is given below:
• C2H4 + H2O → CH3CH2OH
• (This reaction is reversible. In countries where
ethanol from fermentation route is abundantly
available, ethylene is produced from ethanol for
making polyethylene.)
• Fermentation of sugar molasses or starch can
produce ethanol. This route is known for a very
long time. The synthetic route is developed due
to economic considerations
• Isopropyl Alcohol: CHOHCH3CH3
• This is used extensively in inks and cosmetics.
Its properties are given below.
• CAS registry No [67 – 63 – 0]
• Chemical formula CH3CHOHCH3
• Formula weight 60
• Boiling point 82.30 C
• Freezing point - 88.50 C
• Solubility soluble in water, alcohols
and other organic solvents
• Manufacturing processes for Isopropanol:
• Hydration of propylene is the industrial process.
This is similar to the one described for ethanol
from ethylene.
• Indirect hydration:
• 2CH2=CHCH3 + H2SO4 → {(CH3)2CHO}2SO4
• {(CH3)2CHO}2SO4 + H2O → (CH3)=CHOH +
H2SO4
• Direct hydration:
• CH2=CHCH3 + H2O →(CH3)2CHOH
• In another process, acetone is hydrogenated to
isopropyl alcohol.
• (CH3)2CO + H2 → (CH3)2CHOH
 Waste gases for recovery / disposal

Crude isopropanol
Propylene Reactor Hydrolyser and dilute acid for
recovery

water
Sulfuric acid

Block diagram for the manufacture of isopropyl alcohol

• Benzene, Toluene and Xylene:
• These are clubbed together because their
manufacturing process is similar and all
these are aromatic solvents.
• Benzene, Toluene and Xylene (BTX) are
manufactured in refining of crude. No
flow sheet is, therefore, provided.
• Benzene forms azeotropes with many
compounds and hence it is not practical to
distil it directly from the crude.
• It is one of the building blocks for number
of organic chemicals.
• Benzene, Toluene, Xylene … continued

• Until 1940, destructive distillation of coal was the

main source of benzene, toluene and xylene.
Now the main source is crude petroleum.
Catalytic reforming of naphtha or similar
feedstock is the main process where benzene,
toluene and xylenes are formed in different
proportions. The output of these three can be
altered depending upon the demand for a
particular chemical by changing operating
conditions of the reformer accordingly
• Benzene:

• CAS Registry No [71 – 43 – 2]

• Chemical formula C6H6
• Formula weight 78
• Boiling point 80.10 C
• Freezing point 5.50 C
• Solubility Soluble in organic
solvents
• Toluene:

• CAS Registry No [108 – 88 – 7]

• Chemical Formula C6H5CH3

• Formula weight 92
• Boiling point 110.60 C
• Freezing point - 86.70 C
• Solubility Soluble in organic
solvents
• Xylene
• There are three isomers of xylene, namely ortho
xylene, meta xylene and para xylene depending
upon the positions of CH3 groups.
• In ortho two CH3 groups are at 1,2 position, in
meta xylene, two CH3 groups are at 1,3
positions, while that for para it is 1,4.
• The para xylene is also a raw material for the
manufacturing of para terephthalic acid. The
properties of xylene are given here.
• Properties of three isomers are given
below.
• Xylene o-xylene m-xylene p-xylene
• CAS No [95 – 47 -6] [108 – 38 – 7] [106 – 42 – 3]
• Boiling point, 144 139 138
• Freezing point, - 25 - 48 13

• (Boiling and freezing points in 0C)

• The Chemical formula for all isomers is
C6H4(CH3)2
• The formula weight is 106
• They are soluble in organic solvents.
• Butyl alcohol, n- butanol
• CAS Registry Number [71 – 36 – 3]
• Chemical formula CH3(CH2)3OH
• Formula weight 74
• Boiling point 117.70 C
• Freezing point - 89.30 C
• Solubility soluble in alcohol,
organic solvents and
limited quantity in water
• Manufacturing process for n-butanol:

• From propylene, n- butyraldehyde is obtained in

Oxo process. The iso-butyraldehyde is also
produced as a co product and it is separated
from the n – butyraldehyde.
• Vapor phase hydrogenation of n –
butyraldehyde over a catalyst system, of CuO –
ZnO – NiO at temperature around 1950 C and
pressure of 7 atmosphere produces n butanol.
• It can also be produced by fermentation of
molasses using specific microbes.
 Vapor phase Butanol for
n-butarldehyde reactor purification

Hydrogen

Block diagram for the manufacture of butanol

• HEXANE

• This is a very useful solvent/ diluent used

in plastic industry.
• It is inert. It is also used in extraction
processes to recover chemicals, oils etc.
• It is separated from petroleum fractions
and purified by distillation.
• Properties of Hexane are: -

• CAS Registry No [110 – 54 – 3]

• Chemical Formula C6H14
• Formula weight 86
• Boiling Point 69.10 C
• Melting Point - 95.10 C
• Solubility Soluble in organic
solvents
• HEPTANE

• This is a solvent used in polymer industry.

• It is also used in extraction of chemicals,
and oils from seeds.
• It is an inert solvent.
• This is also separated from petroleum
fractions and purified by distillation.
• Properties of Heptane are given below.

• CAS Registry No [142 – 82 – 5]

• Chemical Formula C7H16
• Formula weight 100
• Boiling point 98.40 C
• Freezing point - 90.60 C
• Solubility Soluble in organic
solvents
• Cyclohexanol and
Cyclohexanone

• These are considered together due to

similarity in manufacturing process.
Properties of these two materials are
given here.
• Cyclohexanol
• CAS registry number [108 – 93 0]
• Chemical formula C H OH, (CH ) CHOH
6 11 2 5

• Formula weight 100

• Boiling point 161.10 C
• Freezing point 25.10 C
• Solubility Limited solubility in water:
soluble in organic solvents.
• colorless liquid with odor similar to that of
camphor.
• Cyclohexanone:
• CAS registry number[108 – 94 – 1]
• Chemical formula C6H10O, (CH2)5C=O
• Formula weight 98
• Boiling point 156.70 C
• Freezing point - 47.10 C
• Solubility Similar to cyclohexanol
• liquid having odor similar to that of pepper mint
and acetone.
• Used for manufacture of caprolactam.
• Manufacturing process for
cyclohexanol and cyclohexanone:
• Catalytic air oxidation of cyclohexane
produces a mixture of cyclohexanone
(ketone) and cyclohexanol (alcohol),
known as KA mixture. The two are
separated and purified to obtain
cyclohexanone and cyclohexanol.
• Cyclohexanol can also be produced by
hydrogenation of phenol.
 Cyclohexanol and
Air Oxidation cyclohexanone
reactor (KA mixture)
For separation

Cyclohaxane

Block diagram for the manufacture of

cyclohaxnol and cyclohexanone
 Methyl Ethyl Ketone, MEK
• CAS registry number [78 – 93 – 3]
• Chemical formula CH3 C=OCH3CH2
• Formula weight 72
• Boiling point 79.50 C
• Freezing point - 86.70 C
• Solubility Soluble in organic
solvents
• Manufacturing process for Methyl Ethyl
Ketone, MEK:

• Catalytic dehydrogenation of isobutanol

(sec- butanol) yields MEK.
• CH3CHOHCH2CH3 → CH3C=OCH2CH3 + H2
 Hydrogen to Scrubber

MEK
2 Butanol Reactor Distillation

Heavy
Fractions

Block Diagram for the manufacturing of Methyl Ethyl

Ketone, MEK
• Methyl Isobutyl Ketone: (MIBK)
• CAS Registry Number [108 – 10 – 1]
• Chemical Formula CH2CH(CH3)2C=OCH3
• Formula weight 100
• Boiling point 116.20 C
• Freezing point - 80.30 C
• Solubility Soluble in organic
solvents
• MIBK … continued

• MIBK is another powerful ketonic solvent

used in coating industry.
• It is obtained from vapor phase catalytic
hydrogenation of mesityl oxide which is
obtained from acetone.
Acetone Dehydrating column
Reactor

Alkali Phosphoric acid

Distillation Hydrogenation
Column Mesityl oxide column
column

MIBK
Hydrogen

Block diagram for the manufacture of MIBK

 Diacetone alcohol
• CAS Registry No. [123 – 42 – 2]
• Chemical Formula (CH3)3COHC=OCH3
• Formula weight 117
• Boiling point 164 C
• Freezing point - 47 C
• Solubility Soluble in organic
solvents and water
• This is a powerful solvent used in coating
industry. It is obtained by alkaline
condensation of acetone (Aldol change).
 Neutralization and
Acetone Reactor separation of
diacetone alcohol

Dilute alkali

Block diagram for the manufacture of

diacetone alcohol
 Isophorone
• The properties of this material are
• CAS Registry No. [79 – 59 – 1]
• Chemical Formula C9H14O
• Formula weight 138
• Boiling point 215.2 C
• Freezing point - 8.1 C
• Solubility Soluble in organic
solvents
• Isophorone … continued

• The isophorone is a ketonic solvent.

• It is obtained by alkaline condensation of
acetone.
• This material is a powerful solvent used in
coating industry. CH3 CH3

C CH2

CH2 C
O

C====CH

CH3
Acetone High Pressure
Reactor cool

Alkali Isophoron
Separation e
column

By-products

Block diagram for the manufacture of isophorone

 Ethyl Acetate
• CAS Registry No [141 – 78 – 6]
• Chemical formula C4H8O2
• Formula weight 88
• Boiling point 77.1 C
• Freezing point - 83.6 C
• Solubility Soluble in organic solvents

• It is obtained by the esterification of acetic acid

by ethanol.
• Powerful ester type of solvent used in ink and
paint industry.
 Isopropyl Acetate
• CAS Registry No. [108 – 21 – 4]
• Chemical Formula C5H10 O2
• Formula weight 102
• Boiling point 89 C
• Freezing point - 73 C
• Solubility Soluble in organic solvents
• It is obtained by esterification of isopropyl
acetate. This ester type solvent is used in
the ink industry.
OILS
 OILS
• Oils are used in ink and paint industry more
often. In plastics industry, it may find use as
plasticizers and lubricants. Oils are triglycerides
• CH2COOR1
|
• CHCOOR2
|
• CH2COOR3
where R1, R2 and R3 are long chains consisting
of chain length (C5-C15).
• The hydrocarbon chains may have
unsaturation which provides the active
sites for polymerization. The unsaturation
in oil is expressed in terms of its iodine
value. The higher unsaturation imparts
higher iodine value.
• Generally the drying oils have iodine
value of 140 and above, semi drying oils
between 125 to 140 and that for non
drying it is less than 125.
• Manufacturing of vegetable oils
• Generally oil is produced from seeds or flax by
mechanical expellers and / or by solvent
extraction.
• Oil seeds are dried, crushed and ‘cooked’ at
about 70 to 80 C. Then they are subjected to
hydraulic pressure to separate oil from the seed
(kernel as the case may be). Oil is drained
(filtered) and the cake which is left behind may
be further subjected to solvent extraction.
• The crushed oil seeds may be processed by
screw expeller where the oil seeds are forced
through a conical grating so that oil exudes and
oilcake is extruded from the other end.
• The oil cake can be used as cattle feed or
as a fuel.
• The oil cake can be treated with some
suitable solvent (hexane, heptane, butanol
etc.), to extract remaining oil. In this case,
however, the oil cake is not suitable as
cattle feed.
• The oil may be further modified to monitor
the unsaturation or refined to remove
gums or free fatty acids.
• The oils used in polymer industry (mainly paints
and inks) include linseed oil, tung oil, oiticia oil,
castor oil (dehydrated, hydrogenated), tall oil,
coconut oil, tobacco seed oil, cottonseed oil, rice
bran oil and many more.
• Soya oil is also used in polymer industry.
• If oil is edible, the economic and social issues
compete with each other.
• Some fish oils also are used in polymer industry.
The bad odor is the main issue for their limited
use.
• Cashew Nut Shell Liquid (CNSL)
• CNSL is a monomer obtained as a by product of
cashew industry. It is a naturally occurring
substituted phenolic compound.
• It is a greenish yellow viscous liquid found in the
soft honeycomb of the shell of cashew nut. It is
not oil but it has water repellent properties.
• It can replace phenol in some reactions. CNSL is
used in brake liners as well as in some paints
and polishes. It is also used as insecticide,
fungicide and as an additive in some plastics.
• The cashew nut is attached to the cashew
apple. The cashew apple is used in
making beverage or as a fruit.
• CNSL is abundantly available in many
parts of the world, such as, India, Brazil,
Bangladesh, Tanzania, Kenya, tropical
regions of Africa and South-East and Far-
East Asia.
• The main constituents of CNSL are:
• CNSL is extracted from the nuts by
roasting them and filtering the CNSL. The
shell can be subjected to hot oil bath also
to extract CNSL.
• The roasted shells can be further
subjected to solvent extraction to remove
the remaining CNSL.
• The shell, after removing the CNSL, is
used as fuel.
• The method adapted to extract CNSL
depends mainly on tradition.
• Raw CNSL is heated to decrboxylate it
and therefore anacardic acid is not
present in the commercial CNSL which is
used as a monomer in phenolic resins.
• During heating iodine value is reduced
due to small degree of polymerization.
This enhances the viscosity.
• CNSL is characterized by its viscosity and
iodine value.
• Use of inhibitors such as hydroquonone
controls the loss of iodine value.