PETROCHEMICALS:

C3 Hydrocarbons and Its

Major Derivatives

C3 Hydrocarbons

C3 hydrocarbons comprises of propylene (an olefin) and propane.

Derived from petroleum (crude oil) and natural gas.
Main sources are from oil and gas, because:
they are the least expensive,
most readily available, and
can be processed most easily into the primary petrochemicals.
Consume about 5% of the oil and gas each year to make the
petrochemical products.
Numerous applications - food, clothing, shelter and leisure.
Some synthetics, tailored for particular uses, actually perform better
than products made by nature because of their unique properties.

Important chemical feedstocks

Ethylene and propylene (olefins) are the most important
chemical feedstocks, accounting for 50-60% of all
organic chemicals.
But, due to their relatively high reactivities, only very
limited amounts of olefins exist in natural gas and crude
oil.
Thus, they must be manufactured by cracking
processes.

Major Route
Steam cracking, the major route to propylene.
Its proving incapable of producing sufficient quantities
to meet the growing demand.
So other sources are starting to be used.
For example, upgrading refinery propylene by
purification and catalytic dehydrogenation of propane to
propylene.
- H2
CH3CH2CH3
CH3CH CH2
H2

Where do C3 hydrocarbons are derived

from?
In the USA, the dominant steam cracking
feedstocks are LPG (C3H8 and C4H10) and
NGL (C2H6, LPG, light naphtha).

Where Petrochemicals Originate From?

Primary petrochemicals

Primary Petrochemicals" include: olefins (ethylene, propylene and

butadiene) aromatics (benzene, toluene, and xylenes); and
methanol.

Olefins are unsaturated molecules of carbon (C) and hydrogen (H)

that appear as short chains, of two, three or four carbons in length.

Aromatics contain a six carbon ring structure. The oxygen/hydrogen

(OH) group in methanol denotes that it is an alcohol.

Intermediates and Derivatives

Petrochemical intermediates produced from primary petrochemicals

to form more complicated derivative products.

Petrochemical derivative products can be made in a variety of ways:

directly from primary petrochemicals
through intermediate products which still contain only carbon and
hydrogen and,
through intermediates which incorporate chlorine, nitrogen or
oxygen in the finished derivative.

Propylene

Propylene, like ethylene, is a colourless gas at room temperature.

It is as flammable as LPG (liquefied petroleum gas or propane).
In fact, propylene can be used as a substitute or supplement to
LPG.
The fuel characteristics are nearly indistinguishable. However, the
petrochemicals industry bids propylene away from the fuels market
and gives it a much higher price than LPG.
Propylene is traded commercially in three grades:
Refinery, chemical, polymer grades.
The difference is almost entirely the ratio of propylene to propane in
the stream.

Trading grades

Refinery grade (50-70% propylene)

Chemical grade (90-92%)
Polymer grade is at least (99% propylene)
The remaining percentage is almost all propane in each case.

Refinery grade propylene streams are generally by-products of a

refinerys catalytic cracker, and the propane/propylene ration is
determined by the way the cat cracker is run to make gasoline, not
propylene.
Chemical grade propylene is usually produced in a naphtha or gas
oil cracker. The ratio of propylene and propane is about 92:8 over
most of the operating conditions.
Polymer grade propylene is made by simple fractionation of one of
the less pure propylene streams, refinery or chemical grade. For
applications that require very pure propylene feed.

The logistics of propylene are more conventional than ethylene, but

still expensive. While ethylene is like natural gas, propylene
handling and logistics are almost identical to LPG.
At room temperature, propylene has to be kept in a pressurised
container to keep it from evaporating. It boils at -54F, so cooling it
down to keep it liquid is expensive.
Propylene Properties
Molecular weight
Freezing point
Boiling point
Density at 0C

42.08
-301.5F (-185.3C)
-53.9F (-47.7C)
0.51

Propylene is moved in equally large volumes by pipeline, tank car,

and tank truck. Propylene is moved as a liquid, operating at
pressures of about 200 psi.

Stored in the underground caverns.

Because of the lower pressure requirements than ethylene,

cryogenic storage is rarely used. Storage in the form of steel
spheres (typically 5-10 million pounds) and cylinder or bullets (200500 thousand pounds) are prevalent.

 Unlike ethylene, more propylene has always been produced that has been
needed for the chemical industry. The situation goes back to the advent of
thermal cracking units in refineries in the early part of the 20 th century.
By WWII, with cat cracking units generating larger volumes of by-product
propylene, chemists had been challenged sufficiently to develop both
petrochemical applications and refinery uses for propylene.
As a consequence, large amount of propylene used in the manufacture of
gasoline i.e. alkylation process, in which a high octane C7 HC is made by
reacting propylene with isobutane in the presence of sulfuric of HF acid.
The product is called propylene alkylate and has an octane number of
about 96, so it is a good gasoline blending component.

Propylene Derivatives

Polypropylene
Propylene oxide
Propylene glycol
Isopropyl alcohol
Acetone
Cumene
Oxo alcohols
Acrylic acids
Acrylonitrile

Applications
Consumer products :
Carpets, rope, clothing, plastics in automobiles, appliances, toys,
rubbing alcohol, paints, and epoxy glue.

Polypropylene
Propylene monomer

Properties of Propylene Monomer

Molecular weight

42

Melting point

-185C

Boiling point

-49C

Chemical and Physical Properties

Most commercial polypropylene is isotactic. It has an intermediate level of
crystallinity between that of low density polyethylene (LDPE) and high density
polyethylene (HDPE).

Isotactic
Syndiotactic
PP is normally tough and flexible, especially when copolymerised with
ethylene . This allows polypropylene to be used as an engineering plastic.
It is economical, and can be made translucent when uncolored but is not as
readily made transparent as polystyrene, acrylic or certain other plastics.

Possible Forms

Propylene exist in 3 possible forms:

Melting point
Molecular weight
Density, g/cm3
Crystallinity

Isotactic

Syndiotactic

Atactic

170

135

~500,000

~300,000

Very low

0.91

0.88

Crystalline

Crystalline

Amorphous

Compared to PE, isotactic PP is harder, stronger, has a lower density

(0.91 vs 0.95g/cm3), and higher melting point (170 vs 140C),
is more transparent, and has a higher resistance to chemicals and moisture .

Timeline of Olefin Polymerization

1933- Fawcett and Gibson of Imperial Chemical Incorporated (ICI)

converted ethylene to a high molecular weight polymer (ethylene in
benzaldehyde at high pressure.)
1939- 1955- the first commercial high pressure polyethylene plant is
in operation.
1953- Ziegler, Phillips Petroleum Co., Standard Oil Co., discovered
methods to circumvent the need for high pressure.
1955- The first plant using the Ziegler process came in stream
("came in stream" may be jargon for "it began to operate.")
1957- Phillips and Standard Oil began production of olefins.
Polypropylene was first polymerized on March 11 1954 by Giulio
Natta.

Synthesis of Polypropylene

Polypropylene (PP) is prepared from propylene.

The production of polypropylene from propylene is through ZieglerNatta process.
H H
C C
H CH3

H H
C C
H CH3

propylene

polypropylene

Propylene is cheaper than ethylene because of its stability factor.

Free radical growth in ethylene

Initiation

Propagation

Not through free radical process!

because of the extensive transfer of hydrogens to the propagating

centers which results in a resonance stabilized alkyl radical which
has little tendency to react with another monomer molecule.

Useful polypropylene cannot be made by radical polymerization due

to the higher reactivity of the allylic hydrogen (leading to
dimerization) during polymerization.

If use that process, methyl groups would arranged randomly

producing atactic PP. The lack of long-range order prevents any
crystallinity in such a material, thus giving an amorphous material
with very little strength and only specialized qualities suitable for
niche end uses.

Free radical chain growth in propylene

Synthesis of Polypropylene
Made entirely by low pressure processes at 40-80C
using complex coordination catalysts, such as ZieglerNatta or metallocenes.
A Ziegler-Natta catalyst is able to limit incoming monomers
to a specific orientation, only adding them to the polymer
chain if they face the right direction.
With the methyl group consistently on one side, such
molecules tend to coil into a helical shape that then line up
next to one another to form the crystals that give commercial
polypropylene many of its desirable properties.

Synthesis through catalytic route

Possible configurations of
polypropylene

Important link between the structure of polypropylene and its properties

is tacticity. The relative orientation of each methyl (-CH 3) group relative
to the methyl groups on neighboring monomers has a strong effect on
the finished polymer's ability to form crystals.
Its because each methyl group takes up space and constrains
backbone bending.

Applications

Include the plastic bottle industry (plastic parts) and reusable

containers of various types, packaging, textiles (e.g. ropes, Under
Armour), thermal underwear and carpets), stationery, laboratory
equipment, loudspeakers, automotive components, and polymer
banknotes.
In 2007, the global market for polypropylene had a volume of 45,1
million tons which led to a turnover of about 65 billion US $ (47,4
billion ).

Propylene Oxide
O

CH2 CH2

CH2 CH2 CH3

Ethylene oxide

Propylene oxide

The chemical structure of propylene oxide (PO) differs from EO by the

methyl group. The methyl group in PO increases the reactivity of the
molecule in an adverse way.
It is a chiral compound due to the presence of an asymmetrical carbon
atom in the oxirane cycle. Thus, industrial propylene oxide is a racemic
mixture.

Propylene Oxide Properties

Molecular weight
Freezing point
Boiling point
Specific gravity
Weight per gallon

58.08
-155.2F (104.0C)
93.6F (34.2
0.826 (heavier than water)
6.92 lbs./gal.

PO is a low boiling point, flammable liquid, readily soluble

in water and the more common organic solvents, such as alcohol, ether,
and aliphatic and aromatic hydrocarbons.
Commercial sales involve only technical grade (about 98%).
Bulk movements require a hazardous material shipping label.
Standard transport equipment (trucks, tank cars, and barges) can be used.

History of Propylene Oxide Production

Prior to the late 1970s, almost all PO was produced using the
chlorohydrin route, much of it in the former EO plants.
But it was energy intensive, (the same problem with EO process)
by-product yield too high, and the chlorine waste product was
disposal expense. As a consequence, newer technology emerged.
In the 1980s, the indirect oxidation route evolved.
It involves the oxidation of a hydrocarbon to form a hydroperoxide
that is then reacted with propylene to form PO and an alcohol coproduct. The market value of the alcohol assists materially in
justifying the economics of this alternate route.

The chlorohydrin route

The chlorohydrin route takes two steps.

It is a reaction of propylene with hypochlorous acid (HO-Cl) followed

by dehydrochlorination of the propylene chlorohydrin with calcium
hydroxide.

Chlorine atom and hydroxyl group are added to the propylene

double bond, and then a chlorine atom and a hydrogen atom are
removed, leaving the oxygen bonded to two adjacent carbon atoms
to form propylene oxide.

Process
1. Formation of hypochlorous acid
Cl2 + H2O

HOCl + HCl

Hypochlorous
acid

2. Formation of propylene chlorohydrin

OH Cl
CH3CH CH2 + HOCl
CH3CH CH2
Propylene chlorohydrin

3. Dehydrochlorination to propylene oxide

OH Cl
2CH3CH CH2 + Ca(OH)2

O
2CH3CH CH2 + CaCl2 + 2H2O
Propylene oxide

Dilemma of Chlorohydrin Route

The formation of the hypochlorous acid (HOCl) from Cl and H 2O,

and the reaction with propylene all occur simultaneously (see
Figure).
Propylene reacts readily with chlorine to form that unwanted byproducts, propylene dichloride. To limit that, the HOCl and HCl are
kept very dilute.
But as a consequence, the concentration of the propylene leaving
the reactor is very low, only 3-5%! At any higher concentration, a
separate phase or second layer in the reactor would form. It would
preferentially suck up (dissolve) the propylene and chlorine coming
in, leading to runaway dichloride yields.
The process is so energy intensive.

Unreacted propylene is taken off the top of the reactor and cleaned
up for recycling, by bubbling through a dilute NaOH solution thus
removes chlorine and HCl carried along with propylene by
converting them to NaCl and H2O.

The scrubbed propylene is then taken overhead and is ready as

fresh feed or use elsewhere in the plant.

The dilute propylene chlorohydrin stream is mixed with a solution of

water and 10% slaked lime, Ca(OH)2, and pumped to a vessel called
the hydrolyzer. The chlorohydrin rapidly dehydrates to PO.
The reaction is so fast that the PO has to be sprung from the mixture
before the reaction continues, forming PO. Steam is bubbled through
the reactor helping to flash (vaporise) the PO out of the reaction
zone.
The vapour from the hydrolyzer contains not only water and PO, but
also propylene dichloride and by-products. Fractionation columns are
used to purify the PO to a 99% technical grade.

The indirect oxidation route

This indirect oxidation route takes two steps.

In the first, a HC such as isobutane or ethylbenzene, is oxidised.

The source of the oxygen is air.

The reaction takes place just by mixing the ingredients and heating
them to 250-300F at 50 psi, producing a hydroperoxide.

In the second step, the oxidised HC reacts with propylene in a liquid

phase and in the presence of a metal catalyst at 175-225F and 550
psi to produce PO yields of better than 90%.

Indirect oxidation route to PO (and TBA)

Isobutane
Air (O2)

Oxidation
Isobutane recycle
Propylene recycle

Propylene

Tertiary butyl
hydroperoxide

Epoxidation

Separation
By-products
Propylene oxide
Tertiary butyl alcohol

Reaction sequence
1. Formation of hydroperoxide (oxidation of isobutane)
CH3CHCH3 + O2
CH3
Isobutane

OOH
CH3CCH3
CH3
Tertiary butyl
hydroperoxide

2. Epoxidation of propylene (reaction with propylene)

OOH
CH3CCH3 + CH2 CHCH3
CH3
Tertiary butyl
hydroperoxide

Propylene

O
CH2

OH
CHCH3 + CH3CCH3
CH3

Propylene oxide

Tertiary butyl alcohol

Uses
Between 60 and 70% of all propylene oxide is consumed making
polyether polyols for use in making polyurethane plastics.
Propylene oxide is also used in the production of propylene glycol (using
about 20% of propylene oxide), polypropylene glycols, propylene glycols
ethers and propylene carbonate.
The United States Food & Drug Administration has approved its use to
pasteurize raw almonds beginning on September 1, 2007 in response to
several incidences of contamination by salmonella in commercial
orchards.
It was once used as a racing fuel, but that usage is now prohibited
under the US NHRA rules for safety reasons.

Propylene Glycol
OH OH
CH3CH CH2
Propylene glycol

Propylene glycol is the preferred diol because it forms polyesters

which are compatible with styrene and which show little tendency to
crystallize. It is readily available at low cost.

Propylene Glycol Properties

Molecular weight
Freezing point
Boiling point
Specific gravity
Weight per gallon

76.11
76.0F (-60.0C)
361.1F (183.7C)
1.0381 (heavier than water)
8.72 lbs./gal.

Propylene glycol is available in three grades:

NF (99.99%),
Technical (99%), and
Industrial (95%)
NF = National Formulary

Preparation of PG
PG can be prepared from the hydration of propylene oxide.
O
CH3CH CH2 + H2O
Propylene oxide

H+

OH OH
CH3CH CH2
Propylene glycol

Carried out at about 150F, in the presence of sulfuric acid will open up
the epoxide ring. Water provides the hydroxyl groups to form
propylene glycol.
With plenty of excess water, high yields of propylene glycol are achieved.

Uses

Polyester resins use up about 60% of the propylene glycol (and

most of the dipropylene glycol) manufactured.

The remainder is used as a tobacco and cosmetic humectants

(a chemical that keeps moisture around), automotive antifreeze and
brake fluid ingredients, food additive, and plasticizers for various
resins, and making nonionic detergents and coatings. Propylene
glycol is an excellent solvent.

It is nontoxic, nonflammable and even fit for human consumption. It

is colourless, odourless, sweet-tasting liquid, completely miscible or
soluble in water.

Isopropyl Alcohol

Isopropyl alcohol also known as 2-propanol, iso, isopro, isoprop,

rubbing alcohol, or the abbreviation IPA is a common name for
isopropanol, C3H7OH.
It is the simplest example of a secondary alcohol,
where the alcohol carbon is attached to two other
carbons. It is an isomer of propanol.

OH
CH
H3C
CH3

Characteristic

IPA is a colourless, flammable liquid with that characteristic (strong),

rubbing alcohol odour.

Its soluble in water in all proportions, as well as most organic

solvents.
Isopropyl Alcohol Properties
Molecular weight
Boiling point
Freezing point
Specific gravity
Weight per gallon

60.10
180.5F (82.5C)
-129.1F (-89.5C)
0.785 (lighter than water)
6.55 lbs./gal.

It is commercially available:
Technical grade (91%)
Chemical grade (98%)
Absolute grade (99+%)
Shipments by rail, truck, drum, etc. are routine, except that the
flammability requires hazardous materials warning.

Uses
In 1980, more than 50% of the IPA produced was used to make acetone
(diethyl ketone). By the year 2000, the percent was down to less than 6%.
The cumene plants that co-produce phenol and acetone had almost entirely
replaced the IPA-to-acetone route, eliminating the need for IPA feed.
Now, IPA is used primarily as a coating and processing solvent in paints,
electronic applications, synthetic resins, personal care products, and
cosmetics.
It is also used as a chemical intermediate for isopropyl esters, isopropyl
amines, methyl isobutyl ketone, diisobutyl ketone, and hydrogen peroxide
production.
And of course, IPA is used as rubbing alcohol (cleaning electronic devices
(CD, magnetic tape), because of its innocous nontoxic odour, its low boilong
(vaporization) temperature, and moderate heat of vaporization. It dries
rapidly but wont give you frostbite like liquid butane might.