CASEY LYN L.

PANOGAN
BS- Chemical Engineering 4
MANUFACTURE OF PETROCHEMICAL
Introduction
Natural gas and crude distillates such as naphtha from petroleum refining are used as
feedstock to manufacture a wide variety of petrochemicals that are in turn used in the
manufacture of consumer goods. The basic petrochemicals manufactured by cracking,
reforming, and other processes include olefins (such as ethylene, propylene, butylenes, and
butadiene) and aromatics (such as benzene, toluene, and xylenes). The capacity of naphtha
crackers is generally of the order of 250,000750,000 metric tons per year (tpy) of ethylene
production. Some petrochemical plants also have alcohol and oxo-compound manufacturing
units on site. The base petrochemicals or products derived from them, along with other raw
materials, are converted to a wide range of products. Among them are:
a. Resins and plastics such as low-density polyethylene (LDPE), high-density polyethylene
(HDPE), linear low-density polyethylene (LLDPE), polypropylene, polystyrene, and
b.
c.
d.
e.
f.

polyvinyl chloride (PVC)

Synthetic fibers such as polyester and acrylic
Engineering polymers such as acrylonitrile butadiene styrene (ABS)
Rubbers, including styrene butadiene rubber (SBR) and polybutadiene rubber (PBR)
Solvents
Industrial chemicals, including those used for the manufacture of detergents such as
linear alkyl benzene (LAB) and of coatings, dyestuffs, agrochemicals, pharmaceuticals,
and explosives.

The following are the known petrochemical processes:

1.
2.
3.
4.
5.

Cracking
Steam Reforming
Catalytic Reforming
Alkylation
Hydroformylation

CRACKING
In petroleum geology and chemistry, cracking is the process whereby complex
organic molecules such as kerogens or long chain hydrocarbons are broken down into simpler
molecules such as light hydrocarbons, by the breaking of carbon-carbon bonds in the
precursors. The rate of cracking and the end products are strongly dependent on the
temperature and presence of catalysts. Cracking is the breakdown of a large alkane into
smaller, more useful alkanes and alkenes. Simply put, hydrocarbon cracking is the process of

breaking a long-chain of hydrocarbons into short ones. This process might require high
temperatures and high pressure.
Cracking has the following uses:
It increases the amount of gasoline and other economically important fractions.
It produces alkenes, an important feedstock for chemicals.
A process called thermal catalytic cracking is used to break long chains into shorter
chains which are more useful. High temperature cause bonds to break in the long-chain
alkane. In this process, it involves a temperature of 700-1200 K and a pressure of up to 7000
kPa.
Example:

THERMAL
CRACKING
STEAM REFORMING

Figure 1
Thermal Catalytic Cracking

CATALYTIC

Figure 2
Steam Reforming

Steam

reforming is a method for

producing hydrogen, carbon monoxide, or other useful products from hydrocarbon fuels such
as natural gas. This is achieved in a processing device called a reformer which reacts steam at
high temperature with the fossil fuel. The steam methane reformer is widely used in industry
to make hydrogen. There is also interest in the development of much smaller units based on
similar technology to produce hydrogen as a feedstock for fuel cells. Small-scale steam
reforming units to supply fuel cells are currently the subject of research and development,
typically involving the reforming of methanol, but other fuels are also being considered such
as propane, gasoline, autogas, diesel fuel, and ethanol.

Steam Reformer Process

The process is divided into the generation of a hydrogen rich reformate stream by means of
steam-methane reforming (SMR) and the following hydrogen purification by means of
pressure swing adsorption (PSA).
The process route consists mainly of:
Pre-Treatment of the Feed
The hydrocarbon feedstock is desulphurised using e.g. activated carbon filters,
pressurized and, depending on the reformer design, either preheated and mixed with process

steam or directly injected with the water into the reformer without the need of an external
heat exchanger. The fresh water is first softened and demineralised by an ion-exchange water
conditioning system. One option is high pressure reforming with integrated heat exchangers
and a working pressure of up to 16 bar which reduces the geometric volume of the reformer
vessels and is ideal for a downstream treatment by means of PSA or compression. The other
option is to operate the reformer at low pressures (1.5 bar) with an increased conversion ratio
and compress the reformate prior to purification.
Steam Reforming and CO-Shift Conversion
Methane and steam are converted within the compact reformer furnace at approx. 900
C in the presence of a nickel catalyst to a hydrogen rich reformate stream according to the
following reactions: CH4 + H2O CO + 3 H2 (2) CO + H2O CO2 + H2 .The heat required for
reaction is obtained by the combustion of fuel gas and purge/tail gas from the PSA system.
Following the reforming step the synthesis gas is fed into conversion reactor to produce
additional hydrogen. Heat recovery for steam or feedstock preheating takes place at different
points within the process chain to optimize the energy efficiency of the reformer system
(depending on the reformer design).
Gas Purification PSA-System
Hydrogen purification is achieved by means of pressure swing adsorption (PSA). The
PSA unit consists of four vessels filled with selected adsorbents. The PSA reaches hydrogen
purities higher than 99.999 % by volume and CO impurities of less than 1 vppm (volumetric
part per million) fulfilling the specifications set by the fuel cell bus supplier. Pure hydrogen
from the PSA unit is sent to the hydrogen compressor, while the PSA off-gas from recovering
the adsorbents, called tail gas, is fed to the reformer burner. Depending on the reformer
design, a recuperative burner is used featuring high efficiency and low nitrogen oxide (NOx)
emissions. During normal operation, the burner can be operated solely on the tail gas stream.
CATALYTIC REFORMING
A chemical process used to convert petroleum refinery naphthas distilled from crude
oil (typically having low octane ratings) into high-octane liquid products called reformates,
which are premium blending stocks for high-octane gasoline. The process converts lowoctane linear hydrocarbons (paraffins) into branched alkanes (isoparaffins) and cyclic

naphthenes, which are then partially dehydrogenated to produce high-octane aromatic

hydrocarbons. The dehydrogenation also produces significant amounts of byproduct
hydrogen gas, which is fed into other refinery processes such as hydrocracking. A side
reaction is hydrogenolysis, which produces light hydrocarbons of lower value, such as
methane, ethane, propane and butanes. It is also the conversion of straight chains of alkane
catalytically.
Basic objective of catalytic reforming is:
a. To produce high octave blending stock for motor fuel
b. To produce high value aromatic hydrocarbon such as BTX
BTX (Benzene Toluene Xylene)
Refers to mixtures of benzene, toluene and the three xylene isomers, all of which are
aromatic hydrocarbons.

Figure 3
Catalytic Reforming Process

ALKYLATION
One of the conversion processes used in the petroleum refineries. It is used to convert
isobutane and low-molecular-weight alkenes (primarily a mixture of propene and butene) into
an alkylate, a high octane gasoline component. The process occurs in presence of a strong
acting acid as catalyst. The acid can be either sulfuric acid or hydrofluoric acid (HF).
Depending on the acid used as catalyst the unit takes the name of SAAU (Sulphuric Acid
Alkylation Unit) or HFAU (Hydrofluoric Acid Alkylation Unit).

Figure 4
Alkylation
HYDROFORMYLATION

Also known as oxo synthesis or oxo process, is an important homogeneously

catalyzed industrial process for the production of aldehydes from alkenes. This chemical
reaction entails the addition of a formyl group and a hydrogen atom to a carbon-carbon
double bond. It is important because the resulting aldehydes are easily converted into many
secondary products. For example, the resulting aldehydes are hydrogenated to alcohols that
are converted to plasticizers or detergents.
Figure 5
Hydroformylation
References
Wyszynski, Miroslaw L.; Megaritis, Thanos; Lehrle, Roy S. (2001). Hydrogen from
Exhaust Gas Fuel Reforming: Greener, Leaner and Smoother Engines (PDF) (Technical
report). Future Power Systems Group, The University of Birmingham.
OSHA Technical Manual, Section IV, Chapter 2, Petroleum refining Processes (A
publication of the Occupational Safety and Health Administration)
High-Precision Catalysts: Regioselective Hydroformylation of Internal Alkenes by
Encapsulated Rhodium Complexes Kuil, M.; Soltner, T.; van Leeuwen, P. W. N. M.; Reek, J.
N. H. Journal of the American Chemical Society