CHEMISTRY OF PETROCHEMICAL

PROCESSES
Mohammad Talha Mushir

JILIN CHEMICAL PLANT

EXPLOSIONS

The Jilin Chemical Plant itself was the first major, large scale

chemical industry base to be built in China, producing

chemicals such as benzene, nitrobenzene, and aniline; which are
often used in the production of different plastics.
Nov. 13 2005 Jilin Chemical Plant exploded that killed at least
six people and injured around 70 people.
Nov. 15, 2005 Jilin stopped using water that came from the
Songhua River
Nov. 18, 2005 all water supplies in Jilin were partially
suspended.
Nov. 23, 2005 water supplies in Jilin were eventually restored

MAIN EVENT
Explosions continued throughout the plant for about an hour

and eventually lead to a large scale fire at the plants.

A blockage occurred in the chemical plants processing

nitration tower for the production of benzene. The blockage

and the worker's inability to clear the blockage eventually
lead to an explosion .
The accident site is a nitration unit for aniline equipment.
T-102 tower jammed up and was not handled properly.

 4 days after the explosion the Chinese govt admitted that some

100 tons of chemicals, including benzene, nitrobenzene and

other toxins had made their way into the Songhua River.
The explosion eventually created an 80 km long toxic

chemical slick made up of benzene, nitrobenzene, and aniline.

The blast of the petrochemical plant happened about 350

kilometer away from the China-Russia boundary.

Aromatic hydrocarbons
Benzene, toluene, xylenes (BTX), and ethylbenzene are the

aromatic hydrocarbons with a widespread use as petrochemicals.

They are important precursors for many commercial chemicals

and polymers such as phenol, trinitrotoluene (TNT), nylons, and

plastics.
Aromatic compounds are characterized by having a stable ring

structure due to the overlap of the -orbitals (resonance).

Accordingly, they do not easily add to reagents such as halogens

and acids as do alkenes.

Aromatic

hydrocarbons are susceptible, however,

electrophilic substitution reactions in presence of a catalyst.

to

Aromatic hydrocarbons are generally nonpolar. They are not

soluble in water, but they dissolve in organic solvents such as

hexane, diethyl ether, and carbon tetrachloride.

Extraction of aromatics
Benzene, toluene, xylenes (BTX), and ethylbenzene are obtained

mainly from the catalytic reforming of heavy naphtha. The product

reformate is rich in C6, C7, and C8 aromatics, which could be
extracted by a suitable solvent such as sulfolane or ethylene glycol.

These solvents are characterized by a high affinity for aromatics,

good thermal stability, and rapid phase separation. The Tetra

extraction process by Union Carbide (Figure 2-2) uses tetraethylene
glycol as a solvent.

The feed (reformate), which contains a mixture of aromatics,

paraffins, and naphthenes, after heat exchange with hot raffinate, is

countercurrentIy contacted with an aqueous tetraethylene lycol
solution in the extraction column.

The hot, rich solvent containing BTX aromatics is cooled and

introduced into the top of a stripper column. The aromatics extract

is then purified by extractive distillation and recovered from the
solvent by steam stripping.
Extractive distillation has been reviewed by Gentry and Kumar.

The raffinate (constituted mainly of paraffins, isoparaffins and

cycloparaffins) is washed with water to recover traces of solvent
and then sent to storage.
The solvent is recycled to the extraction tower. The extract, which

is composed of BTX and ethylbenzene, is then fractionated.

Benzene and toluene are recovered separately, and ethylbenzene
and xylenes are obtained as a mixture (C8 aromatics).

Due to the narrow range of the boiling points of C8 aromatics

(Table 2-4), separation by fractional distillation is difficult. A

superfractionation technique is used to segregate ethylbenzene
from the xylene mixture.
Because p-xylene is the most valuable isomer for producing

synthetic fibers, it is usually recovered from the xylene mixture.

Fractional crystallization used to be the method for separating

the isomers, but the yield was only 60%. Currently, industry
uses continuous liquid-phase adsorption separation processes.
The overall yield of p-xylene is increased by incorporating an

isomerization unit to isomerize o- and m-xylenes to p-xylene.

An overall yield of 90% p-xylene could be achieved. Figure 2-

3 is a flow diagram of the Mobil isomerization process. In this

process, partial conversion of ethylbenzene to benzene also
occurs. The catalyst used is shape selective and contains ZSM-5
zeolite.

What is Benzene?
Benzene is clear liquid

solvent made from petroleum.

It used to be used as an all-

round solvent until it was

found to cause cancer. It is
now mostly used to make
other chemicals.
It is highly flammable.
Benzene has a recognizable

odor described as pleasant

and sweet

Benzene molecule

Benzene
Benzene (C6H6) is the simplest aromatic hydrocarbon and by

far the most widely used one.

Before 1940, the main source of benzene and substituted

benzene was coal tar. Currently, it is mainly obtained from

catalytic reforming. Other sources are pyrolysis gasolines and
coal liquids.

 Benzene is an important chemical intermediate and is the

precursor for many commercial chemicals and polymers such as

phenol, styrene for poly-styrenics, and caprolactom for nylon 6.
Benzene evaporates into the air very quickly. Its vapor is heavier
than air and may sink into low-lying areas.
Benzene dissolves only slightly in water and will float on top of
water.

Sources of benzene
Benzene is formed from both natural processes and human

activities.
Natural sources of benzene include volcanoes and forest fires.
Benzene is also a natural part of crude oil, gasoline, and
cigarette smoke.
Some industries use benzene to make other chemicals that are
used to make plastics, resins, and nylon and synthetic fibers.
Benzene is also used to make some types of lubricants, rubbers,
dyes, detergents, drugs, and pesticides.

Exposure to benzene
Outdoor air contains low levels of benzene from tobacco smoke,

gas stations, motor vehicle exhaust, and industrial emissions.

Indoor air generally contains levels of benzene higher than those
in outdoor air. The benzene in indoor air comes from products
that contain benzene such as glues, paints, furniture wax, and
detergents.
The air around hazardous waste sites or gas stations can contain
higher levels of benzene than in other areas.
Benzene leaks from underground storage tanks or from
hazardous waste sites containing benzene can contaminate well
water.
People working in industries that make or use benzene may be
exposed to the highest levels of it.
A major source of benzene exposure is tobacco smoke.

Highest exposures to benzene

Highest exposures occur in the petroleum industry: oilfields,

refineries, pipelines, service stations, etc.
Rubber workers have a very high incidence of AML (Acute
myeloid leukemia).
Tire builders washed tires with Benzene. Vinyl chloride
occurs in high concentrations in rubber compounds.
Vinyl chloride causes brain cancers, liver cancers
(angiosarcoma) and AML

Highest exposures to benzene

Other workers in the plastics industry experience more

exposure to Benzene that leads to death.

Environmental Health Perspectives, Dec. 1996, reported
pilofilm workers had "a significant occurance of acute
myelocytic or acute monocytic Leukemia (AML, AMLL)
diseases. According to the study, AML results when workers
breathe air with 1.0 parts per million of Benzene. This is dose
dependent-the more Benzene, the more the Leukemia.
Plywood and furniture workers have unexpected high exposure
levels.

Mechanism of toxicity
Following exposure, about 10 % of inhaled benzene is

excreted unchanged in the breath.

The remainder is metabolized by hepatic mixed function
oxidize enzymes, found predominantly in the liver, but also in
the bone marrow, which is the target organ of benzene
toxicity.
Benzen induces pancytopenia by disrupting cell production
from the pluripotent stem-cell stage to the functional stage.

Clinical features
Acute poisoning results when benzene
is ingested or inhaled occupationally,
accidentally, or with suicidal or
parasuicidal intent.
Euphoria,
dizziness,
headache,
blurring of vision,
chest tightness,
respiratory depression,
cardiac arrhythmia,
Coma
Direct skin contact with liquid
benzene may produce signs of marked
irritation due to defeating action of the
solvent.

Clinical features
Chronic exposure. The toxic effect of chronic poisoning may

not become apparent for months or years after initial contact

and indeed they may develop after all exposure has ceased.
Anorexia, headache, drowsiness, nervousness, and irritability
are well described.
Anemia (including aplastic anemia), leucopenia,
thrombocytopenia, pancytopenia;
Leukemia (particularly of the myelomonocytic type),
Lymphomas
Chromosomal abnormalities
Cerebral atrophy
A dry, scaly dermatitis may developed on prolonged or repeated
skin exposure to liquid benzene.

Chronic exposure
Men exposed to benzene at

levels close to the permissible

limit are more likely to have
an abnormal number of
chromosomes in their sperm,
researchers report in the
journal Environmental Health
Perspectives.
Known as aneuploidy, this
can adversely impact fertility
and fetal development.

Acute exposure: protective

measures
If the benzene release was outside, move away from the
area where the benzene was released.
If the benzene release was indoors, get out of the
building.
If you think you may have been exposed to benzene,
you should remove your clothing, rapidly wash your
entire body with soap and water.
Quickly take off clothing that may have benzene on it.
Any clothing that has to be pulled over the head should
be cut off the body instead of pulled over the head.

Protective Measures
If your eyes are burning or your vision is blurred, rinse your eyes

with plain water for 10 to 15 minutes.

If you wear contacts, remove them after washing your hands and
put them with the contaminated clothing. Do not put the contacts
back in your eyes (even if they are not disposable contacts).
If you wear eyeglasses, wash them with soap and water. You can
put your eyeglasses back on after you wash them.

Protective Measures
The 8-hour average permissible limit for benzene is one part

per million in the air.

1 ppm

The 15-minute (short-term) limit is 5 parts per million

in the air.

5 ppm

TREATMENT

Following from the contaminated atmosphere,

treatment should be directed towards symptomatic and
supportive measures.
The adequacy of cardiac and respiratory function must
be determined and resuscitation begun if needed.
Patients with altered mental status should immediately
receive I.V. glucose, naloxone and thiamine after blood
is drawn for testing.

TREATMENT
CNS stimulation may require sedation, usually with a

benzodiazepine or barbiturate I.V.

Severe CNS depression require circulatory and ventilatory
support
Endotracheal intubation and rarely tracheotomy may be
necessary.
Corticosteroids are also used .

Medical Monitoring
A medical exam is made available to you if you are exposed

to benzene above 0.5 ppm 30 days or more per year, or above 1

ppm more than 10 days per year.

The medical exam includes a complete physical exam and

blood tests.

The medical exam is made available to you before you start

working around benzene and yearly after that.

Permanent Medical Removal

Permanent medical removal may be required because of the

potential serious health effects of benzene.

Depending on your medical condition, you may not be able to

return to your original position.

If the doctor recommends permanent job removal, we will seek

a job transfer for you.