HALDI

A
INSTIT
UTE
OF
TECHN
OLOGY FEASIBILITY
ANALYSIS
ON
ANILINE FROM NITROBENZENE

Submitted By

NAME ROLL NO.

Nandani Rani 14/CH/25

Neha Mandhare 14/CH/26
Parul Sarraf 14/CH/28
Prabhat Tiwari 14/CH/29
Prashant Kumar 14/CH/30

1.1. INTRODUCTION

Feasibility study is an assessment of the practicality of a proposed project or system. It deals

with the strengths and weaknesses of an existing , opportunities and threats present in the
 environment, the resources required to carry out throughout the plant. In its simplest terms, it is an
analysis of how successfully a project can be completed, accounting for factors that affect it such as
legal, technological, economical and scheduling factors. Project managers use feasibility studies to
determine potential positive and negative outcomes of a project before investing a considerable
amount of time and money into it.

Aniline, also known as amino benzene or benzenamine, is an aromatic amine

with the formula C6H5NH2. It is mainly used as a raw material in the production of
methylene diphenyl di-isocyanate (MDI), an intermediate in polyurethane
manufacture. Aniline is also used as an intermediate for dyes and pigments, explosives,

Table1.1: MSDS Datasheet for Aniline

Physical state and appearance Liquid
Odour Aromatic, Amine like
Taste Burning
Molecular weight 93.13 g/mole
Colour Colourless
pH ( 1% solution/water ) Basic
Boiling Point 184.1 0C (363.4 0F)
Melting Point - 6 0C (21.2 0F)
Critical temperature 425.6 0C (798.1 0F)
Specific Gravity 1.0216 (Water = 1)
Vapor Pressure 0.1 kPa (@ 200C)
Vapor Density 3.22 (Air = 1)
Volatility Not Available
Odour Threshold 2.4 ppm
Water/Oil Dist. Coeff. The product is more soluble in oil, log(oil/water) = 0.9
Ionicity (in water) Not available

Dispersion properties See solubility in water, methanol, diethyl ether

Solubility Soluble in cold water, hot water, methanol, diethyl ether

agricultural chemicals and pharmaceuticals. So, the production of aniline is very much important.
There are many ways to produces Aniline but here we have discussed about Aniline from
Hydrogenation of Aniline. Hydrogenation of nitro-compounds was studied at lab scale to understand
the process.

Hydrogenation of nitro-compounds was studied at lab scale to understand the process.

Catalytic hydrogenation of aromatic nitro compounds is an industrially important process for the
introduction of amino functionality into pharmaceutical and agrochemical intermediates and in the

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 polyurethane chemistry. Aromatic nitro compounds are hydrogenated very easily, and hydrogenations
have been carried out under a wide range of conditions including the vapor phase. They are known to
be potentially hazardous reactions, especially because the hydroxylamine intermediates formed are
often thermally unstable and can disproportionate with a significant temperature increase causing
large explosions.

1.2. PROCESS DESCRIPTION

The Process involves the hydrogenation of
Table 1.2: Materials required
the nitrobenzene to get aniline. Materials
required for this process is shown.
Substrate Nitrobenzene <10ppm
Nitrobenzene is fed to a vaporizer, where it is thiophene
Gas Hydrogen gas of 99.5%
vaporized in a stream of hydrogen (three times
purity at 350 kN/m3
stoichiometric). The mixture is passed into a Catalyst Cu on silica gel
uidized bed reactor containing copper on silica Stream 1400 kN/m2, 197 C & 280
gel catalyst, operated at a pressure, above the kN/m2, 1650C
Cooling 240C
bed, of 140 kN/m2 and temperature 50C. The water
contact time, based on supercial velocity at reaction temperature and pressure and based on an
unexpanded bed, is 10 sec. Excess heat of reaction is removed to maintain the temperature at 270C by a
heat transfer uid passing through tubes in the catalyst bed. The exit gases pass through porous stainless-
steel candle lters before leaving the reactor.

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 The reactor gases pass through a condenser/cooler were the temperature is being cooled down, and
the aniline and water are condensed. The excess hydrogen is recycled via a filter (also called as make up
hydrogen), except for a purge to
maintain the impurity level in the
hydrogen to not more than 5% at the
reactor inlet. The crude aniline and
water are let down to atmospheric
pressure and separated in a liquid/
liquid separator, and the crude aniline Fig 1.1: Reaction involved in the process
containing 0.4% unreacted
nitrobenzene and 0.1% cyclo-hexylamine as well as water is distilled to give rened aniline. Two stills are
used, the rst removing water and lower boiling material, and the second removing the higher boiling
material (nitrobenzene) as a mixture with aniline. The vapor from the rst column is condensed, and the
liquid phases separated to obtain an aqueous phase and an organic phase. A purge is taken from the
organic stream to eliminate the cyclo-hexylamine from the system, and the remainder of the organic
stream is recycled. The cyclo-hexylamine content of the purge is held to not greater than 3% to avoid
difculty in phase separation. In the second column, 8% of the feed is withdrawn as bottoms product.
The purge and the higher boiling mixture are sent away from the plant, and the recovered aniline
returned to the crude aniline storage tank. The aniline recovery efciency in the purge unit is 87.5%,
and a continuous stream of high-purity aniline may be assumed throughout the process.
The aqueous streams from the separators (amine-water) are combined and steam stripped to
recover the aniline, the stripped water (containing not more than 30 ppm aniline and 20 ppm cyclo-
hexylamine) being discharged to drain.
Regeneration of the catalyst is accomplished in place using air at 250350 C to burn off organic
deposits. Regeneration is a lengthy process and generally requires 24 hours, including purging
periods.
The overall yield of aniline is 98% theory from nitrobenzene; i.e., from 100 moles of
nitrobenzene delivered to the plant, 98 moles of aniline pass to nal product storage.

1.3. FLOWSHEET

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1.4. OTHER

PROCESS
AVAILABLE
Other process

Fig 1.2: Aniline production process: hydrogenation of nitrobenzene. Stream (1) nitrobenzene, (2)
hydrogen feed, (3) reactor product gases, (4) condensed materials, (5) non- condensed
materials, (6) crude aniline, (7) aqueous phase, (8) overheads, (9) bottom streams, (10)
overheads containing aniline product and (11) bottoms containing tars
available for the manufacture of aniline is discussed below
Aniline from Ammonolysis of chlorobenzene or phenol
o This process was developed by Halcon[2] in 1982, using a fixed bed catalyst, is
operated by Mitsui Petrochemical/Japan and Aristech/USA.

Aniline from benzene and ammonia reaction -

o Du Pont[3] in 1977 has developed an interesting new manufacturing process for
aniline. Benzene and ammonia are reacted with a NiO/Ni catalyst containing
promoters including zirconium oxide at 350C & 300 bar to give a 97% selectivity to
aniline with a benzene conversion of 13%.

1.5. PROPERTIES OF RAW MATERIALS

Raw materials used in the process are nitrobenzene and hydrogen.

NITROBENZENE

o Nitrobenzene is an aromatic amine with the chemical formula C6H5NO2.

o It is a pale yellow oily liquid.

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o Nitrobenzene is soluble in about 500 parts water and freely soluble in alcohol, benzene, ether,
acetone, and oils.
o It is also combustible with steam.
o It possesses an almond like odour.
o It freezes to give greenish yellow crystals.
o In the laboratory, it is occasionally used as a solvent, especially for electrophilic reagents.
o Nitrobenzene production is highly exothermic in nature so it is one of the most dangerous process
conducted in chemical industry.

PHYSICAL PROPERTIES OF NITROBENZENE

Table 1.3: Physical Properties of Nitrobenzene

Molecular Weight 123.11
Boiling Point 210 - 211 oC
Melting Point 6 oC
Flash Point 88 oC (closed cup)
Vapor Density 4.3 (air = 1)
Vapor Pressure 1 mm Hg at 44.4 oC
Density/Specific Gravity 1.205 at 15/4 oC (water = 1)
Log Octanol/Water Partition Coefficient 1.85
Henry's Law Constant 2.44 x 105 atm-m3/mole
Conversion Factor 1 ppm = 5.04 mg/m3

HYDROGEN

At standard temperature and pressure, hydrogen is a odorless, colorless, tasteless, non-

toxic, nonmetallic and highly combustible diatomic gas with the molecular formula H2.
Most of the hydrogen on Earth present in molecular forms such as water or organic compounds.
Hydrogen readily forms covalent compounds with most non-metallic elements.
Hydrogen plays a particularly important role in acidbase reactions because most of the acid-
base reactions involve the exchange of protons between soluble molecules.
It has two distinct oxidation states, (+1, -1), which make it able to act as an oxidizing and a
reducing agent both.
It is the lightest gas, being about 1/14 as dense as air.
Hydrogen easily reacts (burns) with oxygen at a wide range of mixing ratios and forms water.
Due to this it is possible to use hydrogen as an energy medium.because

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 PHYSICAL PROPERTIES OF HYDROGEN

Table 1.4: Pysical Properties of Hydrogen

Molecular Weight 2.0154 NA
Boiling Point -252.87 oC NA
o
Melting Point -259.14 C 123.11 0C
Enthalpy of -286 kJ/mol
210 211 0C
combustion
Bond energy 435.99 kJ/mol
3
6 0C
Solubility in water 0.0214 cm /g
Density 0.08988 g/L 88 0C (closed cup)

1.6. PROPERTIES OF PRODUCT

Properties of aniline is given below -
o Aniline is colorless, oily liquid which darkens on exposure in air and light
o It possesses odour of rotten fish
o It is slightly soluble in water because they form hydrogen bond with water molecules
o It ignites readily burning with smoky flame characteristic of aromatic compounds
o It is aromatic amine which is slightly weaker base than aliphatic amines and hence
reacts with strong acid to form anilinium (phenyl ammonium) ion i.e.C 6H5-NH3+.
o It also combines with acids to form salts and is combustible.

It is miscible with alcohol, benzene, chloroform, carbon tetrachloride, acetone and most organic
solvent.

PHYSICAL PROPERTIES OF ANILINE:

Table 1.5: Properties of Product

Molecular Weight 93.12
Boiling Point 184 186 oC
Melting Point -6.3 oC (solidifies)
Flash Point 76 oC (169 oF) closed cup
Vapor Density 3.22 (air = 1)
Density/Specific Gravity 1.022 at 20/20 oC (water = 1)
Vapor Pressure 0.489 mm Hg at 25 oC
Log Octanol/Water Partition Coefficient 0.90
Water Solubility 36,070 mg/L at 25 oC

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 Henry's Law Constant 0.136 atm-m3/mole at pH 7.3
Conversion Factor 1 ppm = 3.8 mg/m3

1.7. PRECAUTIONS

Persons considering the use of Aniline should be aware of its hazards and dangers and should
take necessary steps to ensure safe handling.

SAFETY:

Nitrobenzene is highly toxic [Threshold Limit Value 5mg/m3 (The threshold limit value (TLV) of
a chemical substance is a level at which a worker can be exposed day after day for a working lifetime
without adverse effects.] and readily absorbed through the skin.

Prolonged exposure may cause serious damage to the central nervous system (CNS), impair
vision, cause liver or kidney damage, anemia and lung irritation. Inhalation of vapors may induce
headache, nausea, fatigue, dizziness, weakness in the arms and legs, and in rare cases may be fatal.
The oil is readily absorbed through the skin and sue to this it may increase heart rate, cause
convulsions or rarely death. Ingestion may similarly cause headaches, nausea, dizziness, vomiting and
gastrointestinal irritation, loss of sensation/use in limbs and causes internal bleeding.

It is flammable when exposed to heat or flame. Contact with strong oxidizers may cause fire or
explosion. Furthermore, this material is expected to be very toxic to terrestrial and aquatic life.

To avoid the happening of such bad accident, it is necessary to investigate the thermal behavior of
nitrobenzene and aniline. The thermal runaway of such materials is closely related with this
explosion. Therefore, based on the reports made of the above accident, nitrobenzene mixture with
acids and aniline were selected for the study of thermal explosion in theirs manufacture

ENGINEERING CONTROLS:

Equipment DesignThe operation should be carried out in a perfectly closed type system. Equipment
to handle nitrobenzene should be in the open area or well ventilated area due to its toxic nature of the
material,

STORAGE AND HANDLING:

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 Location of Storage Tanks Nitrobenzene is commonly stored in a steel tank. Locate storage tanks
away from any area where fire hazard is acute. Bulk storage tanks should be in the open.

Caution to be Taken During Use

Avoid direct contact with skin.
Persons handling it shall wear personal protective equipment, such as, goggles, aprons,
gloves, and rubber sheets.
Workers should be instructed and guided emphasizing the need for handling nitrobenzene in
accordance with approved method.

DISPOSAL:

Waste may be washed away to a sewer after being diluted with a large quantity of water
(approx. 1% slurry).
Care shall be taken to keep any person away from the place where waste materials are buried.
It shall be made certain that there should be no danger of pollution of underground water
sources used as sources of drinking water.
Small quantities of nitrobenzene or waste may be disposed off by burning.

PRECAUTION OF HYDROGEN
Use adequate ventilation.
Store only where temperatures will not exceed 125 F (52 C).
The must be no sources of ignition in areas where Hydrogen is being stored.
When a cylinder is not in use, close the valve protection cap firmly in place.
Secure cylinders upright at the top & bottom.
Wear safety glasses when handling any compressed gas.

1.8. USE OF ANILINE

It is mainly used as a raw material in the production of methylene diphenyl di-isocyanate (MDI),
an intermediate in polyurethane manufacture. Aniline is also used as an intermediate for dyes and
pigments, agricultural chemicals, explosives and pharmaceuticals. Its main use is in the manufacture
of precursors to polyurethane and other industrial chemicals.

In the early 1940s and 1950s, aniline was used with nitric acid or dinitrogen tetroxide as rocket
fuel for small missiles and the Aerobee [ The Aerobee rocket was a small (8 m) rocket. It was
unguided suborbital sounding rocket used for cosmic radiation and high atmospheric research in
the US in the 1950s] rocket.

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 The largest application of aniline is to produce methylene di-aniline & related compounds by
condensation with formaldehyde. Other uses include herbicides (2%), dyes and pigments (2%) and
rubber processing chemicals (9%),. The principal use of aniline in the dye industry is as indigo.

Many chemicals can be made from Aniline, including:

Antioxidants, activators, accelerators, and other chemicals for the rubber industry

Indigo, aceto-acetanilide, and other dyes and pigments for a variety of applications of use.

Diphenylamine for the rubber, petroleum, agricultural, plastics, explosives & chemical
industries.

Various herbicides and fungacides for the agricultural industry

Organic chemicals, pharmaceutical, and other products

1.9. SUMMARY

Aniline is an important chemical used for various purposes with global annual production of
about 10 billion pounds per year and widely used as a starting material. Almost 80% of aniline
consumption in the US is used from the production of PMDI as an intermediate product that is in turn
used in the manufacture of a wide range of variety of commercial polyurethane products. Survey of
the worldwide aniline production gives an estimate about its competitiveness, not only about its
market, but also a variety of available technologies. Despite growth in aniline demand, there has been
relatively limited process technology develpoment. Therefore, an effort to develop more economic
and environmentally friendly technologies for aniline production has been initiated by major aniline
manufacturers and researchers around the world.

This process has distinctive technical and economic features, which allows to rank it among the
best worldwide.

1.10. RECOMMENDATION
It is one of the widely-used process for the manufacturing of aniline.
Precautions and safety should be taken while handling equipments, raw material, etc.
The drainage system of waste material should be done properly as it will hamper the aquatic life.
Suitable cooling system should be provided which is more economic.
Raw materials should be economically cheap and better in quality.

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 Implementation of high technology development

REFERENCE
1. https://www.safety.caltech.edu/documents/57-hydrogen.pdf
2. http://www.chemengonline.com/aniline-production-nitrobenzene-liquid-phase-intratec-solutions/?
printmode=1
3. https://www.mt.com/dam/mt_ext_files/Editorial/Simple/0/app_note_2007_03hydrogenationreacti
on.pdf
4. https://www.researchgate.net/figure/254216716_fig2_FIGURE-3-Aniline-production-process-
hydrogenation-of-nitrobenzene-Stream-1
5. http://www.lookchem.com/Chempedia/Chemical-Technology/Organic-Chemical-
Technology/7791.html
6. https://books.google.co.in/books?
id=6I3_CAAAQBAJ&pg=PA198&lpg=PA198&dq=ammonolysis+of+chlorobenzene+and+phen
ol+was+proposed+by&source=bl&ots=asH1X5Gws_&sig=zrXNESSzVFb_CvCFIJq05z5LiJ8&
hl=en&sa=X&ved=0ahUKEwjUl_6ek8vSAhVEObwKHesmATsQ6AEIKzAE#v=onepage&q=a
mmonolysis%20of%20chlorobenzene%20and%20phenol%20was%20proposed%20by&f=false

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