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Literature survey
Production of Aniline
[by vapor phase catalytic reduction of
nitrobenzene]
Instructed by:
Dr.Faheem
9/23/2012
Table of Content:
# Topic Pages
1 List of Tables 3
2 List of Figures 5
3 Introduction 5
4 History 6
5 World Production and 7-9
Consumption
6 Uses 9
7 Feedstock and product Description 10-20
8 Process Flow Sheet 21-29
9 Comparison flow sheets 30
10 Basic economic analysis 31
11 Conclusion 32
12 Recommended flow sheet 32
13 References 33
2
List of Tables:
Table (1-1)Aniline Global supply and demand7
3
Table (1-22)Alternative #1...30
List of Figures:
Figure (1-1)Structure of Aniline.5
4
Introduction:
5
History:
Aniline was first isolated from the destructive distillation of indigo in 1826
by crystalline. In 1834, Friedrich Rungeisolated a substance from coal tar
which produced a beautiful blue color on treatment with chloride of lime,
which he named kyanol or cyanol.
Developments in medicine
In the late 19th century, aniline emerged as an analgesic drug, its cardiac-
suppressive side effects countered with caffeine.
6
World production& Consumption of Aniline:
* World production:
MDI [methylene diphenyldisocyanate] has been the driving force behind the
recovery of the aniline business since 1982 when the industry had acapacity
utilization rate of less than 50%. By 1996 capacity utilization
hadapproached 95% in some regions.
Thecapacity ofworld production ofanilinein 1999 was found in these
regions: Western Europe - 47% North America -30% and Asia / Pacific -
19%.
million
Year ton/year
1988 1.5
1996 2.2
1996 2.9
2000 2.97
2010 4
Millions of Pounds
7
Year ton/year
1996 142,700
2000 200,000
2004 435,000
2005 620,000
western europe
china
united states
japan
Rep.of korea
Central/Eastern Europe
India
Central/South africa
other
8
nitrobenzene/aniline/MDI units, will balance out moderate growth in
markets such as the Americas.
Year consumption(kt)
1993 100
1999 148.4
2000 177.9
2004 387
2010 1100
Table (1-4)Anilines china consumption capacity4
Uses
Aniline is mainly used as feed stock for the polyurethane industry. The
largest application of aniline is for the preparation of methylene
diphenyldisocyanate(MDI).Other uses include rubber processing chemicals
(9%), herbicides (2%), and dyes and pigments (2%).Many drugs can be
prepared from aniline such as paracetamol(acetaminophen)and used in the
dye industry as a precursor to indigo.
Application %
Isocyanate 85%
Rubber Chemicals 9%
Agricultural Chemicals Pesticides 3%
Dyes & Pigments 2%
Specialty Fibers 1%
Miscellaneous 1%
Table (1-5)Aniline Uses5
9
Feed stock & product description:
Benzene:
Lambda()max 255 nm
Viscosity 0.652 cP at 20 C
Dipole moment 0D
Nitrobenzene:
10
Ammonia:
Molecular
NH3
formula
11
Std enthalpy of
formation 46 kJmol1
fHo298
Standard molar
193 Jmol1K1
entropySo298
Phenol:
12
Hydrogen:
Molecular H2
Phase gas
(0 C, 101.325 kPa)
Density
0.08988 g/L
Liquid density
0.07 (0.0763 solid) gcm3
at (m.p)
Liquid density
0.07099 gcm3
at (b.p)
Heat of
(H2) 0.904 kJmol1
vaporization
13
Water:
Molecular H2O
formula
Refractive 1.3330
index (nD)
14
Nitric Acid:
Molecular
HNO3
formula
15
Sulfuric Acid:
Molecular
H2SO4
formula
16
Iron:
Molecular formula Fe
Liquid density at
6.98 gcm3
m.p.
Heat of
340 kJmol1
vaporization
Molar heat
25.10 Jmol1K1
capacity
17
Hydrochloric acid:
Odor Pungent
Density 1.490 g L1
18
Ferric chloride:
92 g/100 mL (hexahydrate, 20 C)
Solubility in acetone 63 g/100 ml (18 C)
Methanol highly soluble
Ethanol 83 g/100 ml
Diethyl ether highly soluble
Viscosity 40% solution: 12 cP
19
Aniline:
Molecular C6H5NH2
formula
-6.3 C, 267 K, 21 F
Melting point
Solubility in
3.6 g/100 mL at 20C
water
20
Process Flow Sheets:
Process 1;Ammonolysis of Phenol
24
14
17
V-100 P-102
K-100 10
21
16 13
CRV-100 29
9
Amonia 20 24
1 19
7 8 30
2 V-101
E-103
12 34 Aniline
E-100 E-101
MIX-100 T-100 27
phenol 27 18 28
11 26
P-104 E-104
T-101 25 35
31 E-102
28
36
29 T-102
32 33
P-103 E-105
37
Figure (1-3) Process flow sheet of the production of aniline by Ammonolysis of Phenol.
Process description:-
The process is divided into three sections: the feed preparation section, the
reactor section, and the purification section. In the feed preparation section,
The ammonia feed (stream 1) consists of 203 lb-mol/hr liquid ammonia at
90F. The phenol feed (stream 2) supplies 165.8 lb-mol/hr liquid phenol at
110F and atmospheric pressure. The two feed streams are pumped to
increase the pressure before they are mixed with their respective recycle
streams (stream 16 for ammonia and stream 31 for phenol) by using mixer
21
(MIX-102).(Stream 7) is heated in a heat exchanger (E-100) with the reactor
effluent (stream 10). The heat exchanger effluent (Stream 8) is heated to the
required reactor temperature for the reactor inlet (stream 9). The reactor
section includes the adiabatic reactor (CRV-100) that includes a bed Packed
with a silica-alumina catalyst. In the reactor, three reactions occur:
2 NH3<==> 3 H2 + N2
Stream 20 is then sent to a separator (V-100) to separate the water and the
phenol product. Then, the phenol (stream 21) is recycled to the column (T-
22
101) after pressurize it by using (P-102). The aqueous product (stream 24)
from V-100 will be treated. The bottoms stream (stream 25) is the feed to
the next column (T-102). The main component in the distillate (stream 26)
is aniline which should be pumped by (P-104). The resulting stream (stream
27) is cooled by (E-104) to produce aniline (Stream 28). Then, (stream 29)
should be pumped by (P-103) to get the suitable condition (stream31) for
mixing by (MIX-102). The bottoms product (stream 32) is cooled b (E-105)
to purchase diphenylamine in (stream 33).
Sulfuric
acid
13
Aniline
3 Benzene 12
14 15
1
Nitric
acid CRV-101
5 T-101
2 4
V-100
MIX-100
8
9 CRV-100 6
nitrobenzene
10
11
V-101
7 T-100
RCY-100
Figure (1-4) Process flow sheet of the production of aniline by liquid phase reduction of nitrobenzene.
23
Process description :
First of all, nitric acid and sulfuric acid is mixed together by using an acid
mixer(mix-100). the mixed acid and benzene are fed in a nitrate
reactor(CRV-100) and the reaction will occur as the following chemical
equation :-
Then the reactor effluent will enter the separator (V-100) which will separate
it into two streams which are crude nitrobenzene and the reactor effluent
acid that will be recovered to the reactor feed. The crude nitrobenzene could
be washed by using a dilute alkali (V-101) such as water and sodium
carbonate and distillated by still distillation column (T-100) to produce a
pure nitrobenzene. The crude nitrobenzene will enter a reducer [H2] reactor
(CRV-101) with an iron boring catalyst and hydrochloric acid to produce
aniline and water which will occur as the following chemical equation:-
And the effluent nitrobenzene will be recovered to the reducer reactor. The
aqueous aniline could be heated by steam to get crude aniline which can be
distilled by using still distillation column (T-101) to produce pure aniline.
Yeild : 98%
24
Process 3;Process catalytic reduction of nitrobenzene in a fluidized bed
reactor.
8
5
E-102
3
E-101
Water
Hydrogen
4 10
9
V-100 7
Nitrobenzene 4 T-100 T-101
11
1 2CRV-100 Aniline
P 12
K-100
E-100
Figure (1-5) Process flow sheet of the production of aniline by vapor phase reduction of nitro
benzene.
25
Name of Unit Description
26
Name of stream Description
S1 Nitrobenzene
S2 Hydrogen Feed
S3 Reactor Product Gases
S4 Condensed Materials
S5 Non-Condensable gas
S6 Crude Aniline
S7 Aqueous Phase
S8 Overheads
S9 Bottom Streams
S10 Water
S11 Aniline product
S12 Recycled bottom
Table (1-21) Name of stream
Process description:
The liquid nitrobenzene feed (contains less than 10ppm thiophene) (S1) is
vaporized up by going into vaporizer (E-100) to reach the required
temperature for the fluidized bed reactor after the mixing point between the
nitrobenzene feed (S1) and the hydrogen feed (S2) (which has been
compressed by Recycle Compressor) (K-100).Hydrogen to nitrobenzene
ratio is 9:1.
27
Reaction section:
28
Purification section:
The reactor (RCV-100) product gas mixture (aniline , hydrogen and water)
(S3) will enter the condenser (E-101)and the leaving gas stream (3.5%
water, 0.5% aniline and the balance hydrogen) (S5) which has been recycled
to the compressor (K-100), but a small part is vented to avoid the buildup of
gaseous impurities which exist in hydrogen feed. Moreover the aqueous and
organic phases stream (S4) is separated in a decanter (V-100) which
separates the crude aniline (S6) from the aqueous phase solution (S7). The
organic phase (crude aniline) is consist of aniline up to 0.5% nitrobenzene,
and 5% water is purified by two stage distillation column. After that in the
crude still column (T-100) (stripping) ,aniline and water are removed
overhead while higher boiling organic impurities, such as nitro-benzene
remain in the still bottoms. The overhead product (S9) from the first column
is purified in a finishing still (T-101), Water (S10) is withdrawn from the top
of the column while aniline (S11) is withdrawn in a side stream near the
bottom of the column. The bottom (S12) is recycled to the crude still (T-
100).
Waste treatment:
The best method of treating the aqueous waste resulting from the following
units (nitrobenzene distillation column overhead(stream8), nitrobenzene
wash water(stream7) and the aniline recovery column purge(stream12)), is
the biological treatment due to its inexpensive cost and it's high efficiency
indicator which could of the toxic nature of the waste which may affect the
environment , moreover the physical method that used as stream stripping
and liquid-liquid extraction.
Catalyst Regeneration.
29
Comparison flow sheets:
Alternative 1 phenol ammonia aniline Water
Mole 1 1 1 1
M.wt 94 17 93 18
Ib 94 17 93 18
ton 0.047 0.0085 0.0465 0.009
Ib/Ib of aniline 1.01 0.182 1 0.193
$/Ib 0.745 0.289 0.38 -
Gross Profit = -0.428
Table(1-22) Alternative #1
Alternative 2:
-There is no enough information to calculate the gross profit for the process.
30
Basic economic analysis:
Prices,
Description Weight US$
460.00-
Ammonia US Gulf, spot c.f.r. Tampa tonne 745.00
385.81-
Ammonia US Gulf, spot f.o.b New Orleans ton 771.62
Aniline tanks, f.o.b lb 0.37-0.39
technical grade, 100% basis, tanks, 300.00-
Ferric chloride f.o.b. works lb 351.00
Hydrochloric 22 deg. Be, US Gulf dom. ex-works
acid US NE tonne 85.43
Hydrochloric 22 deg. Be, US Gulf dom. ex-works
acid USG tonne 93.7
Nitrobenzene tanks, f.o.b. lb 0.33-0.34
Sulphuric acid virgin 100%, tanks, works, East Coast ton 1450
57.00-
Sulphuric acid virgin 100%, tanks, works, Southwest ton 85.00
Sulphuric acid virgin 100%, tanks, works, Midwest ton 87
Sulphuric acid virgin 100%, tanks, works, Southeast ton 94
Sulphuric acid virgin 100%, tanks, works, West Coast ton 73.1
Sulphuric acid smelter 100% tanks, works, Gulf Coast ton 94
50.00-
Sulphuric acid smelter 100%, tanks, works ton 62.00
25.00-
Sulphuric acid smelter, tanks, intro. Southeast ton 30.00
Sulphuric acid smelter, 93% tanks, dlvd., Northwest ton 67
40 deg. Be, 42 deg. Be. tanks, c.l., 215.00-
Nitric acid works, 100% basis ton 225.00
1472.31-
Phenol - ton 1507.69
1015.38-
Benzene - ton 1192.31
Hydrogen gas - Ib 0.32
Table (1-25) Cost of materials
31
Conclusion:
We figure out that there are lots of processes to produce aniline.
The production of aniline is takes an active part in America and china.
Locally aniline production is not exist.
At the beginning, aniline was an intermediate substance for (MDS)
production, according to this reason it was produced.
Recommendation:
The process 3 (vapor phase catalytic reduction of nitrobenzene ) is the best
alternative for the production of Aniline due to its inexpensive raw materials
and its highly profit comparing it to the other two alternatives.NitroBenzene
is the classical feedstock for Aniline manufacture. Recently less
chlorobenzene and Phenol are being used in aniline manufacturing processes
in several countries.
32
References:
Web sites;
http://www.springerlink.com
http://www.mpri.lsu.edu
http://www.xakaili.com
http://www.thefreedictionary.com
http://www.chemicalbook.com
http://price.alibaba.com
http://www.icis.com
http://en.wikipedia.org
Books;
33