PROCESS 2: PRODUCTION OF ANILINE VIA AMMONOLYSIS

A. Raw materials

PHENOL

Phenols are family of organic compounds characterized by a hydroxyl (-OH) group attached to a carbon atom
that is part of an aromatic ring. Besides serving as the generic name for the entire family, the term phenol is
also the specific name for its simplest member, monohydroxybenzene (C6H5OH) [1]

Uses

Extraction industry uses phenol in the study and extraction of biomolecules. There is various application of
phenol find by molecular biology in the extraction of nucleic acids from tissue samples for further
investigations.[2]

Two third of total phenol is used in preparing reagents. Reagents are used in plastic manufacturing industries.
When phenol is condensed then it produces bisphenol and acetone. Bisphenol is extensively used in polymer
industry. It synthesizes various epoxide resins and polycarbonates. [3]

Market Analysis

With Asian production levels strong and US domestic demand steady, sources expect that phenol
margins for 2017 producers will stay close to steady. Over the past few years, there have been some shifts
in the global phenol industry and change is predicted to continue through the forecast period. Some of the
larger and more advanced regions have been impacted by the increase in Asia-based supply, which has
caused changes in global trade patterns.
In the Philippines, there are suppliers of phenol such as Shell, Resins Inc., etc. Because phenol is of high
demand, there is also a high supply of it here in the Philippines.[4]

AMMONIA
Ammonia is the simplest stable compound of these elements and serves as a starting material for
the production of many commercially important nitrogen compounds.[5]

Uses

Ammonia is mainly used in agricultural industries. Ammonia is very important source of nitrogen that is
necessary for plant growth. Also, ammonia is used in the production of liquid fertilizer solutions which consists
of ammonia, ammonium nitrate, urea and aqua ammonia. It is also used by the fertilizer industry to produce
ammonium and nitrate salts.

Ammonia is used in the manufacture of nitric acid, certain alkalies such as soda ash, dyes, pharmaceuticals
such as sulfa drugs, vitamins and cosmetics, synthetic textile fibers such as nylon, rayon and acrylics, and
for the manufacture of certain plastics such as phenolics and polyurethanes. Next, the petroleum industry
utilizes ammonia in neutralizing the acid constituents of crude oil and for protection of equipment from
corrosion. Ammonia is used in the mining industry for extraction of metals such as copper, nickel and
molybdenum from their ores.[6]

Market Analysis

Asia pacific was the most lucrative regional ammonia market over the past few years. Emerging
countries are witnessing rapid growth in population, increase in disposable income and a trend shift in dietary
lifestyles. Strong agricultural base in India, China, and South East Asian countries is expected to have a
positive influence on the overall regional ammonia demand. In the Philippines, there are several suppliers of
ammonia such as Linde Group, Marubeni Philippines Corporation, Barron Engineering Supplies Philippines,
etc.[7]
 Process Description

In this process, a mixed-vapor feed of phenol and ammonia is pre-heated and passed over a fixed catalyst
bed reactor (R-101) at 370 C and 1.7 MPa using a Silica- Alumina catalyst. The two feed streams are pumped
to a pressure of 255 psia before they are mixed with their respective recycle streams (stream 6 and stream
17). Ammonia recycle (stream 6) has small amounts of hydrogen, nitrogen and water. The phenol recycle
consists of phenol, aniline and diphenylamine. The cooling of the reactor effluent begins with the cross
exchanger (E-100) which cools stream 10 by about 500 F. The purification of aniline begins with the column
D-100. The pressure at the top of the column is 220 psia and the pressure at the bottom is 222.5 psia. The
distillate (stream 5) is composed of ammonia and water. The components lighter than ammonia will also
appear in the distillate. Therefore, all of the hydrogen and nitrogen will go to stream 5. From the column D-
100, stream 5 goes to a splitter. The splitter sends 98.9% of the stream to stream 6, which is the ammonia
recycle stream. The splitter also sends 1.1% of stream 5 to the gaseous purge, stream 7. The purge is
necessary to avoid any pressure build-up in the process. Stream 7 is a non-product stream, but it is used as
fuel for the heater. The bottoms stream (stream 8) is one of the feeds to the next column. The second column
in the purification section is the drying column (D-101). The pressure at the top of the column is 15 psia, and
the pressure at the bottom of the column stage is 21.25 psia. The key components are water and phenol.
However, some aniline is lost in the distillate because aniline is soluble in water. The distillate contains
99.99% of the water, 6% of the phenol and 5% of the aniline fed to the column. The distillate, stream 9, is
cooled by E-103 to a temperature of 110 F with a pressure of 10 psia. Stream 10 is then sent to a three-
phase separator (V-100) to separate the aqueous product and the liquid (organic) product. The organic
product (stream 12) is recycled to the column. Stream 12 consists of 7% of the ammonia, 3% of the water,
30.5% of the phenol and 86% of the aniline in stream 20. Because stream 12 is below the pressure of the
top stage pressure, P-102 is used to bring the pressure in stream 23 up to 15 psia. The aqueous product
(stream 11) from V-100 is a non-product output stream. This stream will be sent through wastewater
treatment and released off-site. The bottoms stream (stream 13) is the feed to the next column.

The final column is the product column (D-102). The pressure at the top of the column is 2.707 psia, while
the pressure at the bottom of the column is 21.46 psia. Due to a high-boiling azeotrope between phenol and
aniline, the main component in the distillate (stream 14) is aniline. Stream 15 contains all of the water, 19.5%
of the phenol and 92.3% of the aniline from stream 13. Stream 15 must be at least 99 wt% aniline for industrial
use. Because there is a 10 psia pressure drop for liquids in coolers, stream 14 needs to be pumped up to a
pressure of 12.71 psia by P-104. The resulting stream (stream 14) is cooled by E-104. Stream 15, a product
stream, emerges from the cooler at 90o F and 2.707 psia. The azeotrope between phenol and aniline is
recycled. This azeotrope (stream 17) contains 33 wt% phenol, 65 wt% aniline and 2 wt% diphenylamine.
These weight percents account for 80% of the phenol, 7.7% of the aniline and 4.6% of the diphenylamine in
stream 13. Stream 17 is below the pressure of stream 2, therefore it is pumped to a pressure of 255 psia by
P-103. Stream 18 emerges at 373o F and 255 psia. The bottoms product (stream 16) consists of 5% of the
phenol and 95.4% of the diphenylamine in stream 13. Stream 32 must be at least 95 wt% diphenylamine for
industrial use. This stream is then cooled by E-105. Stream 16, a product stream, emerges from E-105 at
130o F and 11.46 psia. This concludes the description of the aniline process.
References

1. Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue
Book). Cambridge: The Royal Society of Chemistry. 2014. p. 690. ISBN 978-0-85404-182-
4. doi:10.1039/9781849733069-FP001. Only one name is retained, phenol, for C6H5-OH, both as a
preferred name and for general nomenclature.
2. Jump up to:a b c d e "NIOSH Pocket Guide to Chemical Hazards #0493". National Institute for
Occupational Safety and Health (NIOSH).
3. Ktt, Agnes; Movchun, Valeria; Rodima, Toomas; Dansauer, Timo; Rusanov, Eduard B.; Leito, Ivo;
Kaljurand, Ivari; Koppel, Juta; Pihl, Viljar; Koppel, Ivar; Ovsjannikov, Gea; Toom, Lauri; Mishima,
Masaaki; Medebielle, Maurice; Lork, Enno; Rschenthaler, Gerd-Volker; Koppel, Ilmar A.;
Kolomeitsev, Alexander A. (2008). "Pentakis(trifluoromethyl)phenyl, a Sterically Crowded and
Electron-withdrawing Group: Synthesis and Acidity of Pentakis(trifluoromethyl)benzene, -toluene, -
phenol, and -aniline". The Journal of Organic Chemistry. 73 (7): 2607
20. PMID 18324831. doi:10.1021/jo702513w.
4. "Nitrogen" (PDF). USGS. 2016. Retrieved 17 February 2016. R. Norris Shreve; Joseph
Brink (1977). Chemical Process Industries (4th ed.). p. 276. ISBN 0-07-057145-7. See also Gas
carrier and Bottled gas.
5. "Ammonium hydroxide physical properties" (PDF). Archived from the original(PDF) on 27
November 2007.
6. Kirschbaum, B; Sica, D; Anderson, F. P. (1999). "Urine electrolytes and the urine anion and
osmolar gaps.". The Journal of laboratory and clinical medicine. 133 (6): 597604. ISSN 0022-
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7. Tajkarimi, Mehrdad; Riemann, H. P.; Hajmeer, M. N.; Gomez, E. L.; Razavilar, V.; Cliver, D. O.; et
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Food Microbiology. 122 (12): 2328.