1.

INFORMATION ABOUT NITRIC ACID PRODUCTION

1.1.NITRIC ACID PROPERTIES AND APPLICATION AREA

Within the last thirty to forty years a very great change has come over the character of the
nitric acid manufactured. at one time the only acid placed on the market was an acid of 55-68
per cent HNO3, and the somewhat stronger “red fuming” acid; at the present time the bulk of
the nitric acid made has a strength of 95 per cent and over .In order to produce an acid of this
strength very considerable difficulties have to be overcome, since 100 per cent. HNO3. is only
stable below 0°C and begins to boil at 86° C, evolving red fumes and partially decomposing
according to the equation. [1]

2HNO3 NO + NO2 + O2 + H2O

As the nitrous gases escape the boiling point of the acid rises, and it is only when a liquid
containing 65 per cent. HNO3 is attained that the mixture distils over unchanged under
atmospheric pressure at 1200 C. These difficulties are now almost completely overcome with
modem apparatus. [1]

The strong nitric acid, possessing a specific gravity of 1.50-1.52, is a powerful oxidising
agent. In fact, it will spontaneously inflame wood or straw if poured upon them in quantity,
and, consequently, is always technically transported in glass balloons, with a packing of sand
or kieselguhr. It is usually only sent by special trains, much in the same way that explosives
are sent. Owing to the difficulty of transport, concentrated HNO3 is usually made on the place
of consumption, e.g., it is far more economical to manufacture nitric acid directly in the
neighbourhood where it is to be consumed than to manufacture it in distant countries, where
the conditions are more favourable, and then send it long distances by sea or rail to the point
of use—as is nearly always done in the case of other heavy chemicals, such as sodium
sulphate or alkali. Concentrated nitric acid is used, mixed with concentrated sulphuric acid,
for nitrating purposes, especially for the manufacture of nitroglycerine and nitrocellulose,
collodion and celluloid. For example, for the manufacture of nitroglycerine a mixture of 36.5
per cent. HNO3 (of 91.6 per cent, strength) and 63.5 per cent. H2SO4, (of 97 per cent,
strength), together with 5 per cent HCl is used. Such an acid must be free from chlorine, and
must not contain more than 0.2-0.3 percent, of nitrous acid. For making such substances as

1
nitrobenzene, picric acid, and other organic nitrogenous bodies, a weaker acid of 1.35-1.40 sp.
gr. mixed with 1-2 parts of sulphuric acid is used. A nitric acid of 1.35-1.40 sp. gr. is also
used for the Glover towers in the manufacture of sulphuric acid. A more dilute nitric acid is
used for making silver nitrate and other nitrates, for etching copper plates, and for dissolving
metals. The red fuming nitric acid, of specific gravity 1.4-1.5, contains dissolved in it oxides
of nitrogen, and is a more powerful oxidising medium than the colourless acid of the same
specific gravity. This acid is made sometimes by adding a little starch to strong nitric acid,
which causes its partial reduction, and sometimes by distilling sodium nitrate with a smaller
amount of sulphuric acid, and at a higher temperature than is required for the production of
the ordinary acid. [2]

Application Areas Of Nitric Acid

The manufacture of nitrogen fertilisers represents by far the largest proportion of the use of
nitric acid. These fertilisers, generally with high nitrogen contents, provide the active nitrogen
in the form of ammonium nitrate or as nitro phosphate formed by the action of nitric acid on
phosphate rock. For these processes “weak” nitric acid (55 to 65 per cent HNO3) is usually
employed. Certain territories, such as Japan, are exceptions to this generalisation, since nitrate
fertilisers for domestic agriculture may not be suitable there, and consumption of the acid by
the explosive and chemical industries is thus more important. In the U.S.A., about 65 per cent
of the nitric acid produced is consumed in the manufacture of fertilisers, for example,
ammonium nitrate, and an additional 4 to 5 per cent is used for products such as potassium
nitrate and nitro phosphates. The remainder (about 30 per cent) is used by the explosives,
plastics and chemical industries. In 2002-2003 nitric acid represented about 25 per cent of the
world’s fixed nitrogen production, but this proportion had dropped to an estimated 22.5 per
cent by 2005-2006. This decline is probably temporary, and is largely attributed to the
sustained expansion of fertilisers obtained directly from ammonia, in particular urea and
complex fertilisers based on ammonium phosphate. Low-cost ammonia from very large
modern plants employing new processes based on hydrogen obtained from petroleum
fractions (output about 1000 tonnes per day), together with increasingly large nitric acid plant
facilities (about 500 tonnes per day), can be expected to effect substantial reductions in nitric
acid production costs. Such reductions may have significant effects on potential applications
in which price considerations have limited or prohibited the use of nitric acid until now. [6]

2
1.2. MANUCAFACTURING OF NITRIC ACID TECHNOLOGIES

Nitric acid is now made on the large scale by three distinct processes:
1. Manufacture from Chile Saltpetre and Sulphuric Acid.
2. Manufacture by Electrical Oxidation of the Atmosphere.
3. Manufacture by Catalytic Oxidation of Ammonia.

1.2.1 MANUFACTURE FROM CHILE SALTPERE AND SULPHURIC ACID

Nearly equal weights of Chile saltpetre, NaNO3, and "oil of vitriol" are heated together in
large iron retorts, often capable of holding some 5 tons or more of the mixture. The quantities
taken correspond to the equation:

NaNO3+H2SO4 HNO3 +NaHSO4 [3]

This reaction is carried to completion at a temperature under 150°C, there by avoiding much
loss by decomposition of the nitric acid. A much higher temperature with half the amount of
sulphuric acid is necessary to cause the formation of the neutral sulphate, according to the
equation:

NaNO3+H2SO4 Na2SO4 +2HNO3

This latter action, however, in the best practice is never used, because the high temperature
necessary to complete the action causes a very considerable decomposition of the nitric acid
formed; also the neutral sodium sulphate remaining sets to a solid mass, and causes great
difficulty as regards removal from the retort; also the action takes a much longer time to
complete and requires more fuel. By working not much over 1500C and using more sulphuric
acid, as corresponds to the first equation, the "bisulphate" is obtained as an easily fusible
mass, which is withdrawn in a fluid condition from the retort merely by opening a plug at the
base. However, in actual practice, right towards the end of the action the temperature is raised
somewhat, when the bisulphate foams somewhat and is probably converted into pyrosulphate,
thus: [3]

NaHSO4 Na2S2O7 +H2O

3
This pyrosulphate (or disulphate) is run off in a fluid condition into iron pans, where it
solidifies and is used for the manufacture of normal sodium sulphate by heating with salt,
NaCl, in mechanical sulphate furnaces. Part of this "nitre cake," as the product is called, is
now converted into sodium sulphide, Na2S.

The kind of sulphuric acid used varies with the nature of the nitric acid it is desired to
produce, for a dilute nitric acid of 1.35-1.4 sp.gr. The first distillate will be strongest, and the
last nearly pure water. Should, however, a stronger HNO3 of over 1.5 sp. gr. be required (as is
now nearly always the case), a more concentrated % 66 sulphuric acid must be employed,
and the NaNO3 is often previously melted. Excess of H2SO4 is bad, for although it does not
injure the quality of the HNO3 produced, yet it diminishes the value of the NaHSO4 or
Na2S2O7 (nitre cake) produced as a by-product for the manufacture of sodium sulphate. [3]

1.2.2. MANUFACTURE BY ELECTRICAL OXIDATION OF THE ATMOSPHERE

The atmosphere contains about 4x1015 tons of nitrogen, together with about one-fifth this
amount of oxygen gas. There is thus an inexhaustible supply of nitrogen available for
conversion into nitric acid or nitrate, and thus available for manorial purposes. The nitrogen in
the air over a single square mile of land amounts to nearly 20,000,000 tons of nitrogen
sufficient, if suitably combined as nitrate or nitric acid, to supply at the present rate of supply
the world with manure for over half a century. The problem of directly uniting the oxygen and
nitrogen of the air to form nitric acid and nitrate was first solved in a commercially successful
form in 1903 by Birkeland and Eyde. In 1907 they established a factory at Notodden, in
Norway, utilising the 40,000. There available from waterfalls. In the same year the Badische
Anilin- und Soda-Fabrik built an experimental works at Christiansand, in Norway, and an
agreement was come to between the interested firms whereby a company possessing a total
capital of 34,000,000 kronen came into existence, which in 1911 opened a large works on the
Kjukan. Falls, near to Notodden, with 125,000 H. P. However, the Badische Anilin- und
Soda-Kabrik have since withdrawn all their capital from the concern, selling all their rights in
the manufacture of nitric acid from the atmosphere to the French. Scandinavian Co. The cause
of this is possibly the perfection by the B.A. S.F. of their process for making synthetic
ammonia cheaply and thence oxidising it into nitric acid. Other works are building or are
built in Norway and Sweden, and similar factories, using different systems as described
below, have come into existence at Innsbruck, in Italy, France, the United States and other

4
countries possessing considerable water power for the generation of electrical power.
Altogether the industry is now well established.

At the present time, however, I H. P. per year can only produce -h to I ton of nitrate per year.
There are, it is calculated, some 5 to 6 million H. P. available in Norway, and some 50,000 to
60,000 H.P. available in Europe, so that were it possible to harness all this power for the sole
manufacture of nitrates from the air it would be possible to produce some 50,000,000 tons of
nitrate annually. The amount now produced is far under 200,000 tons annually. The process
adopted for making nitric acid from the air is to oxidise the latter by means of an electric arc,
whereby the nitrogen and oxygen directly unite to form nitric oxide, NO. This latter takes up
oxygen from the air to form nitrogen peroxide, and the nitrogen peroxide is then absorbed by
water, with the production of nitric and nitrous acid. [4]

Figure-1 Block diagram of Combustion of Air Process

Theoretical: When air is strongly heated, atmospheric oxygen and nitrogen directly unite to
form nitric oxide, NO, according to the equation:
N2 + O2 2NO - 43.200 cal.

NO is endothermic, and like other endothermic substances its stability increases as the
temperature rises, and it is capable of existing in very large quantities at very high
temperatures, such as 3,ooo°-5,ooo° C. It is also capable of existing stably below i,ooo° C.,
but is unstable at intermediate temperatures. Hence in order to isolate reasonable quantities of

5
NO we must (1) cause the formation of NO to take place at very high temperatures, such as
3,000C°-10,000oC, when large amounts are formed ; (2) then extremely rapidly cool the NO
formed through the intermediate unstable range of temperature, 2,500°C, to a stable low
temperature, 1.000° C. If the cooling is effected quickly enough, although some of the NO is
decomposed as it cools through the unstable lower temperature, yet sufficient survives so as to
make an appreciable amount still existing at 1,000° C, which then ceases to decompose
further, and so is available for conversion into nitric acid. Now in practice the intense heating
of the air to very high temperatures such as 3,000-5,000° C, necessary to cause a reasonable
oxidation of the air to NO, is always produced by a high tension alternating current of some
5,000 volts. This electric current not only produces the union of the O and N as a purely
thermal effect, but also ionises the air and causes a direct union by means of electrical energy,
much as ozone is formed from oxygen by means of a silent electrical discharge. So that much
larger quantities of NO are obtainable than strictly corresponds to the thermal conditions [4].

1.2.3. MANUFACTURE BY CATALYTIC OXIDATION OF AMMONIA

(OSTWALD METHOD)

NH3, has been manufactured extremely cheap by several methods, directly from its elements,
also by passing steam over nitro lime. It has, consequently, greatly fallen in price, and has
thus become available as the starting-point for the manufacture of nitric acid. Kuhlmann in
1830 oxidised ammonia, using platinum as a catalyst, but ammonia was in those days too
expensive for practically producing nitric acid by this process. About 1900 Prof. Wilhelm
Ostwald, together with his assistant, Dr Brauer re-investigated the process, and an
experimental plant was erected in which some 150 tons of dilute nitric acid were produced per
month. Even at that time, however, ammonia seems to have been too expensive for the
process to compete with the sodium nitrate process of manufacture. Recently, however,
ammonia has been produced at one-fourth its former price (by the synthetic process), and so
the difficulty as regards the first cost of ammonia appears to have vanished Also the process
in its original form was imperfect. The technical details were gradually improved, and in 1909
a factory was built at Gerte, Westphalia. Numerous other factories are now being erected.
Works exist in Belgium, near Dagenham on the Thames, Traflbrd Park, Manchester, in
Scotland and Ireland. Rudolph Messel has pointed out that the production of nitric acid from
the air (see above) is at present confined to countries producing water power, and that the

6
resulting nitric acid is very difficult to transport; on the other hand, ammonia is producible
almost everywhere (since not much energy is required in its production), and can, with an
Ostwald plant, be readily oxidised on the spot to nitric acid. Consequently this new process,
especially since the production of synthetic ammonia, may ultimately prove the most
important technical method for producing nitric acid [5].

Figure-2 Block diagram of catalytic oxidation of ammonia process

Reaction in the chain also takes place at high temperatures and moderate pressure (with a
Pt/Rh catalyst):
4NH3 + 5O2 → 4NO + 6H2O

The nitric oxide is then quenched in water, with the following two reactions usually occurring
in an absorption unit:

2NO+O2→2NO2
3NO2 + H2O → 2HNO3 + NO

With the net effect of making a nitric acid solution, which can then be distilled to higher
purity and carried on to make potassium nitrate (by, say, reacting it with potassium
hydroxide). This is the Ostwald process, which had been patented back in 1902 and could
have been the impetus for developing the Haber-Bosch process in the first place [5].

7
1.3. RAW MATERIAL PROPERTIES AND APPLICATION AREA

Properties Of Ammonia

Ammonia is a colourless gas, hazardous and corrosive. It is easily liquefied due to the strong
hydrogen bonding between molecules; the liquid boils at −33.3 °C, and freezes at −77.7 °C to
white crystals. Ammonia is easily liquified at under the normal temperature and pressure.
Liquid ammonia has a very high standard enthalpy change of vapourization and can therefore
be used in laboratories in non-insulated vessels without additional refrigeration.

It is miscible with water. Ammonia in an aqueous solution can be expelled by boiling. The
aqueous solution of ammonia is basic. One of the most characteristic properties of ammonia is
its basicity. It combines with acids to form salts.
Approximately 83% (as of 2004) of ammonia is used as fertilizers, also making explosive and
refrigeration for industry.

Figure-3 The properties of ammonia are summarized

8
Application Areas Of Ammonia

Ammonia is used in the manufacture of NITRIC ACID; certain ALKALIES such assoda ash;
DYES; PHARMACEUTICALS such as sulfa drugs,vitamins and cosmetics;synthetic textile
FIBERS such as nylon, rayon and acrylics; for the manufacture of certain PLASTICS such as
phenolics and polyurethanes.
Ammonium Nitrate besides its fertilizer usage is widely employed in the production of
EXPLOSIVES.
Ammonia is used in such METAL TREATING operations as nitriding, carbonitriding, bright
annealing, furnace brazing, sintering, sodium hydride descaling, atomic hydrogen welding
and other applications where protective atmospheres are required.
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.
Ammonia is used in several areas of WATER and WASTEWATER TREATMENT, such as
pH control, in solution form to regenerate weak anion exchange resins, in conjunction with
chlorine to produce potable water and as an oxygen scavenger in boiler water treatment.
Ammonia is used in STACK EMISSION CONTROL SYSTEMS to neutralize sulfur oxides
from combustion of sulfur-containing fuels, as a method of NOx control in both catalytic and
non-catalytic applications and to enhance the efficiency of electrostatic precipitators for
particulate control.
Ammonia is used as the developing agent in PHOTOCHEMICAL PROCESSES such as
white printing, blue printing and in the diazo duplication process.
Ammonia is a widely used refrigerant in INDUSTRIAL REFRIGERATION SYSTEMS
found in the food, beverage, petro-chemical and cold storage industries.
Ammonia is used in the RUBBER INDUSTRY for the stabilization of natural and synthetic
latex to prevent premature coagulation.
The PULP AND PAPER INDUSTRY uses ammonia for pulping wood and as a casein
dispersant in the coating of paper.
The FOOD AND BEVERAGE INDUSTRY uses ammonia as a source of nitrogen needed for
yeast and microorganisms.
The decomposition of ammonia serves as a source of hydrogen for some FUEL CELLS.

9
Ammonia is used by the LEATHER INDUSTRY as a curing agent, as a slime and mold
preventative in tanning liquors and as a protective agent for leathers and furs in storage.
Weak ammonia solutions are also widely used as COMMERCIAL AND HOUSEHOLD
CLEANERS AND DETERGENTS.

Other Raw Materials Water and Air

Properties of Air

Earth's atmosphere is composed of air. Air is a mixture of gases, 78% nitrogen and 21%
oxygen with traces of water vapor, carbon dioxide, argon, and various other components. We
usually model air as a uniform (no variation or fluctuation) gas with properties that are
averaged from all the individual components. Any gas has certain properties that we can
detect with our senses. The values and relations of the properties define the state of the gas.
We are all aware that pressure and temperature of the air depend on your location on the earth
and the season of the year. And while it is hotter in some seasons than others, pressure and
temperature change day to day, hour to hour, sometimes even minute to minute during severe
weather. The values presented on the slide are simply average values used by engineers to
design machines. That's why they are called standard values. We also know that all of the
state-of-the-gas variables will change with altitude, which is why the typical values are given
at sea level, static conditions. Because the gravity of the Earth holds the atmosphere to the
surface, as altitude increases, air density, pressure, and temperature (for lower altitudes)
decrease. At the edge of space, the density is almost zero. The variation of the air from the
standard can be very important since it affects flow parameters like the speed of sound.[9]

Properties of Water
A water molecule is formed when two atoms of hydrogen bond covalently with an atom of
oxygen. In a covalent bond electrons are shared between atoms. In water the sharing is not
equal. The oxygen atom attracts the electrons more strongly than the hydrogen. This gives
water an asymmetrical distribution of charge. Molecules that have ends with partial negative
and positive charges are known as polar molecules. It is this polar property that allows water
to separate polar solute molecules and explains why water can dissolve so many substances.

10
Water is a good solvent due to its polarity. When an ionic or polar compound enters water, it
is surrounded by water molecules. The relatively small size of water molecules typically
allows many water molecules to surround one molecule of solute. The partially negative
dipoles of the water are attracted to positively charged components of the solute, and vice
versa for the positive dipoles [10]

11
Physical, Chemical and Thermodynamic Properties of Raw Materials and Product

Compone Fire Storage Physical and Chemical Hazardous Waste

nts fighting chemical Stability, Decompositi Disposal
measures properties reactivity on
Products

- Must - Store in a -Boiling Point:- -Stable - Explosive -Suitably

wear cool, well- 33°C (Stable at room or violent diluted
1. protective ventilated -Freezing point:- temperature. reactions can product
Ammonia clothing area with 78°C Ammonia will occur from may be
and a containers -Solubility in react mixing applied to
positive tightly closed. Water: 89.9 exothermically ammonia agricultural
pressure. Also handling g/100cc at 0ºC with acids and with land as
Stop source and storage -Vapor pressure: water) halogens, fertilizer.
if requirements 10 atm at strong Keep spill
possible. for anhydrous 25.7ºC oxidizers, from
Cool fire ammonia as a -Evaporation strong entering
exposed hazardous rate: Faster than mineral streams,
containers material. water acids, nitric lakes or
with water - acid, any water
spray. Stay Appearance&od fluorine, systems.
upwind and or: Colorless nitrogen -
use water gas/liquid and oxide... Flammabili
spray to pungent odor -Ammonia is ty limits in
knock -Heat capacity at incompatible air:%16-25
down vapor constant pressure or has
and dilute. (Cp) (1.013 bar hazardous
and 15 °C: 0.037 reactions
kJ/(mol.K) with Silver,
Acetaldehyd
e, Boron,
Sulfur, etc..

2. Water - Not fire - Keep - Appearance: - Stability: - Whatever

and container Clear, colorless Stable under - Water is cannot be
explosion. tightly closed. liquid. ordinary non- saved for
-In the Suitable for - Odor: Odorless. conditions of use hazardous. recovery or
event of a any general - Solubility: and storage. recycling
fire, wear chemical Complete - Hazardous should be
full storage area. (100%) Decomposition flushed to
protective Protect from - Products: Not sewer.
clothing freezing. SpecificGravity: applicable. - If material
approved Water is 1.00 - Hazardous becomes
self- considered a - pH: 7.0 Polymerization: contaminat
contained non-regulated Will not occur. ed during
breathing product, but - Boiling Point: - use,
apparatus may react 100°C (212F) Incompatibilities dispose of
with full vigorously - Melting Point: : accordingly
face piece with some 0°C (32F) Strong reducing . Dispose
operated in specific - Vapor Density agents, acid of
the pressure materials. (Air=1): Not chlorides, container
demand or - Avoid applicable. phosphorus and unused
other contact with trichloride, contents in
positive all materials phosphorus accordance

12
 pressure until pentachloride. with
mode. investigation federal,
shows state and
substance is local
compatible. requiremen
ts.

3. Nitric -Not - Separated - Appearance: - The substance - Nitric acid - Whatever

acid combustible from colourless to decomposes on is extremely cannot be
but combustible yellow liquid, warming hazardous; it saved for
enhances and reducing with pungent producing is corrosive, recovery or
combustion substances,ba odour. nitrogen oxides. reactive, an recycling
of other ses, organics - Boiling point: The substance is oxidizer, and should be
substances. food and 121°C a strong oxidant a poison. managed in
Gives off feedstuffs . - Melting point:- and reacts an
irritating or Cool. Dry. 41.6°C violently with appropriate
toxic fumes Keep in a - Relative combustible and and
(or gases) well- density (water = reducing approved
in a fire. ventilated 1): 1.4 materials, e.g., waste
Heating room. - Solubility in turpentine, facility.
will cause water: miscible. charcoal, Processing,
rise in - Vapour alcohol. The use or
pressure pressure, kPa at substance is a contaminati
with risk of 20°C: 6.4 strong acid, it on of this
bursting. - Solubility: it is reacts violently product
- Risk of soluble in water with bases and is may
fire and in all corrosive to change the
explosion proportions. metals forming waste
on contact - Concentration: flammable/explo manageme
with many Nitric acid can sive gas. nt options.
common be concentrated - Reacts State and
organic up to 68% violently with local
compounds. organic disposal
compounds. regulations
may differ
from
federal
disposal
regulations.
Dispose of
container
and unused
contents in
accordance
with
federal,
state and
local
requiremen
ts.

4.Air - Non- - Compressed - Appearance: - Normally stable - Containers - Waste

flammable. gases can This product is a in gaseous state. may rupture disposal
Air will present colorless, Compressed Air or explode if must be in
support significant odorless gas. which contains exposed to accordance
combustion safety excess oxygen heat. with
of hazards. Store Freezing/Melting may present the appropriate
flammable cylinders point (10 Psi): - same hazards as Federal,
materials. away from 216.2°C Liquid Oxygen State, and

13
 Use heavily - Solubility in and could react local
extinguishi trafficked Water at 0°C: violently with regulations.
ng media areas and 0.0292 organic Return
appropriate emergency - Evaporation materials, such cylinders
for exits. Rate: Not as oil and grease. with any
surrounding - Post “No applicable - Hazardous residual
fire. Smoking or - pH: Not Polymerization: product to
Open Flames” applicable Will not occur. Air
signs in - Gas Density - Conditions to Liquide.
storage or use 21.1°C and 1 Avoid: Avoid Do not
3
areas. atm: (1.2 kg/m ) exposing dispose of
cylinders to locally.
extremely high For
temperatures, emergency
which could disposal,
cause the secure the
cylinders to cylinder
rupture. and slowly
discharge
the gas to
the
atmosphere
in a well-
ventilated
area or
outdoors,
away from
all sources
of ignition.

5. NaNO3 - - Keep - Physical State: - Chemically - Avoid - If empty,

Decompose containers solid stable. contact with do not
s on tightly closed - Color: blue eyes, skin, reuse
heating. in a dry, cool - Appearance: and clothing. container.
- Thermal and well- prills, crystals, Wash with Do not
decompositi ventilated flakes soap and place
on can lead place. Do not - Odor: fertilizer water after product
to release of contaminate - Solubility: handling. down any
irritating water, food, Highly soluble Avoid indoor or
gases and or feed by (>80%) breathing outdoor
vapours. storage or dust. drain.
disposal. Contaminat
ed
product
should be
disposed of
in an
approved
landfill
disposal
facility in
accordance
with
appliable
Federal/
Provincial,
and/or local
regulations.

14
NATIONAL LEGISATION AND COMPETENT AUTHORITIES
ƒ By-Law on Air Quality Control (AQC);
 air quality standards for 10 pollutant parameters both in terms of long and short-term
limit values,
 target limits and alert thresholds for SO2 and particulate matter, the measures in
general to be taken when alert thresholds are reached,
 principles for measurement and analysis.

Table…The long and short term Standard for various air pollutants that (AQC)

http://www.abgs.gov.tr/tarama/tarama_files/27/SC27DET_06.37.AirFrameDir-DAUGHTERS.96_62.pdf

15
1.4. MARKET DEMAND

World annual consumption is approximately 60 million tonnes [7]

Figure-4 Uses of nitric acid in the world

Annual consumption in Turkey is approximatly 1,3 million tonnes [7]

Figure-5 Uses of nitric acid in Turkey

16
MARKET DEMAND FOR AMMONIA

Ammonia application area

Fertilizer
Industry

Ammonia is widely used fertilizer and chemical industry. In fertilizer industry is included
%75 of total market share and chemical industry is included %25 of total market share.

AMMONIA IN FERTILIZER INDUSTRY

Table : Ammonia manufacturer in fertilizer industry

Company Plant Location Capacity (ton/yr)
Gemlik Gemlik 300.000
İgsaş Yarımca 396.000
Qeshm 360.000
TOTAL 1.056.000
Appendix
Ammonia is used widely in fertilizer industry. Approximately 1.056.000 tonnes per year
ammonia is produced in Turkey for fertilizer industry.

17
AMMONIA IN CHEMICAL INDUSTRY
Market share of ammonia for chemical industry includes %25 of total market. Ammonia is
used for dry, perfume, paint and wiper. %25-32 by weight ammonia is used in this industry.
Using in chemical industry nitric acid provide by export.

1.4.1. NITRIC ACID IN FERTILIZER INDUSTRY

Table-1 Nitric manufacturer in fertilizer industry

COMPANY PLANT LOCATION PRODUCT CAPACTY (ton/yr)

Gemlik Gemlik Nitric Acid 363.000
Toros Mersin Nitric Acid 363.000
Yıldız Kütahya Nitric Acid 201.000

Nitric acid is used widely in fertilizer industry. Approximately 1,3 million tonnes nitric acid is
produced in Turkey and 920.000 tonnes nitric acid is produces for fertilizer industry. So,
market states of the fertilizer industry was examined and export and import data were given
Table 2 and Table 3.

Table-2 Export of ammonium nitrate fertilizer

YEAR AMOUNT OF EXPORT (ton/yr)

2000 6000
2001 46000
2002 37000
2003 35000
2004 59000

18
2005 40000
Appendix 2
Understanding to this table, there was not big change about amount of export according to
years. Thought that the same trends, observed in the long term.

Table-3 Import of ammonium nitrate fertilizer

YEAR AMOUNT OF IMPORT (ton/yr)
2000 652000
2001 493000
2002 666000
2003 886000
2004 913000
2005 763000
Appendix 3
Since 2005, amount of import was increased every year. But at 2005, with building a new
fertilizer plant (İgsaş), amount of import was decreased. Due to this venture, for a long term
between import and export difference will not change. So, fertilizer industry will need new
ventures.

1.4.2. NITRIC ACID IN CHEMICAL INDUSTRY

Market share of nitric acid for chemical industry includes %25 of total market. Nitric is used
as chemical solution, produced of TNT and nylon about %65 by weight. Using in chemical
industry nitric acid provide by import.

Fertilizer industry has three big companies. These plants are produced also their raw
materials. (ammonia, nitric acid). For take part in this sector, nitric acid’s manufacturing cost
should be lower than these plants. Examined rates of export and import for fertilizer industry
is a big gab was observed. But, capacity of plants in Turkey and low price of imported
products causes competitiveness is difficult. If after the nitric acid production fertilizer
produced, take place is suitable in this industry.

19
In chemical industry, all nitric acid as chemical solution is exported. So, for take part in this
sector, nitric acid’s manufacturing cost should be lower than exported product cost. There is
no domestic producer, so competition can be more comfortable.

1.5. SELECTION OF PLANT LOCATION

The location of the plant can have a crucial effect on the profitability of a project, and the
scope for future expansion. Many factors must be considered when selecting a suitable site,
and only a brief review of the principal factors will be given in this section. The principal
factors to be considered are:
 Location, with respect to the marketing area.
 Raw material supply.
 Transport facilities.
 Availability of labour.
 Availability of utilities: water, fuel, power.
 Availability of suitable land.
 Environmental impact, and effluent disposal.
 Local community considerations.
 Climate.
 Political strategic considerations.

Table-4 Plant Location

City Cost of field Water source
(TL/m2)
Kırıkkale 70-300 Kızılırmak
Samsun 150-300 Yeşiırmak-
Kızılırmak
Sakarya 200-400 Sakarya Nehri
Tekirdağ 200-600 Çorlu Deresi

20
Bursa 200-600 Ulubat Gölü
[Ref 11]
Although land prices are cheap in Kırıkkale and Samsun, plant location was selected Sakarya.
Sakarya, prefer the grounds for being close to industrial cities as İstanbul, İzmir and Bursa.
Available conditions of utilities were determined according to Appendix 4.

Plant capacity was selected as 300.000 ton/year

1.6. COMPARISION OF TECHNOLOGIES

Manufacturing of nitric acid from Chile Saltpetre and sulphuric acid process was firstly
eliminated. NaNO3 is raw material for this methods and this is consumed away around the
world. So; this method was not suitable for long term investments.

Manufacturing of nitric acid by electrical oxidation of the atmosphere process, air and water
are raw materials. For this method, raw materials are common substances and access to raw
materials very easy. Nitrogen is oxidized at electrical arc and the operation condition is nearly
1500 0C,1 atm. Catalyst was not use for this method so, utility cost was not include catalyst
cost. Energy requirement should be consulted to ensure this condition. And the operation
safety is important for this process. Process need for additional equipment because of final
product quality. For NO limitation according to legislation, auxiliary equipments are needed.
Manufacturing of nitric acid by catalytic oxidation of ammonia process, ammonia, air and
water are raw materials Amount of raw materials, their storage condition and the transporting
is the important for this process. Ammonia is also used widely in chemical industry, so
supplying of ammonia has some problems. Ammonia is oxidized at reactor with platin
catalyst, and the operation condition is nearly 800 0C, 1 atm. Catalyst regenerated time is also
the effect of process cost. Also this method is needed additional equipment because of final
product quality and auxiliary equipments are needed for NO limitation according to
legislation.

21
Table-5 Comparison Table Of Manufacturing Nitric Acid Technologies

1st process 2nd process

(Oxidation of Ammonia) (Combustion of Air)

Raw materials *NH3 *Air

*Air *Water
*Water

* Difficult *Easy than 1st process

Attainability of raw material (NH3 is product of another (this raw materials are reached
process, also required the extra at anytime)
cost for transportation)

Storage conditions of raw *Required the stainless steel *Not required the storage
material tank for ammonia
(NH3 is storaged at 8,8 atm and
20 oC, so tank’s more thick
because of high pressure)

Corrosivity of raw material *More corrosion *Not corrosion than 1 st process

(NH3 reacts with H2O,also
ammonia is basic )

Number of equipments *2 main equipment *2 main equipment

(also have a lot of auxiliary (less than auxiliary equipments)
equipments)

22
Operation safety *Safety *Not safety than 1st process
(this reaction is occur high (Because this reaction is occur
temp.(800 oC) at reactor) very high temp. (1500 oC)at
electrical arc)

Quality of product *%60 (HNO3) *%35 (HNO3)

(some equipments (for
concentrated) is required
because of this product is used
at chemical industry).

2. FLOWSHEETING FOR AMMONIA OXIDATION PROCESS

2.1. DESIGN BASIS

NAME OF THE METHOD Oswalt Method (Ammonia Oxidation)
PLANT INFORMATION
Plant Location Sakarya
Design Capacity (ton/yr) 300.000
Purity (%) 60
RAW MATERIALS
NH3
Available Conditions 25°C, 1 atm
Phase Liquid
Purity %99
O2
Source Air
Available Condition 25°C, 1 atm
Phase Gas
H2 O
Source River
Available Condition 25°C, 1 atm
Phase Liquid
RAW MATERIAL FEED RATIO
NH3/( NH3+Air) 0,10

23
OVERALL CONVERSION %90
PRODUCT SPECIFICATION
Product Nitric Acid
Composition %60 (by wt)
Phase Liquid
UTILITIES Electricity, Water
WATER
Source River
Available Condition 25°C, 1 atm
Phase Liquid
REACTOR
Function Ammonia oxidation
Conversion %98
Catalyst Pt
Catalyst Regeneration Time (month) 18
Operation Type Adibatic
Operational Temperature (°C) 800
Operational Pressure (atm) 1
Material of Construction Stainless Steel
ABSORBER
Function Absorption of NO2 with H2O
Absorbtion Degree %92
Operation Type Adiabatic
Operational Temperature (°C) 40
Operational Pressure (atm) 6
Material of Construction Stainless Steel
WASTE MANANGEMENT
NOx Limitation 200 ppm

24
2.2. EQUIPMENT SUMMARY TABLE FOR AMONIA OXIDATION PROCESS

Name Code Function Temperatu Pressure Material of Utility Operation

re (atm) Constructi Type
(0 C) on
Storage ST-101 Storage of 20 1 Stainless -
Tank NH3 Steel

Filter F-101 Cleaning 20 1 Stainless

of NH3 Steel

Evaporator E-101 Evoparate 20 1 Stainless Steam

d of NH3 Steel

Filter F-102 Cleaning 20 1 Stainless

of air Steel

Mixer M-101 Mixing of 20 1 Stainless

air and Steel
NH3
Heat HE-101 Heating of 20-800 1 Stainless Steam
Exchanger gas Steel
mixture
for rxn
condition
Reactor R-101 Reaction 800 1 Stainless Catalyst Adiabatic
of amonia Steel (Pt)
oxidation

25
Compressor C-101 Compress 1-6 Stainless Electric Polytrophi
ed of Steel c
gasses
Waste Heat B-101 Cooling of 6 Stainless Water
Boiler gas Steel
mixture
Condenser CD-101 Coolig of 250-40 6 Stainless Water
gas Steel
mixture
for NO
oxidation
Absorber A-101 NO2 40 6 Stainless Adiabatic
absorbed Steel
with H2O
for
producing
nitric acid
2.4. FLOW DIAGRAM

26
 Figure-6 Flow diagram of ammonia oxidation process

3. CALCULATIONS OF AMMONIA OXIDATION PROCESS

3.1. MATERIAL BALANCE FOR AMMONIA OXIDATION PROCESS

For capacity;
ton kg kmol mol year day
300000  1000   1000    157molHNO3 / s
year ton 63kg kmol 8400day 3600sn

%60 HNO3 (by weight) is manufactured by used this process.

27
Material Balance in Overall System

nH2O

nair
(0,21O2) nHNO3(aq)=157 mol/s
(0,79N2)
Overall System
(0,88)
nNH3 nNO

nO2 nN2

4NH3+5O2 4NO+6H2O
2NO+O2 2NO2
3NO2 + H2O 2HNO3 +NO
4NH3 + 6O2 + NO2 2HNO3 + 3NO + 5H2O Net rxn (XA=0.88)

Degrees of freedom;
ndf= 6 unknowns (nair, nNH3, nH2O, nNO, nN2, nO2)
-3 atomic balances (H, O, N)
-1 inert gases (N2)
ndf=2 ( not soluable)
Assumptions;
-1 feed ratio (nNH3/ nNH3+ nair=0,1)
-1 overall conv. (0,88)
ndf=0 (soluable)
For overall conversion; 4  (nNH3)in  0,88=2  (nHNO3)out
nNH3in=82 mol/s

n NH 3
For feed ratio;  0,1
n NH 3  nair

82
 0,1
82  n air

28
 nair  738mol / s

%60 (by weight) HNO3(aq), this value is calculated %30 (by mole) HNO3(aq).

H balance;
3n NH 3in  2nH 2Oin  0,3nHNO3out  0,7(2)nHNO3out

nH 2Oin  10,5mol / s

N balance;
n NH 3in  0,3nHNO3out  n NOout

n NOout  34,9mol / s

O balance;
0,42nairin  nH 2Oin  (0,3(3)nHNO3out  0,7nHNO3out )  n NOout  2nO 2out

n NOout  2nO 2out  69,3

nO 2out  17,2mol / s

N2 balance;
nairin (0,79)  n N 2out

n N 2  583mol / s

Results of material balance for overall system;

29
 nH2O=10,5mol/s

nair=738mol/s
(0,21O2)
(0,79N2)
nHNO3(aq)=157 mol/s
Overall System
(0,88)
nNH3=82mol/s nNO=34,9mol/s

nO2=17,2mol/s nN2=583mol/s

Material Balance of Reactor

nair=738mol/s
(0,21O2)
(0,79N2) nH2O
reactor
(0,96)
nNH3=82mol nNO
/s

nO2 nN2

%96
Reactions: 4NH3+5O2 4NO+6H2O

Degrees of freedom;
ndf= 4 unknowns (nH2O, nNO, nN2, nO2)
-3 atomic balances (H, O, N)
ndf=1 ( not soluable)
Assumption;
-1 rxn. conv. (0,96)
ndf=0 (soluable)

N balance;

30
 n NH 3in (0,96)  n NOout

n NOout  78,7mol / s

O balance;
(0,42)nairin  n NOout  nH 20out  2nO 2out

n H 2Oout  2nO 2out  231,3

H balance;
3n NH 3in  2nH 2Oout

nH 2Oout  123mol / s

nO 2out  54,2mol / s

n N 2inout  583mol / s

Results of material balance for reactor;

nair=738mol/s
(0,21O2)
(0,79N2)
nH2O=123 mol/s
Reactor
(0,96)
nNH3=82mol/s nNO=78,7mol/s

nO2=54,2mol/s nN2=583mol/s

Material balance for condenser

NO2(n1)
nNO=78,7mol/s NO(n2)
nH2O=123mol/s Condenser H2O(n3)
nO2=54,2mol/s N2(n4)
nN2=583mol/s
O2(n5)

%95
Reaction: 2NO+O2 2NO2

31
Degrees of freedom;
ndf= 5 unknowns (n1, n2, n3, n4, n5)
-3 atomic balances (H, O, N)
-1 inert gases (N2)
ndf=1 (not soluable)
Assumption;
-1 conv. (0,95)
ndf=0 (soluable)

For conversion; 2n NO in  (0,95)  2n1

n1  nNO 2out  74,8mol / s

H balance;
2nH 20in  (0,95)  2n3

n3  nH 2Oout  123mol / s

N balance;
n N 0in  n1  n2

n2  n NOout  4mol / s

O balance;
n N 0in  nH 2Oin  (nO 2in  2)  2n1  n2  n3  2n5

n5  nO 2out  16,8mol / s

Results of material balance for condenser;

nNO=78,7mol/s NO2(n1)=74,8mol/s
nH2O=123mol/s NO(n2)=4mol/s
nO2=54,2mol/s Condenser H2O(n3)=123mol/s
nN2=583mol/s N2(n4)=583mol/s
O2(n5)=16,8mol/s

32
Material balance for absorber tower

H20(n4) NO(n1)
N2(n3)
O2(n2)

Absorber
nNO=4mol/s
nNO2=74,8mol/s
nH2O=123mol/s
nO2=16,8mol/s nHNO3(aq)=157mol/s
nN2=583mol/s

3NO2 + H2O 2HNO3 +NO

Degrees of freedom;
ndf= 4 unknowns (n1, n2, n3, n4)
-3 atomic balances (H, O, N)
-1 inert gases (N2)
ndf=0 (soluable)

N Balance;
n NO 2in  n NOin  n1  (nHNO3out  0,3)

n1  n NOout  35mol / s

H balance;
2n4  (2  nH 20in )  (nHNO3out  0,3)  (nHNO3out  0,7  2)

n4  nH 2Oin  10,5mol / s

O balance;
n4  (2  n NO 2in )  n NOin  nH 20in  (2  nO 2in )  n1  (2  n2 )  (nHNO3out  0,3  3)  (nHNO3out  0,7)

n1  2n2  69,5mol / s
n2  nO 2out  18,9mol / s

n3  n N 2out  583mol / s

33
Results of material balance for absorber;

H20(n4)=10,5mol/s NO(n1)=35mol/s
N2(n3)=583mol/s
O2(n2)=18,9mol/s

Absorber
nNO=4mol/s
nNO2=74,8mol/s
nH2O=123mol/s
nO2=16,8mol/s nHNO3(aq)=157mol/s
nN2=583mol/s

NOx Emission:

𝟑𝟒.𝟗 𝒎𝒐𝒍 𝟑𝟎 𝒈 𝟏𝟎𝟎𝟎 𝒎𝒈 𝟏𝟎𝟎𝟎 µ𝒈

× 𝟏 𝒎𝒐𝒍 × × = 1.05 × 109mg/s NO
𝒔 𝟏𝒈 𝟏 𝒎𝒈

61764000 µg NO /m3
gas
𝟔𝟑𝟓 𝒎𝒐𝒍 𝒈𝒂𝒔 𝟐𝟗 𝒈 𝟏𝒄𝒎𝟑 𝟏𝒎𝟑 𝒎𝟑
× × × = 𝟏𝟕 𝒈𝒂𝒔
𝒔 𝟏 𝒎𝒐𝒍 𝟏. 𝟏 𝒈 𝟏𝟎𝟎𝟎𝒄𝒎𝟑 𝒔

Legal Limitation: 200 ppm; process need an auxiliary for environment safety.

3.2. STREAM SUMMARY TABLE

34
Stream no 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Temp. 25 25 25 25 25 25 800 800 990 250 40 20 46 46
(oC)
Pres. 1 1 1 1 1 1 1 1 6 6 6 1 1 1
(atm)
Phase liq. liq. gas gas gas gas gas gas gas gas gas gas aq. gas
Molar flow 82 82 82 738 738 820 820 839 839 839 802 10,5 157 635
rate (mol/
s)
component
mol flow
(mol/s)
NH3 82 82 82 - - 82 82 - - - - - - -
O2 - - - 155 155 155 155 54,2 54,2 54,2 16,8 - - 17,2
N2 - - - 583 583 583 583 583 583 583 583 - - 583
NO - - - - - - - 78,7 78,7 78,7 4 - - 34,9
NO2 - - - - - - - - - - 74,8 - - -

H2O - - - - - - - 123 123 123 123 10,5 - -

HNO3 - - - - - - - - - - - - 15735 -
 3.3. ENERGY REQUIEMENTS FOR AMMONIA OXIDATION PROCESS

3.3.1. Calculation Of Heat Exchanger Before Reactor

Table-6 Entalphy of Components at 25oC, 1 atm and 800oC,1 atm

Component(g) ni(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)

NH3 82 -46.1 82 H1
N2 583 0 583 23.8
O2 155 0 155 25.3
[Ref 12]

1073
CpNH3=∆H0f + ∫298 𝐶𝑝𝑑𝑇
1073
H1= −46.1 + ∫298 ( 27.551 + 2.563𝑥10−2 T + 0.990x10−5 T 2 − 6.687x10−9 T 3 )dT
H1=-9.2
∆ H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖
Q=[(82x-9.2)+(155x25.3)+(583x23.8)]-[(82x-46.1)]
Q= 2.1x104kj/s=2.1x104 kW

3.3.2. Calculation Of Reactor

36
 8000C, 1atm 8000C, 1 atm
Reactor

NH3=82mol/s NO=78.7mol/s
O2=155mol/s H2O=123mol/s
N2=583mol/s O2=54.2mol/s
N2=583mol/s

Table-7 Entalphy of Components at 800oC and 1 atm

Component(g) nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)

NH3 82 H1
O2 155 25.3 54.2 23.8
N2 583 23.8 583 25.3
NO 78.7 H2
H2O 123 H3
[Ref 12]

1073
CpNH3=∆H0f + ∫298 𝐶𝑝𝑑𝑇
1073
H1= −46.1 + ∫298 ( 27.551 + 2.563𝑥10−2 T + 0.990x10−5 T 2 − 6.687x10−9 T 3 )dT
H1=-9.2kj/s

1073
CpNO=∆H0f + ∫298 𝐶𝑝𝑑𝑇
1073
H2= 90.3 + ∫298 ( 29.322 − 0.094𝑥10−2 T + 0.974x10−5 T 2 − 4.134x10−9 T 3 )dT
H2=1.2kj/s

1073
CpH2O=∆H0f + ∫298 𝐶𝑝𝑑𝑇
1073
H3= −241.8 + ∫298 ( 29.163 + 1.449𝑥10−2 T − 0.202x10−5 T 2 )dT
H3= -210kj/s

∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖

∆H=[(-1139.34) - (17042.5)] = -18181kj/s
3.3.2.1. Calculation Of ∆HRXN.XA
37
 4NH3 + 5O2 4NO +6H2O at 8000C (XA=0.96)

∆Hrxn=∑ 𝑛𝑝𝑟𝑜𝑑𝑢𝑐𝑡. 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − ∑ 𝑛𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡. 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

∆Hrxn=[(4∆HNO+6∆HH20) - (4∆HNH3+5∆HO2)]
∆Hrxn=[(4x78.7x1.2x102) + (6x123x-2.1x102)] –[(4x82x-9.2)]
∆Hrxn= -1.14x105 kj/s
∆Hrxn.XA = -1.14x105 x0.96= -1.1x105

∆HTOTAL=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖 + ∆Hrxn.XA

∆HTOTAL=Q=[(-18181) + (-1.1x105)]
∆HTOTAL=Q= -1.3x105 kj/s

3.3.3. Calculation Of Waste-Heat Reboiler

9900C, 6atm Waste-Heat 2500C, 6 atm

Reboiler

NO=78.7mol/s NO=78.7mol/s
H2O=123mol/s H2O=123mol/s
O2=54.2mol/s O2=54.2mol/s
N2=583 mol/s N2=583mol/s

Table-8 Entalphy of Components at 990oC, 6 atm and 250oC, 6 atm

Components(g) nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)

NO 78.7 81.9 78.7 97.12
H2O 123 83.164 123 53.276
O2 54.2 31.361 54.2 15.475
N2 583 38.9 583 15.262
[Ref 12]
∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖
∆H=[(23932.78) - (41053.17)]
∆H= -17120kj/s
3.3.4. Calculation Of Condenser Before Absorber at 6 atm

38
2NO + O2 2NO2................ ∆Hrxn= -5292kj/s.

Table-9 Entalphy of Components at 250oC, 6 atm and 40oC,6 atm

Components nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)

NO(g) 78.7 97.12 4 90.8
H2O(l) 123 53.276 123 3.30
O2(g) 54.2 15.475 16.8 9.1
N2(g) 583 15.262 583 9.07
NO2(g) 74.8 33.8
[Ref 12]
∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖 + ∆HrxnXA
∆H=[(8738.03) - (23932.78)] +-5292kj
∆H= -20486.75 kj/s

3.3.5. Calculation Of Energy Balance For Absorber

Table-10 Entalphy of Components at 40oC, 6 atm and ToC, 1 atm

39
Component(s) nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)
H2O(l) 133.5 3.3
NO(g) 4 90.8 32 90.4+29.5x10-3T
N2(g) 583 23.8 583 29x10-3T
O2 16.8 9.1 18.9 29x10-3T
NO2 74.8 33.8 29x10-3T
HNO3(aq) 157 -206.57+110x10-3T
[Ref 12]

∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖

∆H=0=34.8T – 304.2 - 87.75 – 1215
T=46oC

3.3.6.1. Calculation of ∆HRXN.XA at 40oC, 6 atm

3/ 2NO + O2 2NO2
2/ 3NO2 + H2O 2HNO3 +NO
4NO + 3O2 +2H2O 4HNO3.............(net reaction)

∆Hrxn=∑ 𝑛𝑝𝑟𝑜𝑑𝑢𝑐𝑡. 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − ∑ 𝑛𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡. 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

∆Hrxn=[(4∆HHNO3) - (4∆HNO+3∆HO2+ 2∆HH20)]
∆Hrxn=[(4x157x-206.57)] – [(4x4x90.8) + (2x133.5x3.3)]
∆Hrxn= - 1320 kj/s
∆Hrxn.XA = -1320x0.92= -1215kj/s

Total Energy Requirement

Heat Exchanger=2.1x104kW
Reactor= -1.3x105 kW
Waste-Heat Boiler= -17120 kW
Condenser= -20486.75 kW
Absorber( Reaction)= -1215 kW
Total= - 1.5x105 kW
3.4. CALCULATION COSTS OF 1ST PROCESS

40
Calculation of equipments size and amount of utilities were given Appendix 1.
Raw Material
𝑚𝑜𝑙 17𝑔 1𝑘𝑔
NH3= 82 =1.3kg/s
𝑠 1𝑚𝑜𝑙 1000𝑔
𝑘𝑔 3600𝑠 8400ℎ 1$ 1𝑡𝑜𝑛
1.3 150 1𝑡𝑜𝑛 = 5.8x106$/yr
𝑠 1h 1𝑦𝑟 1000𝑘𝑔

𝑚𝑜𝑙 29𝑔 1𝑚3 1𝑘𝑔 3600𝑠 8400ℎ 1$

Air=738 0.25 1𝑚3 = 13.2x105$/yr
𝑠 1𝑚𝑜𝑙 1.226𝑘𝑔 1000𝑔 1h 1𝑦𝑟

𝑚𝑜𝑙 18𝑔 1𝑘𝑔 3600𝑠 8400ℎ 1$

Water=10.5 0.53 = 3x103 $/yr
𝑠 1𝑚𝑜𝑙 1000𝑔 1h 1𝑦𝑟 1000𝑘𝑔

Heat Exchanger
𝑘𝑔 3600𝑠 8400ℎ 1$
Utility (water)= 38.4 0.08 = 9.3x104 $/yr
𝑠 1h 1𝑦𝑟 1000𝑘𝑔

Purchased cost of heat exchanger=10000$

Depreciation of heat exchanger=1000$/yr

Condenser
𝑘𝑔 3600𝑠 8400ℎ 1$
Utility (water)= 60 0.08 1000𝑘𝑔 = 1.5x105 $/yr
𝑠 1h 1𝑦𝑟

Purchased cost of heat condenser=7500$

Depreciation of heat condenser=750$/yr

Waste-Heat Boiler
𝑘𝑔 3600𝑠 8400ℎ 1$
Utility (water)= 31.3 0.08 1000𝑘𝑔 = 7.6x104 $/yr
𝑠 1h 1𝑦𝑟

Purchased cost of heat Waste-Heat Boiler=2000$

Depreciation of heat Waste-Heat Boiler=200$/yr

Absorber
Purchased cost of heat absorber=45000$
Depreciation of heat absorber=4500$/yr

Total Cost
41
Fixed Cost (Dep. of equipments) = 6450 $/yr
Operational Cost (Water + Raw material) = 319000 + 7123000= 7442000 $/yr
Total Cost: 7.44x106 $/yr

Table-11 Operational cost table included raw material and utility cost.

operational cost

Raw material

Utility
%99

Table-12 Total cost table included operational and fixed cost (raw material, utility and
depreciation of equipments)

total cost

operational cost

fixed cost
%99

4. FLOWSHEETING FOR COMBUSTION OF AIR METHODS

42
 4.1 DESIGN BASIS

NAME OF THE METHOD Brikeland and Eyde (Combustion of Air)

PLANT INFORMATION
Plant Location Sakarya
Design Capacity (ton/yr) 300.000
Purity (%) 35
RAW MATERIALS
O2
Source Air
Available Condition 25°C, 1 atm
Phase Gas
H2 O
Source River
Available Condition 20°C, 1 atm
Phase Liquid
RAW MATERIAL FEED RATIO
H2O/Air 0,50
OVERALL CONVERSION %72
PRODUCT SPECIFICATION
Product Nitric Acid
Composition %35 (by wt)
Phase Liquid
UTILITIES Electricity, Water
WATER
Source River
Available Condition 25°C, 1 atm
Phase Liquid

ELECTRICAL ARC

43
 Function Combustion of air
Conversion %72
Operational Temperature (°C) 1500
Operational Pressure (atm) 1
Material of Construction Stainless Steel
ABSORBER
Function Absorption of NO2 with H2O
Absorbtion Degree %92
Operation Type Adiabatic
Operational Temperature (°C) 40
Operational Pressure (atm) 6
Material of Construction Stainless Steel
WASTE MANANGEMENT
NOx Limitation 200 ppm

4.2. EQUIPMENT SUMMARY TABLE FOR COMBUSTION OF AIR PROCESS

44
 Name Code Function Temperat Pressure Material of Utility Operation
ure (atm) Constructi Type
(0 C) on
Electrical EA-101 Combustion 1500 1 Stainless Electric
Arc of air Steel

Compressor C-101 Compressed 1500-1813 1-6 Stainless Electric Polytrophi

of gasses Steel c

Waste Heat B-101 Cooling of 6 Stainless Water

Boiler gas mixture Steel

Condenser CD-101 Cooling of 250-40 6 Stainless Water

gas mixture Steel
for NO
oxidation
Absorber A-101 NO2 40 6 Stainless Adiabatic
absorbed Steel
with H2O
for
producing
nitric acid

4.4. FLOW DIAGRAM FOR COMBUSTION OF AIR METHODS

45
Figure-Flow diagram for combustion of air process

46
5. CALCULATIONS FOR COMBUSTION OF AIR PROCESS

5.1. MATERIAL BALANCE OF COMBUSTION OF AIR PROCESS

For capacity;
ton kg kmol mol year day
300000  1000   1000    157molHNO3 / s
year ton 63kg kmol 8400day 3600sn

%35 HNO3 (by weight) is manufactured by used this process.

Overall Material Balance

N2 + O2 → 2 NO
2NO + O2 → 2 NO2
3NO2 + H2O → 2 HNO3 + NO
Net Reaction : N2 + O2 + 2NO + 2 H2O → 4 HNO3

Degrees of Freedom:
N DF = 5 unknowns ( nair , nH2O , nO2 , nN2 ,nNO )
-3 atomic species ( H,N,O )
+2
Assumption: - 1 Overall Conversion (%72)
-1 Feed Ratio (nH2O / nair =0.5)

47
 0
%35 (by weight) HNO3(aq), this value is calculated %13 (by mole) HNO3(aq).

H atomic balance:
2 nH2Oin = n HNO3out (0,13 + 2 (0,87) )
2 nH2Oin = 157×1,87
nH2Oin = 147 mol /s
𝑛 𝐻2𝑂
Feed Ratio: = 0,5
𝑛𝑎𝑖𝑟

nair in = 147/0,5 =294 mol /s

N atomic balance:
nair in ( 0,79)(2) = 2 nN2out + n HNO3out (0,13) + nNOout
2 nN2out + nNOout = 444 mol/s

O atomic balance:
nair in ( 0,21)(2) + nH2Oin = 2 nO2out + n HNO3out ( (0,13×3) +0,87) + nNOin
294 ( 0,21)(2) + 147 = 2 nO2out + 157 ( (0,13×3) +0,87) + nNOout
nNOout =76 mol/s
2 nN2out + nNOout = 444 mol/s
nN2out = 202 mol /s

Result Of Overall Material Balance

48
Material Balance For Electrical Arc

N2 + O2 → 2 NO (conversion: %98)

Degrees of Freedom:
N DF = 3 unknowns (nO2, nN2, nNO)
-2 atomic species (N, O)
+1
Assumption: - 1 Reaction Conversion (%72)
0

Overall Conversion:
nair in (0,21) (0,20) = nO2out
294 (0,21) (0,20) = nO2out
nO2out = 12 mol/s

N atomic balance:
nair in ( 0,79)(2) = 2 nN2out + nNOout
2 nN2out + nNOout = 464 mol/s

O atomic balance:
nair in ( 0,21)(2) = 2 nO2out + nNOout
294 ( 0,21)(2) + 147 = 2 nO2out + 157 ( (0,13×3) +0,87) + nNOout
nNOout =99,5 mol/s
2 nN2out + nNOout = 464 mol/s

49
nN2out = 202 mol/s
Result Of Material Balance For Electrical Arc

Material Balance For Condenser

2NO + O2 → 2 NO2 (conversion: %98)

Degrees of Freedom:
N DF = 3 unknowns (nO2, nNO2, nNO)
-2 atomic species (N, O)
+ 1
Assumption: - 1 Reaction Conversion (%98)
0
Overall Conversion:
12 (0,02) = nO2out
nO2out = 0,3 mol/s

N atomic balance:
99,5in= nNO2out + nNOout

50
O atomic balance:
99,5 + 2 (12) = 2 nNO2out + nNOout + 2nO2out
2 nNO2out + nNOout = 12
nNO2out + nNOout = 99,5
nNO2out = 23,5 mol/s
nNOout = 76 mol/s

Result Of Material Balance For Condenser

Material Balance For Absorber

3NO2 + H2O → 2 HNO3 + NO (conversion:%92)

Degrees of Freedom:
N DF = 3 unknowns (nH2O, nO2, nNO )
-3 atomic species (H, N, O)

51
 0
N atomic balance:
23,5 + 76 = nNO out + nHNO3out (0,13)
23,5 + 76 = nNOout + 157 (0,13)

O atomic balance:
23,5 (2) + 76 + 2(12) = 2 nO2out + 76 + nHNO3out( (0,13×3)+0,87)
23,5 (2) + 76 + 2(12) = 2 nO2out + 76 + 157 ( (0,13×3)+0,87)
nO2out = 0,3 mol /s

Result Of Materıal Balance For Absorber

NOx Emission:

𝟕𝟔 𝒎𝒐𝒍 𝟑𝟎 𝒈 𝟏𝟎𝟎𝟎 𝒎𝒈 𝟏𝟎𝟎𝟎 µ𝒈

× × × = 2.3 × 109 mg/s NO
𝒔 𝟏 𝒎𝒐𝒍 𝟏𝒈 𝟏𝒎𝒈

315068000 mg NO /m3
gas
𝟐𝟕𝟖 𝒎𝒐𝒍 𝒈𝒂𝒔 𝟐𝟗𝒌𝒈 𝟏𝒎𝟑 𝟏𝒌𝒎𝒐𝒍 𝒎𝟑
× × × = 𝟕. 𝟑 𝒈𝒂𝒔
𝒔 𝟏 𝒌𝒎𝒐𝒍 𝟏. 𝟏 𝒌𝒈 𝟏𝟎𝟎𝟎𝒎𝒐𝒍 𝒔

52
Legal Limitation: 200 ppm; process need an auxiliary for environment safety.
5.2. STREAM SUMMARY TABLE FOR COMBUSTION OF AIR PROCESS

Stream No 1 2 3 4 5 6 7 8

Temperature ( 0 C ) 25 1500 250 40 25

Pressure (atm) 1 1 6 6 6 1 6 6

Phase Gas Gas Gas Gas Liquid Liquid Gas Aq.

Mass Flow Rate (kg/ 8,5 9 9 9 9 4,12 7,95 4,95

s)
Mole Flow Rate 294 313,5 313,5 313,5 302 147 278 157
(mol /s)
Composition

N2 232 202 202 202 202 - 202 -

O2 62 12 12 12 0,34 - 0,3 -

NO - 99,5 99,5 99,5 76 - 76 -

NO2 - - - - 23,5 - - -

H2 O - - - - - 147 - -

53
HNO3 - - - - - - - 157

5.3. ENERGY REQUIREMENT FOR COMBUSTION OF AIR PROCESS

5.3.1. Calculation For Energy Required At Electric Arc (25oC to 1500 oC)

5.3.2. Calculation For Energy at Electric Arc

25oC, 1atm 1500oC, 1 atm

Electric arc
N2=232mol/s N2=202mol/s
O2=62mol/s O2=12mol/s
NO=99.5mol

N2 + O2 2NO ........∆Hrxn=29890 kj/s (XA=0.80)

Table-13 Entalphy of Components at 25oC, 1 atm and 1500oC, 1 atm

Component nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)

O2 62 0 12 50.78
N2 232 0 202 48.06
NO - - 99.5 150.2
[Ref 12]
∑∆H= ∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖 + ∆Hrxn.XA
∑∆H= [(12x50.78+ 202x48.06 + 99.5x150.2)] - [0] + ∆Hrxn.XA
∑∆H= 49174.4 kW

5.3.3. Calculation For Energy Waste-Heat Reboiler

18130C, 6atm 2500C, 6 atm

N2=202mol/s N2=202mol/s
O2=12mol/s O2=12mol/s
NO=99.5mol/s NO=99.5mol/s

54
Table-15 Entalphy of Components at 1813oC, 6 atm and 250oC, 6 atm
Components nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)
N2 202 64.798 202 15.265
O2 12 156.0 12 15.475
NO 99.5 152.5 99.5 97.12
[Ref 12]
∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖
∆H= [(202x15.265 + 12x15.475+ 99.5x97.12) - (64.8x202 + 156x12 + 152x99.5)]
∆H= -17153 kj/s

5.3.4. Condenser Calculation Before Absorber at 6 atm

2NO + O2 2NO2................ ∆Hrxn= -5292kj/s.

Table-16 Entalphy of Components at 250oC, 6 atm and 40oC, 6 atm

Component nin(mol/s) (Hi)in(j/mol) nout(mol/s) Hout(j/mol)
N2 202 15.265 202 9.07
O2 12 15.475 0.34 9.1
NO 99.5 97 76 90.8
NO2 23.5 34.3
[Ref 12]

∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖 + ∆HrxnXA

∆H=[(202x9.07 + 9.1x0.34 + 76x90.8) - (202x15.265 + 12x15.475 + 99.5x97)] + (5292x0.98)
∆H= -1002 kj/s

55
5.3.5. Calculation Of Energy Balance For Absorber

Table-17 Entalphy of Components at 250oC, 6 atm and ToC,1 atm

Component nin(mol/s) (Hi)in(kj/mol) nout(mol/s) Hout(kj/mol)
H2O 147 3.3
NO 76 90.8 76 90.4+29.5x10-3T
N2 202 23.8 202 29x10-3T
O2 12 9.1 0.3 29x10-3T
NO2 23.5 33.8 29x10-3T
HNO3(aq) 157 -206.57+110x10-3T
[Ref 12]
∆H=Q=∑𝑜𝑢𝑡𝑝𝑢𝑡 𝑛𝑜𝑢𝑡. 𝐻𝑜𝑢𝑡 − ∑𝑖𝑛𝑝𝑢𝑡 𝑛𝑖. 𝐻𝑖
∆H=0=25.4(T – 25) - 25561
T=69oC

56
5.3.5.1. Calculation Of ∆HRXN.XA at 40oC, 6 atm
3/ 2NO + O2 2NO2
2/ 3NO2 + H2O 2HNO3 +NO
4NO + 3O2 +2H2O 4HNO3.............(net reaction)

∆Hrxn=∑ 𝑛𝑝𝑟𝑜𝑑𝑢𝑐𝑡. 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − ∑ 𝑛𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡. 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

∆Hrxn=[(4∆HHNO3) - (4∆HNO+3∆HO2+ 2∆HH20)]
∆Hrxn=[(4x157x-206.57)] – [(4x76x90.8) + (2x147x3.3)]
∆Hrxn= -1600kj/s
∆Hrxn.XA = -1600x0.92= -1472kj/s

Total Energy Requirement

Electric Arc =49174.4 kW
Waste-Heat Boiler= -17153 kW
Condenser= -1002 kW
Reaction= -1472 kW
Total= 29547 kW

57
5.4. CALCULATIONS COSTS FOR COMBUSTION OF AIR PROCESS

Equipments size calculations and amount of utilities were given at Appendix 2.

Raw Material
𝑚3 3600𝑠 8400ℎ 1$
Air=7.7 0.25 1𝑚3 = 5.8x105$/yr
𝑠 1h 1𝑦𝑟

1𝑘𝑔 3600𝑠 8400ℎ 1$

Water=2.6 0.53 = 0.41x105$/yr
𝑠 1h 1𝑦𝑟 1000𝑘𝑔

Electric Arc
Purchased cost of Electric Arc=2.25x106$
Depreciation of Electric Arc=2.25x105$

Condenser
𝑘𝑔 3600𝑠 8400ℎ 1$
Utility (water)= 33.4 0.08 = 8.1x104 $/yr
𝑠 1h 1𝑦𝑟 1000𝑘𝑔

Purchased cost of heat condenser=80000 $

Depreciation of heat condenser=8000 $/yr

Waste-Heat Boiler
𝑘𝑔 3600𝑠 8400ℎ 1$
Utility (water)= 26 0.08 1000𝑘𝑔 = 6.3x104 $/yr
𝑠 1h 1𝑦𝑟

Purchased cost of heat Waste-Heat Boiler=5000 $

Depreciation of heat Waste-Heat Boiler=500 $/yr

Absorber
Purchased cost of heat absorber=60000 $
Depreciation of heat absorber=6000 $/yr

Cost of electricity
29547kW x 0.045$/kW.h x 8400h/yr = 1.2x107$/yr

58
Total Cost
Fixed Cost (Dep. Of equipments)= 239500 $/yr
Operational Cost (Water + Raw material + Electricity)
= 144000 + 621000+1.2x107 = 1.28x107$/yr
Total Cost: 1.3 x107$/yr

Table-18 Operational cost table include raw material and utility cost.

Operational Cost
6%

Raw material
Utility

94%

Table-19 Total cost graphic include operational and fixed cost. (Raw material, utility and
depreciation of equipments)

Total cost
2%

operation cost
fixed cost

98%

59
 6. RESULTS
6.1. COMPARASION TABLE
Method of Production
Quality of product
Plant capacity (ton/year)
Efficiency
Number of main equipment
Material construction of
equipment
Raw materials
Amount of raw material
Cost of raw material
Reaction condition
Low, medium or high pressure
Catalyst
(regenerated time:18
Amount of catalyst
Cost of catalyst (Pt)
Energy Requirement
Utilities
Utility cost
Safety
Waste management
Total cost ($/ton)
1st Process 2nd Process
(Oxidation of NH3) (Combustion of Air)
%50-60 %35
300000 300000
%92-98 %72
2 2
Reactor, absorber Electrical arc, absorber
Stainless steel Stainless steel
NH3, air, water Air, water
NH3:155 ton/yr Air: 1,38  108 m3/yr
Air: 2,5  107 m3/yr Water: 6,7  105 ton/yr
Water: 130 ton/yr
NH3: 5,8x106 $/yr Air: 6200 $/yr
Air:1,32x10 $/yr Water: 6,21x105 $/yr
Water: 3000 $/yr
800 oC 2000-3000 oC
Atmospheric pressure
Pt, Fe2O3, Cr2O3 Catalyst is not used
(Commercially Pt)
month)
300 mg Pt/ton nitric acid -
158 $/ton
-1.5x105 kW +9199 kW
Electric
Water Water
Water:3.2x105 $/yr Electric:1.28x107 $/yr
Water: 1.4x105 $/yr
Pressure may be higher Temperature is very higher
61764ppm 315068 ppm
Limitation: 200 ppm Limitation: 200 ppm
25 189
60
 6.2. COST ANALYSE

Contents of Depracia Contents of Raw Utility Utility Total

Equipment tion of Raw Material Cost Cost
Equipme Material Cost ($/year) ($/yr)
nts ($/year)
($/year)
NH3
Ammonia Heat Exchanger 6450
Oxidation Condenser 7,1 x 106
Process Water 3.2x105 7,4x106
Waste Heat Air
Boiler

Absorber Water

Electrical Arc
Combustio Air Electricity
5
n of air Condenser 2,39x10
Process 6,27x105 1.28x107 1.3x107
Waste Heat
Boiler Water Water

Absorber

For first method manufacturing cost; 25 $/ton

For second method manufacturing cost; 189 $/ton
Sales pricing cost in Turkey; 400$/ton

61
6.3. DECISION OF FINAL METHOD AND FLOWSHEETING
According to market search, produced for chemical industry was decided. Chemical industry
was selected as the target market. Final product quality was determined as %65 by weight for
chemical industry and plant location was determined Sakarya.

After all researc and calculations, two processes were comparated according to safety,
economical feasibility, environmental safety. With regart to safety and environmental
feasibility both of two process were same. According to economical feasibility, also two
process was suitable as compared to nitric acid sales price at now. But; while for first method,
manufacturing cost was 24$/ton, for second method manufacturing cost was 189$/ton. So,
ammonia catalytic oxidation method was more economical than combustion of air method.

After this report, ammonia catalytic oxidation method was selected as suitable nitric acid
production methods.

62
6.3.1. DEVELOPMENT FINAL FLOWSHEETING OF AMMONIA OXIDATION
PROCESS

63
NAME OF THE METHOD Oswalt Method (Ammonia Oxidation)
PLANT INFORMATION
Plant Location Sakarya
Design Capacity (ton/yr) 300.000
Purity (%) 65
RAW MATERIALS
NH3
Available Conditions 25°C, 1 atm
Phase Liquid
Purity %99
O2
Source Air
Available Condition 25°C, 1 atm
Phase Gas
H2 O
Source River
Available Condition 25°C, 1 atm
Phase Liquid
RAW MATERIAL FEED RATIO
NH3/( NH3+Air) 0,10
OVERALL CONVERSION %96
PRODUCT SPECIFICATION
Product Nitric Acid
Composition %65 (by wt)
Phase Liquid
UTILITIES Electricity, Water
WATER
Source River
Available Condition 20°C, 1 atm
Phase Liquid

EVAPORATOR 64
Code E-101
 Function Evaporated of ammonia
Material of construction Stainless steel
Operational Temperature (°C) 25-800
Operational Pressure (atm) 1
MIXER
Code M-101
Function Mixing of ammonia and water
Operational Temperature (°C) 800
Operational Pressure (atm) 1
Material of construction Stainless steel
Utility Electricty
HEAT EXCHANGER
Code HE-101
Function Cooling of gas mixture
Operational Temperature (°C) 900-250
Operational Pressure (atm) 6
Material of construction Stainless steel
Utility Water
Utility Available Conditions 20°C, 1 atm
REACTOR
Code R-101
Function Ammonia oxidation
Conversion %98
Catalyst Pt
Catalyst Regeneration Time (month) 18
Operation Type Adibatic
Operational Temperature (°C) 800
Operational Pressure (atm) 1
Material of Construction Stainless Steel

CONDENSER
Code CD-101

65
 Function Cooling of gas mixture for NO oxidation
Operational Temperature (°C) 250-40
Operational Pressure (atm) 6
Material of Construction Stainless Steel
Utility Water
Utility Available Conditions 20°C, 1 atm
ABSORBER
Code A-101
Function Absorption of NO2 with H2O
Absorbtion Degree %92
Operation Type Adiabatic
Operational Temperature (°C) 40
Operational Pressure (atm) 6
Material of Construction Stainless Steel
EVAPORATOR
Code E-102
Function Vaporazition of water for making %65 by
weight nitric acid
Operational Temperature (°C) 20-100
Operational Pressure (atm) 1
Material of construction Stainless steel
WASTE MANANGEMENT
NOx Limitation 200 ppm

6.3.2. EQUIPMENT SUMMARY TABLE FOR AMONIA OXIDATION PROCESS

66
 Name Code Function Temperatue Pressure Material of Utility Operation
(0 C) (atm) Construction Type
Storage ST-101 Storage of 20 1 Stainless Steel -
Tank NH3
Filter F-101 Cleaning of 20 1 Stainless Steel
NH3
Evaporator E-101 Evoparated 20 1 Stainless Steel Steam
of NH3
Filter F-102 Cleaning of 20 1 Stainless Steel
air
Mixer M-101 Mixing of 20 1 Stainless Steel
air and NH3
Heat HE-101 Heating of 20-800 1 Stainless Steel Steam
Exchanger gas mixture
for rxn
condition
Reactor R-101 Reaction of 800 1 Stainless Steel Catalyst Adiabatic
ammonia (Pt)
oxidation

Compressor C-101 Compressed 1-6 Stainless Steel Electric Polytrophic

of gasses

Waste Heat B-101 Cooling of 6 Stainless Steel Water

Boiler gas mixture

Condenser CD-101 Coolig of 250-40 6 Stainless Steel Water

gas mixture
for NO
oxidation
Absorber A-101 NO2 40 6 Stainless Steel Adiabatic
absorbed
with H2O for
producing
nitric acid
Evaporator E-102 Evaporated 20-100 1 Stainless Steel
of water and
making %65
by wt nitric
acid
Absorber A-102 NO 40 6 Stainless Steel Adiabatic
absorbed
with H2O for
waste
management

6.3.4. DESCRIPTION OF FLOWCHART

67
NH3 in storage tank was sent to filter for purification from impurity. After the filter; ammonia
was sent to evaporator and NH3 was evaporated in the evaporator. Other hand; air was sent to
filter for purification from impurity. Air from the filter and ammonia from the evaporator
were mixed in mixer. This mixing was sent to heat exchanger for heating of gas mixture from
25°C to 800°C. Steam was used as utility for heat exchanger. Gas mixture which include N 2,
O2 and ammonia was sent to reactor. Operational conditions of reactor were 800°C and 1 atm.
In reactor; ammonia was oxidated and NO was generated and platin was used as catalyst.
Reaction’s conversion was %98. After the reactor, pressure was increased from 1 atm to 6 atm
with compressor. Temperature was increased from 800°C and 960°C with compressor. Then,
gas mixture was sent to waste heat boiler, in there temperature was decreased from 960°C to
250°C. After the waste heat boiler, utility water was evaporated. Steam which generated in
waste heat boiler was used heat exchanger utility for heat exchanger before the reactor. Gas
mixture was condensed from 250°C to 40°C in condenser. NO was oxidated to NO2 after the
waste heat boiler. NO, NO2, N2 and O2 gas mixture was sent to absorber. Absorber’s
operational conditions was 40°C and 6 atm. Water was sent to absorber. In absorber, NO2 was
absorbed with water and nitric acid (%60 by wt) was generated. NO, N2 ve O2 gas mixture
was exited at top stream and nitric acid was exited at bottom stream. Nitric acid %60 by
weight was sent to evaporator. In evaporator, water was evaporated and nitric acid was
formed as %65 by weight.

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6.3.5. FLOW DIAGRAM

Figure-8 Development flow diagram for ammonia oxidation methods

69
6.3.6. CALCULATION OF CONCENTRATED NITRIC ACID

Material balance for concentrated nitric acid (%65 by weight);

Water in aqua solution at first;

nH 20  157(0,70)  110mol / s

Nitric acid in aqua solution at first;

nHNO3  157(0,30)  47mol / s

For making %32,5 by mole HNO3;

47
 0,325
47  n H 2O

nH 20  98mol / s

Amount of water to be vaporization;

110  98  12mol / s

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CALCULATION OF ABSORPTION OF NOx FOR WASTE MANAGEMENT
Material balance for absorber tower
Possible legislation value; 200 mg NOx/m3 gas

mgNO
200ppm= 200
m 3 gas

1gr 1molNO
200mgNOx x  6,7 x10 3 molNO (should be out of absorber)
1000mg 30 gr

1000dm 3 1lt gr 1mol

1m 3 gasx 3
x 3
x1,25 x  41,6 mol gas
1m 1dm lt 29 gr
n NO  n N 2  41,6mol

n N 2  41,5mol
so assumption variables for waste management ;
nNO = 6,7x10-3 mol /s
nN2 = 41,5 mol/s

nH20 nNO= 6,7x10-3 mol /s

nN2= 41,5 mol/s
Absorber

nNO=34.9mol/s

nair

nHNO3

2NO + O2 2NO2
3NO2 + H2O 2HNO3 +NO

Degrees of freedom;
ndf= 3 unknowns (nH20, nair, nHNO3)
-3 atomic balances (H, O, N)
-1 inert gases (N2)
ndf=0 (soluable)

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N 2 inert Balance;
0.79nair  n N 2out

nair  52.5mol / s
H balance;
2(n H 2O )  0,3(n HNO3out )  2 x0,7(n HNO3 )

nH 2O  0,85nHNO3
O balance;
(n NOin )  nH 20in  (0.42  nairin )  (n NOout )  (3x0,3nHNO3out  0,7nHNO3 )

35  n H 20in  (0.42  52,5)  (6.7 x10 3 )  1,6n HNO 3

n H 2O  57  1,6(n HNO3 )

n H 2O  65mol / s
n HNO3  76mol / s

Results of material balance for absorber;

nH2O= 65 mol/s nNO=6,7x10-3 mol/s

nN2=41,5 mol/s

Absorber
nNO= 35 mol/s

n air =52,5 mol/s nHNO3(aq)=76 mol/s

72
 6.3.7. STREAM SUMMARY TABLE

Stream no 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Temp. 25 25 25 25 25 25 800 800 990 250 40 20 46 46 -- --

(oC)
Pres. 1 1 1 1 1 1 1 1 6 6 6 1 1 1 1 1
(atm)
Phase liq. liq. gas gas gas gas gas gas gas gas gas gas aq. gas aq. aq.
Molar flow 82 82 82 738 738 820 820 839 839 839 802 10,5 157 635 157 143
rate (mol/
s)
component
mol flow
(mol/s)
NH3 82 82 82 - - 82 82 - - - - - - - - -

O2 - - - 155 155 155 155 54,2 54,2 54,2 16,8 - - 17,2 - -

N2 - - - 583 583 583 583 583 583 583 583 - - 583 - -
NO - - - - - - - 78,7 78,7 78,7 4 - - 34,9 - -
NO2 - - - - - - - - - - 74,8 - - - - -

H2O - - - - - - - 123 123 123 123 10,5 - - 12 98

HNO3 - - - - - - - - - - - - 157 - - 47

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 7. DISCUSSION

In this project, suitable nitric acid production method was selected. For this aim, plant
capacity was determined as 300.000 ton/year from market analysis.

According to market analyses; nitric asit is widely used fertilizer industry (%75), chemical
industry, making an explosive and nylon (%25) in our country. Most of the fertilizer
companies, used of nitric asit is manufactured by them. Because these companies are not
often buy the nitric acid, selling the nitric acid is very difficult these companies. On the other
hand, the nitric acid which is used as a chemical solution at chemical industry is generally
imported. So, this situation mean that high cost of Turkey. The nitric acid which will
produced should manufacture an optimum condition

Flow rate of the final product was calculated as 157 mol/s. Plant location was determined as
Bursa. Three method use for nitric acid production. These are; manufacture from Chile
Saltpetre and sulphiric acid, manufacture by electrical oxidation of the air and manufacture by
catalytic oxidation of ammonia. After this report; suitable nitric acid production method was
determined.

74
Manufacture from Chile Saltpetre and sulphiric acid process was eliminated at first. Using
raw material of this method is consumed away in the world. So; this method was not suitable
for long term investments. For this reason, manufacture by electrical oxidation of the air and
manufacture by catalytic oxidation of ammonia methods examined in detail.

In catalytic oxidation of ammonia method, water, air and ammonia were used as raw material.
Final product quality (nitric acid) for this method was %60 by weight. Three reactions were
occured in the reactor and conversion of this reaction was %98. Platin was used as catalyst in
reactor. Operational conditions of reactor was 800°C and 1 atm. Reactor pressure was 1 atm
because; catalyst poisions at high temperature. After the reactor; pressure was increased from
1 atm to 6 atm with compressor. NO oxidation reaction conversion was high at high pressure.
So; pressure was increased. For this method, overall conversion was calculated as %96.
Amounts of the raw material were calculated and energy requirement was calculated. In this
process, while heat exchanger before the reactor was requirement energy; reactor, waste heat
boiler and condenser were generated energy. Energy recovered of the system was calculated
as -1.5x105 kW. For this method, approximately cost was calculated. This cost was included
raw material cost, utility cost and depreciation of equipments. Cost of catalyst was included in
utility cost. Raw material cost which include ammonia, water and air was calculated as
1,7x107 $/year. Utility cost (water) was calculated as 3,2x105 $/year. Electricty cost was not
calculated because; 1.5x105 kW energy was provided from the overall system. Depreciation
of the equipments which heat exchanger, absorber, condenser, reactor, waste heat boiler was
calculated as 6450 $/year.

Total cost was calculated as 7.4x106 $/year. Raw material cost was the most highest cost and
it was included %99 of the total cost.

In manufacture by electrical oxidation of the air method; air and water were used as raw
material. Final product quality (nitric acid) for this method was %35 by weight. Three
reactions were occured. First reaction is combustion of air. Other two reaction was the same
with ammonia oxidation process. Combustion of air was provided in electrical arc.
Operational conditions of electrical arc were 1 atm, 1500°C. In this condition, N2 was
combusted with O2. N2, O2 and NO gas mixture was cooled for NO oxidation. So, waste heat
boiler and condenser were used and temperature was decreased at 40°C. Pressure was
increased from 1 atm to 6 atm. Becuse; NO oxidation was increase with high pressure.

75
Overall conversion for this process was calculated as %72. After the determination; amount of
the raw materials was calculated. Energy requirement of this system was calculated as 9199
kW. Total cost was calculated and this cost was included raw material cost, utility cost and
depreciation of equipments. Raw material cost which include air and water was calculated as
6,21x105 $/year. Utility cost (water and electricty) was calculated as 5.7x106 $/year.
Electricity cost was included %99 of the total cost. Depreciation of the equipments which
electrical arc, waste heat boiler, condenser and absorber was calculated as 2,4x105 $/year.
Total cost of this system was calculated 1,3x107 $/year. Utility cost was included %95 of the
total cost.

After this calculations, for manufacturing cost for the ammonia oxidation process was 24
$/ton, for combustion of air process manufacturing cost was calculated as 43 $/ton. In
ammonia oxidation, raw material cost was very higher. This cost was included %99 of the
total cost. In combustion of air method, utility cost was very higher. This cost was included
%95 of the total cost. While final product quality for ammonia oxidation process %60 by
weight, for combustion of air method was %35 by weight. Nitric acid was usually used as
%55-65 according to market analysis and in chemical industry for chemical material was used
as %80-90. So, combustion of air method was need auxilary equipments after the absorber for
concentrated nitric acid production.

For two method, high pressure was selected after the first reaction unit. Because; eqipments
size was smaller with high pressure. Efficienty of the oxidation and absorption was higher at
high pressure. Wall thickness was calculated for high pressure and this difference was not
effected of the equipment cost.

Nitric acid sales price is 400$/ton in Turkey. For first method, manufacturing cost was
25$/ton, for second method manufacturing cost was 44$/ton. So, both of two process
economical feasible.
Amount of NO emission was 35 mol/s for ammonia oxidation method and also it was 76
mol/s for combusiton of air method. So, ammonia oxidation process is more friendly than the
other.

After the all calculations, both of two method according to technical feesibility,
environmental friends, and safety were suitable. But, ammonia oxidation method was more

76
economical than combustion of air method. So, manufacture by catalytic oxidation of
ammonia method was selected as suitable nitric acid production method.

8. RECOMMENDATIONS

After end of this project, 1st process (oxidation of ammonia) which is the most suitable
process to produce nitric acid was selected. Ammonia, water and air are used as raw materials
in this process. Ammonia is bought from anywhere with money. Also ammonia is widely
used in chemical industry, so supplying of ammonia has some problems for future. We could
have produced the ammonia for required to our use. Then this ammonia may use to produce
the nitric acid. But this situation is not suitable for short-term investment. Because,
establishing the system which produced to ammonia is caused high cost. If long-term
investment is made for future, ammonia will produced by our.

We target that the produced nitric acid (%60’s) is sold at chemical industries as a chemical
solution. But these companies were used %65’s nitric acid, so auxiliary equipment is required
in system. This equipment is concentrated the nitric acid.

77
 8. REFERENCES

1. Horton,A., “European Chemical News, Large Plant Supplemen”, Page 56, September
30, 1996.
2. Oosterwijk,D.C., “The Choice of a Nitric Acid Plant”, Page 44, 1966.
3. Crosslev, A. W., "The Utilisation of Atmospheric Nitrogen'" (Thorpe's " Dictionary of
Applied Chemistry," ) Vol. III., Page. 698, 1912.
4. Norton,T., E.,"Consular Report on the Utilisation of Atmospheric Nitrogen.",
Washington, 1912.
5. Spratt.,D.,A.,“Nitrogen Fertiliser Chemical Process, Noyes Development
Corporation”, New York, 1965
6. Harrison,R.,H., Lobe.,L.A, “Chemical Engineering Program”, Page 49,349 ,1993.
7. http://resources.schoolscience.co.uk/johnsonmatthey/page8.htm, 20.02.2011
8. http://ekutup.dpt.gov.tr/ab/, 20.02.2011
9. http://www.grc.nasa.gov/WWW/K-12/airplane/airprop.html
10. .http://www.edinformatics.com/interactive_molecules/water.htm
11. http://www.gib.gov.tr/fileadmin/user_upload/ArsaArazi2010
12. http://www.webbok.nist.gov/chemistry/fluid/ 20.02.2011

78
NOMENCLATURE

n: Number of mole, mol

m: Mass of material, kg
xs: Mass or mole fraction in general
: density, kg/m³
Q: Heat transferred, kj/s
Cp: Heat capacity at consant pressure, kj/kg.
A= Heat Transfer surface, m2
T : Temperature difference, oC
Tlm: logarithmic mean temperature difference, C
U: overall transter coefficients; W/m2K

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80