NITROGEN

INDUSTRIES
CELAJES & JAGOLINO
 CONTENT
01 INTRODUCTION

02 HISTORY

03 SYNTHETIC AMMONIA

04 RATE AND CATALYSIS OF REACTION

05 MANUFACTURING PROCEDURES

06 SYNTHESIS SYSTEMS

07 DEFINITION &USES OF COMPOUNDS WITH NITROGEN

CONTENT
INTRODUCTION
Nitrogen from air is the major ingredient of fertilizers.
Primary sources of agricultural nitrogen before
synthetic nitrogen by products were:
Wastes and manures of various types or their decomposition products
Ammonium sulfate- by product of coal coking

They were messy and insufficient to meet needs.

Chilean saltpeter, saltpeter from human and animal urine, ammonia recovered
from coal manufacture became important. But then was replaced by synthetic
ammonia and nitrates.

Ammonia is base from which virtually all nitrogen containing products are
derived.
 HISTORY
According to Priestly and Cavendish, Alkalis were formed by passing electric sparks through air and
produced nitrates by dissolving the oxides of nitrogen.

This process was commercialized but found to be elusive because it is efficiently low and consumes
much energy.

Nitrogen has fixed as calcium cyanamide, but this process is too expensive except for producing
chemicals requiring the cyanamide configuration.

Other processes such as thermal processing to mixed oxides of nitrogen (NOx), cyanamide
formation, aluminum nitride formation, and decomposition to ammonia were used but show little
promise although they are technically possible.
 HISTORY
Haber and Nernst made careful studies of the equilibrium between nitrogen and hydrogen under
pressure to form ammonia and discovered several suitable catalysts. No high-pressure apparatus was
then available, so they had to invent it as they went along.

Also, Haber and Bosch worked out a process for obtaining inexpensive hydrogen and nitrogen by a
workable process.
The obvious electrolysis of water for hydrogen production and the distillation of liquid air to provide
nitrogen proved unduly expensive.

They derived in other process and by 1913, with their cooperative efforts, A commercial high-pressure
synthesis of ammonia was made possible. This energy intensive process has undergone considerable
modifications through the years, resulting in prices which have not escalated as rapidly as energy prices
in general. Major improvements are very recent and continuing at a fast pace.
RAW MATERIALS USED TO MANUFACTURE NH3
& NITROGENOUS FERTILIZERS
SYNTHETIC AMMONIA
Ammonia is the most important nitrogenous material. Major amounts of this
material are created synthetically, and the rest is still obtained as a by-
product. Chilean salt pepper (NaNO3) continues to be mined and is a
significant source of fixed nitrogen. It is used directly as a fertilizer, in heat
treating, paper pulping, nitric acid and nitrates manufacture, nitric acid ester
and nitro compound manufacture, explosives of various types, and as a
refrigerant.

Note: Urea, Hydroxylamine, and hydrazine are made from it. Amines, amides, and
miscellaneous other organic compounds are derived from Ammonia.
RATE AND CATALYSIS OF
REACTION
Reaction Equilibrium
“Greater Rate means reduced equipment size and consequent equipment cost.”

Rate of reaction must be increased substantially to keep the small size of the equipment.
For commercial synthesis, they require an efficient catalyst to increase the reaction rate to
an acceptable figure.

Plants use iron with added promoters-oxide of aluminum, zirconium, or silicon at about 3%
concentration and potassium oxide about at about 1% as its catalyst.

Catalysts are also deactivated by contact with copper, phosphorus, arsenic, sulfur, and
carbon monoxide. Catalysts are sufficiently robust to withstand higher levels of impurities
and effective at lower temperatures (permitting higher equilibrium conversions) would be
most valuable.
RATE ANDCATALYSIS OF
REACTION
N and H chemically react with surface interactions or absorbed. They then form H, N, NH,
NH2, NH3 in that order and is followed by desorption.

Space Velocity is the volume of gases corrected to standard condition that pass over one
volume of catalyst per unit minute.

Note: Percentage of ammonia produced at given temperature and pressure and for a given
catalyst varies. With increase in space velocity results to a decrease in percent ammonia
produced.

Therefore, most industrial units use a space velocity between 10000 to 20000 per hour.
RATE AND CATALYSIS OF
REACTION
RATE AND CATALYSIS OF
REACTION
MANUFACTURING PROCEDURES

https://www.youtube.com/watch?v=9P1iZBV-EKw
MANUFACTURING PROCEDURES
Manufacturing consists of six phases, such as: Manufacture of reactants, purification, compression, catalytic reaction, recovery of
ammonia formed, and recirculation.

Cost is greatly influenced by pressure, temperature, catalyst, and raw materials used.

To lessen the cost, industries’ focus is on heat recovery and reuse.

Elimination of intermediate storages, single train construction, and the use of rotary (replacing reciprocating) compressors made
tanks to become much larger (1650 t/day).

Due to the great increase of cost in energy, it made to become more complex because of the need of energy conservation.
In 1950, 55.9 GJ/t were required for ammonia production. And by 1982 it was reduced to 26 GJ/t and continues to decrease. Many
plants produce steam for outside use while requiring little use of energy for input. This leads to keeping the prices of ammonia at
a low cost.

In 1982, Hydrogen manufacturing process in the United state was a combination process of natural gas, air, and steam with
addition of heat over a catalyst produces a 3:1 ration of Hydrogen and Nitrogen mixture with carbon Dioxide and water.
Other systems used are electrolysis of water, by-product hydrogen, cracking of hydrocarbons, coal-water and hydrocarbon-water
interactions, and partial oxidation of Hydrocarbons.
SYNTHESIS SYTEMS
An ammonia-synthesis converter consists of
a high-pressure shell containing a catalyst
section and a heat exchanger. The catalyst
section is a cylindrical shell that fits inside
the pressure shell, leaving an annular space
between the two. The catalyst section
contains several beds supported on screen
grids. Cold feed gas quench is injected
before each catalyst bed to maintain the
catalyst at optimum temperature for
maximum yield. Also, the top bed contains
the smallest quantity of catalysts. Heat
exchanger is located beneath the catalyst
section which preheats fresh inlet gas
against hot reacted gas from the last
catalyst bed. Top quench point permits the
introduction of feed gas without preheating
and provides temperature control to the first
bed.
SYNTHESIS SYTEMS
All ammonia syntheses are based on the overall reaction. It is quite an exothermic
reaction, so its converter design must be protected from overheating to ensure
control at the optimum temperature for conversion and to prevent metallurgical
deterioration of its shell at the high pressure and temperature.

Ammonia synthesis gas is prepared by high-pressure catalytic reforming of

hydrocarbon feed. Natural Gas is usually freed of Sulfur in the process of steam over
a nickel catalyst in the primary reformer, then is subjected to a catalytic “shift” at a
lower temperature in the process of air in one or more secondary reformers.

Purpose of shift reaction is to:

1.Produce more hydrogen per unit fuel.
2.Oxidize much of the carbon monoxide to the more easily removed carbon dioxide.

Also, it is customary to add an oversize charge to the low-temperature shift catalyst

bed.

This “guard” catalyst captures sulfur and chlorine poisons that extend the main
catalyst’s life over 100 percent.
SYNTHESIS SYTEMS
After CO2 removal by water and then chemical absorption, any residual CO and CO2
is completely converted to methane in the Methanator. This methane is an inert gas
with respect to the ammonia catalyst. Through out this process, conservation and
reuse of heat is very vital that it has been said that an ammonia plant is really a
steam generating plant that incidentally produces ammonia. There is more steam
produced than ammonia with a ratio of 4:1.

After catalytic methanation, the 3:1 hydrogen-nitrogen mixture freed of carbon

containing compounds except for a little methane is raised to the full level reaction
pressure by means of a turbine-driven centrifugal compressors. Various methods of
temperature regulations are used in the converters: heat exchange coils are inserted,
or cold gas injected between the beds. Ammonia is then recovered by refrigeration or
absorption and handled as an anhydrous liquid under modest pressure.

After removing ammonia, the remaining gases are far too valuable to discard. They
contain all the inert fed to the system (CH4, Ar, Ne, etc.) at the highest
concentration. The concentration of inert is regulated by removing (purging) of this
gas continuously. Before, it was burned but when the fuel is quite cheap. But it is now
stripped of its undesirables and reused.
COST
Major items that influence the final cost of ammonia production are
the method of hydrogen production and selected feedstock. 40 to 45
GJ per metric ton is used for ammonia production. Energy can be
theoretically reduced to 21 GJ per metric ton with simplified
processing procedures, improved catalysts, and operation at low
pressure that can be done by a one-stage compressor. Plants
designed to produce ammonia at 27 GJ are readily available but
unfavorable economic conditions prevent its construction and the
retrofitting of improvements are reduced.
IMPORTANT CHANGES OF SYNTHESIS
SYTEM CONVERTER
1.Operation without duplicating equipment and eliminating intermediate storage.

2.Use of quality catalyst to operate economically at lower pressure.

3.Large capacity compressors, better catalysts, and better converters.

4.Reduction of cost of reforming by raising the temperature of the primary reformer and
using a preheating process of air in the endothermic secondary reformer.

5.Narrowing of variation and given consistently better operation at nearer to maximum

conditions using digital computer control for process variables.

6.Removal of CO2 by water absorption but the final stripping requires the use of alkaline
reagent.

7.Bleed gas from synthesis loop are recovered with substantial reduction in energy
requirement per unit product.

8.Highly developed and vastly improved synthesis converters.

9.Low-cost ammonia recovery from converter outlet gases has several options.
DEFINITION & USES OF COMPOUNDS WITH NITROGEN CONTENT

Nitrogen
Name Definition & Uses
Content

Ammonium nitrate is a chemical that exists in multiple concentrations and physical forms. It
Ammonium Nitrate 33% is principally used as an agricultural fertilizer, in the manufacturing of first aid products, and as
an explosive used in the mining and construction industries.

Ammonium sulfate is a commercially useful inorganic salt. As a soil fertilizer, it is most

frequently used. It has 24% sulfur and 21% nitrogen. About half of all fertilizers used worldwide
Ammonium Sulfate 21% are made of sulfur. It is common knowledge in nitrogen management that ammonium-based
fertilizers are susceptible to ammonia (NH3) volatilization in soils with pH values greater than
7, yet this has not always been taken into consideration when making fertilization decisions.

There are three possible ammonium orthophosphates, only two of which are manufactured
on any scale. Monoammonium phosphate (MAP) is readily made by reacting ammonia with
Ammonium phosphoric acid, centrifuging, and drying in a rotary dryer. It is used in quick-dissolving
28.18%
Phosphate fertilizers and as a fire-retarding agent for wood, paper, and cloth. Diammonium phosphate
(DAP) requires a two-stage reactor system in order to prevent the loss of ammonia. A
granulation process follows the completion of the reaction in a rotary drum.
DEFINITION & USES OF COMPOUNDS WITH NITROGEN CONTENT
Urea is, in many ways, the most convenient form of fixed nitrogen. It has the highest nitrogen
content available in a solid fertilizer. It is easy to produce as prills or granules and easily
transported in bulk or in bags with no explosive hazards. It dissolves readily in water, leaves
Urea 46% no salt residue after use on crops, and can often be used for foliar feeding. In addition to
fertilizer use, it is used as a protein food supplement for tuminants, in melamine production,
and as an ingredient in the manufacture of resins, plastics, adhesives, coatings, and ion-
exchange resins.

Sodium nitrate is a chemical compound with the formula NaNO₃. This alkali metal nitrate salt
is also known as Chile saltpeter to distinguish it from ordinary saltpeter, potassium nitrate.
Sodium Nitrate 16%
Sodium nitrate has both fertilizer and industrial uses: fluxes, fireworks, pickling, heat-treating
mixes, and tobacco additives.

Potassium nitrate is manufactured in two ways: (1) by reacting nitric acid with potassium
chloride with a chlorine by-product, and (2) by reacting sodium nitrate with potassium
Potassium Nitrate 13% chloride and crystallizing out the salt. It is an excellent fertilizer with two useful fertilizing
components: 13% N and 44% K2O. Other uses include explosives, ceramics, and heat-treating
salts.

At one time, cyanamide was a useful agricultural fertilizer; later, its major importance came
from its derivative, dicyandiamide. Its use has now sharply diminished until only one small
Cyanide 53.85% plant remains. Its production is of considerable historical interest because a large plant was
built to produce it at the end of World War I, but it was never successful commercially. Earlier
editions of this book give details of its production.
 REFERENCES
(No date) Chemical Process Industry - accessscience from McGraw-Hill Education.
Available at: https://www.accessscience.com/content/chemical-process-
industry/127600.

Shreves, A.G. (1985) Chemical Process Industries. McGraw Hill Book Company,
Singapore.