UCB

In the UCB process (Fig. 4) [12], a heat exchanger in the pressure reactor uses a part of the
heat of reaction to make steam. Ammonia and 52 -63 % HNO3 are preheated and sprayed
into the sump of the reactor.

The pressure in the reactor is approximately 0.45MPa (4.5 bar), the temperature is 170 -180
.C, and the pH is 3 - 5. The pH is kept in this range by controlling the ratio of reactants. The
heat exchanger cools the reaction mixture, and neutralization follows a stable course. The
75 -80 % NH4NO3 solution leaving the reactor is concentrated to 95 % by evaporation in a
falling film evaporator. The heat of reaction generates

1) process steam out of the evaporating water from the nitric acid. This is used in the
process to preheat boiler feed water and nitric acid and to operate the falling film
evaporator.

2) pure steam up to 0.55MPa (5.5 bar) in the heat exchanger. This can be fed into the steam
pool and used for other purposes.

The pH 3 - 5 reduces nitrogen losses into the process steam. The working conditions are
adjusted so that excess process steam does not accumulate.

STAMICARBON

Another process that works under pressure is the Stamicarbon process (Fig. 5) [13]. The
neutralizer is a loop reactor that opens into a separator. The reaction solution is circulated
without a pump by heat generated. Nitric acid (60 wt%), preheated ammonia, and a small
quantity of sulfuric acid are introduced at the lower end of the loop. The reactor operates at
0.4MPa (4 bar) and 178 .C. The ammonium nitrate solution formed in the reactor has a
concentration of 78 %. The steam removed at the top of the separator is passed through a
mist eliminator and is mainly used to concentrate the NH4NO3 solution to 95 % in a
vacuum evaporator. Excess steam is condensed, and ammonia is recovered from the
condensate and returned to the reactor. In a second evaporator, the concentration can be
increased to 98 . 99.5 % using fresh steam. The temperature of the ammoniumAnother
process that works under pressure is the Stamicarbon process (Fig. 5) [13]. The neutralizer
is a loop reactor that opens into a separator. The reaction solution is circulated without

a pump by heat generated. Nitric acid (60 wt%), preheated ammonia, and a small quantity
of sulfuric acid are introduced at the lower end of the loop. The reactor operates at 0.4MPa
(4 bar) and 178 .C. The ammonium nitrate solution formed in the reactor has a
concentration of 78 %. The steam removed at the top of the separator is passed through a
mist eliminator and is mainly used to concentrate the NH4NO3 solution to 95 % in a
vacuum evaporator. Excess steam is condensed, and ammonia is recovered from the
condensate and returned to the reactor. In a second evaporator, the concentration can be
increased to 98 . 99.5 % using fresh steam. The temperature of the ammonium nitrate
solution is kept below 180 °C throughout neutralization and evaporation.

NSM/NORSK

The NSM/Norsk Hydro pressure process (Fig. 6) [14] uses preheated ammonia and nitric
acid. The pressure in the reactor is between 0.4 and 0.5MPa (about 4.5 bar), and the
temperature ranges from 170 to 180 .C, conditions corresponding to a 70 . 80 % solution.
Forced circulation and a thermal siphon effect circulate the solution through the reactor.
Some of the heat of reaction is used to generate pure steam in an external boiler; some
vaporizes water in the reactor, producing process steam, which is used to concentrate the
ammonium nitrate solution to 95 %. The ammonia losses are kept small by washing the
process steam with nitric acid, which is added to a circulating ammonium nitrate solution.
Further concentration of the NH4NO3 solution, to 99.5 %, is carried out with steam in a
special vacuum evaporator.

STENGEL

In the United States the Stengel process is significant [15], [16]. It produces anhydrous
ammonium nitrate directly. The ammonia and the ca. 58%nitric acid are preheated with
fresh steam and fed into a packed vertical tube reactor at 0.35MPa (3.5 bar) and 240 .C.
The mixture of NH4NO3 and steam is expanded into a vacuum in a centrifugal separator.
After stripping with hot air, a 99.8 % NH4NO3 melt is discharged, onto a cooled steel belt,
solidified, and then broken up or granulated. The steam is removed at the top.

In all these processes the maintenance of the desired pH is most important. Where the
reaction temperatures are below 170 .C, the pH is kept between 2.4 and 4 to minimize
nitrogen losses. In pressure neutralizers, a higher pH, 4.6to 5.4, is necessary on account of
the higher temperatures and greater danger of decomposition.

A PARTIR DE NITRATO DE CALCIO PROCESO BASF

The production of nitrophosphate fertilizers by digestion of crude phosphate with nitric acid
in the Odda process produces as a byproduct calcium nitrate tetrahydrate, Ca(NO3)2 E
4H2O, in considerable quantities (¨Fertilizers). The output of nitrophosphates is
increasing, while demand for calcium nitrate is declining. In a process introduced some
years ago, the calcium nitrate tetrahydrate is treated with ammonia and carbon dioxide to
form ammonium nitrate and calcium carbonate:

The accompanying heat is adequate to evaporate all the water. However, a direct procedure
is not possible because of the unfavorable equilibrium at elevated temperatures. In the
BASF process (Fig. 7), heat removal is separated from the reaction of Ca(NO3)2 with
(NH4)2CO3: NH3 and CO2 are dissolved in a circulated NH4NO3 solution, and the heat
given off is removed. The calcium nitrate tetrahydrate is also dissolved in anNH4NO3
solution. The two solutions are then reacted at ca. 50 .C; the heat produced is minimal. The
grain size of the calcite precipitated can be influenced by the way the reactants are
introduced. After reaction the approx. 65%NH4NO3 solution is separated from CaCO3 on
a belt filter and concentrated by evaporation. TheCaCO3 still contains small amounts of
ammonium compounds and phosphate and is mostly used for the production of calcium
ammonium nitrate. If the calcium nitrate is suitably prepared before conversion, quite pure
CaCO3 may be produced. For directly converting calcium nitrate and at the same time
removing the heat of reaction, Hoechst developed a special vertical reactor [17]. The
gaseous CO2 is introduced at the bottom, and the ammonia is introduced in three zones,
each cooled with water.