Nitrogen Products

AMMONIA
• Once called “Spirit of Hartshorn”
• Chemical Formula is NH3
• Uses: 1. Fertilizers
2. Manufacture of fertilizers and other
nitrogen compounds like nitric acid
and nitrates
3. Refrigerant
4. Manufacture of explosives
AMMONIA
• Common manufacturing process: Haber Process by Haber Bosch in 1913.

▫ N2 + 3H2  2NH3, a reversible and exothermic process)

▫ To favor forward reaction:

a. low temperature of 500oC
b. High pressure of 200 atm
c. Use catalyst such as Fe with oxides of Al, K and Fe

▫ This yields an 8% to 10% conversion

▫ Sources are Air, water and hydrocarbons

AMMONIA
• Steps in the manufacture of NH3
▫ Production of reactant gases
▫ Purification of reactant gases (CO is removed
since it will poison the catalyst)
▫ Compression
▫ Catalytic conversion
▫ Recovery of NH3 : a. Liquefaction
b. Absorption
(NH3 + H2O  NH4OH)
▫ Recycling
FLOW CHART

NH3,
Compressed H2 H 2 N2
& N2 Converter Product NH3
Absorber/
Condenser
inert

Recycle purge
NITRIC ACID
• Common name: Aqua fortis
• Chemical Formula: HNO3
• Uses: 1. Manufacture of explosives
2. Preparation of inorganic nitrates and
fertilizers
3. Metal pickling
4. Separation of gold and silver
NITRIC ACID
• Manufacturing process
▫ Batch process (Pot still process)
(H2SO4 + NaNO3  NaHSO4 + HNO3)
▫ When the reaction ceases, the pot still may be emptied
and another batch of the feed will be charged.
Reactant HNO3
cooler

Pot Still

Niter cake
NITRIC ACID
• Manufacturing process
▫ Continuous process (Ostwald process)
 The raw feed is a mixture of ammonia and air. A mixture of about NH 3 is mixed with 10 volumes
of compressed air is heated at 600 – 700 oC and is then fed to a converter using Pt as catalyst.
(4NH3 + 5O2  4NO + 6H2O : ammonia oxidation)
 The remaining O2 is then used to oxidize the NO to NO 2.
(NO + 1/2 O2  NO2)
 The nitrogen dioxide is then cooled and absorbed by water.
(2NO2 + H2O  2HNO3 + NO)
 NO is then mixed with air again to be oxidized to NO 2.

 The overall reaction: NH3 + 2O2  HNO3 + H2O

A side reaction that lowers the product yield
4NH3 + 3O2  2N2 + 6H2O
FLOW DIAGRAM
Absorber
Absorbing
1o Air Gas
medium

Burner Converter A
Gas Gas B
Charge S
Burner Converter O
R
B
E
R

Product
• In a Haber plant the gas leaving the CuCl tower contains
75.16 % H2 , 24.57 % N2 and 0.27 % inert A. The gas entering
the first bank of converters contains 79.52 % H2 while the gas
leaving the absorber, which follows the first bank, contains
80.01 % H2. Absorption of NH3 is substantially complete, and
the design of the absorber is such that the amount of
permanent gases removed from the system in the absorbing
medium is negligible. What is the efficiency of utilization of
H2 in the first bank? What is the per cent conversion of H2
per pass, i.e. the moles H2 reacting to form NH3 per 100 moles
of H2 entering the converters?
FLOW CHART
75.16 % H2 NH3,

24.57 % N2 H2, N2, P

0.27 % inert Converter inert Absorber

Product NH3

80.01 % H2
R,
Recycle G, purge
 P

H2 balance:
75.6 = P(1.5) + 0.8001 G
N2 + inert balance:
24.57+0.27 = P(0.5) + (1-0.8001)G
Required: efficiency of utilization of H2
Conversion per pass of H2 P = 48.56 mol
Basis: 100 moles of fresh Feed G = 3.44 mol
 P = 48.56 mol

 Efficiency of utilization of H2 =

= x 100 = 96.91 %
G = 3.44 mol
Required: efficiency of utilization of H2
Conversion per pass of H2
Basis: 100 moles of fresh Feed
 P = 48.56 mol
M
Balance at point of mixing
OMB: 100 + R = M
H2 balance:
G = 3.44 mol 75.16 + 0.8001 R = 0.7952 M
Required: efficiency of utilization of H2
R = 889.90 mol
Conversion per pass of H2
M = 989.90 mol
Basis: 100 moles of fresh Feed
 P = 48.56 mol
M
 Conversion per pass of H2 =

R = 889.90 mol

= x 100 = 9.26 %
G = 3.44 mol
Required: efficiency of utilization of H2
Conversion per pass of H2
Basis: 100 moles of fresh Feed
• A synthetic ammonia unit with a single converter is converting a fresh feed
gas containing 75.8 % H2, 23.7 % N2 and 0.5 % inert. The gas leaves the
converter containing 18.6 % NH3 and 70 % H2. This converted gas is fed to
a cooler under conditions of temperature and pressure such that most of
the ammonia leaving the converter is condensed to a liquid and removed.
On reduction of pressure all the dissolved gases are evolved from this
liquid ammonia. These are compressed and returned to the system just
before the cooler. The residual gases from the cooler are recycled to the
inlet of the converter, except for a purge provided in the recycle line. The
uncondensed ammonia leaving the cooler in those gases is found to be 8 %
of that leaving the converter. Calculate the amount and composition of the
purged gases per 100 moles of feed gas, and determine the net moles of
residual gas recycled to the converter inlet per 100 moles of feed gas.
FLOW CHART
75.80 % H2 18.6 % NH3
23.7 % N2 70 % H2 P
0.5 % inert Converter Product NH3
Cooler
CG

8 % of NH3 in CG
R,
Recycle G, purge
Required: G, R per 100 moles of Fresh Feed
Composition of G
Basis: 100 moles of fresh Feed
 In AG:
NH3 = 0.08(18.6) = 1.488 mol
H2 = 70 mol
N2 + inert = 100 – 18.6 – 70 = 11.4 mol
AG Total AG = 82.888
  mol %
NH3 1.488 1.80
Basis: 100 moles of CG H2 70 84.45
N2+ inert 11.4 13.75
  82.888 100.00
  At whole system

H2 balance:
75. 80 = P(1.5) +
NH3 1.488
H2 70 G
N2+ inert 11.4
82.888 N2 + inert balance:
23.7+0.5 = P(0.5) + [
Required: G, R per 100 moles of Fresh Feed
G
Composition of G
Basis: 100 moles of fresh Feed P = 46.23 mol, G = 7.40 mol
 P = 46.23 mol

 % inert In G
= x 100 = 6.76 %

  %
G = 7.40 mol
NH3 1.80
H2 84.45
P = 46.23 = 0.92(0.186CG) N2 6.99
CG = 270.16 mol inert 6.76
  100.00
OMB:
270.16 = 46.23 + R + 7.40
R = 216.53 mol
Oxidation of ammonia
• An ammonia-oxidation unit using platinum-iridium catalyst discharges converted
gases from the catalyst chamber through a heat exchanger for preheating the
incoming air.. It is desired to determine the conversion efficiency of this unit. To this
end, a sample of the combustion gases is withdrawn at the outlet of the heat
exchanger, where the temperature of the gases has dropped to 515 oF. The analysis
of the gas can be reported in various ways. It is not uncommon to report the fixed
nitrogen in terms of NO2 and NO, evaluating this in the basis of the state of
oxidation as actually determined. However, this method of reporting is in large
measure unrealistic because of the fact that the NO is in process of oxidation to NO2
by the oxygen in the mixture itself, not only in its flow throuvg the heat exchanger
but also in the gas phase of the sampling flash itself before the analysis is complete.
Oxidation of ammonia
The ratio as determined analytically is therefore dependent on the point
in the equipment at which the sample is taken and on the conditions of
sampling and absorption that bear no relation to plant operation and
performance. The really significant information afforded by the
analytical procedure is the determination of the total fixed nitrogen in
the original gas sample and the determination of what may be called the
active oxygen. The latter is the sum of all the oxygen combined with
nitrogen and that present in the form oxygen gas which can combine
with the fixed nitrogen if this is present in sufficient amount and
suitable opportunity for combination is afforded.
Oxidation of ammonia
Active oxygen does not include any oxygen in the
form of water, because such oxygen is not available
for nitrogen oxidation. In any event the result must
be reported on a suitable basis; 100 moles of free
N2 is probably the best for this purpose
NH3 + O2  NO2 + NO + H2O + N2
O2
N2 N2

Fixed N2 = N2 in NO2 and NO

Active O2 = O2 in NO2 , NO + unused O2

• In the case of being considered, the analyst elected to report his
results in still a third way. He took the analytical data an
calculated what the gas analysis would have been on the basis of
purely hypothetical an indeed unrealistic assumption: (1)that the
gas samples be allowed to stand long enough that all NO would
oxidized to NO2 and no further., (2) that no fixed n nitrogen would
condensed out of the gas despite the presence of water, and (3) the
the NO2 will be present in the gas as such and none as N2O4.
On the basis he reported 11.2 % NO2, 2.2 % O2
and 86.6 % N2.
Calculate the conversion efficiency.
air
11.2 % NO2
2.2 % O2
NH3 86.6 % N2.
Converter
 A

 Conversion efficiency
F H2O = x 100
= x 100 = 89 %
Required: conversion efficiency
Basis: 100 moles of dry converter gas
H balance: n H2O = F(1.5)
N2 Balance: F (0.5) + (0.79 A) = 11.2(0.5) + 86.6
O2 balance: 0.21A = 11.2 + 2.2 + n H2O (0.5)
F = 12.58
A = 108.75
n H2O = 18.87
 A
  Balance:
N2
100 (0.5) + (0.79 A) = x + x
F H2O Active O2 balance
= x
Required: conversion efficiency 0.21A - 100(1.5)(0.5)
Basis: 100 moles of NH3
A = 864.29 mol
 Conversion efficiency x = 44.51 mol
= x 100
Let x = fixed N2  Conversion efficiency
= x 100 = 89 %

 O2 balance: 0.21 A = x + 100 (1.5)(0.5)