COMSATS UNIVERSITY ISLAMABAD

LAHORE CAMPUS

Course Title : CHEMICAL PROCESS INDUSTRIES

Assignment : 03
Submitted By : Mujtaba Hassan
Registration No. : CIIT/FA20-CHE-062/LHR
Section : A
Submitted To : DR.FARUKH JAMEEL
There are three major classes of urea processes, based on the type or quantity of recycle: once
through processes, partial recycle processes and total recycle processes. At least 75% of the
urea produced today is by total recycle systems.

(1) Once-through processes:

In this process liquid NH3 is pumped through a high pressure plunger pump and gaseous CO2 is
compressed through a compressor up to the urea synthesis reactor pressure at an NH3 to CO2
feed mole ratio of 2/1 or 3/1. The reactor usually operates in a temperature range from 175 to
190 0C. The reactor effluent is let down in pressure to about 2 atm and the carbamate
decomposed and stripped from the urea-product solution in a steam heated shell & tube heat
exchanger. The moist gas, separated from the 85-90 % urea product solution, & containing
about0.6 tons of gaseous NH3 per ton of urea produced is usually sent to an adjacent
ammonium nitrate or ammonium sulfate producing plant for recovery. An average conversion
of carbamate to urea of about 60 % is attained. Excess heat is removed from the reactor by
means of a low pressure st9eam-producing coil in an amount of about 280,000 cal/Kg urea
produced.

(2) Partial recycle processes:

This process is termed partial recycle because only excess ammonia is recovered and recycles to
the reactor. The synthesis is carried out with as much as 200% excess ammonia. This process is
also similar to that of the once through process, with one additional step: the reactor effluent
contacting urea ammonium carbamate, water, and excess ammonia. Passes through an
expansion valve reducing the pressure to a few hundred KPa depending on the particular
process design. The steam goes to an ammonia separator where excess ammonia is removed,
condensed, and recycled to the reactor. This is necessary to recover some of the cost of using
excess ammonia.
Also if passed directly to the carbamate decomposer, the excess ammonia could hinder the
decomposition of the carbamate. The steam containing urea, carbamate and water goes to a
carbamate decomposer which dissociates the carbamates to ammonia and carbon dioxide. The
aqueous urea solution is separated and goes to further processing or shipment.

(3) Total recycle processes:

The total recycle process is most widely used process in the urea manufacturing industry. It was
essential to recover all of the gases for recycle to the synthesis to optimize raw material
utilization and since recompression was too expensive an alternative method was developed.
This involved cooling the gases and re-combining them to form carbamate liquor which was
pumped back to the synthesis. A series of loops involving carbamate decomposers at
progressively lower pressures and carbamate condensers were used. This was known as the
"Total Recycle Process". A basic consequence of recycling the gases was that the NH 3/CO2 molar
ratio in the reactor increased thereby increasing the urea yield.

Significant improvements were subsequently achieved by decomposing the carbamate in the

reactor effluent without reducing the system pressure. This "Stripping Process" dominated
synthesis technology and provided capital/energy savings. Two commercial stripping systems
were developed, one using CO2 and the other using NH3 as the stripping gases.
Since the base patents on stripping technology have expired, other processes have emerged
which combine the best features of Total Recycle and Stripping Technologies. For convenience
total recycle processes were identified as either "conventional" or "stripping" processes.

Block flow diagrams for CO2 and NH3 stripping total recycle processes are:

Question#2
Synthesis of Ammonia:
In theory, the synthesis of ammonia based on a methane feedstock, is:

0.88 CH4 + 1.24 H2O 0.88 CO2 +3 H2

3 H2 + N2 (from air) 2 NH3
In industrial ammonia production, the process may be subdivided into the following sections:

A. Desulphurization
 Primary Reform
 Secondary Reform
 Removal of Carbon Dioxide (CO2)
B. Methanation
C. Synthesis of ammonia

The goal of synthesis gas preparation is to produce a gas mixture of nitrogen and hydrogen as
pure as possible in the stoichiometric ratio of 1:3. This can be done with different techniques.
Currently in operation in Europe, the main types of production process for synthesis gas
preparation are:

1. Steam reforming of natural gas or other light hydrocarbons (liquidities natural gas,
liquidities petroleum gas, naphtha)

2. Partial oxidation of heavy fuel oil or natural gas

Overall, gasification of hydrocarbons or coal can be seen as a partial oxidation at elevated

temperatures. The main products are hydrogen and carbon monoxide. The necessary oxygen
can be supplied either as steam, as oxygen or as air. If a catalyst is used and steam is the
primary gasification medium, then the process is called steam reforming. If the reactant is
oxygen or air and no catalysts are used, the process is called partial oxidation.

About 85 % of world ammonia production is based on steam reforming concepts. Comparing

natural gas reforming, heavy oil and coal gasification gives the approximate relative energy
consumption. Based on the known resources of fossil fuel, it is likely that natural gas will
predominate as feedstock for the production of ammonia for the next 50 years at least. Today,
about 77 % of world ammonia production is based on natural gas. In a long-term perspective,
50 to 100 years from now, coal may take over as feedstock, based on world reserves and
consumption rate. Heavy oil may be attractive under special economical concerns, when
natural gas is no longer available and the partial oxidation process could solve a waste problem
(e.g. heavy residues and recycled plastics)

Three reforming techniques and one partial oxidation technique (of heavy residues) will be
described briefly. Conventional steam reforming will be described more in detail and only
deviations and additions will be stated for the other processes.
 Block flow diagram

Desulphurization
Most of the catalysts involved in the ammonia production process are sensitive to Sulphur and
Sulphur compounds. The first step is therefore to desulphurize the feedstock. The feed gas is
preheated to 350-400°C and is then treated in a desulphurization vessel. The Sulphur that is not
already in the form of hydrogen sulphide (H2S) is hydrogenated to hydrogen sulphide, typically
using a cobalt molybdenum catalyst. The hydrogen sulphide is then adsorbed on pelleted zinc
oxide:

R-SH + H2 H2S + RH
HCl+NaAlO2 AlOOH+NaCl
H2S + ZnO ZnS + H2O

By this reaction, the Sulphur is removed to less than 0.1 ppm S in the gas feed. The hydrogen
consumed in the reaction is usually recycled from the ammonia synthesis section.

Primary Reformer
The gas from the desulphurizer is preheated with steam to 500-600°C before entering the
primary reformer. The process steam comes from an extraction turbine. In some plants a
performer is used, in that case the gas steam mixture is reheated again in the section between
the performer and primary reformer.
The primary reformer consists of a large number of high-nickel chromium alloy tubes filled with
nickel-containing reforming catalysts. The reaction taking place is as follows:

CH4 + H2O CO + 3 H2
CO + H2O CO2 + H2

The first reaction is highly endothermic and additional heat is required to raise the temperature
at the reformer outlet. The heat is supplied from burning of natural gas or other gaseous fuel, in
the burners of a radiant box containing the tubes where the reactions take place. The flue-gas
from the combustion of this fuel is the main source of emissions from the plant, consisting of
carbon dioxide (CO2), nitrogen oxides (NOX) and small amounts of Sulphur dioxide (SO2) and
carbon monoxide (CO) (BAT N° 1, 1995). Large amounts of carbon dioxide can also be released
at the carbon dioxide removal stage if it is not used as feedstock in the production of urea.

Secondary Reformer
In the secondary reformer the remains of hydrocarbon are converted. To do this the
temperature must be raised to increase the conversion. This is done by combustion of part of
the gas with air. The air not only provides oxygen for the combustion but also nitrogen for the
final synthesis of ammonia that takes place further on in the process chain. The process gas is
mixed with air in a burner and then passed on over a second nickel-containing reformer
catalyst.
CH2+H2O 3H2+CO

Conversion of Carbon Monoxide

After the secondary reformer up to 99 % of the hydrocarbon feed is converted but there is still
a 12-15 % content of carbon monoxide left. After cooling the carbon monoxide is therefore
converted into carbon dioxide by using iron oxide/chromium oxide catalysts at high
temperature and then copper oxide/zinc oxide-based catalysts at low temperature. This carbon
monoxide conversion reduces the carbon monoxide content to about 0.2-0.4 %. A low residual
carbon monoxide content is important for the efficiency of the process.

Carbon Dioxide Removal

The process gas now contains mainly hydrogen (H2), potassium (K2), carbon dioxide (CO2) and
excess process steam. Before ammonia can be synthesized carbon dioxide has to be removed.
This is done in a chemical or a physical absorption process. The typical range of heat
consumption in the modern chemical absorption process is 30-60 MJ/kmol CO2. The physical
absorption process may be designed for zero heat consumption but the mechanical
requirements also have to be considered. Before entering the carbon dioxide removal system
the process gas is cooled and the heat released during cooling is in many cases used for other
heat demanding processes.
K2CO3+H2O+CO2 2KHCO3
Methanation
As the ammonia synthesis catalysts are sensitive to carbon monoxide and carbon dioxide, these
have to be removed completely by conversion to methane. With a nickel containing catalysts
the following reactions take place at around 300°C:

CO + 3 H2 CH4 + H2O
CO2 + 4 H2 CH4 + 2H2O

Methane will not react in the synthesis of ammonia, but water must be removed before
entering the reaction chamber. Also, the synthesis gas is compressed before the final process
stage.

Synthesis of Ammonia
The synthesis of ammonia takes place on an iron catalyst at around 100-250bar and 350-550°C:

N2 + 3H2 2 NH3

The reaction is exothermic and produced ammonia is separated by cooling. The equilibrium
conditions of the reaction are quite unfavorable resulting in a poor conversion factor of only 20-
30 % per pass. Loop pressure is maintained by substituting the ammonia that has been lead off
with fresh synthesis gas.

The produced ammonia contains inserts (methane and argon). The level of inserts is kept low
by taking out a purge stream from the loop. The purge stream is scrubbed with water to
remove ammonia and is then used as fuel or sent to the desulphurization section where
hydrogen is recovered.