COMSATS UNIVERSITY ISLAMABD,

LAHORE CAMPUS
(CHEMICAL ENGINEERING DEPARTMENT)

CHEMICAL PROCESS INDUSTRIES

Assignment 5

MARYAM FATIMA
SECTION A
SEMESTER 3
ASSIGNMENT # 5 (CPI)

Table of Contents
QUESTION # 1:...................................................................................................................................2
Once Through Process:.......................................................................................................................2
Partial Recycle Process:......................................................................................................................2
Total Recycle Process:.........................................................................................................................3
Total-recycle processes Classification:...........................................................................................3
1. Hot-gas mixture recycle:.....................................................................................................4
2. Separated-gas recycle:.........................................................................................................4
3. Slurry- recycle:.....................................................................................................................4
4. Carbamate-solution recycle:...............................................................................................4
5. Stripping:..............................................................................................................................4
QUESTION # 2:...................................................................................................................................5
Partial Oxidation Process of Natural Gas:........................................................................................5
Production of Ammonia:.....................................................................................................................5
1. Desulphurization:....................................................................................................................5
2. Primary Reforming:................................................................................................................5
3. Second Reforming:..................................................................................................................6
4. Shift conversion:......................................................................................................................6
5. Carbon Dioxide Removal:.......................................................................................................6
6. Methanation:............................................................................................................................6
7. Ammonia Synthesis:................................................................................................................6
8. Refrigerator and storage:........................................................................................................6
Chemical Reactions:........................................................................................................................6
Block Flow Diagram:..........................................................................................................................7

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ASSIGNMENT # 5 (CPI)

QUESTION # 1:
Define and explain Once Through, Partial Recycle, Total Recycle process in manufacturing of
urea?

Once Through Process:

The once through process is simplest and least expansive (both capital and opera ng cost)
Least flexible and cannot be operated unless some provision is made to u lize large amount of
ammonia and off-gas.
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 190oC. 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 about 0.6 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 steam-producing coil in an amount of about 280,000
cal/Kg urea produced.

Partial Recycle Process:

Partial recycle Part of the off gas is recycled back to the reactor. The amount of ammonia is
reduced to 15% to that of once through that must be used in other processes. Investment cost
is somewhat lower than the total recycle process, this advantage apparently does not
compensate the inflexibility arising from the necessity to operate a co- product plant with
mutual interdependency problems. Total recycle At an economical conversion rate of NH3
and CO2 to urea, the process is designed to efficiently separate urea from the other reaction
components, to recover excess NH3, and to decompose residual ammonium carbamate to
NH3 and CO2 for recycling into the process. This is usually realized by stripping (s ll at high
pressure) and subsequent depressurise On heating of the urea sol on or combinations of both.

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ASSIGNMENT # 5 (CPI)

The partial-recycle method of the Mitsui Toatsu is representative of the first technique.
Liquid NH3 and gaseous CO2 are pumped into a 200 atm urea reactor. By correct balance of
excess NH3 and carbamate solution recycling feed, the temperature of the reactor is
maintained at about 185 ° C. Approximately 100%-110% of the excess NH 3 is used; around
70% of the NH3 and 87% of the CO2 are converted to urea. In some other method, the
remaining 30 percent of the NH3 needs to be used. The effluent in the reactor contains around
80% urea. The activity of the urea plant must also align with that of the co-product plant, as
in the once-through process. Such partial-recycle processes vary in detail, but similar results
are obtained.

Total Recycle Process:

In total recycle process, all the unconverted ammonia-carbon dioxide mixture is recycled to
the urea reactor in complete recycling processes (conversion is about 99 percent), and no co-
product of nitrogen is needed. This is the most versatile of the urea processes since it relies
only on the availability of CO 2 and NH3 from the activity of its supporting ammonia plant.
However, in terms of investment and operating costs, it is also the expensive.
The effluent of the urea reactor includes urea and water arising from the synthesis reaction;
unconverted carbamate and excess ammonia are also included. To give a urea solution
relatively free of the other materials and to recycle the CO 2 and NH3 in the synthesis reactor,
these ingredients must be segregated. It must be decomposed according to the equation, to
distinguish carbamate from urea:
NH2 CO2 NH4 → CO2 + 2NH3
This reaction is the reverse of the synthesis process's first step and is extremely endothermic
(37.7kcal/g-mole). Different combinations of providing heat, reducing friction, and 'stripping'
achieve decomposition, reducing the partial pressure of one or more ingredients. NH 3 and
CO2 are separated as gases from the urea solution, followed by some of the vapor-forming
water. Naturally, when the temperature is reduced or the pressure is raised, the CO 2 and NH3

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ASSIGNMENT # 5 (CPI)

can recombine (releasing heat). A carbamate solution is therefore formed by condensing by

cooling or compressing a gaseous mixture of CO2, NH3, and H2o.
Total-recycle processes Classification:
Total-recycle processes can be classified in five groups according to the recycle principle:

1. Hot-gas mixture recycle:

Reciprocating compressors with an inter stage temperature of 260 °-270 °C and a pressure of
120-130 atm were used to compress the hot gas in five stages. To condense the gases (with
carbamate formation), it was then cooled to 160 ° C and the heat was recovered as steam.
2. Separated gas recycle:
To overcome the difficulties of the process of mixed hot gas recycling, the separate-gas
recycling method was created. Without difficulties caused by carbamate formation, the CO2
and NH3 can be separately compressed.
3. Slurry- recycle:
The slurry-recycle process's principle is that the gas mixture goes to a reactor where a light
paraffin oil is applied. In the reactor, carbamate is shaped in oil as a suspension. This
suspension is pumped into the urea synthesis unit along with fresh CO 2 and NH3 containing
35-40 percent solids. The mixture then passes through decomposers, and for reuse, the oil is
removed from the decantation.
4. Carbamate-solution recycle:
In carbamate-solution-recycle process advantage is taken of ammonium carbamate solubility
in water to recycle with water the reagents not transformed into urea. These solution recycle
processes are generally referred to as "Conventional" processes.
5. Stripping:
In stripping processes, the bulk of carbamate decomposition can thus take place at the same
pressure as the synthesis reaction and, moreover, heat of reaction can be recovered at higher
temperature in the carbamate condenser circuit. However, the synthesis reaction is run at
lower pressure because striping efficiency drops off at higher pressure.

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ASSIGNMENT # 5 (CPI)

QUESTION # 2:
Write down the partial oxidation process of natural gas for the synthesis of ammonia. The
explanation should in step wise and briefly explains each step according to BFD in the reference
material.

Partial Oxidation Process of Natural Gas:

Hydrogen is derived exclusively from carbonaceous materials, primarily hydrocarbons and
water. These materials are decomposed by the application of energy, which may be electrical,
thermal, and chemical. Hydrogen is also being produced by partial oxidation of
hydrocarbons. Partial oxidation process uses natural gas as raw material. There are three
commercial versions of the process which differ primarily from there design and operation of
the partial oxidation burner which is used as a source to provide thermal energy. Where % of
gases is classified as 0.4% methane producing 99.598% hydrogen. The hydrocarbon is fed to
combustion chamber at 1300-1500 degree centigrade. Pressure of 2 to 4MPa. In the chamber
following reactions occur.
CH4 + 2O2 → CO2 + 2H2O
This reaction being extremely exothermic produces enough energy which can sustain the
other two reactions. After primary and secondary reforming.
CH4 + CO2 → 2CO + 2H2
CH4 + H20 → CO + 2H2O
The net reaction is as follows
CH4 + 1/2O2 → CO + 3H2
For efficient operation, heat recovery is done using waste heat boilers. The product gas is
then cooled by direct contact water scrubber and a filter. After which it is passed through an

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absorber to remove unused CO2. There is two stage absorbing and removal of CO2 and CO.
Also, sometimes methanator is used. After which it is pumped to first stage absorber to
remove the unwanted gas and hydrogen gas. CO2 is stripped out of stream and hydrogen gas
is recovered for further use in production of ammonia.

Production of Ammonia:
Ammonia is produced by the reaction of nitrogen and hydrogen at elevated temperature and pressure
in the presence of catalyst. The water-soluble ammonia production process can be divided into eight
basic steps as shown in the Block Flow diagram below.

1. Desulphurization:
The natural gas reservoir is heated and move towards Desulphurizer in the presence of catalyst to
remove any traces of sulfur that can poison the other river-building elements in the process.

2. Primary Reforming:
The steam is mixed with natural gas and the combined stream continues to heat up and transfer tubes
to a conversion furnace containing nickel oxide catalyst. This is where conversion occurs when
methane of natural gas is slowly converted into hydrogen, carbon dioxide and carbon monoxide.

3. Second Reforming:
The gas process that leaves the main transformation is transferred to a second converter is a
refractory-lined container filled with nickel oxide catalyst. The controlled air volume is also
introduced into the hot air first causing heat which is part of the process the gas increases its
temperature high enough to eliminate the conversion of the remaining methane into additional
hydrogen, carbon dioxide and carbon monoxide.

4. Shift conversion:
In the transformation process, carbon monoxide formed in the first and second stages of repair is also
used in a two-phase process. This gas is first transferred to the top of the iron - chromium catalyst
followed by continuous cooling and heat recovery, and then to the catalyst -zinc catalyst. At this stage
carbon monoxide and water are almost completely converted to hydrogen and carbon dioxide.

5. Carbon Dioxide Removal:

Carbon dioxide (CO2) is extracted from the gas process by absorbing a solution of potassium
carbonate known as Benfield. Electricity is touched with Benfield's solution on Absorber and left on
top. The solution itself is regenerated by heating in the exhaust column and the emitted CO2 can be
released into the atmosphere or used as a feedstock for methanol production.

6. Methanation:
The gas emissions that leave Absorber primarily contain hydrogen and nitrogen in addition to the
small amount of carbon oxides not included. As this can cause toxic ammonia synthesis catalyst the
concentration should be reduced to less than 10 p.p.m. In Methanator carbon oxide is converted back
into methane over a nickel solid substance in a reverse reaction to that of the vapor converter.

7. Ammonia Synthesis:
The gas process that leaves the Methanation is compressed and sent to an ammonia synthesis reactor
which is a container containing four beds of catalyst. The first bed is iron oxide which is magnetite
while the other three contain catalyst-based ruthenium.
This final guide allows the conversion of hydrogen and nitrogen into ammonia at low pressures and at
high temperatures and high yields.
The gas is turned into all four beds and leaves a transformer containing about 20% ammonia.

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ASSIGNMENT # 5 (CPI)

8. Refrigerator and storage:

The impurities from the ammonia solution have cooled in line with the supply gas, cooling water, and
refrigerated ammonia liquid to dissolve the ammonia in the stream at 280F. This liquid is pumped
from the storage tanks to keep it in a liquid state. Unprocessed hydrogen and nitrogen are returned to
the synthesis converter as a licensed stream for reuse of gas.

Chemical Reactions:
ZnO + H2S → ZnS + H2O

CH4 + 2H2O→ 4H2 + CO2

CO + H2O→H2 + CO2

CO + H2O → CO2 + H2
O2 + 2CH4→2CO + 4H2
O2 + CH4→CO2 + 2H2
2O2 + CH4 →2H2O + CO2

CO + H2O → CO2 + H2

2CO + 3H2 →CH4 + H2O

CO2 + 4H2→CH4 + 2H2O

N2 + 3H2 →2NH3
Commercial NH usually synthesized from nitrogen and hydrogen reaction, which is called
3
Haber process.

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ASSIGNMENT # 5 (CPI)

Block Flow Diagram: