3 PROCESS DESCRIPTION

By reacting hydrogen with nitrogen at a molar ratio of 3 to 1, anhydrous ammonia is

synthesized, then the gas is compressed and cooled to -33 ° C (-27 ° F). Nitrogen is obtained
from the environment, while hydrogen is obtained either from natural gas catalytic steam
reforming (naphtha: methane [CH4] or octane) or from brine electrolysis at chlorine plants.
[1][2]

3.1 MAIN SECTIONS

To manufacture synthetic ammonia using the catalytic steam reforming method, seven
process steps are required:
1. Naphtha Hydro-Desulphurization
2. Pre-Reforming, Primary reforming based on Steam-Naphtha/ Natural gas reforming
process
3. Secondary Reforming
4. Carbon monoxide Conversion (HTSC and LTSC)
5. CO2 Removal
6. Methanator, Ammonia synthesis
7. Recovery, Cracking, Liquefaction & Storage.

3.1.1 Desulphurization:
Most of the catalysts used in the process are sensitive to Sulphur and Sulphur compounds.
mg
The feedstock normally contains up to 5(m3 )as Sulphur compounds. But the feedstock of the
Reforming catalyst should contain less than 0.5 ppm of Sulphur. This is important since the
Sulphur decreases the reforming catalyst activity. The feedstock is mixed with a stream of
synthesis gas and is heated to around 350-400 ° C. The mixture is passed through the hydro
finer catalyst bed where it lowers the Sulphur to H2 S in the naphtha. The naphtha is then
condensed by cooling, and in a stripping column, the H2 S is removed. Sweet naphtha
(naphtha storage tank) from Stripper is refrigerated and sent to the Sweet Naphtha Tank.
[2][3]
Natural gas is mixed along with recycle gas and pre-heated to 360°C. Sweet Naphtha (from
the Sweet Naphtha storage tank) is mixed with a recycled stream of synthesis gas and heated
in the Process Naphtha Vaporizer to around 400 ° C. Naphtha feedstock and Natural Gas are
combined and moved at 360 ° C to the desulphurization vessel. The gas mixture went
through a cobalt molybdenum catalyst (CoMox) bed, where H2 S was reduced to unconverted
Sulphur remaining in the Naphtha & Natural Gas. This H2S is then absorbed into the bed of
zinc oxide (ZnO) found in the lower portion of the vessel. In this way, the Sulphur content of
the feedstock is lowered to less than 0.5 ppm (by weight) below the limits set by the
reforming catalyst manufacturer. [2][3]
R − SH + H2 → H2 S + RH
H2 S + ZnO → ZnS + H2 O
3.1.2 Steam Reforming
 Pre-reforming:
The Desulphurization mixed feedstock is then mixed with the Steam Process and Hydrogen
Gas Recycle Until the Feedstock Pre-heater joins. In the pre-heater feedstock, the
temperature of the inlet to the pre-reformer The reformer was elevated to 320° C. Both
hydrocarbons comprising the naphtha are decomposed in pre-reformer Towards methane.
This is an exothermic response and the temperature of the outlet of the pre-reformer is 522
° C.
The reformer outlet is combined at Primary reforming with process vapor and mixed feed
temperature
𝐶𝑛 𝐻2𝑛+2 + 2𝐻2 𝑂 ↔ 𝐶𝑛−1 𝐻2𝑛 + 𝐶𝑂2 + 3𝐻2 − 𝐻𝑒𝑎𝑡
 Primary Reforming:
The reforming response is essentially the reaction to carbon output between hydrocarbons
and steam Hydrogen and monoxide. This reaction takes place at a pressure of 34.45 bar and
at an operating temperature of 580℃. The reforming reactions are endothermic and the
reaction is provided with the necessary heat. To by:
Heating the reactants by preheating; · Conducting the reactions in externally heated tubes.
The supply of heat is made from flue gas provided in the reforming furnace by the
combustion of naphtha. The Strength of the Reforming Furnace is Modular "construction of
gas norm, which is brick lined rectangular box like structure in which the structure is
bricked." There are vertically suspended tubes. The furnace is made up of 90 fired top
burners and 264 tubes. Eight rows, each row containing 33 tubes, are organized. Reforming
naphtha / NG in Steams [2]
𝐶𝐻4 + H2 O ↔ CO + 3H2
CO + H2 O ↔ CO2 + H2

 Secondary Reforming:
The calculated amount of preheated nitrogen needed for the synthesis of ammonia is
described in secondary Reformer. The Reformer. Air is applied from the primary reformer
to the hot gas. The oxygen in the air responds to a portion of the Gas, which increases the
temperature. The heated mixture then flows through a catalyst bed and the catalyst bed The
main reformer 's methane present in the gas reacts with excess steam to produce more
Hydrogen, carbon monoxide and carbon dioxide.
The reaction of the methane steam is endothermic and Therefore, after an initial sharp
increase, the temperature of the gas mixture decreases as the gas moves through. A
secondary reformer at 970℃ leaves the catalyst bed and the reformed gas.[4]
𝐶𝐻4 + 2𝑂2 + 𝑁2 → 2 𝐻2 𝑂 + 𝐶𝑂2 + 𝑁2
3.1.3 Carbon monoxide Conversion
The water-gas shift reaction plays a major role in hydrogen and ammonia plant design and
operation. Good performance of the shift catalysts, and attainment a close approach to
equilibrium and hence minimization of the CO slip from the catalyst system is critical to the
efficient and economic operation of the plant and ensures maximum hydrogen production
from the hydrocarbon feedstock
CO shift converter combines water and the carbon monoxide from syngas to form CO2 and
more H2, and then acid gas removal isolates the hydrogen for ammonia synthesis .
which is following the chemical reaction
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2
The reaction is exothermic and high conversions are desired by low temperature and high
steam ratio. Ammonia plants usually operate a two stage system - a High Temperature Shift
(HTS) followed by a Low Temperature Shift (LTS) - with a suitable form of inter- bed cooling
[5]
 HTSC (High Temperature shift conversion)
Modern catalysts for the high temperature shift stage operate typically in the temperature
range 350-360°C down to approx. 2.5 % CO on dry basis at the reactor outlet
The catalysts are formulated from chromia, iron oxide and copper oxide, and feature
enhanced activity and efficient operation at low steam to carbon ratios. [7]
CO concentration is reduced to about 3% by volume by means of water gas shift reaction at
a temperature of about 630 to 640°K. They are cooled before being sent to the secondary
reformer. The process gas is passed over Iron Oxide catalyst in the HT converter where CO
reacts with steam to form 𝐶𝑂2 and Hydrogen. A layer of Alumina balls is placed over the top
catalyst bed with the aim of filtering any solid particles entering the gas to be treated and for
the uniform distribution of gas through the catalyst bed.
 LTSC (Low Temperature shift conversion)
Corresponding operating temperatures for the low temperature shift section are 180-270°C
down to approx. 0.2 % CO on dry basis at the reactor outlet.
VULCAN VSG-C111 catalysts are based on copper oxide supported on a matrix of zinc oxide
and alumina. The established product, VSG-C111 is also available in a smaller pellet size, to
allow optimization of performance and pressure drop. [7]
The reaction occurs at a temperature of about 523 K. Concentration of CO in the exit gas is
reduced to about 0.3 % by volume. The gas leaving the HT converter is then cooled and sent
to LT converter where the gas passes over Copper catalyst. The remaining CO is converted
to CO2 in shift convertor.
3.1.4 CO2 Removal
In this step, CO2 in the final shift gas is removed. CO2removal can be done by using 2
methods: monoethanolamide (C2H4NH2OH) scrubbing and hot potassium scrubbing. In
order to help extract CO2, roughly 80 percent of ammonia plants use monoethanolamine
(MEA). In water fortified with effective corrosion inhibitors, the CO2gas is passed upwards
through an adsorption tower countercurrent to a 15 to 30 percent solution of MEA. After
CO2 is consumed, the amine solution (carbon dioxide regenerator) in the reactivating tower
is preheated and regenerated. By steam stripping and then by heating, this reacting tower
extracts CO2. The CO2 gas (98.5 percent CO2) is either vented into the atmosphere or used
in other areas of the plant complex for chemical feedstock. After being refrigerated in a heat
exchanger and solution cooler, the regenerated MEA is pumped back to the absorber tower.
[1]
𝐶𝑂 + 3𝐻2 ↔ 𝐶𝐻4 + 𝐻2 𝑂 (𝑣)

3.1.5 Methanation
The small quantities of CO and CO2 left in the synthesis gas are toxic to the ammonia
synthesis catalyst and must be separated from the methanator by conversion to CH4 :-
CO + 3H2 ↔ CH4 + H2 O
CO2 + 4H2 ↔ CH4 + 2H2 O
The reactions take place in a reactor packed with a nickel containing catalyst at about 300 °
C. Methane in the synthesis reaction is an inert gas, but before entering the converter, the
water must be separated. First, this is achieved by cooling and condensing downstream of
the methanator and eventually by condensing / absorption in the loop or in a make-up gas
drying unit in the product ammonia. [2][3]

3.1.6 synthesis gas compression and ammonia synthesis

Modern ammonia plants use centrifugal compressors for synthesis gas compression,
normally powered by steam turbines, with steam generated in the ammonia plant. The
cooling compressor, necessary for the condensation of the ammonia product, is also
normally powered by a steam turbine.
Ammonia synthesis takes place at pressures typically in the range of 100 − 250 bar and
temperatures in the range of 350 − 550℃ on an iron catalyst:-
N2 + 3H2 ↔ 2NH3
In a liquid-vapor separator, concentrated ammonia is separated from the unconverted
synthesis gas and sent to a let-down separator. The unconverted synthesis is compressed
and preheated before entering the synthesis converter which contains iron oxide catalyst. It
condenses and removes ammonia from the exit steam, then transfers it to the let-down
separator. To stop the accumulation of inert gases such as argon in the circulated gas supply,
a small part of the overhead gas is purged.
Ammonia in the let-down separator is flashed to 1 bar at-33°C to remove impurities from the
liquid. The flash vapor is condensed in the let-down chiller where anhydrous ammonia is
drawn off and stored at low temperature. [1][2][3]

3.1.7 Process Block Diagram:

Figure 3-1:Block Flow Diagram For Ammonia Synthesis

3.1.8 Process Flow Diagram:

Figure 3-2:Process Flow Diagram For Ammonia Synthesis.

3.2 REFINANCE
https://www3.epa.gov/ttnchie1/ap42/ch08/final/c08s01.pdf
http://environmentclearance.nic.in/writereaddata/Online/TOR/0_0_06_Mar_2015_19184
62501Annexure-Pre-feasibilityReport(PFR)File.pdf
https://www.fkit.unizg.hr/_download/repository/booklet1.pdf
https://essentialchemicalindustry.org/chemicals/ammonia.html?fbclid=IwAR0L-
rfV5Dx5b1i0ei8frktaQs3asg87c429ihO3pCwiXozb-6AM9ElPqKE
https://www.slideshare.net/l16cn/water-gas-shift-reactor-design
https://www.slideshare.net/GerardBHawkins/hts-high-temperature-shift-catalyst-
comprehensiev-overview
https://patents.google.com/patent/EP0353453A2/en