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PROCESS DESCRIPTION :

Ammonia is produced from a gaseous mixture of Hydrogen (H 2) and Nitrogen (N2) in the
stoichiometric ratio 3 to 1. For our Ammonia plant, the sources of Hydrogen (H 2) and Nitrogen
(N2) are Natural gas & atmospheric air respectively.

The main process steps that are to be followed for producing Ammonia are summarized
below:
1. Desulphurization of process Natural gas
2. Primary & Secondary steam reforming
3. High & low temperature shift conversion
4. CO2 removal system (Benfield process)
5. Methanation
6. Ammonia synthesis & Refrigeration
7. Purge Gas Recovery (PGR) Unit

1. Desulphurization of process Natural gas:

The Natural gas receives at Ammonia plant is divided into two streams namely process
natural gas which is used for producing H2 & CO2 and fuel natural gas that generates
heat for primary steam reforming. The process natural gas & recycle hydrogen from final
separator out (Methanator down stream) after compression receives heat from the
convection coils 1-E-104A/B(NG preheater) is passed at temperature 380 0C through
Hydrogenator containing CoMo catalyst where organic Sulphur in natural gas is
converted into inorganic sulphur(H2S). The process gas is then introduced to Sulphur
Adsorber containing two beds of ZnO catalyst where ZnO reacts with H 2S producing ZnS
& H2O that ensures Sulphur content less than 0.1 ppm on dry volume basis at the IRF
inlet process gas at all times. Generally it is considered that the natural gas may contain
maximum 10 ppm Sulphur by volume.

2.1. Primary steam reforming:

The treated process gas after mixing with process steam receives heat from process gas &
steam preheater (1-E-101) is then passed at temperature 520 0C through Haldor Topsoe
side fired box type heater having 200 catalyst tubes containing NiO catalyst arranged
equally in two chambers. The furnace consists of 480 radiant wall burners that are
mounted equidistantly in six horizontal rows on the two walls of each chamber. 80
burners fired with off gas are mounted in 5 th row & 400 burners fired with natural gas are
mounted in the remaining 5 rows. The steam reforming of hydrocarbons is highly
endothermic reactions & the necessary heat of reaction for primary steam reforming is
supplied as indirect heat by firing in the 1RF furnace. Fuel natural gas & off gas/flash gas
are the heat sources for primary steam reforming. The methane slippage at the exit of
primary reformer (1RF) is about 14.3 mol.% (dry basis) at temperature 778 deg.C &
Steam/carbon ratio 3.2.

The steam reforming of Natural gas can be described by the following reactions:

CnHm + 2H2O  Cn-1Hm-2 + CO2 + H2 - Heat


CH4 + H2O  CO + 3H2 - Heat
CO + H2O  CO2 + H2 + Heat

The reactions of higher hydrocarbons start at temperature 5000C & that of methane at
6000C.
The equilibrium for the reaction: CH4 + H2O CO + 3H2 – Heat is governed by more
steam, higher temperature & low pressure resulting in lower Methane content.

2.2. Secondary steam reforming:

Reactions in Secondary Reformer:

H2 +1/2O2  H2O + Heat


CH4 + 2H2O  CO + 3H2 - Heat
CO + H2O  CO2 + H2 + Heat

Process air after compression receives heat from process air preheater (1-E-102A/B) in
convection section is mixed with primary reformer outlet process gas containing mainly
H2, CO, CO2, H2O & unconverted CH4 in the upper empty space of the Secondary
reformer, where combustion of Hydrogen will give rise of process gas temperature to
1200~1300 deg.C. The gas mixture is then passed through the catalyst bed containing
NiO catalyst where the reforming reaction is completed with simultaneously cooling of
the gas. The Methane content at the exit of 2RF about 0.6 mol.% (dry basis) at
temperature 950 deg.C. The process air flow to 2RF is to be maintained properly to keep
H2/N2 ratio of 3 to 1 at Ammonia converter inlet.

3.1. High temperature shift converter (HTS):


Shift reaction:

CO + H2O  CO2 + H2 + Heat

Process gas leaving 2RF flows through No.-1 HP WHB (1-E-108) & HP steam
presuperheater (1-E-109) in order to achieve temperature about 360 deg.C at HTS inlet
by heat transfer to the mentioned Exchangers. The process gas is then introduced to HTS
containing promoted iron oxide catalyst that reduces CO content from 12.45 mol.% to
2.84 mol% (dry basis). As the reaction is exothermic, therefore, the temperature rises
across the catalyst bed is about 66 deg.C. The equilibrium of the shift reaction is favoured
by lower temperature and more water while the reaction rate will be higher at higher
temperature.

3.2. Low temperature shift converter (LTS):

The process gas at the exit of HTS is then passed through Trim heater (1-E-203), No.-2
HP WHB (1-E-201) & No.-2 HP BFW preheater (1-E-202) in order to achieve
temperature about 210 deg.C at LTS inlet by heat transfer to the mentioned Exchangers.
The process gas is then introduced to LTS having two beds of catalyst containing oxides
of Copper, Zinc& Chromium on top and oxides Copper, Zinc & Aluminum on bottom
that reduces CO content about 0.28 mol.% (dry basis).

4. CO2 removal system (Benfield process):

The main equipments of CO2 removal system are split type Absorber, two-stage
Regenerator and a 4-stage flash drum with steam ejectors.

The process gas at the outlet of Low temperature shift converter is cooled down to 100 0C
at the inlet of Absorber by transferring heat through a series of Exchangers (1-E-209, 1-
E-204, 1-E-301 & 1-E-206). The process gas then passes through the Absorber which is a
column having three packed beds reducing CO 2 content from 17.8 mol% to 0.1 mol%
(dry basis) by aqueous hot Potassium carbonate solution according to the following
chemical reaction:

K2CO3 + CO2 + H2O  2 KHCO3


The aqueous hot Potassium carbonate solution contains approx. 29% K 2CO3 partly
converted into KHCO3 as main absorbent, 2.9% Diethanolamine (DEA) as an activator &
a corrosion inhibitor, V2O5 of 0.8%.
The CO2 loaded solution (Rich solution) is expanded through a hydraulic Turbine for
energy recovery & fed to the No. 1 Regenerator having two packed beds where part of
the CO2 is flashed of as the pressure is reduced to 0.95 Kgf/cm2G.

About 87% of HPC solution is fed to the flash drum from No. 1 Regenerator where
additional steam for the regeneration is recovered by reducing the pressure in four steps
to approx. 0.43 Kgf/cm2G by means of four ejectors. The sources of motive steam are LP
steam that is generated from 1-E-204 & imported LP steam from LP steam header. Then
the flashed solution from the flash drum is pumped by HPC solution circulation pump (1-
P-301 A/B) back to the Absorber below the upper bed at a temperature of about 113 0C
where it is mixed with the solution from the top before flowing downwards through the
lower beds in counter current with process gas.

On the other hand, about 13% of HPC solution is fed to the No. 2 Regenerator from No. 1
Regenerator via semi lean solution pump (1-P-305 A/B) where the solution is received
extra heat from 1-E-301 & 1-E-302 releasing more steam & CO 2 that pass through the
top No. 2 Regenerator to the No. 1 Regenerator bottom. The regenerated solution from
the No. 2 Regenerator is cooled down to 70 0C & introduced to the top of Absorber for
the final absorption of the gas.

5. Methanation:

The Methanation is based on the reverse of the reforming reaction aiming to bring down
the CO and CO2 percentage below 10 ppm at the down stream of methanator. CO and
CO2 gases are poisonous for the converter catalyst on the other hand CH 4 gas will remain
as inert for rest of the process. The process mainly consists of a catalyst loaded vessel
Methanator (1-R-301) along with a methanator heat exchanger (1-E-306), for inlet
temperature control. Exothermic reactions taken place in the methanator in presence of
Ni catalyst are –

CO + 3 H2 ↔ CH4 + H2O + Heat


CO2 + 4 H2 ↔ CH4 + H2O + Heat

Process gas from absorber top at 70 ºC entered the methanator at around 300 ºC through
methanator heat exchanger. From reaction equilibrium lower temperature favors the
formation of methane. But considering reaction rate temperature maintained near 300 ºC.
The temperature rises across the catalyst bed is about 29 ºC. This outlet higher
temperature gas is the main source of heat for the methanator inlet gas and a branch of
inlet stream gets heat from the methanator trim heater (1-E-203) which is located at the
downstream of high temperature shift converter (1-R-201).

6. Ammonia Synthesis & Refrigeration:

The exothermic catalytic reaction of ammonia synthesis is –

3 H2 + N2 ↔ 2 NH3 +Heat

A radial type converter with the gas flowing through the two catalyst beds in radial
direction is used for the synthesis reaction. The converter is loaded with promoted iron
catalyst containing small amounts of non-reducible oxides. The equilibrium concentration
of ammonia will be favored by high pressure and low temperature. Only 25 % conversion
takes place per pass. So there is a closed loop circulation of synthesis gas maintained
from which the product ammonia is taken out and a small amount of gas is continuously
purged. Loop normal operating pressure is 133 – 144 Kg/Cm2 g and the converter inlet
temperature is maintained at around 250 – 260 ºC.

The methanator outlet gas is pressurized by synthesis gas compressor (1-K-403).


Compression takes place in three stages divided into two casing with inter stage cooling.
Compression of the make up gas to the ammonia synthesis loop takes place in the first
casing as well as in the main part of the high pressure casing. Compression of the recycle
gas from the synthesis loop is carried out in one impeller placed in the discharge end of
the high pressure casing (1-K-404). The converter exit gas temperature is 442 – 340 ºC.
There are eight numbers of heat exchangers (1-E-501/502/503/504/505/506/508) in series
in the synthesis loop at the down stream of ammonia converter. A considerable amount of
heat that is liberated by the reaction in the converter is utilized for production of HP
steam and for preheating of BFW in 1-E-501 and 1-E-502 respectively. 1 st ammonia
chiller (1-E-506) and 2nd ammonia chiller (1-E-508) are the parts of refrigeration loop
used liquid ammonia as refrigerant. Refrigeration gas compressor (1-K-405) is used to
compress the refrigerant ammonia.

After the chiller 1-E-508 liquid ammonia is separated from the bottom of separator 1-S-
501 and the non condensable gases are recycled back to the ammonia converter through
the recycle gas compressor (1-K-404). The pressure drop of the synthesis loop is
compensated by recycle part of the synthesis gas / recycle gas compressor.

Continuous accumulation of inert will increase the loop pressure as well as reduce the
reaction rate considerably, and it is more economic to purge a certain amount of the
circulating synthesis gas from the loop and thereby remove the main part of the inert
gases. The purge is taken after the 2nd cold heat exchanger (1-E-507) where the
concentration of inert is high and sent to the Purge Gas Recovery Unit (PGRU) at a rate
of 29946 Nm3/Hr so that the desired inert level (approx. 8% at the converter inlet) is
obtained in the loop. The make-up gas is also introduced into the loop between 2 nd cold
heat exchanger (1-E-507) and 2nd ammonia chiller (1-E-508) right after the purge taken
out. Recovered hydrogen gas from PGRU is added to the make-up gas at the 3 rd suction
of synthesis gas compressor (1-K-403).

From separator 1-S-501 liquid ammonia is let down to 16.2 Kg/Cm2 g at let down vessel
(1-S-502) and inert is removed. Then it comes to flash vessel (1-S-503) from which
liquid ammonia is pumped to urea plant at pressure and temperature of 11 Kg/Cm2 g and
5 ºC respectively. There is also provision for storage of ammonia in ammonia storage
tank (6-T-201) at atmospheric pressure and -32.7 º C temperatures.

7. Purge Gas Recovery (PGR) Unit:

PGR unit is a package unit that is designed to recover hydrogen and ammonia from purge
gas which is purged from ammonia synthesis and refrigeration section. The recovered
hydrogen gas is fed to the inter stage of the synthesis gas compressor (1-K-403) as
additional make-up gas while the recovered liquid ammonia is fed to the let down vessel
(1-S-502). The off gas that is also recovered from PGR unit is fed to the off gas burners
of the primary reformer (1-H-101).

The plant may be conveniently split into two sections as 1) Pretreatment Section and 2) Low
Temperature Section.

1) Pretreatment Section: Here the ammonia content of the feed gas is recovered by means of a
water wash system. Any residual ammonia together with water contamination is then
removed by absorption on molecular sieve so as to make the gas suitable for the low
temperature section.
The purge from ammonia synthesis loop is fed to the purge gas absorber (1-C-602)
through feed gas pre heater (1-E-601) at 115.0 Kg/Cm2 g and +5 ºC. Ammonia is
absorbed in a 1 mole % aqueous ammonia solution. The ammonia rich solution from
the base of 1-C-602 is heated in the rich solution pre heater (1-E-602) and passed into
ammonia regeneration column (1-C-603). The top product of the regeneration column
which is 99.85 (mol %) liquid ammonia is pumped and recovered to the let down
vessel. The feed gas leaving the absorber (1-C-602) top passes to the adsorbers (1-V-
601 A/B) where the residual ammonia and water vapor are removed on molecular
sieve. The adsorbers operate automatically on a six hours cycle which is PLC
controlled. The gas leaving the on-stream adsorber is then feed to the low temperature
section (Cold Box).

2) Low Temperature Section (Cold Box): The incoming gas from the adsorber is
cooled and partially condensed in the heat exchangers 1-E-606 A/B against returning
hydrogen product and fuel gas product. The two phase mixture is separated in feed gas
separator (1-S-601). The vapor forms the hydrogen product which is recovered at the
3rd inter stage of synthesis gas compressor and the liquid makes up the fuel gas
product. The condensed liquid in 1-S-601 is expanded to fuel gas pressure across the
level control valve (1-LV-607). The resultant low pressure two phase mixture at the
down stream of level controller is fed into the distillation separator (1-S-602). The
outlet of 1-S-602 goes to the off gas header through heat exchangers 1-E-606 A/B.
Part of the fuel gas stream is used for regeneration of the adsorbers then again
recombine with the remaining fuel gas.