Process Description

The SMR process of M/s. HTAS involves

replacement of front-end with conventional SMR
together with revamping of synthesis loop by
replacing present S-200 converter with S-300 to
maintain the production of Ammonia at current
level. The process steps followed in this scheme
are:
 Carbon Methanation
Desulphurization dioxide and
removal compression

Ammonia
Reforming
CO Synthesis
Conversion and
Refrigeration
Hydrogenation-Desulphurization
The natural gas feedstock contains upto 10 wt. ppm of
sulphur compounds which have to be removed in order
to avoid poisoning of the reforming catalyst in the
primary reformer, and the low temperature shift
catalyst in the CO converter. After desulphurization,
the the content of sulphur is less than 0.1 wt. ppm. The
desulphurization takes place in two stages. The organic
sulphur compounds are converted to H2S in
Hydrogenator and the H2S absorption will take place
in Sulphur Absorber.
The reaction involve in hydrogenator:

RSH + H2 → RH + H2S
R1SSR2 + 3H2 → R1H + R2H + 2H2S
R1SR2 + 2H2 → R1H + R2H+ 2H2S
(CH)4S + 4H2 → C4H10 + H2S
COS + H2 → CO + H2S
The reaction took place in ZnO
absorber:

ZnO + H2S  ZnS + H2O

ZnO + COS  ZnS + CO2
Primary reformer
 Radiant Zone
 Convection Zone
REFORMING
The reforming of the hydrocarbon feed takes place in two
stages, a direct fired primary reformer and an autothermal
catalytic secondary reformer. The hydrocarbon feed
coming from the desulphurization unit is mixed with
steam. The steam/carbon ratio is 3.0. The reaction mixture
is preheated and taken to the primary reformer, where it is
decomposed into hydrogen, carbon monoxide, and carbon
dioxide over a nickel catalyst by heat supply. In the
secondary reformer preheated air is added, and the heat
thus generated by burning of the gas decomposes the
methane. The methane concentration in the outlet gas
from the secondary reformer is 0.6 mol% (dry basis).
 Inlet Pigtail

E-201
3rd floor Burner
E-202-1 Block

2nd floor
E-203

E-204-1 1st floor

ID fan
E-206
E-202-2
E-205-2

E-204-2

E-205-1

Outlet Pigtail Hot collector

E-201 Cold collector

8/17/2009
10
The steam reforming process can be
described by the following :

CnH2n+2 + 2H2O  Cn-1H2n + CO2 + 3H2 - heat

CH4 + 2H2O  CO2 + 4H2O - heat
CO2 + H2  CO + H2O - heat
Burner details :
It is a side fired furnace. There are 6 rows of
burners along with furnace walls.
Total number of burners 216
No. of burners in each radiant zone 108
No. of burners along each wall 54
No. of radiant burners wall 2x2
No. of burner row in each wall 6
No. of burners in each row 9
CO Shift Conversion
The CO conversion takes place in two adiabatic stages. The
high temperature CO converter contains a Cu-promoted high
temperature shift catalyst, which features high activity and
high mechanical strength. The low temperature CO converter
is loaded with low temperature shift catalyst, which is
characterised by high activity, high strength, and highly
sensitive towards sulphur poisoning. After reforming, about
12.7% CO is present in the gas (dry basis). In the high
temperature CO converter, the CO content is reduced to
approximately 3.1 vol%, and the temperature increases from
360oC to 438oC. It is then cooled to 205oC and passed on to
the low temperature CO converter, in which the CO content
is reduced to approximately 0.3 vol%, while the temperature
increases to 227oC.
The carbon monoxide in the process gas leaving
the reformer section is converted into carbon
dioxide and hydrogen according to shift reaction:

CO + H2O  CO2 + H 2 + heat

Carbon dioxide removal
For removal of the carbon dioxide, the activated MDEA
process is used. Main equipment in the MDEA process is
the CO2 absorber and the CO2 stripping column. CO2 is
removed from the process gas by counter-current
absorption in two stages. In the lower part of the
absorber, flash-regenerated solution is used for bulk CO2
removal. In the upper part of the absorber, strip-
regenerated solution is used for scrubbing. Thus, nearly a
complete removal of CO2 with only 0.05 vol% CO2 (on
dry basis) left in the treated gas.
The CO2 is removed from the gas by absorption in the
aMDEA solution Containing 40% aMDEA. The aMDEA
solution contains an activator, which increases the mass
transfer rate of CO2 from gas to the liquid Phase. The rest
of the solution is water. The over all reactions occurring
during the CO2 absorption process are :

R3N + H2O + CO2  R3NH+ HCO3-

2R2NH + CO2  R2NH2+ + R2N-COO-
Methanation and compression
After the CO2 removal, the gas contains 0.05% CO2
and 0.3% CO (dry basis). These compounds are
poisons to the ammonia catalyst and must be removed
before the gas is taken to the synthesis section. This is
done in the methanator, where CO and CO2 react with
H2 to form CH4, which is harmless to the ammonia
catalyst. The reaction takes place over a nickel-based
catalyst. The content of CO + CO2 is reduced to less
than 5 ppm. The inlet temperature to the reactor is
300oC, and the outlet temperature is 322oC.
Methanator has one catalyst bed loaded with PK-7R nickel based catalyst. The
methanation reaction starts at 280 Deg C & causes temperature increase in the
catalyst bed. The inlet temp must be controlled to ensure a sufficiently low
content of CO & CO2 in the effluent gas. the catalyst should not be exposed to
more than 420Deg over an extended period of time.
The synthesis gas is compressed to 177 kg/cm2g in the existing centrifugal type
two-casing synthesis gas compressor. In order to match the required suction
pressure of the existing synthesis gas compressor, GB601, a synthesis gas
booster, is foreseen to be installed upstream GB601, increasing the pressure of
the make-up gas from 25 to 39.6 kg/cm2g. The discharge stream from
synthesis gas booster is chilled to 8oC with evaporating ammonia in the
process gas chiller before further compression in GB601, thereby reducing the
load on the existing compressor. Any traces of impurities in the make-up gas,
such as H2O and CO2, are removed in a molecular sieve installed between
synthesis gas booster and GB601. In this way the ammonia synthesis catalyst is
protected against poisoning by H O and CO and in addition any risk of
plugging the equipment in the loop with ammonium carbamate is eliminated.
The methanation process take place in the
Methanator (R-301), and the reaction involved
Are the reverse of the reforming reaction:

CO + 3H2  CH4 + H2O + heat

CO2 + 4H2  CH4 + 2H2O + heat
 AMMONIA SYNTHESIS
The Ammonia synthesis process takes place in the ammonia converter according to the
following reaction scheme. 2H2 + N2 = 2NH3 + Heat. The reaction is reversible and only
part of hydrogen and nitrogen is converted to ammonia when the gas passes through the
catalyst bed. In ammonia converter, about 20% of the nitrogen and hydrogen is
converted into ammonia. The unconverted remainder is recycled to the converter after
separation of liquid ammonia product. The ammonia synthesis loop has been designed
for a maximum pressure of 260kg/cm2g. The normal operating pressure would be about
187 kg/cm2g at inlet to the ammonia converter depending on the load and the catalyst
activity. At reduced load, the loop pressure would decrease. Normal operating
temperatures would be in the range of 370 to 510 deg C for the 1st bed, 425 to 480 deg C
for the second bed and 420 to 460 oC for the third bed in R-501. After synthesis gas has
passed through R-501, the effluent gas is to be cooled down to a temperature at which
most of the ammonia condenses. A considerable amount of heat released by this
reaction is utilized to produce medium pressure steam in the MP steam Boiler (E-501) &
in the synthesis economizer (A-EA601 A/B) to pre-heat boiler feed water for auxiliary
boilers. The mixture of synthesis gas & liquid ammonia passes from Cooled condenser to
ammonia separator, in which the liquid ammonia is separated at a temp of 10 deg C. The
liquid ammonia is depressurized and taken to product let down tank in which the main
part of the gases dissolved in ammonia is liberated and ammonia product is drawn from
the bottom
Purge gas recovery section
A small amount of purge is taken from synthesis
section in order to maintain inert concentration
in loop. Otherwise :
a) loop pressure will increase
b) N2/H2 ratio will disturbed
c) conversion will disturbed
Process condensate stripper
Process condensate from different section of
process is treated here for the impurities.

NH3 + H2O  NH4+ + OH-

CO2 + H2O  H+ + HCO3-
HCO3-  CO32- + H+
NH3 + HCO3-  NH2COO- + H2O
 Catalyst Type & Volume

Sulphur Primary
Hydrogenator
Absorber Reformer
• TK-250 • HTZ-5 • RK-211 (2.9 m3)
• Co Mo based • ZnO based • R-201 (6.7 m3)
• Vol- 4.9 m3 • 10.7 m3 • R-67-7h (9.6 m3)
 Catalyst Type & Volume
Secondary
HT CO conv. LT CO Conv.
Reformer
• RKS-2P (2.1 m3) • SK-201-2 • LSK (3.4 m3)
• RKS-207h (15 m3) • 33.5 m3 • LK-821-2 (46.1
m3 )
• RKS-2 (2.1 m3) • Fe/Cu/Cr
• Cu/Zn/Cr
Catalyst Type & Volume

Ammonia
Methanator
Syn. Conv.
• KMIR (8.9 M ) 3
• PK-7R
• KMI (39.4 M )
3
• Ni> 23 wt. %
• Iron based
• 14.3 m3