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Process condensate stripper performance in ammonia plants

Article · January 2012

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 process condensate treatment

Process condensate
stripper performance
in ammonia plants
A project was recently completed on the development of steam results in larger impurity concentra-
tions in the condensate (>10 ppm) leaving
an alternative process route for the removal of methanol, the stripper. In the case of older genera-
ammonia and carbon dioxide from process condensate tion plants, this recovered condensate
sometimes cannot be directed back to the
in an ammonia fertilizer plant. As part of this project, boiler and is instead downgraded to cool-
a performance analysis study on three representative ing tower water (CTW), where methanol
accentuates the growth of algae and other
process condensate strippers operating under different micro-organisms resulting in high cooling
conditions in Indian fertilizer plants was initiated and tower treatment costs.
In recent years, continuous improve-
results compared. Steady state simulation runs on these ments have been made to the process
stripper variants using CHEMCAD simulation software condensate stripping operation. However,
no effort seems to have been made to
were carried out. The effect of stripper operating pressure eliminate the use of superheated steam
and temperature and steam tonnage on the stripper for stripping. Some of the accumulated
impurities are also released as objection-
performance is reported by S. Krishnaswamy,
able emissions from process vents caus-
S. M. Nazir, P.V.K. Srikanth and K. Ponnani of BITS, ing environmental pollution. This formed
the genesis of a recently completed project
Pilani – Goa Campus.
Birla Institute of Technology and Science
(BITS), Pilani – K K Birla Goa Campus
(Grants-in-Aid Bill No: 15061/2/2006,

I
n the ammonia manufacturing process,
when syngas is cooled after the low
temperature shift (LTS) step, the unre-
acted steam (used in reforming and shift
conversion) forms a condensate stream
which contains impurities, the major ones
being ammonia (NH3), methanol (CH3OH)
and carbon dioxide (CO2). The syngas from
this step goes to a CO2 separation step
where another stream containing mostly
water and an equilibrium amount of CO2
is formed. This stream normally known as
“Benfield” condensate is subsequently
pressurised and added to the condensate
stream obtained at the end of the LTS step.
The resultant stream called “process”
condensate1, 2 typically contains ammo-
nia, methanol and carbon dioxide, each in
the range of 300 to 2000 ppm by weight,
depending on the variations in process and
operating conditions in a plant. A compre-
hensive analysis and characterisation of
process condensate has been carried out
by the investigators earlier and reported.3
The current method of treating proc-
ess condensate involves steam stripping
to reduce the ammonia, methanol and
carbon dioxide content to below 5 ppm
by weight for each and re-use the purified
condensate as boiler feed water (BFW).
The stripper has to operate under severe
operating conditions where a large amount
of superheated steam is consumed mak-
ing it a highly energy intensive operation.
Even then, the BFW specifications for recy-
cle are hard to achieve. This can result in
degradation of condensate to lower duty or
rejection and increase of stripper steam.
In typical large sized old and new gen-
eration ammonia plants, where the proc-
ess condensate flows are in the region of
40 t/h, the quantity of superheated strip-
per steam used is typically 10 t/h to 14
t/h. Any attempt to reduce the quantity of
Department of Fertilizers, Ministry of
Chemicals and Fertilizers) on the develop-
ment of an alternative route for treatment
of process condensate.
As part of this project, it was proposed
to conduct a comparative performance
study using CHEMCAD simulation on three
stripper variants (based on varying operat-
ing conditions) generally used for process
condensate treatment in existing fertilizer
plants across India of different vintages
and using different technologies. This study
provided an insight into better understand-
ing of process condensate stripper opera-
tions prior to development of an alternative
energy efficient and cost effective process
route for process condensate treatment.
Process description
A typical flow sheet of a stripper used for
treating process condensate in existing

Nitrogen+Syngas  315 | January - February 2012 1

 process condensate treatment

inlet temperature on the removal of CO2,

Fig 1: Typical flowsheet for process condensate treatment in fertilizer units
NH3 and CH3OH from process conden-
overhead steam sate in the case of high pressure stripper
variant. It is seen that increasing steam
temperature i.e. additional superheat has
practically no effect on stripping of carbon
dioxide, ammonia and methanol. A similar
stripper effect was observed in the case of the low
and medium pressure stripper variants.
steam inlet It was also observed that an increase in
degree of superheat resulted in increased
carryover of process condensate in the
stripper feed stripper bottom stripper overhead stream.
Table 5 shows the effect of steam inlet
pressure on the removal of CO2, NH3 and
CH3OH from process condensate in the
pump outlet case of higher pressure stripper variant.
process condensate
heat exchanger It is seen that increasing steam pressure
has no effect on stripping of methanol
pump and carbon dioxide, but the ammonia con-
bottom to BFW centration in the stripper bottom stream
* Slight variation in operating conditions possible, may vary from plant to plant increases. A similar effect was observed in
the case of the low and medium pressure
stripper variants. An increase in steam
Table 1: Stripper operating conditions in different fertilizer units pressure directly results in an increase in
ammonia solubility in process condensate,
Stripper variants LP stripper MP stripper HP stripper thereby making it difficult to separate. In
Operating pressure, MPa 0.35 1.1 3.8 addition, increasing inlet steam pressure
Steam inlet temperature, °C 130 200 375 for a particular temperature reduces the
Steam flow rate, t/h 19 8 15 degree of superheat resulting in decreased
Process condensate flow rate, t/h 95 40 42 carryover of process condensate in the
* Slight variation in operating conditions possible, may vary from plant to plant stripper overhead stream.
Tables 6, 7 and 8 show the effect of
increase in superheated steam tonnage on
ammonia plants is shown in Fig. 1. The proc- The electrolyte NRTL or E-NRTL4,5 was the removal of CO2, CH3OH and NH3 from
ess condensate in pumped to the stripper found suitable as it considers electrolyte process condensate in the case of high,
where it comes in direct contact with super- interactions, which are predominant in medium and low pressure stripper vari-
heated steam which strips the condensate the process condensate because of the ants. An increase in steam tonnage has
of ammonia, methanol and carbon diox- presence of ammonia and carbon diox- no effect, whatsoever on the stripping of
ide. The bottom stream from the stripper ide. Tables 2 and 3 show the overhead carbon dioxide. In Table 6 (which shows
exchanges energy with the condensate feed and bottom stream process conditions the analysis of high pressure stripper
stream before being directed to the boiler obtained from simulation in comparison variant), methanol concentration reduces
feed water (BFW) section. The overhead with plant data for all three stripper vari- below 5 ppm at a steam inlet flowrate of
steam from the stripper containing impuri- ants under consideration. Good agree- 12 t/h. However for the same stripper, the
ties (depending on its operating conditions) ment is observed confirming once again steam requirement is to the tune of 42
is appropriately integrated with the ammonia the choice of thermodynamic model used. MT/hr to bring ammonia concentration in
manufacturing process. The operating condi- process condensate to below the desired
tions of three stripper variants practiced in Effect of steam operating concentration of 5 ppm. In the medium
Indian fertilizer industries and used in the and low stripper variant, it is seen that
present study are given in Table 1. conditions the concentration levels of carbon-dioxide,
methanol and ammonia drop below 5
CHEMCAD process simulation A CHEMCAD sensitivity analysis was sub- ppm if 9 t/h and 7 t/h of stripping steam
sequently carried out to study the effect is used respectively. It is clear from the
The stripper shown in Fig. 1 was simulated of steam temperature, pressure and flow above results that operating the stripper
using CHEMCAD process simulation soft- rate on removal of ammonia, methanol and under low pressure conditions results in
ware. The VLE in the water-NH3-CO2-CH3OH carbon dioxide from process condensate. less usage of steam. The low pressure
system is highly complex since the liquid Representative results are presented on a stripper operates under these conditions
phase is ionic. Several thermodynamic 40 t/h process condensate basis and dis- (refer Table 1). Operating the stripper at
models were chosen and investigated to cussed herewith. higher pressures, results in increased
describe the VLE of the proposed system. Table 4 shows the effect of steam usage of steam which counters the effect

2 Nitrogen+Syngas  315 | January - February 2012

 process condensate treatment

pose ammonium bicarbonate. The decom-

Table 2: Comparison of simulation results with plant data (stripper overhead)
posed ammonia is then difficult to strip due
Stripper Plant data Simulation data to its equilibrium solubility in water/steam.
pressure T P Flow rate T P Flow rate This idea was further tested using a
(MPa) (°C) (MPa) (t/h) (°C) (MPa) (t/h) Gibbs reactor module in CHEMCAD using
0.35 140 0.3 18 137 0.3 19 which the ammonium bicarbonate decom-
1.1 175 0.8 8 170 0.8 8 position reaction was studied. The effect of
3.8 246 3.7 16 245.6 3.7 15 pressure on decomposition temperature of
ammonium bicarbonate is shown in Fig. 2.
Pressure is observed to have an adverse
Table 3: Comparison of simulation results with plant data (stripper overhead) effect on the decomposition of ammonium
bicarbonate raising its decomposition
Stripper Plant data Simulation data temperature, even in the lower range of
pressure T P Flow rate T P Flow rate pressures. It is clear that stripper operat-
(MPa) (°C) (MPa) (t/h) (°C) (MPa) (t/h) ing temperatures need to be maintained
0.35 143 0.3 96 137 0.3 94 above the decomposition temperature of
1.1 175 0.8 40 170 0.8 39 ammonium bicarbonate and subsequently
3.8 246 3.7 41 245 3.7 42 explains the severity of stripping operation
conditions for treatment of process con-
densate in existing ammonia plants.
Table 4: Effect of steam inlet temperature on stripping of CO2, NH3 and CH3OH The ammonium bicarbonate decompo-
(high pressure stripper variant, stripper bottom) P = 3.8 MPa, flow rate = 14.7 t/h sition was further studied using the Gibbs
reactor module. The temperature was var-
Steam Stream composition (ppm) Condensate carryover (t/h)* ied at a constant pressure of 0.1 MPa (g)
T (°C) CO2 CH3OH NH3 H2O and the bicarbonate ion concentration at
250 0 0.05 1728 - a NH4HCO3 feed concentration of ,2300
300 0 0.02 1691 - ppm by weight was tracked in the simula-
350 0 0.00 1651 - tion. This is presented in Fig. 3. It can be
400 0 0.00 1610 0.53 seen that at low pressures, even at 105 to
450 0 0.00 1566 1.41 110°C, complete decomposition of ammo-
* Condensate carryover in overhead stream (t/h) nium bicarbonate occurs easily even with
such high concentration. This supports the
idea of operating strippers at lower pres-
Table 5: Effect of steam inlet pressure on stripping of CO2, NH3 and CH3OH sures, thereby reducing severity of opera-
(high pressure stripper variant, stripper bottom) T = 375°C, flow rate = 14.7 t/h tion with maximum separation.
The simulation studies suggest that it is
Steam Stream composition (ppm) Condensate carryover (t/h)*
better to use a low pressure stripper with
P (MPa) CO2 CH3OH NH3 H2O
lower degree of superheat. Steam usage
3.0 0 0 1164 1.91 and degree of superheat can be optimised
3.5 0 0 1497 0.68 in existing strippers, more so in the case of
4.0 0 0 1727 - low and medium stripper operation. How-
4.5 0 0 1890 - ever, operating conditions must be chosen
* Condensate carryover in overhead stream (t/h) above an optimum level in all three strip-
per variants so as not to have contaminant
breakthrough in the recovered process con-
of ammonia solubility at these pressures. higher (in the high pressure stripper). densate at the bottom of the stripper.
Existing high pressure stripper variants in It is also observed that the steam inlet
fertilizer plants in India consume 14 t/h temperature increases with an increase Conclusion
of steam as against 42 t/h required for in operating pressure, i.e. stripping condi-
stripping ammonia from process conden- tions become more severe. It is evident that A comprehensive study on three strip-
sate. It is clear that by compromising on ammonia and carbon dioxide must exist in per variants prevalent in existing fertilizer
steam usage, this stripper variant does not strippable form as free ammonia and carbon units indicated that operating the process
strip ammonia completely and is utilised dioxide for separation to take place. However condensate stripper at low pressures is a
only to direct the overhead steam with under prevalent pH conditions of process better option in terms of energy usage and
impurities mainly methanol and carbon condensate of around 8.23, these two impu- would give complete separation of CO2,
dioxide back to the reforming process. It is rities cannot exist in free form and combine CH3OH and NH3 from process condensate.
observed again that increasing steam ton- to form ammonium bicarbonate salt which Steam flow rate is found to have a strong
nage results in condensate carryover in the cannot be stripped using steam. It thus influence on the separation of ammonia
stripper overhead stream, the effect being becomes obvious that a significant part of and methanol. With an increase in strip-
prominent when the degree of superheat is high enthalpy of steam is used to decom- per operating pressure, the solubility of

Nitrogen+Syngas  315 | January - February 2012 3

 process condensate treatment

ammonia in process condensate increases

Table 6: Effect of steam inlet flow rate on stripping of CO2, NH3 and CH3OH
resulting in higher steam usage to counter
(high pressure stripper variant, stripper bottom) P = 3.8 MPa, T = 375°C
the effect of solubility. Process conden-
Steam Stream composition (ppm) Condensate carryover (t/h) sate strippers can operate at any pres-
flow rate (t/h) CO2 CH3OH NH3 H2O sure provided the superheated steam inlet
6 0 97.0 2422 - temperature is sufficient to decompose
12 0 0.2 1882 - ammonium bicarbonate. The formation
18 0 0 1318 0.58 of ammonium bicarbonate in the process
24 0 0 730 1.48 condensate under the prevailing pH condi-
30 0 0 208 2.38 tions has implications on operating condi-
36 0 0 21 3.28 tions of the stripper. There is a strong case
42 0 0 1.4 4.17 for having a relook at high pressure steam
stripping operation for treatment of process
* Condensate carryover in overhead stream (t/h) condensate. n

Acknowledgements
Table 7: Effect of steam inlet flow rate on stripping of CO2, NH3 and CH3OH
(medium pressure stripper variant, stripper bottom) P = 1.1 MPa, T = 200°C) The authors gratefully acknowledge the
financial support provided by the Ministry
Steam Stream composition (ppm) Condensate carryover (t/h) of Chemicals and Fertilizers, Department of
flow rate (t/h) CO2 CH3OH NH3 H2O Fertilizers, Govt. of India for this project. The
3 0 162 1925 - help and support from Zuari Industries – Goa,
6 0 53 348 - Rashtriya Chemicals and Fertilizers (RCF) –
9 0 1 2 - Mumbai, Tata Chemicals and BITS, Pilani – K
12 0 0 0 - K Birla Goa Campus is highly appreciated.
15 0 0 0 -

* Condensate carryover in overhead stream (t/h) References

1. Technology Transfer Network, Inorganic
Chemical Industry AP-42, U. S. Environmen-
tal Protection Agency, North Carolina, 1995
Table 8: Effect of steam inlet flow rate on stripping of CO2, NH3 and CH3OH 2. Ministry of State for Environmental Affairs,
(low pressure stripper variant, stripper bottom) P = 0.35 MPa, T = 215°C) Government of Egypt, Inspection Manual for
the Fertilizer Industry, pp 21–30, 2002
Steam Stream composition (ppm) Condensate carryover (t/h) 3. Dixit, O., Krishnaswamy, S., and Ponnani K. N.,
flow rate (t/h) CO2 CH3OH NH3 H2O “Ammonia plant analysis”, Issue 302, Novem-
ber/December 2009, Nitrogen + Syngas
3 0 117 59 -
4. Chen, C.-C., and L.B. Evans, A local compo-
5 0 36 0 - sition model for the excess Gibbs energy of
7 0 1 0 0.01 aqueous electrolyte systems. AIChE Journal,
9 0 0 0 0.15 1986. 32 (3): p. 444-454
11 0 0 0 0.30 5. Mock, B., L.B. Evans, and C.-C. Chen, Ther-
modynamic representation of phase equi-
* Condensate carryover in overhead stream (t/h) libria of mixed-solvent electrolyte systems.
AIChE Journal, 1986. 32 (10): p.1655-1664.

Fig 2: Effect of pressure on decomposition temperature of Fig 3: Effect of temperature on bicarbonate ion
ammonium bicarbonate concentration at 0.1 MPa pressure

260 2500
240
220 2000
temperature, ºC

concentration, ppm

200
1500
180
bicarbonate
160 1000 CO2
140
500
120
100 0
0 1 2 3 4 40 60 80 100 140
pressure, MPa temperature, ºC

4 Nitrogen+Syngas  315 | January - February 2012

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