PURGE GAS RECOVERY UNIT

Objective: In order to achieve optimum conversion in synthesis convertor, it is necessary to purge a certain
quantity of gas from synthesis loop so as to reduce inerts concentration in the loop.

This purge gas containing about 60% Hydrogen was fully utilised as primary reformer fuel. The recovered
hydrogen is sent back to the synthesis loop to increase production or save energy, as the quantity of hydrogen
produced by steam reforming can be reduced.

Type of the Processes:

Following process are used for recovery of Hydrogen from purge gases.

1. Membrane,
2. Pressure swing adsorption (PSA) processes and,
3. Cryogenics Process

Above all process have all been commercially applied for the recovery of hydrogen from the purge gas. Purge
gas is drawn from the loop after the second cold exchanger just before addition of the make-up gas. At this
point the gas has the maximum content of inerts.
 Hydrogen recovery & purity:
1. Membrane: Membrane separators are widely accepted to recover hydrogen from purge gas and recover
typically 85-90% hydrogen, with a hydrogen purity of 87-90%.

2. Cryogenics Process: The cryogenic process operates at high pressures (7.0 M.Pa) and can achieve a hydrogen
recovery of 90-98%. Pre-treatment of the purge gas to remove ammonia and water is required for the cryogenic
process.

3. Pressure swing adsorption: Pressure swing adsorption has been used for ultra-high-purity hydrogen from the
purge gas and has a somewhat lower hydrogen recovery (70-85%) than the membrane and cryogenic processes. No
pre-treatment is required, and water and ammonia are removed by PSA in addition to argon and methane.

Different types of hydrogen recovery technology Suppliers:

Air Products, Air Liquid, Linde, and UOP.
 Brief Description of the Process:
1. HYDROGEN RECOVERY WITH MEMBRANE PROCESS:

Membrane systems are based on the difference in permeation rates between hydrogen and impurities across a
gas-permeable polymer membrane. Permeation involves two sequential mechanisms: the gas-phase
component must first dissolve into the membrane and then diffuse through it to the permeate side. Solubility
depends primarily on the chemical composition of the membrane and diffusion on the structure of the
membrane. Gases can have high permeation rates as a result of high solubility, high diffusivity, or both. The
driving force for both solution and diffusion is the partial pressure difference across the membrane between
the feed and permeate sides. Gases with higher permeability, such as hydrogen, enrich on the permeate side of
the membrane, and gases with lower permeability enrich on the non-permeate side of the membrane because
of the depletion of components with high permeability.

The effect of hydrogen purity on recovery is much more

dramatic with membrane systems than with PSA or
cryogenics units. A fairly small change in hydrogen purity
can change the recovery significantly.
BENEFITS-
Efficient and economical hydrogen recovery: typically 80% to 98% recovery of feed H2 with a purity of 90 volume %
to 99 volume % .
1. Handles high feed pressures up to 170-175 Bar.
2. Reduce flaring and correct refinery fuel balance
3. Proven performance, long membrane life, many references

2. PSA PROCESS:
POLYBED™ Pressure Swing Adsorption units for hydrogen purification are based on the ability of adsorbents to
absorb more impurities at high gas-phase partial pressure than at low partial pressure. Impurities are adsorbed in
an absorber at high partial pressure and then desorbed at low partial pressure. The impurity partial pressure is
lowered by swinging the absorber pressure from the feed pressure to the tail gas pressure and by using a high-
purity purge gas. The driving force for the separation is the difference in impurity partial pressure between the feed
and tail gas. A minimum pressure ratio of approximately 4:1 is required. The feed pressure is usually in the range of
14 to 35 atm. Optimum tail-gas pressure is as low as possible.
Because vacuum is normally avoided, tail-gas pressures less than 1 atm is typically used when high hydrogen
recovery is desired.

BENEFITS-
The two key advantages of the PSA process are its ability to remove impurities to any level and to produce a high-
purity high-pressure hydrogen product. The purity of the hydrogen product from a PSA unit is typically in excess of 99
vol-% and frequently 99.999 vol-%. Removal of CO and CO2 to a volume level of 0.1 to 10 ppm is common and readily
achieved.
3. HYDROGEN RECOVERY WITH CRYOGENIC PROCESS:

This process is based on the difference in boiling points of liquid gases in the stream. Ammonia line 1 PGR and IGP is
based on this process. The Energy saving is 0.11 Gcal/MT ammonia with purge gas recovery for 1864TPD ammonia
plant and correspondingly 0.06Gcal/MT urea.
1. Hydrogen gets liquefied at -253°C atm pressure.
2. Nitrogen gets liquefied at -196°C atm pressure.
3. Methane gets liquefied at -161°C atm pressure.
4. Ammonia gets liquefied at -33°C atm pressure

PURGE GAS RECOVERY DESIGN BASIS :

PURGE GAS RECOVER ADVANTAGES
1. Hydrogen in 15000 Nm³/hr of purge gas is around 9000 Nm³/hr. The equivalent feed saving in primary reformer
is around 2.175 T/hr of NG.
2. Or feed can be maintained same increase ammonia production and hence urea production provided there are no
bottlenecks.
3. Consequent to this primary reformer pressure is reduced increasing conversion and less energy in GV or back
pressure is increased saving energy in synthesis compressor and better absorption in GV.
4. Reduction in firing in primary reforming corresponding to the reduction in feed and increases in methane slip.
5. Moreover a saving of less than 7 T/h SM steam in reforming countered by loss in production of HP steam in RG
boiler.

PURGE GAS RECOVER DISADVANTAGES

1. Process air to be made up in secondary reformer equivalent to hydrogen recovered (for feed 15000 Nm³/hr) is
around 3.8 KNm³/hr.
2. However process air reduced due to reduction in feed is around 3.5 KNm³/hr
3. So net increase in process air in secondary reformer is around 0.3 KNm³/hr
4. Loss of CO2 around 2.66 KNm³/hr which means under full load, load on CDR (Carbon Dioxide Recovery) is
increased being a costly affair. However, energy on GV is also reduced.
5. Although fuel is reduced in primary corresponding to the reduction in feed, fuel is increased to compensate the
energy of hydrogen from recovery fuel gas.
6. Overall however there is net energy saving in the PGR project and is considered feasible.
CONCLUSION

The installation of a purge gas converter ensures a very Efficient use with respect to hydrogen and nitrogen balancing.
An increased ammonia production, along with hydrogen recovery and environmental regulation, has been obtained.
Furthermore, fixed capital investment for raw gas purification and preparation sections reduces. A cryogenic purge gas
recovery unit recovering hydrogen at a pressure of 85 kg/cm2 g improved the efficiency of ammonia synthesis loop.
Ammonia recovery unit was provided prior to the hydrogen recovery unit to minimize ammonia loss and finally leading
to NOx reduction in the primary reformer.