Engineering Practice

Onsite Nitrogen Generation

Via PSA Technology
Ongoing advances in both adsorbent materials and system engineering allow todays
pressure swing adsorption (PSA) systems to produce nitrogen of varying purities and
volumes at relatively low cost compared to cryogenic air separation
Saeid Mokhatab
Consultant
Stefano Corso
Comelt S.p.A.

itrogen production that is

carried out using pressure
swing adsorption (PSA)
technology over a carbon
molecular sieve (CMS) is considered
to be a mature, cost-effective and
highly efficient method to produce
nitrogen to meet a wide range of
purity and flow requirements. Ongoing increases in efficiency in PSAbased nitrogen-generation facilities
are being driven by enhanced CMS
materials (Figure 1) and process improvements. This article provides
an overview of the fundamentals
of PSA-based nitrogen generation,
while focusing specifically on innovative practices and improved CMS
materials. Together, these advances
contribute to continuous improvement in PSA system performance,
giving chemical process industries (CPI) plant operators a proven
way to produce a reliable and
low-cost supply of high-purity dry
nitrogen onsite.

Introduction
Thanks to its inertness and low reactivity, nitrogen in both the gaseous and liquid state is used in a
wide range of applications in many
industrial sectors. These include the
production of foods and beverages,
chemicals and pharmaceuticals;
petroleum processing; the thermal
treatment of metals; the manufacture of flat glass, semiconductors
and electronics; and many more.
Industrial facilities that require large
volumes of nitrogen always look for
48

efficient methods of onsite nitrogen production

to meet all of the specifications related to purity, flow requirements,
power
consumption,
footprint and portability
[1].
Nitrogen gas is produced by separating air
into its primary component molecules (nitrogen and oxygen), using
one of two methods:
1. Traditional cryogenic
fractionation of air that
has been liquefied; or 2. FIGURE 1. Carbon molecular sieve (CMS) pellets, typically manuSeparation of gaseous factured from coconut shells, provide the surface area and pore
structure needed to separate oxygen and nitrogen from a comair using pressure swing pressed air inlet stream (Credit: Comelt S.p.A.)
adsorption
(PSA)
or
membrane-based separation systems. If large volumes of economically produce nitrogen from
nitrogen with extremely high purity compressed air at a variety of vol(99.998%) are required, cryogenic umes. For instance, todays systems
fractionation of air remains the most can handle an inlet air stream of less
efficient and economical technology than 5,000 to more than 60,000
option [2]. This is the oldest method std. ft3/h, reliably producing N2 that
of nitrogen production, and it has the meets purity requirements from 95
ability to produce both gaseous and to 99.9995% [1].
liquid nitrogen (for daily use and as a
However, the capital and operatbackup supply). Cryogenic fraction- ing costs of a PSA system are diation of air is typically carried out in rectly correlated with the purity of the
large-scale commercial plants that nitrogen produced, and these costs
then deliver the produced nitrogen climb rapidly once nitrogen with puto users.
rity greater than 99.5% is required. In
However, at many CPI facilities, some cases, it can be cost-effective
enriched nitrogen is produced on- to produce higher-purity nitrogen by
site using smaller-scale PSA separa- first producing 99.5%-purity nitrotion or membrane-based separation gen using a PSA system, and then
systems. PSA systems operate on using a palladium or copper unit to
the principle of physical adsorp- remove residual levels of oxygen in
tion of the oxygen in air by carbon the nitrogen product. Such systems
molecular sieve materials (such as can bring down residual oxygen to
those shown in Figure 1), leaving 13 ppm.
an enriched nitrogen stream as the
Membrane-based separation sysproduct; the process is illustrated in tems, which typically produce niFigure 2. Todays PSA systems can trogen at relatively low capacity (up
CHEMICAL ENGINEERING

WWW.CHEMENGONLINE.COM

JULY 2016

nitrogen-production options (introduced more recently than cryogenic

and adsorption processes). In recent
years, ongoing improvements in
membrane materials have helped to
make membrane systems attractive
for somewhat larger nitrogen flow requirements.

Gas out = N2
CMS
Pore size 3.0 angstrom
02 molecule 2.9A
N2 molecule 3.1A

N2
O2

N2

O2

CMS

N2

O2

O2

O2

N2

O2

O2

O2
O2

O2

O2

Selecting the right system

O2
O2

N2

Air in = N2 + O2

FIGURE 2. Within the CMS pellets, oxygen is preferentially adsorbed, allowing a nitrogen-rich product
stream to be captured for use onsite (Credit: SHL)

to 40,000 std. ft3/h) with a purity of

9599.5%, use several semi-permeable membrane modules. Each
membrane module contains thousands of hollow-fiber membrane

strands that remove oxygen, water

vapor and carbon dioxide from the
compressed-air inlet stream, via selective permeation. Membrane technology is the newest of the three

When selecting the most appropriate

nitrogen-production process, several
parameters should be considered.
Purity and capacity are the most
important factors that can affect
the choice of production methodology, and hence, have a direct impact on the unit cost of the nitrogen
produced. The use of a PSA nitrogen-generation system, which can
be designed to meet all types and
patterns of nitrogen flow steady,
periodic and erratic has grown
in popularity during the last several
decades, thanks to the simplicity,
performance, flexibility, reliability and
relatively low capital and operating
costs of this production route.

MONITOR VISCOSITY SIMPLY

SENSE MIXER MOTOR HORSEPOWER
WITH UNIVERSAL POWER CELL
PROFILING A PROCESS

EASY INSTALLATION

VERSATILE

24

POWER DECREASE
SHOWS BATCH
IS DONE

22
20

18

POWER
SENSOR

16
14

SENSITIVE

12
10

CONVENIENT OUTPUTS

DRY MIX
HIGH SPEED

ADD LIQUID
LOW SPEED

MIXER
MOTOR

BEGIN HIGH
SPEED MIX

6
4
2
0

BATCH 1

BATCH 2

BATCH 3

CALL NOW FOR YOUR FREE 30-DAY TRIAL 888-600-3247

WWW.LOADCONTROLS.COM
Circle 07 on p. 62 or go to adlinks.chemengonline.com/61497-07
CHEMICAL ENGINEERING

WWW.CHEMENGONLINE.COM

JULY 2016

49

However, the optimal nitrogenproduction rate using a PSA system

based on CMS pellets is around
3,000 Nm3/h of N2 produced (>95%
purity). Within that range, PSA is a
more economical option than O2/
N2-separation by air liquefaction
and cryogenic separation, or by
membrane-based separation. The
principles of PSA-based nitrogengeneration technology using CMS
and several important aspects of
process engineering knowhow are
discussed below.

Carbon molecular sieves

CMS is part of a special class of activated carbons that have non-crystalline (amorphous) structure with a
relatively narrow pore-size distribution. This material provides molecular separations based on the rate of
adsorption of nitrogen, rather than
the differences in adsorption capacity between oxygen and nitrogen.
Figure 2 shows the inner structure

take more time to penetrate the CMS

material and be adsorbed (Figure 2).
Initially, oxygen preferentially enters
the micropores. However, after a few
hours, equilibrium is achieved and
when that occurs, CMS adsorbs
roughly equal amounts of nitrogen
and oxygen.

Nitrogen production via PSA

The PSA process makes use of
cyclic pressurization and depressurization steps, where more oxygen is adsorbed on the CMS during
the high-pressure cycle, and then
released when the pressure is reduced. Figure 3 shows a typical PSA
nitrogen-generation system, consisting of two interconnected CMS
(adsorber) columns that have automatic changeover valves. Through
cyclic operation of the valves, the
two columns alternate in function, so
that compressed, dry air flows into
one column (during the adsorption
phase). Once the adsorption phase

To meet longterm performance objectives, the CMS

media must be replaced regularly. If system performance
begins to decline, the CMS also should be replaced, and
such a revamp provides a good opportunity to adjust or
update the existing design concept to ensure that the
desired nitrogen requirements are still being met
of a CMS material that is appropriate for the separation (removal) of
O2 molecules from N2 molecules in
the compressed-air inlet, to yield an
enriched nitrogen stream (Note: Carbon molecular sieves are selective
for oxygen, while zeolite molecular
sieves are selective for nitrogen).
CMS that is used to separate nitrogen and oxygen from air in PSA
systems is typically manufactured
from coconut shells, in pellet form,
with pellet diameter from 1.0 to 1.8
mm. Such pellets have the most
suitable pore size and maximum surface area to allow for the separation
of nitrogen and oxygen from air during the continuous, cyclical process
of adsorption (pressurizing) and desorption (depressurizing).
Due to the presence of micropores in a very small size range, oxygen
molecules are able to penetrate the
CMS pellets relatively fast, whereas
the slightly larger nitrogen molecules
50

is complete and the pressure in that

column is reduced (toward atmospheric pressure), depressurization
takes place (desorption phase). Assuming that Column C1 is operating
in adsorption mode, the CMS in that
tank adsorbs oxygen from the inlet
air and the product nitrogen stream
leaves the adsorber and is fed to the
end user via a receiver tank.
At the same time, the second column (C2) is operating in its desorption phase. As C2 is depressurized
toward atmospheric pressure, the
oxygen that was adsorbed by the
CMS media is released, creating an
oxygen-enriched gas (off-gas) that is
vented to the atmosphere as an inert
exhaust stream.
Once the operation cycle is complete, the valves are activated in
such a way that C1 again operates
in desorption mode, while C2 operates in adsorption mode. This cyclic
pressure-swing operation allows for
CHEMICAL ENGINEERING

continuous nitrogen production.

Short cycles between adsorption
and desorption are typically adopted,
in order to obtain the higest possible
oxygen load by the CMS media (to
allow the target nitrogen stream
to be quickly and efficiently separated from the inlet compressed-air
stream). In a typical PSA system, the
usual adsorption-desorption cycle
time lasts just 45 to 90 seconds.
At the end of the desorption cycle,
pressure is equalized between the
two adsorbers (for a few seconds),
and another cycle begins.
For the sake of process optimization, the pressure release into the atmosphere can be cut off shortly before the end of the cycle by closing
the waste-gas valve. This so-called
cutting technique leads to higher
nitrogen purities (<1 vol.% residual oxygen in the product nitrogen
stream), because toward the end of
each desorption cycle, a major proportion of nitrogen still remains in the
pore structure of the CMS substrate.
This provides a slight initial pressure
of pure nitrogen at the start of the
next adsorption cycle, which benefits the overall adsorption sequence.
The cutting time (to achieve oxygen content in the product nitrogen
of <1%) is typically set according to
the following procedure:
Measurement of O2 concentrations in the exhaust gas
Observation of the (declining) O2
concentrations in the exhaust gas
Determination of the time taken up
to the moment when the dropping
O2 concentration has gone down
to 21 vol.%.
The time measured (in seconds), plus
the cutting time to which the closing
times of exhaust valves, is typically
set via a controller.

PSA plant configuration

A standard PSA nitrogen-generation plant typically includes four
major sections:
1. Air compressor for the inlet air
2. Air pretreatment (which typically
involves the use of a mist eliminator to remove water droplets and
very small amounts of entrained
oil, plus a carbon filter to remove
residual oil vapors prior before the
inlet stream enters the buffer tank)
3. Adsorption-desorption columns
4. Product-delivery system (typically
WWW.CHEMENGONLINE.COM

JULY 2016

many advantages, allowing CPI operators to produce nitrogen in the required purities and volumes, to meet
a diverse range of chemical process
applications. Ongoing advances in
both the CMS adsorbent materials
and the overall process design and
engineering have led to continuous
improvements and advancements
of such systems for air separation, allowing them to be used as a
cost-effective alternative to more
costly cryogenic air separation in
n
many applications.
Edited by Suzanne Shelley

References
1. Ivanova, S., and Lewis, R., Producing Nitrogen via Pressure Swing
Adsorption, Chem. Eng. Prog., June 2012, pp. 3842.
2. Smith, A.R., and Klosek, J., A Review of Air Separation Technologies and Their Integration with Energy Conversion Processes, Fuel
Processing Technology, Vol. 70, 115134, 2001.

FIGURE 3. A typical onsite PSA system uses two vessels, both filled with CMS pellets. They operate in an
alternating mode, so that at any time, one is in pressurization mode to enable air separation (to allow the
nitrogen product stream to be collected), while the other tank is in depressurization mode, to allow the
adsorbed oxygen to be released to the atmosphere (Credit: Claind S.r.l.)

a nitrogen receiver/buffer tank plus

an oxygen analyzer ahead of delivery to the customer)
Similarly, PSA nitrogen-generation
plants are usually operated with an
upstream refrigeration dryer (Note:
The use of refrigerated dryers eliminates the requirement for purge air,
resulting in a capital-cost reduction,
but this design introduces more water
vapor into the CMS columns [1]). As
an alternative, the PSA system can
also be operated with a desiccant
layer arranged in the bottom part of
the PSA adsorbers to remove moisture from the inlet air stream.
To ensure reliable operation of the
PSA plant, moisture in the inlet air
should be maintained at rate lower
than the rate corresponding to the
pressure dewpoint +2C (<5.57
g H2O/m of air at 8 bars). Excessive levels of moisture will contaminate the CMS columns and reduce
the efficiency of the nitrogen generation process.
Long-term practical experience
with PSA plants has shown that, as
long as the specified conditions are
strictly observed, the entire CMS bed
can expect a lifespan of five years or
more. The CMS material must be filled
homogeneously into adsorbers, and
these vessels should be equipped
with a bottom gas-inlet system. The
recommended procedure is to fill the
CHEMICAL ENGINEERING

CMS pellets homogeneously into adsorbers using the snow-storm-filling

device, which distributes the desiccant and CMS evenly over the entire
adsorber cross-section as it enters
the column. This procedure ensures
the highest bed densities in one filling step (higher than that produced
using vibration or other commonly
used methods), and leads to optimal
system performance.

Regular maintenance is key

To meet longterm performance objectives, the CMS media must be
replaced regularly, according to system-specific revamp requirements. If
the performance of an existing PSA
facility begins to decline, the CMS
should be replaced. Such a revamp
provides a good opportunity to adjust the existing design concept to
ensure that the nitrogen requirements of the user are still being met.
Upgrading to the most modern CMS
materials allow operators to optimize the existing plant toward higher
production rates and better gas
quality. Along with a safety inspection and replacement of worn parts,
such a periodic inspection, upgrade
and retrofit allows operators to stay
abreast of the most state-of the-art
technology.
The inherent flexibility and reliability of todays PSA systems provides

WWW.CHEMENGONLINE.COM

JULY 2016

Recommended reading
1. Billiet, C., Advanced Energy Saving Pressure Swing Nitrogen Generators, Nano-porous Solutions Ltd., UK, March 2013.
2. Crittenden, B., and Thomas, W.J., Adsorption Technology & Design, Elsevier, USA, April 1988.
3. GasTec, An Introduction to Pressure Swing Adsorption (PSA)
Nitrogen Generation System, Rev.1, GasTec, Malaysia, Nov. 30,
2012.
5. Mayekawa Mfg. Co., Ltd., PSA Nitrogen Generating System,
Mayekawa Mfg. Co., Ltd., Japan, 2012.
6. Moreiraa, R.F.P.M., Jose, H.J., and Rodriguesb, A.E., Modification of Pore Size in Activated Carbon by Polymer Deposition
and Its Effects on Molecular Sieve Selectivity, Carbon, Vol. 39,
22692276, 2001.
7. Schroter, H.J., Gahlen, R.N., and Knoblauch, K., NitrogenPSA Plants Know-How Handbook, Bergwerksverband GmbH,
Germany 1991.

Authors
Saeid Mokhatab is an internationally recognized gas-processing
consultant (Dartmouth, NS, Canada; Email: smokhatab@gmail.
com) who is actively involved in
supporting adsorption projects in
the hydrocarbon processing industry, from conception to operation. Mokhatab has developed innovative solutions and process
configurations for difficult-to-treat feed streams, to help
maximize the use and life of adsorbents, and also provides customized training programs to optimize adsorption systems based on the specific needs of operation
personnel.
Stefano Corso is an area sales
manager of Comelt S.p.A. (Via
Sondrio, 4, 20063, Cernusco sul
Naviglio, Italy; Email: s.corso@
comelt.it), in the activated carbon
and adsorbents field. He started
his professional experience with a
multinational petrochemical and
chemical company operating in
the optimization of industrial processing plants through chemical treatments. For 15
years, Corso developed his chemical and sales experiences in the adsorbents field (molecular sieve and silica
gel) at Grace Davison, and after that as a specialist on
carbon molecular sieves with CarboTech AC GmbH,
Germany.
51