PSA TechnologyMore than a hydrogen

purifier
TOBIAS KELLER and GOUTAM SHAHANI, Linde Engineering
Pressure swing adsorption (PSA)
technology is well known for hydro
gen (H2 ) purification of syngas
which is produced by steam methane
reforming (SMR), partial oxidation
(POX) or gasificationand refinery
offgases. PSA technology can also be
used for other gas separation tasks,
such as separating valuable C2+ fractions from refinery offgases, the purification of methane (CH4 ), capturing
carbon dioxide (CO2 ), and generating
oxygen (O2 ) or nitrogen (N2 ).
The selection of the best technology for a given gas separation requires a thorough understanding of
Weak

Hydrogen/Helium
Oxygen
Argon
Nitrogen
Carbon monoxide
Methane
Carbon dioxide
Ethane
Ethylene
Propane
Butane
Propylene
Ammonia
Hydrogen sulfide
Mercaptans
BTX
Water

Strong

FIG. 1. Attractive forces for different

gas molecules.

the available production technologies (SMR, POX and gasification)

and separation technologies (membrane, cryogenics, absorption and
adsorption). Recent developments
have made the recovery of CO2 or
C2+ technically feasible and economically viable with PSA technology.
The main application for PSA in a
refinery is the recovery and purification of H2 from gas streams. The hydrogen product can be obtained at high
purity up to 99.9999% and high recovery rates up to 92%. PSA systems and
vacuum (regenerated) pressure swing
adsorption (VPSA) systems can be
applied for the bulk removal of CO2
and the recovery and purification of
CO2 for liquefaction. Refinery offgas
(ROG) streams containing H2, CH4 and
C2+ hydrocarbons are usually available in refineries and are often used
as fuel. It is possible to process these
gas streams and recover C2+ by PSA
or VPSA as a way to capture greater
value of C2+, which can then be used as
a chemical feedstock. In this case, the
C2+ fraction is recovered on low pressure, while H2 and CH4 will stay on the
high pressure side. Several units have
been placed into commercial operation with very attractive payback.
In a refinery, low-purity O2 can be
used to enrich the combustion air in
Adsorption
isotherms

Adsorption
loading
0 C
30 C
Differential
loading

50 C
200 C

Desorption
loading
PA
Desorption pressure

Partial pressure

PA
Adsorption pressure

FIG. 2. Amount of adsorbed impurity per amount of adsorbent.

Product
Repressurization
Pressure equalization
Purging

Feed

fluid catalytic cracking (FCC) and

sulphur recovery unit (SRU) operations. The production of gaseous O2 at
capacities of up to 10,000 Nm3/h and
purity of 90%94% can be most effectively achieved by VPSA process,
which offers low specific energy consumptions and operational simplicity,
including simple startup and turndown capability.
N2 is used in a refinery for inerting and blanketing, and PSA systems
can also be used to generate N2 for
capacities up to 5,000 Nm3/h and purities of 2% to 0.1% (and lower) residual O2. Unlike H2 PSA, CO2 PSA
and oxygen VPSA systems, the N2
PSA is based on the difference in kinetics of adsorption of O2 on carbon
molecular sieve.
PSA technology is based on a
physical binding of gas molecules to
a solid adsorbent material, which can
be a combination of activated carbon,
silica gel, carbon molecular sieve or
zeolite. The attractive forces between
the gas molecules and the adsorbent
material depend on the gas component, type of adsorbent material, partial pressure of the gas component and
operating temperature. Highly volatile compounds with low polarity such
as H2 or helium (He), are essentially
not adsorbed compared to molecules
such as CO2, CO, N2 and hydrocarbons. The relative attractive force of
various gas molecules with a typical
adsorbent material is shown in FIG. 1.
The PSA process works at constant temperature and uses the effect
of alternating pressure and partial
pressure to perform adsorption and
desorption. Adsorption of impurities
is carried out at high pressure to increase the partial pressure and, therefore, the loading of the impurities on
the adsorbent material. Desorption or
regeneration takes place at low pressure to reduce the residual loading of
the impurities, as much as possible,
to achieve a high-purity product and
high differential loading between adsorption and desorption, thereby providing high recovery.
Because heating or cooling is not
required, cycle time can be short.
Changes in temperature are caused
only by heat of adsorption and desorp-

tion and depressurization, resulting in

long adsorbent material lifetime.
Most PSA systems are based on
equilibrium considerations (FIG. 2).
Adsorption isotherms show the relation between partial pressure of a gas
molecule and its equilibrium loading
on the adsorbent material at a given
temperature. Adsorption is carried out
at high pressure, typically in the range
of 1040 bar, until equilibrium loading is reached, at which time the adsorbent material must be regenerated
to avoid impurity breakthrough to the
product. This regeneration is done
by lowering the pressure to slightly
above atmospheric pressure, resulting
in a corresponding decrease in equilibrium loading. Thus, the impurities
on the adsorbent material are desorbed
and the adsorbent material is regenerated. The amount of impurities removed from a gas stream in one cycle
corresponds to the difference between
adsorption and desorption loading.
PSA System. A simplified schematic of
an H2 PSA system is shown in FIG. 3.
The main process steps are:
Adsorption. The feed gas is fed
upwards through the adsorber
vessels. The impuritieswater,
heavy hydrocarbons, light
hydrocarbons, CO and N2
are selectively adsorbed in the
vessel from the bottom to the
top. High-purity H2 flows to
the product line. The adsorber
vessels on adsorption are placed
on staggered cycles, resulting
in a highly flexible purification
unit that is not influenced by
fluctuations of the composition,
temperature or pressure of the
feed gas stream. The PSA system
allows high performance by
the maximum utilization of the
H2 stored in an adsorber at the
end of adsorption for pressure
equalization, re-pressurization
and purging of other adsorbers.
Pressure Equalization. To
recover most of the H2 stored
in an adsorber vessel at the end
of the adsorption step, several
pressure equalization steps are

See PSA TECHNOLOGY, page 11

Offgas
Adsorption

Pressure equalization and regeneration steps

FIG. 3. A simplified schematic of a PSA (H2 ) system.

10 SundayMonday, March 2930, 2015

FIG. 4. Modern PSA plant and CO cold box associated with a steam methane reformer.
American Fuel & Petrochemical Manufacturers|International Petrochemical Conference

IPC celebrates 40 years of supporting

American manufacturing
2015 marks the 40th anniversary of the AFPM
International Petrochemical Conference (IPC),
which has grown from a breakfast meeting for 125
to a global conference of over 3,000 attendees.
From our beginnings as the National Petroleum Association (NPA) in 1902, the association
has successfully worked on behalf of American
manufacturers. NPA was founded with the goal of
securing good to the independent oil refiners of
Pennsylvania and Ohio. The Western Petroleum
Refiners Association (WPA) was created in 1912,
merging with the Texas Petroleum Refiners Association in 1920 and with the Arkansas-Louisiana
Refiners Association in 1936.
The petrochemical industrys technological antecedents were in the European coal chemicals industry, largely developed in Germany in the late

1800s through to World War II. Improvements in

this technology, married with feedstocks from oil
and natural gas by US companies, created the petrochemical industry as we know it today.
NPA and WPA then merged in 1961 to become
the National Petroleum Refiners Association
(NPRA). In 1975, the Petrochemical Committee
proposed to the NPRA Executive Committee that a
separate conference be organized a week following
the Annual Meeting. There were about 1,400 registrants for 1976, and the program of that first meeting included the Monday morning breakfast with a
presentation on the newly passed Toxic Substances
Control Act. The topics of discussion included
feedstocks from non-oil sources, government overregulation, financial capital access, and problems
of the European petrochemical industry.

1976 was not a happy one for the US: the bicentennial year came hard on the heels of the Vietnam War and the civil strife that it engendered;
President Richard Nixon resigned; and the first energy crisis of 19731974 hit. The following years
brought challenges for the global petrochemical industry: crude oil prices ran up to $40/bbl or more
in 19791980 and fell to $10/bbl or less in 1986;
tax structures were significantly altered; the Berlin
Wall came down and with it the Soviet Union and
the Eastern Bloc; and technological advancements
and globalization significantly affected the way
petrochemical businesses were organized.
After 1976, the IPC settled into a period of steady
growth in attendance, from 1,400 in 1976 to almost

See 40TH ANNIVERSARY, page 12

PSA TECHNOLOGY, continued from page 10

performed. After termination
of regeneration of the adsorbant
material, the pressure is
increased back to adsorption
pressure level by such pressure
equalization steps and the
process starts again from
the beginning.
Regeneration. Once the
pressure equalization adsorption
steps are completed, the
adsorber material is regenerated
by depressurization in the
counter-current direction to

tail gas pressure (blow-down

step) to remove the impurities
from the adsorbent; and a purge
step carried out at tail gas
pressure level with pure H2
from other adsorber vessels
to desorb the residual impurities
from the adsorbent.
PSA Equipment. The typical
scope of supply of PSA units
includes prefabricated valve
skid, adsorber vessels, specially
selected adsorbant material, tail
gas drum and process control

system. The scope of the PSA

system can be altered to suit
specific needs: for example, a
feed gas compressor or tail gas
compressor can be included
as an integrated solution.
Key benefits of the process
control system include highpurity H2 at constant flow and
pressure; steady tail gas flow
and pressure; high H2 recovery
by optimizing equalization and
purge steps; and low sound
emissions, among others.

Selecting the most appropriate PSA

technology can improve the overall
profitability of a refinery by reducing cost and providing improved reliability, flexibility and environmental
performance. For more details, attend
Tobias Kellers (Linde Engineering)
session today at 4:30 p.m.

LITERATURE CITED
Shahani, G. H., and C. Kandziora, CO2 Emissions
from Hydrogen Plants: Understanding the
Options, 2014 AFPM Annual Meeting, Orlando,
Florida, 2014.
2
www.linde.com.
1

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