Hydrogen Recovery

by Pressure
Swing Adsorption

Contents.

3 Introduction

4 The process

5 The PSA sequence

6 Scope of supply

7 The advantages

8 Contact

Introduction.
The experience.
The use of the Pressure Swing Adsorption (PSA) process
has seen tremendous growth during the last decades
mainly due to its simplicity and low operating costs.
Major applications have been the recovery of high purity
hydrogen, methane and carbon dioxide as well as the
generation of nitrogen and oxygen. In addition, it has
gained significance for the bulk removal of carbon
dioxide from direct reduction top-gases.
Linde as the world leader in adsorption technology
has designed and supplied more than 500 PSA plants
including the worlds largest units and units with
highest availability.
The Linde hydrogen PSA units
The well proven Linde High Performance Pressure Swing Adsorption (PSA) units are designed
for the recovery and purification of pure hydrogen from different hydrogen - rich streams, such
as synthesis gases from steam reforming or gasification processes, or from various off-gases in
refinery or petrochemical plants.
Capacities range from a few hundred Nm/h to
large scale plants with more than 400,000 Nm/h.
The hydrogen product meets every purity require-

ment up to 99.9999 mol-% and is achieved at

highest recovery rates.
Main hydrogen consumers are refineries requiring this valuable gas for example for their hydrocracking, dearomatization or desulphurization
processes.
As a second group of users the petrochemical
industry has a considerable demand for hydrogen for its processes (e.g. methanol and ammo-

nia synthesis). Additionally, Linde provides PSA

solutions to a variety of other consumers like the
electronics, biomass, and steel industries.
Lindes PSA systems have proven to be successful in cases where performance, flexibility, availability and reliability are the determining factors.
High quality and easy accessibility to all components minimize and facilitate maintenance to the
maximum extent.

The process.
Separation by adsorption
The Pressure Swing Adsorption (PSA) technology
is based on a physical binding of gas molecules
to adsorbent material. The respective force acting between the gas molecules and the adsorbent material depends on the gas component,
type of adsorbent material, partial pressure of
the gas component and operating temperature.
A qualitative ranking of the adsorption forces is
shown in the figure below.
The separation effect is based on differences in
binding forces to the adsorbent material. Highly
volatile components with low polarity, such as
hydrogen, are practically non-adsorbable as
opposed to molecules like N2, CO, CO2, hydrocarbons and water vapour. Consequently, these
impurities can be adsorbed from a hydrogencontaining stream and high purity hydrogen is
recovered.

Adsorption and regeneration

The PSA process works at basically constant
temperature and uses the effect of alternating
pressure and partial pressure to perform adsorption and desorption. Since heating or cooling is
not required, short cycles within the range of
minutes are achieved. The PSA process consequently allows the economical removal of large
amounts of impurities.
The figure on page 5 illustrates the pressure
swing adsorption process. It shows the adsorption isotherms describing the relation between
partial pressure of a component and its equilibrium loading on the adsorbent material for a
given temperature.

After termination of regeneration, pressure is

increased back to adsorption pressure level and
the process starts again from the beginning.

Pressure swing adsorption plant in Leuna, Germany

Qualitative ranking of adsorption forces

Hydrogen

weak

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

Adsorption is carried out at high pressure (and

hence high respective partial pressure) typically
in the range of 10 to 40 bar until the equilibrium
loading is reached. At this point in time, no
further adsorption capacity is available and the
adsorbent material must be regenerated. This
regeneration is done by lowering the pressure
to slightly above atmospheric pressure resulting
in a respective decrease in equilibrium loading.
As a result, the impurities on the adsorbent
material are desorbed and the adsorbent material
is regenerated. The amount of impurities removed from a gas stream within one cycle
corresponds to the difference of adsorption to
desorption loading.

strong

Adsorption isotherms

Adsorption loading

Differential loading

0C

30C
50C

Desorption loading

200C
PD
Desorption pressure

Partial pressure

PA
Adsorption pressure

Adsorption and regeneration by pressure swing

The PSA sequence.

A PSA plant consists basically of the adsorber
vessels containing the adsorbent material, tail
gas drum(s), valve skid(s) with interconnecting
piping, control valves and instrumentation as
well as a control system for control of the unit.
The pressure swing adsorption process has four
basic process steps:
Adsorption
Depressurization
Regeneration
Repressurization
To provide continuous hydrogen supply, minimum 4 adsorber vessels are required. The figure
on page 6 shows the combination of the sequences of four adsorber vessels as a pressure-timediagram.
Adsorption
Adsorption of impurities is carried out at high
pressure being determined by the pressure of
the feed gas. The feed gas flows through the
adsorber vessels in an upward direction. Impurities such as water, heavy hydrocarbons, light
hydrocarbons, CO2, CO and nitrogen are selectively adsorbed on the surface of the adsorbent

material. Highly pure hydrogen exits the adsorber vessel at the top. After a defined time, the
adsorption phase of this vessel stops and regeneration starts. Another adsorber takes over the
task of adsorption to ensure continuous hydrogen supply.

total number of adsorbers and the process conditions, one to four of these so-called pressure
equalization steps are performed. Each additional pressure equalization step minimizes
hydrogen losses and increases the hydrogen
recovery rate.

Regeneration
The regeneration phase consists of basically
five consecutive steps:
Pressure equalization
Provide purge
Dump
Purging
Repressurization

Provide purge (step PP)

This is the final depressurization step in co-
current direction providing pure hydrogen to
purge or regenerate another adsorber.

The steps are combined so as to minimize hydrogen losses and consequently to maximize the
hydrogen recovery rate of the PSA system.
Pressure equalization (step E1)
Depressurization starts in the co-current direction from bottom to top. The hydrogen still stored
in the void space of the adsorbent material is
used to pressurize another adsorber having just
terminated its regeneration. Depending on the

Dump (step D)
At a certain point of time, the remaining pressure must be released in counter-current direction to prevent break-through of impurities at
the top of the adsorber. This is the first step of
the regeneration phase when desorbed impurities leave the adsorber at the bottom and flow
to the tail gas system of the PSA plant.

Scope of supply.
Purging (regeneration)
Final desorption and regeneration is performed
at the lowest pressure of the PSA sequence.
Highly pure hydrogen obtained from an adsorber
in the provide purge step, is used to purge the
desorbed impurities into the tail gas system.
The residual loading on the adsorbent material is
reduced to a minimum to achieve high efficiency
of the PSA cycle.

Pressure

Repressurization (steps R1/R0)

Before restarting adsorption, the regenerated
adsorber must be pressurized again. This is
accomplished in the pressure equalization step
by using pure hydrogen from adsorbers presently
under depressurization. Since final adsorption
pressure cannot be reached with pressure
equalization steps, repressurization to adsorption pressure is carried out with a split stream
from the hydrogen product line.
Having reached the required pressure level
again, this regenerated adsorber takes over the
task of adsorption from another vessel having
just terminated its adsorption phase.

The typical scope of supply of Lindes PSA

units includes:
Prefabricated valve skid
Adsorber vessels
Specially selected adsorbent material
Tail gas drum
Process control system
The scope can be altered to best suit clients
needs. Based on the customers requirements,
feed gas compressor or tail gas compressor
systems can be offered through Linde as an
integrated PSA solution.

PSA valve skid

Pressure time diagram

Adsorber A
Adsorption

E1

R0
PP

R1
D

Regeneration

Adsorber B
Adsorption

R0

E1

R1
PP

D
Regeneration

Adsorber C
Adsorption

R0

E1
D
Regeneration

PP

R1

Adsorber D
R0

Adsorption

E1
PP

Regeneration

R1
Time

Two pressure swing adsorption units in Canada

The advantages.
The Linde High Performance PSA units provide
remarkable advantages such as:
Lindes 30 years of expertise in adsorption
technology
Based on specific customer requirements, Linde
specialists select the optimal PSA system for distinct purification tasks in order to achieve a perfect balance between plant performance and
investment costs.

Quality and reliability

PSA process requirements make an informed
selection of specially proven plant components
(e.g. switching valves and related instrumentation) necessary. Linde only uses suitable and
thoroughly selected, tested and approved plant
components. This guarantees highest reliability
of Lindes PSA systems.
Outstanding availability
Linde PSA systems are characterized by an outstanding availability of hydrogen supply. With its
special features such as operation with reduced
number of adsorbers, adsorber group isolation
and redundant control system, Linde PSA systems
achieve virtually 100% on-stream performance
and availability.
Excellent flexibility
Linde PSA systems achieve excellent flexibility
in coping with varying feed gas conditions and
hydrogen demands to match individual client
needs.

Modular design and prefabricated equipment

Linde High Performance PSA systems are prefabricated to the maximum extent. The valve skid
containing switching and control valves, instrumentation and interconnecting piping is completely prefabricated, preassembled and tested
prior to delivery. This design philosophy reduces
time and costs for erection and commissioning
on site to the absolute minimum.
Easy maintenance
Maintenance necessity is limited to routine actions, which can be carried out by the operators
on site. Linde pays highest attention to proper
accessibility of all valves and instruments inside
the valve skid. Hence, maintenance assistance
from Linde is normally not required, but is certainly available at any time.

Designing processes constructing plants.

Lindes Engineering Division continuously develops extensive process engineering know-how in the planning,
project management and construction of turnkey industrial plants.
The range of products comprises:
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Synthesis gas plants
Hydrogen plants
Gas processing plants
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Air separation plants
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Biotechnology plants
Furnaces for petrochemical plants and refineries

The Engineering Division

and its subsidiaries manufacture:
Packaged units, cold boxes
Coil-wound heat exchangers
Plate-fin heat exchangers
Cryogenic standard tanks
Air heated vaporizers
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plant construction.

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