50 Years of PSA Technology for H2 Purification | 1

50 Years of PSA Technology for H2 Purification

The first industrial application of Pressure Swing Adsorption (PSA) went on stream in
1966 at a Union Carbide production facility. Today, more than 1,000 Honeywell UOP
PSA systems have been designed, fabricated and delivered worldwide, representing
about 25 million Nm³/h of pure hydrogen produced. This summary paper presents an
overview of Honeywell UOP’s PSA innovation over the past 50 years and highlights
key developments that have led to UOP PSA systems being the process of choice
in hydrogen generation and recovery systems.

Wim Elseviers, Paula Flowers Hassett, Jean-Louis Navarre, and Michael Whysall
UOP LLC, A Honeywell Company

1. Introduction 2. Description of a PSA Unit

In the 1950s, Union Carbide developed synthetic zeolites The basic flow diagram of a UOP PolybedTM PSA System
that enabled the development of the pressure swing is shown in Figure 1.
adsorption process. It became possible to extract high Product
H2 @ High Purity
purity hydrogen from a syngas mixture produced by the High Pressure

steam reforming of hydrocarbons. The new materials had

the property to capture impurities while hydrogen was Feed Gas
essentially not adsorbed. The ability to completely adsorb H2 + Impurities
High Pressure
impurities allowed for the production of high purity
hydrogen (typically 99.9+ mol-%) in a single unit with
Tail Gas
virtually little consumption of utilities, contrary to the H2 Purity 99.9 – 99.9999%
H2 Recovery 80 – 90% Impurities (+H2)
traditional multiple-unit flow schemes utilizing acid gas H2 Feed pressure 6 - 40 bar g Low Pressure
H2 Product pressure 5 - 39 bar g
removal wash systems and methanation reactors.

The main developments in PSA technology have been:

Figure 1: PSA Basic Flow Diagram
Extension of the initial system featuring four adsorbers,
A PSA installation consists of five major components:
to systems with 10 or more adsorbers;

Development of high-performance adsorbents to Carbon steel adsorber vessels designed for fatigue
achieve the higher hydrogen recoveries and purities; service

Addition of alternative operation modes (switchover) A selected mix of adsorbent materials

with a reduced number of adsorbers in service for full A valve and piping skid that houses all automatic
on-line maintenance; process switching valves, manual isolation valves, feed,
product, tail gas pipe and internal connection headers
Development of the fully automatic operation of PSA
and local instrumentation, connected to the adsorber
systems for unattended operation, thanks to
vessels
advancements in process controllers
A tail gas drum to mix the tail gas and minimize the
composition variations
The control system ensuring the correct operation of
the PSA unit
50 Years of PSA Technology for H2 Purification | 2

The following process parameters influence the design and Single Train PSA Capacity Meeting Refinery Demands
performance of a Polybed™ PSA unit: 350
Period
4 bed Hysiv Unit
5
300 First New

Product Capacity (1000 Nm3/h)

Polybed Systems
Feed Gas Composition: The PSA process can handle Increasing Product 16-bed
Period 4 223,000
Adsorbent
14-bed
Ultra Large Capacity
250 253,000
feed gas with a wide variety of impurities including but not New Adsorbents

limited to water, carbon oxides, methane, nitrogen and C2+ 200

Fast cycle
12-bed
hydrocarbons. Generally, feed gases containing less than Period 3 113,000
150
12-bed
50 vol-% hydrogen cannot be economically upgraded in a Period 2 71,000
14-bed
100
10-bed 100,000
PSA system. 47,000
Period 1
50
4-bed
Hydrogen Recovery: Recovery is the ratio of the 0
1966 1976 1986 1996 2006 2016
quantity of hydrogen from the feed that is recovered in the
Year
product. Recovery is influenced by product purity, feed
Figure 2: Single Train PSA Capacity Milestones
composition (nature and quantity of impurities) and
pressure conditions. First Period [1966 – 1976]:
4-Adsorber Hysiv Systems
Feed and Tail Gas Pressure: The adsorption
pressure can be fixed by either the available feed pressure The industrial story of Pressure Swing Adsorption started
or the required product pressure. The feed pressure range in the early 1960s using a 5-step PSA cycle in a four-
is usually between 10 and 40 bar g, with extremes going as adsorber in-line configuration and a tail gas drum. The first
low as 6 bar g or as high as 67 bar g. commercial PSA unit was started up in 1966. The PSA
cycle was performed by mechanical stepping switches
Product Purity: The product purity requirements
while the controls relied on hard-wired electronic and
influence the recovery, as the difference between 1 or 100
pneumatic valves. Hydrogen recovery from feed varied
ppm mol of a controlling impurity (CO, N2, CH4) demands
between 65-75% depending on the operating conditions.
more or less adsorbent utilization during adsorption.
The demand for hydrogen in these applications was such
PSA Adsorbents: UOP develops and manufactures its
that the majority of the PSA systems installed had a
own zeolites and has other adsorbents custom made.
product rate between 400 and 1,000 Nm³/h with a few units
Adsorbents are tailored to meet the application specific
reaching to 5,000 or even 7,000 Nm³/h.
demands and project requirements.
By the end of the period about 70 units had been started
Process Cycle Time: The size of a PSA adsorber is
up in the U.S. and Europe under the “Hysiv” trade name to
proportional to the amount of impurities to be adsorbed per
purify syngas from steam reformers and to recover
cycle. PSA adsorber size will increase with increasing
hydrogen from refinery off-gas and ethylene plants.
impurities flow rate during the adsorption step and
decrease with the adsorption time. Second Period [1977-1986]: The Early
Large Capacity Polybed™ Systems
3. Historical Development
of PSA Technology PSA technology benefitted from Union Carbide’s
developments of tailor-made synthetic zeolites that could
The development of PSA technology by UOP and its be tested in a customized pilot test facility.
predecessors can be described in terms of five periods
(Figure 2). In 1976, the Polybed PSA process created an opportunity
to go beyond the four-bed configuration and install units
with 10 or more adsorber vessels. The first 10-bed PSA
system (1975) produced 47,000 Nm³/h of pure hydrogen
from synthesis gas from a steam reformer. The Polybed
50 Years of PSA Technology for H2 Purification | 3

cycle allowed the design of systems to take full advantage Third Period [1987-1999]:
of the feed pressure and to recover more hydrogen. New Ever Increasing Product Capacity
PSA configurations were used including five-, six-, and
The development of high performance adsorbents (1989)
eight-bed systems to optimize the performance, the size,
produced a generation of units that were smaller and
and thus the cost control of the PSA system.
hence cheaper per unit of product, or a better adsorption
This development of PSA technology coincided with the capacity for specific contaminants. Stringent specifications
quest for more environmentally friendly transportation on transportation fuels and dieselization of fuel market led
fuels. As an increasing number of hydrotreating and to a large number of hydroprocessing units being installed
hydrocracking units went on stream, more steam reformer together with a dedicated PSA-based hydrogen plant and
units were installed to produce on-purpose hydrogen. The additional hydrogen recovery from refinery off-gas
major steam reformer licensors quickly realized that the dedicated PSA systems (Figure 3).
then standard hydrogen plant flow scheme treatment using
two levels of water gas shift carbon monoxide shift
reactors, a carbon dioxide wash system and a methanator
to convert the remaining traces of carbon oxides to
methane could be replaced by a PSA. PSAs produced a
pure hydrogen stream that met the requirements of high
conversion refinery processes and saved significant
operating cost in terms of energy required to regenerate
the CO2 solvent. The PSA yielded higher purity product at
99.9%, compared with 95-97% for the “conventional”
process. The PSA also improved energy-efficiency by
utilizing the PSA tail gas as fuel to the burners of the steam
Figure 3: 12-bed Polybed PSA (Belgium)
reformer, hence reducing the intake of feed wasted as fuel.
During the same time period, refiners started to understand More than 300 UOP PSA systems were delivered and
that recovering hydrogen from secondary refinery streams started up worldwide between 1987 and 1999. Most units
containing more than 50- mol-% hydrogen at PSA feed were in the U.S. and Europe with new growth in the Middle
pressure saved significant money. A new application East, Far East and South America. About 20 PSA systems
known as Refinery Off-Gas PSA emerged and developed were installed in non-hydrogen services such as for
to become today’s second largest PSA application. methane and helium, or monomer recovery and
purification. The Polybed PSA Systems commercialized in
Developments in control system philosophy and equipment
this period benefited from increased reliability and lower
were instrumental to enable the improvements in the PSA
maintenance requirements through specific valve
technology. The introduction of programmable logic
development programs, introducing the use of butterfly
controllers (PLC) allowed for faster and more accurate
valves.
control and reduction of cycle times. The first computer
controlled PSA unit went on stream on a 10-bed PSA Further optimization of the skid design for maintenance
system in 1979. The concept of “stacked skid” (1984) access and reduced bed-mode operation with minimum
introduced the installation of the PSA switching valves on capacity losses, resulted in the single central skid design
two levels in the skid, coping with plot plan restrictions in as the best configuration. The isolation of vessels in pairs
crowded refineries. (1988) allow the simultaneous removal of a single pair of
adsorbers for maintenance using manual isolation valves
More than 200 PSA systems were delivered spreading to
that isolate the adsorbers and their valves from the rest of
new geographies such as the Middle East and Far East.
the system, which remains in operation.
50 Years of PSA Technology for H2 Purification | 4

The concept of expandable PSA units (1999) resulted in a

lower total cost by spreading CAPEX over time
synchronized to scheduled future system capacity
increases.

Further advances in PLC controller technology (e.g. CPU

calculations capacity, memory size, redundancy, etc.),
detailed understanding of vessel fatigue designs, the
selection of specially designed, and high reliability
components resulted in the “zero-downtime PSA” concept.
No single failure inside the Polybed PSA system results in
a PSA shutdown.
Figure 4: Twin 14-bed Polybed PSA (Venezuela, 2000)
A large number of 10- and 12-bed Polybed PSA Systems
started in this period. Some systems produce more than Fifth Period [2014-onwards]
110,000 Nm³/h pure hydrogen. New Adsorbents

Fourth Period [2000-2013]: The current generation of Polybed™ PSA systems is

Ultra Large Capacity Units, characterized by advancement induced by the availability

First 16 Adsorber Polybed™ System of improved computational capabilities of personal

computers and advanced adsorption simulation programs.
The demand for pure hydrogen continued to be strong in A new generation of ultra-high-performance adsorbents
st
the first decade of the 21 century. Recovering and allows further reduction in the installed adsorbent volume
upgrading hydrogen from oil sands fields required very per ton of hydrogen recovered without sacrificing purity or
large amounts of hydrogen. A new patent enabled this recovery.
challenge in the most cost effective way. A large PSA
CFD (Computational Fluid Dynamic) models help
patent granted in 2001, resulted in the first (twin) 2x14-bed
optimizing the flow distribution in the adsorber vessels and
PSA system, which went on stream in Venezuela (2000).
designing more effective flow distribution internals.
Each train produced 2x100,000 Nm³/h of pure hydrogen
(Figure 4). Three years later, in 2003, the first single-train Detailed piping stress calculations are used in the design
16-bed PSA system went on stream in Alberta, Canada. of the skid to optimize the selection of pipe wall thickness
This flagship system produces 223,000 Nm³/h of pure for the material stress levels caused by the pressure swing.
hydrogen from a single train steam reformer.
Modern PLC’s have calculation and memory capabilities
More than 300 Polybed PSA systems were started-up in
that go beyond the requirements of a large PSA system.
this period primarily in the traditional three applications –
Proven standard PSA software applications interfaced with
steam reforming, refinery off-gas and ethylene – with
a fully detailed and customized Human-Machine Interface
plants in North America, Europe, the Middle East, India,
(HMI) have been developed on several PLC platforms.
South America and Russia. Non-refining applications
emerged such as the removal of carbon dioxide at low feed
UOP and Honeywell have optimized Honeywell’s Experion
pressure such as from DRI (Direct Reduction of Iron ore)
PKS C300 DCS system for PSA sequencing applications,
came into being.
including all optimization algorithms, allowing advanced
alarm management, asset management and remote
process monitoring from the plant’s main DCS. More than
10 PSA systems controlled by the Experion C300 DCS are
currently in various stages of project execution, while
50 Years of PSA Technology for H2 Purification | 5

almost as many systems have been successfully Since its advent in the 1960s, continuous technical
commissioned and started through July 2015. developments have supported the wide use of PSA
systems in demanding applications. The authors believe
PSA’s installed in H2 plants make a separation between H2 that the current state of the technology will continue to be
and all other impurities, in order to arrive at a product purity surpassed and that PSA systems of the future will feature
of 99.9% H2. Executing the removal of CO, CO2, N2, CH4 higher performance and will be even better integrated in
and H2O, the PSA replaces the functions of a CO2 solvent the refining, petrochemical and chemical industry.
wash system and methanator. Changing the PSA
adsorbent mix allows moving the key component for the Product Largest
purification from H2 to CO2. This was applied in a large Single Train First Plant On
Feed Source Nm3/h Stream No. Plants
steel plant in Korea (Figure 5) where PSA technology was
used instead of a solvent wash for the removal of CO2 from Steam Reformer 253,657 1966 437

a reactor effluent, with the aim of maximizing the recovery Refinery Streams 190,612 1971 246

of H2 and CO for the downstream iron making. Ethylene Off-Gas 122,793 1968 144
Methanol Off-Gas 39,595 1972 38
Misc. Off-Gas 50,155 1966 51
Partial Oxidation/
84,169 1974 28
Syngas
Coke Oven Gas 12,201 1979 19
Natural Gas 7,691 1973 17
OleflexTM
56,194 1990 16
Process Net Gas
Ammonia
58,662 1970 14
Off-Gas

Styrene Off-Gas 10,002 1970 12

Chlorine Off-Gas 24,637 1968 11

Steel Industry
Gas 150,000 2006 2

Polyethylene 3,117 2001 2

Total Units 1037

Figure 5: 20-bed PSA in CO2 Removal Service
(Korea, 2013) Table 1: UOP Polybed™ PSA Applications
(July 2015)
4. Conclusion
Pressure Swing Adsorption has become one of the
refinery’s key technologies to achieve its operational and
economical objectives. In deep conversion refineries, the
hydrocracking unit relies on a constant delivery of
hydrogen at high purity and controlled impurity levels.

Next to refinery applications, which amount for about 65%

UOP LLC, A Honeywell Company
of the installed PSA systems, and steam cracker 25 East Algonquin Road
applications (about 15% of the total), the technology has Des Plaines, IL 60017-5017, U.S.A.www.uop.com
been used in a number of niche applications where sharp
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separation and high reliability are required (Table 1). December 2015 UOP7232