Chapter 3

Materials for Hydrogen

Separation and Purification

Department of Mechanical Engineering, Yuan Ze University

Hydrogen production technologies have the potential to nearly eliminate

carbon emissions and dependency on oil. However, current technology
options for hydrogen production and CO2 separation are typically more
expensive than traditional energy production.
Different methods are used but the most promising technique for
removing unwanted contaminants uses dense thin-metal membrane
purifiers which are compact, relatively inexpensive and simple to use.

Hydrogen separation membrane technologies have the potential to play an

important role in near-zero-emission plants because membranes can produce
hydrogen economically, at large scale, and with very low levels of impurities.

Hydrogen separation membranes are commercially available, but most

developments have sprung from advancements in hydrogen separation
from steam methane-reforming plants or refineries.
Most membranes used today are susceptible to contaminants commonly
found in coal-derived syngas, such as sulfur, ammonia, mercury, and
trace metals.
Gas cleanup technologies will minimize many of these contaminants, but
trace amounts will break through, and system upsets will inevitably occur.
Considering that most membrane materials are very expensive,
optimizing and demonstrating resistance to common contaminants is
needed.

Department of Mechanical Engineering, Yuan Ze University

Conventionally, cold-gas cleanup methods have been employed to

remove contaminants from coal gasification syngas streams.
Methods such as Rectisol or Selexol are commercially available
and are very effective at removing contaminants but also have high
capital and operational costs.

Significant economic benefits can be realized by utilizing warm-or

hot-gas-cleaning techniques.

The Department of Energy (DOE) has reported that thermal

efficiency increases of 8% over conventional techniques can be
realized by integrating warm-gas cleanup technologies into
integrated gasification combined-cycle (IGCC) plants.

Hydrogen separation membranes typically operate at warm-gas

cleanup temperatures, so they are a good match for IGCC projects
employing warm-gas cleanup and carbon capture.
Department of Mechanical Engineering, Yuan Ze University

Conventional Hydrogen Separation

Processes
Pressure swing adsorption (PSA)
PSA is the most common method used today for hydrogen separation.
PSA is based on an adsorbent bed that captures the impurities in the syngas stream at

higher pressure and then releases the impurities at low pressure.

Multiple beds are utilized simultaneously so that a continuous stream of hydrogen at

purities up to 99.9% may be produced.

PSA is used for the removal of carbon dioxide (CO2) as the final step in the large-scale

commercial synthesis of hydrogen. It can also remove methane, carbon monoxide,

nitrogen, moisture and in some cases, argon, from hydrogen.

Temperature swing adsorption (TSA) is a variation on PSA, but it is not widely used
because of the relatively long time it takes to heat and cool sorbents.

Electrical swing adsorption (ESA) has been proposed as well, but it is currently in
the development stage.

Cryogenic processes also exist to purify hydrogen, but they require extremely low
temperatures and are, therefore, relatively expensive.

Department of Mechanical Engineering, Yuan Ze University

Pressure swing adsorption (PSA)

Department of Mechanical Engineering, Yuan Ze University

Pressure swing adsorption (PSA)

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.
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 requirement up to
99.9999 mol-% and is achieved at highest recovery rates.

Department of Mechanical Engineering, Yuan Ze University

Pressure swing adsorption (PSA) 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.
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 as N2, CO, CO2, hydrocarbons and water
vapour. Consequently, these impurities can be
adsorbed from a hydrogen-containing stream and high
purity hydrogen is recovered.

Department of Mechanical Engineering, Yuan Ze University

Pressure swing adsorption (PSA) The

process

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.
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. After termination of regeneration, pressure
is increased back to adsorption pressure level and the process starts again from the
beginning.

Department of Mechanical Engineering, Yuan Ze University

Pressure swing adsorption (PSA) The

process

The figure 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.

Department of Mechanical Engineering, Yuan Ze University

Pressure swing adsorption (PSA) The

PSA sequence
Pressure equalization (step E1)
Provide purge (step PP)
Dump (step D)
Purging (regeneration)
Repressurization (steps R1/R0)

Department of Mechanical Engineering, Yuan Ze University

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Principles of Hydrogen Separation Membranes

Most hydrogen separation membranes operate on the principle that only

hydrogen can penetrate through the membrane because of the inherent
properties of the material.
The mechanism for hydrogen penetration through the membrane
depends on the type of membrane in question.
Most membranes rely on the partial pressure of hydrogen in the feed
stream as the driving force for permeation, which is balanced with the
partial pressure of hydrogen in the product (permeate) stream.
Figure 1 illustrates the basic operating principles of hydrogen separation
membranes for use in coal-derived syngas.
This figure shows a tubular membrane, but plate and frame-style membranes have also

been developed.
The syngas in stream refers to the feed gas into the membrane module.
The permeate stream, which in this case is made up of mostly hydrogen, has
permeated through the membrane wall.
The remaining gases (raffinate stream) are what is left of the feed stream once the
permeate is separated.
A sweep gas such as nitrogen may be used on the permeate side to lower the partial
pressure and enable more hydrogen to pass through the membrane.
Department of Mechanical Engineering, Yuan Ze University

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Hydrogen Separation Membranes, Energy & Environmental Research Centers (EERCs) National Center for
Hydrogen Technology (NCHT), TechnicalDepartment
Brief, May
2010.
of Mechanical Engineering, Yuan Ze University

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Types of Membranes

Hydrogen Separation Membranes, Energy & Environmental Research Centers (EERCs) National Center for
Hydrogen Technology (NCHT), Technical
Brief, May
2010.Engineering, Yuan Ze University
Department
of Mechanical

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Commercially Available Membranes

Air Liquide has technology called MEDAL that is typically used in

refinery applications for hydrotreating. The membrane is selective to
components other than hydrogen, including H2O, NH3, and CO2 and,
therefore, would probably not be a good fit in most coal gasification
applications.
Air Products offers a line of hydrogen recovery membranes referred
to as PRISM membrane systems. The PRISM membrane is
intended for separations in hydrocracker and hydrotreater systems
or for CO purification in reformer gases. The systems are lowtemperature and not intended for processing on coal-derived
syngas.
Wah-Chang offers small-scale PdCu membranes for commercial
sale that are capable of producing an ultrapure stream of hydrogen
from syngas. The one drawback of the membrane (like many Pdbased membranes) is that it has a very low tolerance to H 2S and
HCl, both of which are commonly found contaminants in coalderived syngas.
Department of Mechanical Engineering, Yuan Ze University

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Palladium membrane
hydrogen purifiers

The palladium membrane is typically a metallic

tube of a palladium and silver alloy material
possessing the unique property of allowing only
monatomic hydrogen to pass through its crystal
lattice when it is heated above 300C.

Department of Mechanical Engineering, Yuan Ze University

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Tokyo-Gas Co.

Figure 1 The principle of a hydrogen separation

reformer

Figure 2. A 40 Nm3/h-class hydrogen separation

reformer and a CO2 separation and recovery unit

http://www.tokyo-gas.co.jp/techno/challenge/014_e.html
Department of Mechanical Engineering, Yuan Ze University

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Japan Petroleum Energy Center

A high-efficiency process for purifying hydrogen with new hybrid separation

membrane is being developed for application to hydrogen production units
at refineries. The 99.99% pure hydrogen produced in this process will be
used for fuel cell vehicles.
http://www.pecj.or.jp/english/technology/technology06.html
Department of Mechanical Engineering, Yuan Ze University

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Making high-purity hydrogen with palladium

Metal membrane made of palladium can be used to sieve hydrogen from mixed gas. Its
separation mechanism is shown in Figure 1.
A hydrogen molecule is dissociated into two atoms on the membrane surface, dissolved within
the membrane, diffused by weaving through metal atoms, recombining on the other side of the
membrane and thus permeating through it.
Molecules other than hydrogen cannot permeate the membrane as it is difficult for them to
dissociate, dissolve and diffuse.
In manufacturing semiconductor and
LED, super high-purity hydrogen is
needed, and palladium membrane is
used to produce 99.9999999 % pure
hydrogen.
Unlike distillation which involves
gas-liquid transformation, this
separation process has good energy
efficiency, and is thought promising
for hydrogen production for fuel
cells.
By supplying high-purity hydrogen
obtained through metal membrane,
the use of platinum as fuel cell
catalyst can be reduced.
Figure 1: Principle of hydrogen separation through metal
membrane
http://www.aist.go.jp/aist_e/aist_today/2008_29/feature/feature_03.html
Department of Mechanical Engineering, Yuan Ze University

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Palladium Membrane Purification (Johnson

Palladium membrane hydrogen purifiers operate via pressure driven diffusion across
Matthey)

palladium membranes. Only hydrogen can diffuse through the palladium.

The palladium membrane is typically a metallic tube comprising a palladium and silver alloy
material possessing the unique property of allowing only monatomic hydrogen to pass
through its crystal lattice when it is heated above nominally 300 C.
The hydrogen gas molecule coming into contact with the palladium membrane surface
dissociates into monatomic hydrogen and passes through the membrane.
On the other surface of the palladium membrane, the monatomic hydrogen is recombined
into molecular hydrogen the ultrapure hydrogen used in the semiconductor process.

Palladium purifiers provide <1 ppb

purity with any inlet gas quality.
Impurities removed include O2, H2O,
CO, CO2, N2 and all hydrocarbons
(THC) including methane (CH4).
Maximum operating pressure is 250
psig at 300 to 400C; high pressure
vessels can be designed as well.
Normal life expectancy of a
palladium membrane purifier is 5
years and no routine maintenance
required.

http://pureguard.net/cm/Library/Palladium_Membrane_Purification.html
Department of Mechanical Engineering, Yuan Ze University

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Catalytic recombination
or deoxygenation
purifier
Catalytic recombination or deoxygenation is used to remove

oxygen (O2) impurities. The process is also known as a

'deoxo' process.

The oxygen reacts with the hydrogen to form water vapor,

which can then be removed by a dryer if necessary.

The catalysts that are used are based on platinum group

metals (PGM).

A typical system could handle up to 3% O2 in H2 in the feed,

and reduce the O2 content to less than 1ppm.

Department of Mechanical Engineering, Yuan Ze University

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References

http://www.tokyo-gas.co.jp/techno/challenge/014_e.html
http://www.pecj.or.jp/english/technology/technology06.html
http://www.aist.go.jp/aist_e/aist_today/2008_29/feature/feature_03.h
tml
http://pureguard.net/cm/Library/Palladium_Membrane_Purification.h
tml
Hydrogen Separation Membranes, Energy & Environmental
Research Centers (EERCs) National Center for Hydrogen
Technology (NCHT), Technical Brief, May 2010.
Hydrogen Recovery by Pressure Swing Adsorption, Linde,
Germany.

Department of Mechanical Engineering, Yuan Ze University

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