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Hydrogen Recovery

by Pressure
Swing Adsorption
2

Contents.

3 Introduction

4 The process

5 The PSA sequence

6 Scope of work

7 The advantages

8 Contact
3

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 Capacities range from a few hundred Nm/h to As a second group of users in the petrochemical
The well proven Linde high performance PSA large scale plants with more than 400,000 Nm/h. industry has a demand for hydrogen for its
units are designed for the recovery and purifi- The hydrogen product meets every purity re- methanol and ammonia synthesis, MTBE pro-
cation of pure hydrogen from different hydrogen quirement up to 99.9999 mol-% and is achieved cesses, etc.
-rich streams, such as synthesis gases from at highest recovery rates.
steam reforming process, partial oxidation or Lindes PSA systems have proven to be success-
gasification, as well as from various off-gases Main hydrogen consumers are refineries re- ful in cases where performance, flexibility, avail-
in refineries or petrochemical processes, e.g. quiring this valuable gas for example for their ability and reliability are the determining factors.
ethylene off-gas, coke oven gas, methanol and cracking, dearomatization or desulphurization High quality and easy accessibility to all compo-
ammonia purge gas. processes. nents minimize and facilitate maintenance to
the maximum extent.
4

The process.
Separation by adsorption Adsorption and regeneration
The Pressure Swing Adsorption (PSA) technology The PSA process works at basically constant Adsorption is carried out at high pressure (and
is based on a physical binding of gas molecules temperature and uses the effect of alternating hence high respective partial pressure) typically
to adsorbent material. The respective force act- pressure and partial pressure to perform adsorp- in the range of 10 to 40 bar until the equilibrium
ing between the gas molecules and the adsorb- tion and desorption. Since heating or cooling is loading is reached. At this point in time, no
ent material depends on the gas component, not required, short cycles within the range of further adsorption capacity is available and the
type of adsorbent material, partial pressure of minutes are achieved. The PSA process conse- adsorbent material must be regenerated. This
the gas component and operating temperature. quently allows the economical removal of large regeneration is done by lowering the pressure
A qualitative ranking of the adsorption forces is amounts of impurities. to slightly above atmospheric pressure resulting
shown in the figure below. in a respective decrease in equilibrium loading.
The figure on page 5 illustrates the pressure As a result, the impurities on the adsorbent
The separation effect is based on differences in swing adsorption process. It shows the adsorp- material are desorbed and the adsorbent material
binding forces to the adsorbent material. Highly tion isotherms describing the relation between is regenerated. The amount of impurities re-
volatile components with low polarity, such as partial pressure of a component and its equili- moved from a gas stream within one cycle
hydrogen, are practically non-adsorbable as brium loading on the adsorbent material for a corresponds to the difference of adsorption to
opposed to molecules as N2, CO, CO2, hydrocar- given temperature. desorption loading.
bons and water vapour. Consequently, these
impurities can be adsorbed from a hydrogen- After termination of regeneration, pressure is
containing stream and high purity hydrogen is increased back to adsorption pressure level and
recovered. the process starts again from the beginning.

Qualitative ranking of adsorption forces Pressure swing adsorption plant in Leuna, Germany

Hydrogen weak

Oxygen
Argon

Nitrogen

Carbon monoxide
Methane

Carbon dioxide

Ethane
Ethylene
Propane
Butane
Propylene
Ammonia
Hydrogen sulfide
Mercaptanes
BTX

Water strong
5

Adsorption isotherms

Adsorption loading

0C
Differential loading

30C

50C

Desorption loading

200C

PD Partial pressure PA
Desorption pressure Adsorption pressure

Adsorption and regeneration by pressure swing

The PSA sequence.


A PSA plant consists basically of the adsorber material. Highly pure hydrogen exits the adsor- total number of adsorbers and the process con-
vessels containing the adsorbent material, tail ber vessel at top. After a defined time, the ad- ditions, one to four of these so-called pressure
gas drum(s), valve skid(s) with interconnecting sorption phase of this vessel stops and regen- equalization steps are performed. Each addi-
piping, control valves and instrumentation and eration starts. Another adsorber takes over the tional pressure equalization step minimizes
a control system for control of the unit. task of adsorption to ensure continuous hydro- hydrogen losses and increases the hydrogen
The pressure swing adsorption process has four gen supply. recovery rate.
basic process steps:
Adsorption Regeneration Provide purge (step PP)
Depressurization The regeneration phase consists of basically This is the final depressurization step in co-
Regeneration five consecutive steps: current direction providing pure hydrogen to
Repressurization Pressure equalization purge or regenerate another adsorber.
Provide purge
To provide continuous hydrogen supply, mini- Dump Dump (step D)
mum 4 adsorber vessels are required. The figure Purging At a certain point of time, the remaining pres-
on page 6 shows the combination of the sequen- Repressurization sure must be released in counter-current direc-
ces of four adsorber vessels as a pressure-time- tion to prevent break-through of impurities at
diagram. The steps are combined so as to minimize hydro- the top of the adsorber. This is the first step of
gen losses and consequently to maximize the the regeneration phase when desorbed impuri-
Adsorption hydrogen recovery rate of the PSA system. ties leave the adsorber at the bottom and flow
Adsorption of impurities is carried out at high to the tail gas system of the PSA plant.
pressure being determined by the pressure of Pressure equalization (step E1)
the feed gas. The feed gas flows through the Depressurization starts in the co-current direc-
adsorber vessels in an upward direction. Impuri- tion from bottom to top. The hydrogen still stored
ties such as water, heavy hydrocarbons, light in the void space of the adsorbent material is
hydrocarbons, CO2, CO and nitrogen are selec- used to pressurize another adsorber having just
tively adsorbed on the surface of the adsorbent terminated its regeneration. Depending on the
6

Scope of work.
Purging (regeneration) The typical scope of supply
Final desorption and regeneration is performed of Lindes PSA units includes:
at the lowest pressure of the PSA sequence. Prefabricated valve skid
Highly pure hydrogen obtained from an adsorber Adsorber vessels
in the provide purge step, is used to purge the Specially selected adsorbent material
desorbed impurities into the tail gas system. Tail gas drum
The residual loading on the adsorbent material is Process control system
reduced to a minimum to achieve high efficiency
of the PSA cycle. The scope can be altered to best suit clients
needs. Based on the customers requirements,
Repressurization (steps R1/R0) feed gas compressor or tail gas compressor
Before restarting adsorption, the regenerated systems can be offered through Linde as a
adsorber must be pressurized again. This is integrated PSA solution.
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 adsorp-
tion pressure is carried out with a split stream
from the hydrogen product line.
Having reached the required pressure level PSA valve skid

again, this regenerated adsorber takes over the


task of adsorption from another vessel having
just terminated its adsorption phase. Pressure time diagram

Adsorber A
Pressure

Adsorption E1 R0

PP R1
D
Regeneration

Adsorber B
R0 Adsorption E1

R1
PP D
Regeneration

Adsorber C
R0 Adsorption

E1
D PP
Regeneration R1

Adsorber D
R0 Adsorption

E1

PP D
Regeneration R1

Time
7

Two pressure swing adsorption units in Canada

The advantages.
The Linde high performance PSA units provide
remarkable advantages such as:

Lindes expertise in adsorption technology Availability Modular design and prefabricated equipment
Based on customers requirements, the Linde The Linde PSA systems are characterized by an Lindes high performance PSA systems are pre-
PSA specialists will select the optimum PSA outstanding availability of hydrogen supply. fabricated to a maximum extent. The valve skids
system for the specific purification task in terms With its special features such as operation with containing switching and control valves, instru-
of optimum ratio between plant performance reduced number of adsorbers, adsorber group mentation and interconnecting piping are com-
and investment cost. isolation and redundant control system, Lindes pletely prefabricated, preassembled and tested
PSA units achieve virtually 100% on-stream prior to delivery. This design philosophy reduces
Quality performance and availability. time and costs for erection and commissioning
The high switching cycles of PSA units require on site to and absolute minimum.
special equipment distinguished by a high de- Flexibility
gree of durability. Linde only applies qualified Excellent flexibility to match actual clients Easy maintenance
components, which meet these demands per- needs are achieved with Lindes PSA systems Maintenance is limited to easy and quick rou-
fectly and which are proven during many years as they are capable of providing a high degree tine actions which can be carried out by the
of experience. of flexibility to cope with feed gas conditions operators on site. Highest attention is given to
and varying hydrogen demand. a proper accessibility of all valves and instru-
Reliability ments inside the valve skid. Assistance from
The use of selected and suitable components Linde is hence normally not required but is
implies the high reliability of Lindes PSA sys- certainly available at any time convenient to
tems. Especially high performance switching client.
valves are used in Lindes PSA process.
Collaborate. Innovate. Deliver.

Lindes Engineering Division is a leading player in the international plant engineering business. Across the globe, we have
delivered more than 4,000 plants and cover every step in the design, project management and construction of turnkey
industrial facilities. Our proven process and technology know-how plays an indispensable role in the success of our customers
across multiple industries from crude oil, natural gas extraction and refining to chemical and metal processing.

At Linde, we value trusted, lasting business relationships with our customers. We listen carefully and collaborate closely with
you to meet your needs. This connection inspires us to develop innovative process technologies and equipment at our high-
tech R&D centres, labs and pilot plants designed in close collaboration with our strategic partners and delivered with passion
by our employees working in more than 100 countries worldwide.

From the desert to the Arctic, from small- to world-scale, from standardised to customised builds, our specialists develop plant
solutions that operate reliably and cost-effectively under all conditions.
You can always rely on us to deliver the solutions and services that best fit your needs anywhere in the world.

Discover how we can contribute to your success at www.linde-engineering.com

Get in touch with our adsorption plant team:


Phone: +49 89 7445-0, e-mail: adsorption@linde-le.com

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