Selection of a Hydrogen Separation Process

Geoffrey Q. Miller, and Joerg Stöcker

Introduction
The three main processes for hydrogen upgrading in refineries are the pressure swing adsorption process,
the selective permeation process using polymer membranes, and the cryogenic separation process. Each of
these processes is based on a different separation principle, and, consequently, the process characteristics
differ significantly. Selection of an appropriate hydrogen separation process depends not only on
economics, but also other project considerations such as process flexibility, reliability, and ease of future
expansion. A review of the separation process characteristics and equipment is given below, followed by
discussions of other project considerations. General and application-specific selection guidelines are then
presented, along with process integrations which take advantage of the complementary characteristics of the
three processes.
Process and Equipment Description:
Pressure Swing Adsorption (PSA) Systems
The PSA process for hydrogen purification is based on the capacity of adsorbents to adsorb more
impurities at high gas-phase partial pressure than at low partial pressure. The principle of the process is
illustrated in Figure 1A. Impurities are adsorbed in an adsorber at higher partial pressure and then desorbed
at lower partial pressure. The impurity partial pressure is lowered by “swinging” the adsorber pressure from
the feed pressure to the tail gas pressure, and by using a high-purity hydrogen purge. Hydrogen is adsorbed
in only small amounts. The process operates on a cyclic basis. Multiple adsorbers are used in order to
provide constant feed, product and tail gas flows. Each adsorber undergoes the same process steps in the
same sequence, but the steps are staggered with respect to time. A simple cycle sequence chart is shown in
Figure 1B for a system with four adsorbers.
The driving force for the separation is the impurity partial pressure difference between the feed and the tail
gas. A minimum pressure ratio of approximately 4:1 between the feed and tail gas pressure is usually
required for hydrogen separations. However, the absolute pressures of the feed and tail gas are also
important, particularly to hydrogen recovery. The optimum feed pressure range for PSA units in refinery
applications is 200-400 psig. The optimum tail gas pressure is as low as possible. Since vacuum is
normally avoided, tail gas pressure between 2 and 5 psig are typically used when high recovery is needed.
2
Figure 1A
Adsorption Isotherms
Wt-% Loading
(lbs impurity/100 lb adsorbent)
Heavy
Component
(C5 H12)
Intermediate
Component
(CH4)
Light
Component
(N2)
Pressure Swing
Impurity Partial Pressure
􀀁X3
􀀁X1
􀀁X2
UOP 3111-1
Figure 1B
PSA Cycle Sequence Chart
Adsorption
E=
PP =
P=
BD =
R=
E1
BD
E1
R
P
PP
E1
E1
BD
Adsorption
PP
R
P
Adsorption
BD
E1
P
R
E1
E1
R
PP
Adsorption
2 E1 PP BD P
3
4
1
Vessel 411 Cycle
Time
Equalization (CO/Current Depressurization)
Provide Purge (CO/Current Depressurization)
Purge
Blowdown (Counter/Current Depressurization)
Final Repressurization
UOP 3111-2
3
The 2 psig pressure can be used when the tail gas is to be compressed, and 5 psig can be used when the tail
gas is sent directly to fuel burners, as in steam reforming applications. Process performance is much more
sensitive to tail gas pressure than feed gas pressure, as shown in Figure 2, which shows the influence of a
system pressure levels on hydrogen recovery for a fixed feedstock and process configuration.
Figure 2
Effect of Pressure Levels on PSA System Recovery
Feed Pressure, psig
Base
-2
-4
-6
200 350
Hydrogen
Recovery,%
Tail Gas Pressure = 5 psig
Tail Gas Pressure, psig
Base
-5
-10
-15
5 60
Hydrogen
Recovery,%
Feed Pressure = 300 psig
-20
UOP 3111-3
The product hydrogen from a PSA unit is available at essentially feed pressure. There is a nominal 10 psi
pressure drop between feed and product. The product gas will contain only the less-strongly adsorbed
components of the feed gas in detectable levels. The PSA separation is chromatographic in nature, meaning
that the lightest impurities will appear first in the product, followed by the more strongly adsorbed
impurities. Relative adsorptivity of typical feed impurities is given in Figure 3.
Two of the advantages of the PSA process are its ability to remove impurities to any level (e.g., ppmv
levels if desired), and to produce a very high purity hydrogen product. Typical PSA hydrogen product
purities range from 99 to 99.999 vol-%. Removal of CO and CO2 to 0.1-10 ppmv levels is common and
easily achieved. The impact of product purity on hydrogen recovery for PSA systems is small, as shown in
Figure 4. High hydrogen purity is often of benefit to downstream processes, and because of this, most
units are designed to produce the high purities mentioned above.
4
Figure 3
Relative Strength of Adsorption of Typical Impurities
Non-Adsorbed Light Intermediate Heavy
H2 O2 CO C3H6
He N2 CH4 C4H10
Ar C2H6 C5+
CO2 H2S
C3H8 NH3
C2H4 BTX
H2O
Figure 4
Effect of Product Purity on PSA System Hydrogen Recovery
Product H2 Purity, vol-%
-1
-2
-3
97 99.9
Hydrogen Recovery, %
(Impurity = CH4)
Base
UOP 3111-4
The tail gas from a PSA unit is almost always used as fuel. The economics of the PSA process depend
strongly on the ability to use the tail gas at low pressure. When the tail gas must be compressed to the
refinery fuel gas system pressure, the cost of the compression equipment can equal the cost of the PSA
unit. For this reason, selection of the appropriate tail gas pressure is extremely important.
5
The hydrogen recovery achievable by PSA units is moderate, typically 80-92% at optimum conditions, and
60-80% when the tail gas is delivered at higher (40-80 psig) pressure. The system configuration is varied to
optimize the recovery for specific pressure levels, flow rates and stream compositions.
Figure 5 shows a typical UOP POLYBED PSA unit. These units use skid-mounted construction, which
improves quality control and simplifies installation and commissioning. The adsorbers and piping are
carbon steel. The automatic valves are the only moving parts in the system, and through proper
specification of these valves, high reliability is achieved. Control of the process is effected by a
microprocessor-based control system with a CRT operator interface. Alternate modes of operation are
preprogrammed
into the control system in order to allow uninterrupted operation in the event of a valve or
instrument malfunction.
Figure 5
UOP POLYBED® PSA Unit
Commercial units normally use between 4 and 12 adsorbers. More adsorbers are used to provide higher
hydrogen recovery and/or for higher capacity. Adsorbents are individually selected for each application and
are loaded into the adsorbers on site. Proper selection of the adsorbents is critical to both the performance
of the unit and adsorbent life. The adsorbers are good for the life of the equipment in properly designed and
operating units.
6
Membrane Systems
Selective permeation through polymer membranes is a relatively recent and rapidly evolving commercial
separation development. The process is based on the difference in permeation rates between hydrogen and
impurities. Permeation involves two sequential mechanisms: the gas phase component must first dissolve
into the membrane, then diffuse through it to the permeate side. Different components have different
solubilities and permeation rates. The former depends primarily on the chemical composition of the
membrane and the latter on the structure of the membrane. Gases can have high permeation rates due to
high solubilities, high diffusivities, or both. Relative permeabilities of typical components are given in
Table 1. Absolute permeation rates will vary depending on the type of membrane.
Table 1
Relative Membrane Permeabilities
Relative Permeability High Medium Low
Components H2 C1 C2+
H2O O2 N2
H2S
CO2
The driving force for both solution and diffusion is the partial pressure difference across the membrane,
between the feed and permeate sides. Gases with higher permeabilities, such as hydrogen, enrich on the
permeate side of the membrane, while gases with lower permeabilities enrich on the non-permeate side of
the membrane due to depletion of components with permeabilities. The first fraction of gas to permeate
through the membrane will consist primarily of the components with the highest permeability. As a larger
fraction of the feed gas is allowed to permeate, there is an increase in the relative amount of the
components with lower permeabilities in the permeate stream. Hence, in hydrogen separations, higher
purity hydrogen is associated with lower recovery, and lower purity hydrogen is associated with higher
recovery. The effect of hydrogen purity on recovery with membrane systems is much more dramatic than
for PSA or cryogenic systems, as illustrated in Figure 6. Inspection of this figure shows that a change in
hydrogen product purity from 98 mol-% to 95 vol-% can result in a 25% increase in hydrogen recovery.
Higher hydrogen recovery also requires that more membrane area be provided. The membrane area required
under fixed feed composition and system pressure levels increases exponentially at high hydrogen recovery.
The performance of a specific membrane system, i.e., the recovery vs. product purity relationship for a
given feedstock, is primarily dependent upon the feed to permeate ratio, and is only slightly dependent on
7
the absolute pressure levels. However, the area requirement is inversely proportional to the feed pressure.
For this reason, it is often preferable to compress the feed gas to achieve the required pressure ratio rather
than permeate, even though the permeate flow is always smaller.
Figure 6
Hydrogen Recovery vs. Product Purity Membrane Systems
Hydrogen Recovery, %
96
92
94
50
Hydrogen Recovery, %
Relative Permeability: 30
98
40 60 70 80 90 100
100
Pressure Ratio 5:1
Pressure Ratio 2.5:1
UOP 3111-5
There are two types of membranes currently in commercial use for hydrogen upgrading: asymmetric and
composite. Asymmetric membranes are composed of two layers of a single polymer. There is a dense layer
which performs the separation and a microporous substrate layer whose function is to provide mechanical
support. The polymers used for this type of membrane must have both acceptable permeation characteristics
and mechanical properties. Hence, the ability to tailor membrane properties to specific applications is
limited for this type of membrane. Composite membranes consist of two different polymers; the separation
polymer is coated on the substrate polymer. This allows selection of a separation polymer based on its
permeation characteristics without regard for its mechanical properties. Furthermore, since only very small
quantities of separation polymer are required even for large commercial installations, expensive polymers
of limited availability can be used, without significantly increasing cost or delivery time.
Membranes are manufactured as hollow fibers or as flat sheets. Both types of membranes are packaged as
modules, which allows standardization of equipment. Hollow fiber membrane systems have the advantage
that a larger surface area can be packaged in a given number of modules. The membrane modules are
skid-mounted along with the pretreatment section of the system. All equipment is carbon steel, and the
8
control components are straightforward. In large installations requiring many modules, care must be taken
to provide for even flow distribution among modules. A typical UOP Advanced Membrane System is
shown in Figure 7.
Figure 7
UOP Advanced Membrane Systems
Cryogenic Systems
The cryogenic process is a low temperature separation process which uses the difference in boiling
temperatures (relative volatilities) of the feed components to effect the separation. Hydrogen has a high
relative volatility compared to hydrocarbons. The simplest and most common version of the cryogenic
process is the partial condensation process. The partial condensation process condenses the required amount
of feed impurities by cooling the feed stream against the warming product and tail gas streams in brazed
aluminum multipass heat exchangers. The refrigeration required for the process is obtained by
Joule-Thomson refrigeration derived from throttling the condensed liquid hydrocarbons. Additional
refrigeration, if required, can be obtained by external refrigeration packages or by turboexpansion of the
hydrogen product.
The partial condensation process is normally applied to hydrogen/hydrocarbon streams and is best
illustrated by example. A typical flow schematic for the process is shown in Figure 8. A suitably pretreated
hydrogen/hydrocarbon feed at 300-1200 psig and ambient temperature is fed to the cryogenic unit. The unit
is cooled in exchanger X-1 to a temperature which condenses the majority of the C2+ hydrocarbons.
9
Figure 8
Partial Condensation Cryogenic Process
S-1
S-4
S-2
S-3
X-2
X-1
Insulation
Feed
L.P.
Fuel
M.P.
Fuel
Hydrogen
Product
Cold Box
Casing
S=
X=
Separator
Exchanger
UOP 3111-6
The two-phase stream is then separated in separator S-1. The hydrogen-methane vapor from separator S-1 is
sent to exchanger X-2 where it is cooled to a temperature low enough to provide the required hydrogen
product purity. The cooled stream enters separator S-2 and the vapor from S-2 becomes the hydrogen
product after it is rewarmed. The C2+-rich hydrocarbon liquids from separator S-1 are throttled to a pressure
which will result in vaporization when exchanged against the incoming feed stream in exchanger X-1. This
stream can be withdrawn separately at its highest pressure as a by-product, or mixed with the membrane
reject stream at a lower pressure. The methane-rich liquid from separator S-2 is throttled to a pressure at
which it will boil while providing the necessary temperature differential to cool the feed to the S-2
temperature. The S-2 temperature sets the hydrogen product purity by controlling the amount of methane
which remains in the vapor phase. It is usually necessary to bleed a portion of the hydrogen product stream
into the fuel stream. This has the effect of reducing the methane partial pressure in the fuel stream and
thereby lowering its boiling point. The amount of hydrogen product bleed required depends on the required
hydrogen product purity and the required fuel gas pressure. Thus, there is a trade-off between hydrogen
purity, recovery, and tail gas pressure. The relationship among these variables is shown in Figure 9.
10
Figure 9
Hydrogen Purity vs. Recovery – Cryogenic System
Hydrogen Recovery, %
88
80
84
92
Hydrogen Producy Purity, vol-%
96
90 94 96 99 100
100
10 psig Fuel Gas
92
60 psig Fuel Gas
UOP 3111-7
The additional separators S-3 and S-4 shown in the cryogenic process flow schematic are used to provide
the proper distribution of liquid and vapor into the multiple passes of the heat exchangers.
Separate hydrocarbon streams rich in C4+, ethane/propane, etc., can easily be obtained through the use of
more separators at intermediate temperatures. The ability to produce hydrocarbon by-product streams is an
important advantage of the cryogenic process.
If there are insufficient hydrocarbons or insufficient pressure available to provide the required amount of
refrigeration by the Joule-Thomson effect alone, then additional refrigeration can be obtained by expansion
of the hydrogen product or by a packaged refrigeration system. Expansion of the hydrogen product, of
course, lowers the product hydrogen pressure. Refrigeration at 0 to -40°F is normally used if external
refrigeration is chosen.
If the feed to the cryogenic unit contains significant amounts of low boiling constituents such as CO and
nitrogen, and these are to be removed by the cryogenic unit, a methane wash column is used. This column
uses liquid methane to wash the impurities from the hydrogen product stream. It is necessary if CO is to
be reduced to ppmv levels in the hydrogen product.
11
The cryogenic process is thermodynamically more efficient than the other hydrogen upgrading processes.
High hydrogen recovery (92-97%) is easily achieved at 95+ % hydrogen purity and the penalty in recovery
for increased hydrogen purity is less than for membrane systems, as illustrated in Figure 9.
The equipment used in a partial condensation cryogenic unit consists of multipass heat exchangers,
throttling valves, separators and piping. These components are normally grouped together in an insulated,
low pressure carbon steel vessel (cold box). The valves are the only system components requiring
maintenance, and access to these valves from outside the cold box casing is provided. A UOP cryogenic
unit is shown in Figure 10.
Project Considerations: Operating Flexibility
In this context, operating flexibility will be defined as the ability to operate under variable feed quality
conditions, either on a short-term or long-term basis. Variations in feed composition are common in
refinery applications. When the source of the feed is a catalytic process, there is often a gradual change in
feed quality as the catalyst activity changes. More sudden changes occur when the feedstock to the
upstream unit changes. In addition, in many cases, a combination of streams are sent to a hydrogen
upgrading system, and feed quality changes can be rapid and substantial as one or more streams are added
or subtracted from the combination. Thus, operating flexibility should consider not only ultimate response
to feed quality changes, but also the response time.
The PSA process is the most flexible process of the three under consideration in its ability to maintain
hydrogen purity and recovery under changing conditions. As the concentration of a feed impurity increases
in the feed (at constant feed pressure), the partial pressure of the impurity also increases. As shown in
Figure 1A, an increase in impurity partial pressure normally results in an increase in the amount of the
impurity which will be adsorbed. Thus, the process is to a large extent self-compensating, and even
relatively large changes in feed impurity concentrations have little impact on performance.
If the feed impurity concentration to a PSA unit changes, product purity can be maintained by a simple
cycle time adjustment to maintain product purity. UOP has introduced a patented product purity control
system for its POLYBED PSA units, which automatically adjusts cycle time to account for feed quality
changes, eliminating the need for operator intervention. The response time for a PSA unit is rapid but not
12
Figure 10
UOP Cryogenic Unit
abrupt; the system will respond to a step change in feed quality in 5-15 minutes. The time to reach steadystate
upon restart following shutdown is also short, on the order of one hour for most systems.
In membrane processes, increases in feed impurity concentrations tend to cause increases in product
impurity concentrations. Product purity can be maintained for small feed composition changes by adjusting
the feed-to-permeate pressure ratio, but the relatively strong impact of product purity on recovery for these
systems means that hydrogen recovery can be significantly affected. In most refinery membrane
applications, however, the major product impurity is methane, and this can be allowed to increase in the
13
product slightly without major downstream impact. The response time of membrane systems is essentially
instantaneous, and corrective action has immediate results, but operators have less time to react. The startup
time required by the process is extremely short.
The cryogenic process is less flexible than the other processes. Particular attention must be given to the
high freezing point constituents which are removed in the pretreatment system, since failure to remove
these contaminants can result in plugging of the heat exchangers. Changes in the concentration of the lower
boiling components of the feed affect the product purity directly. Recovery is not strongly affected.
Changes in feed quality are compensated for by operator adjustment of the hydrogen-methane separator
temperature (separator S-2 in Figure 8) by increasing or decreasing the amount of product hydrogen bleed.
Response time is not as rapid as for PSA or membrane systems. Start-up is 8-24 hours depending on the
procedure used.
Turndown
Turndown can be an important factor in process economics because many installations are expected to
operate at reduced capacity for the first few years after commissioning. Large operating penalties due to
poor turndown performance can significantly reduce the return on investment, and should be accounted for
in economic comparisons.
All three processes have good turndown characteristics when properly designed. PSA units can maintain
both recovery and product purity at throughputs ranging from approximately 30-100+ % of design by
adjustment of the cycle time. Between 0 and 30% of design product rates, purity can be maintained but
recovery is reduced unless special provisions are made in the design.
Membrane systems are also normally capable of maintaining product purity rates from 30-100+ % of
design. Recovery will be sacrificed at turndown to a varying extent. Turndown is accomplished by either
reducing feed pressure, increasing permeate pressure, or by isolating modules from the system. The first
two methods can be used for short-term operation, and the latter when operating at significantly reduced
capacity for extended periods. The number of modules in the system is also a consideration when deciding
whether isolation is appropriate.
The turndown capability of cryogenic systems depends on the design. Partial condensation units can
maintain product purity at slightly reduced recovery at flows down to 30-50% of design. The theoretical
lower limit of turndown is determined by the heat leak to ambient, which is typically less than 30% of
design throughput. If the cryogenic system contains a methane wash column, turndown is limited to about
50% of design throughput by column hydraulics.
14
Reliability
Reliability of the hydrogen separation processes is an important project consideration, particularly if the
process is a primary source of make-up hydrogen to a hydroprocessor or other mainstream refinery process.
Reliability is normally measured by on-stream factor relative to unscheduled shutdowns. However, the
ability to produce usable product is also a reliability consideration since off-specification product affects the
downstream processes even if a shutdown of the separation process is avoided.
Membrane systems are extremely reliable with respect to on-stream factor. The process is continuous
and has few control components which can cause a shutdown. On-stream factors approaching 100% with
respect to unscheduled shutdowns are possible. However, if product purity is of critical importance (this
is rare in most membrane applications), a relatively high degree of operator attention may be required to
assure production of usable product under varying feed conditions, and this should be considered in the
selection process.
PSA systems are also highly reliable. While there are numerous valves associated with the process, these
are the only moving parts of the system, and field experience has proven that with proper valve selection,
on-stream factors of 99.8+ % can be achieved. Furthermore, UOP’s POLYBED PSA units are designed
with alternate modes of operation, in which 100% of design capacity can be achieved while bypassing any
failed valve or instrument, with only a slight loss of recovery. Product purity is maintained, and there is
no interruption of hydrogen supply. Failures are automatically detected and bypassed by the
microprocessor-based control system. The PSA process can also maintain product purity under changing
feed conditions, adding to its effective reliability.
The cryogenic process has been considered by refiners to be less reliable than the PSA or membrane
processes. This is not due to the process itself, which is relatively simple and has few moving parts.
Rather, it is due to the need for feed pretreatment and the types of refinery streams normally processed.
Feed pretreatment, as previously stated, is critical to the process reliability. Failure of the pretreatment
system will usually result in contaminants freezing in the cold box, leading to shutdown. In this case, a
“thaw” is necessary prior to restart. The pretreatment system itself is often more complex than the
cryogenic system. Also, cryogenic systems normally are used to process combined refinery streams of
relatively low hydrogen content, which can result in high feed quality variations. An exception to this is
the TDA application discussed in a later section, which is an established cryogenic application and
illustrates the inherent reliability of the process.
15
Ease of Future Expansion
In some case, future expansion is contemplated even during the initial phase of a project. Membrane
systems are ideally suited for expansion, since this only requires the addition of identical modules (the
pretreatment system can normally be sized for future expansion without a significant cost increase). PSA
systems can also be expanded, but a true expansion, as opposed to a debottleneck, requires additional
design considerations and adds cost in the initial phase of the project.
Future capacity increases from cryogenic units can often be obtained without modification to the cold box
itself through addition of a tail gas compressor. Lowering the pressure of the tail gas provides results in
larger heat exchanger temperature driving forces. The resulting increase in heat exchange capacity can be
used to condense additional feed impurities. The cost impact of designing in this way for future expansion
is small.
PSA units can be easily debottlenecked by cycle modification. Changing the number of hydrogen recovery
steps allows significant increases in throughput with relatively minor recovery losses. Cycle modifications
are easily performed by changing the control system software. UOP has debottled several PSA units in this
manner. Typically, capacity increases of up to 25% can be achieved with only a few percentage points loss
in hydrogen recovery. PSA unit operating at a high tail gas pressure can also be expanded significantly by
the addition of a tail gas compressor, which allows operation at lower tail gas pressure. In this case, both
capacity and recovery can be increased substantially.
By-Product Recovery
In many refinery hydrogen upgrading processes, the impurities to be rejected include hydrocarbons, which,
if separated, can have value significantly above fuel value. This is particularly true for olefin-containing
streams. The relative amounts of high-value hydrocarbons and the incremental cost of further separation
determine whether by-product recovery should be considered.
The cryogenic process is best suited to applications involving by-product hydrocarbon recovery. Even with
a simple partial condensation process, it is possible to recover separate hydrocarbon streams containing
C2/C3 and C4+ components. Recovery of these components is generally quite high with typical overall
values of 90% for the C2/C3 components and up to 100% of the C4+. These streams can be delivered at
moderate pressure to existing refinery processing units for final processing.
The membrane process is also used in these applications, since the hydrocarbon-rich stream is available
at high pressure. However, the membrane process is not capable of providing separate streams rich in
specific hydrocarbon fractions. This must be done in downstream units such as a cryogenic system.
16
The non-permeate stream from a membrane system can also be sent to a turboexpander plant for
further processing.
By-product hydrocarbon recovery is normally not economical when the PSA process is used, because
the single hydrocarbon-rich tail gas is delivered at too low a pressure. PSA processes producing
separate tail gas streams rich in specific components have been designed, but have not found wide
commercial application.
Combinations and separation processes, such as cryogenic and PSA processes, or membrane and cryogenic
processes, may be applicable to these applications. This topic is covered in more detail in a later section.
General Process Selection Guidelines: Pretreatment Requirements
Pretreatment considerations are important to the selection of a hydrogen separation process. The extent to
which feed pretreatment is required affects cost, operating flexibility and ease of operation. The PSA
process usually requires the least pretreatment. The process can treat most vapor phase feedstocks without
additional conditioning. Entrained liquids, including water and condensed hydrocarbons, must not be
present in the feed, as these will permanently damage the adsorbents used in the process. A well-designed
knockout drum with mist eliminator, located as close as possible to the unit, suffices for most refinery
applications. In cold climates, heat tracing and insulation of the feed piping is used to avoid condensation.
PSA units commonly process feedstocks saturated with water and/or hydrocarbons. If the feed is
compressed upstream of the PSA unit, a non-lubricated feed compressor should be used (multi-stage oil
separators, followed by an activated carbon bed to reduce oil levels to the ppb range, have also provided
satisfactory results when lubricated compressors were used). If liquids do enter with the feed gas under
upset conditions, only the bottom portion of the adsorbent bed will be affected, which usually results in a
slight loss of capacity. This capacity can often be recovered by cycle time adjustment.
Since essentially all feed contaminants in refinery applications, including HCl, H2S, BTX, and water
among others, are more strongly adsorbed than hydrogen, they will not appear in the product stream. The
contaminants will be concentrated in the tail gas at a lower partial pressure than in the feed. A knowledge
of which contaminants and their maximum concentration in the feed is important to the design of a PSA
unit, since strongly adsorbed components can permanently deactivate some adsorbents intended for
removal of light components. Experience in the application and in adsorbent selection are essential to
avoiding this problem.
Membrane systems can also be permanently damaged by liquids. Entrained liquids in the feed, even
from relatively short-term upsets, can damage an entire unit because of the large amount of feed gas
processed per module. Membrane units cannot directly process saturated feeds, because the non-permeate
17
remains at feed pressure and the condensibles are concentrated. The dew point of the non-permeate stream is
higher than that of the feed gas. Pretreatment of saturated feedstocks for membrane applications normally
consists of a knock-out drum with mist eliminator, coalescing filter, and a heater. The feed is normally
heated to approximately 20°F above the tail gas dew point. The extent of superheat required depends on
the design recovery and purity in addition to the feed properties. Units operating at higher hydrogen
recoveries require more heating. Good feed temperature control is important, because operation at higher
temperatures increases permeability at the expense of selectivity, and the membrane itself can be damaged
by high temperatures.
Certain feed contaminants cannot be completely removed by the membrane process, and pre- or
post-treatment is necessary if these contaminants are not acceptable in the product steam. Important
examples are H2S, CO and CO2. These components cannot normally be reduced to ppmv levels by
membrane purification alone.
Pretreatment for cryogenic units involves removal of those components which would freeze out at low
operating temperatures. Water in the feed should be removed to less than 1 ppmv. CO2 is normally
removed to less than 100 ppmv. Molecular sieve prepurifiers are commonly used for this purpose. Other
components, such as H2S and heavy hydrocarbons, are tolerable to a limited extent. An extensive
knowledge of the solubility of contaminants at the system operating temperatures, as well as experience
with normal fluctuations of feed contaminant levels, is required for proper design. Many operating
problems in cryogenic units are attributed to failure of the pretreatment system, usually due to operation
outside design limits.
Feed Composition
Feed composition has a large impact on the selection of a hydrogen separation process. Most refinery
hydrogen streams available for upgrading are comprised primarily of hydrogen and C1-C6+ hydrocarbons,
with other contaminants such as H2S, water, aromatics, HCl, etc., being present in some cases. Other
streams contain carbon oxides and nitrogen. The composition of the feed and its variability affect the
performance, reliability, and pretreatment required by the three upgrading processes.
Higher hydrogen content of the feed favors the PSA and membrane processes, and lower hydrogen content
favors cryogenic separation. Streams with 75-90 vol-% hydrogen are most economically upgraded by PSA
or membrane processes with the selection being based on flow, pressure, and pretreatment requirements.
Cryogenic upgrading is applicable to large streams with 30-75 vol-% hydrogen. The larger the methane
content of a stream, the more Joule-Thomson refrigeration is available to the cryogenic process.
18
Heavier hydrocarbons (C5+) are important factors in the design of all three processes. Membrane systems
will remove these components, but higher concentrations increase the dew point of the non-permeate,
which makes the reliability of the system more dependent on the proper operation of the pretreatment
system. PSA systems will remove heavier hydrocarbons, but increased concentrations result in larger
systems with lower recovery due to the difficulty in stripping these impurities from the adsorbents. Heavier
hydrocarbons concentrations in the feed to a cryogenic unit must be limited in order to avoid freezing in
the process, which makes this system also more dependent on the operation of the pretreatment facilities.
Benzene is of particular concern in the membrane and cryogenic processes because of its high boiling point.
Streams with significant quantities of CO, CO2, and nitrogen, such as the effluent from a stream reformer,
are almost always upgraded by the PSA process, as this is the only process which can remove these
components easily and completely. In particular, the removal of CO and CO2 to 10-15 ppmv is often a
requirement and this can only be achieved by the PSA process in a single step.
If H2S is present and must be removed, the membrane process is not suitable, because H2S has a relatively
high permeation rate and will leave with the hydrogen product. If H2S is present at concentrations above a
few hundred ppmv, the PSA process is favored because the cryogenic process will need separate upstream
H2S removal.
Feed Pressure and Product Flow
Feed pressure and product flow rates are best considered together when selecting a hydrogen purification
process because the three processes have drastically different economies of scale. Thus, although high
available feed pressure favors both the membrane and cryogenic processes, there are few cases where the
selection between these processes is difficult, because membrane systems are economical for smaller flow
rates and cryogenic systems for much large flow rates.
Membrane systems are the lowest capital cost alternative for small (less than 5 MMSCFD product) flow
rates, excluding the cost of compressors, for hydrogen/hydrocarbon separations. Since the cost of a
membrane system is proportional to the number of modules required, there is little economy of scale for
larger flow rates and the process is rarely economical for large (>25 MMSCFD product) flow rates.
Exceptions are if the feed gas is already at high pressure or if there is downstream hydrocarbon recovery
from the non-permeate, where the high pressure of this stream can be used to advantage. For small flow
rates at high pressure, such as a purge stream from the high pressure separator of a hydroprocessor,
membrane systems are the most economical. This is the most common refinery membrane application.
PSA systems have moderate capital costs in the small flow range, and have good economies of scale. PSA
systems can be economical for flow rates from 0.5-90+ MMSCFD for hydrogen/hydrocarbon steams at
19
200-450 psig. Many refinery streams are available at these pressures. For very small flow rates, less than
about 1 MMSCFD of product hydrogen, PSA systems will compete economically with membrane systems
if recovery is not important and/or if the available feed pressure is low. If there is an excess of feed
available, and only a small quantity of upgraded hydrogen is required, the PSA can be designed for high
tail gas pressure and tail gas compression will not be required. PSA units cannot take advantage of high
available feed pressures (700-1000 psig), and in many cases the feed will be lowered to a more optimum
pressure. Thus, the PSA product delivery pressure will be comparable to the delivery pressure from a
membrane unit, and the tail gas will be at lower pressure.
The capital and operating costs associated with feed, product, and/or tail gas compression are almost
always a significant portion of the total separation system costs. Compressor requirements often determine
which process is most economical.
Cryogenic systems have high capital costs at low product rates, but have excellent economies of scale. For
example, the capital cost of a cryogenic system producing 80 MMSCFD of product hydrogen is only about
three times higher than one producing only 10 MMSCFD. Cryogenic units are most applicable for feed
pressures of 300 psig or greater, and for larger systems. Credit for by-product recovery makes the system
more economical at lower flow rates. Unfortunately, there are few large, high pressure raw hydrogen
streams available in most refineries.
In general then, small systems with high available feed pressure favor membrane systems, small systems
with low feed pressure favor PSA and membrane systems (compression requirements usually dictating
selection), and large systems at high pressure favor cryogenic systems, when hydrogen upgrading alone
is considered.
Product Purity
Hydrogen product purity, and the levels of specific product impurities, are of course critical to process
selection. As previously mentioned, cryogenic and membrane processes normally produce hydrogen at 90-
98 vol-%, whereas the PSA process normally produces hydrogen at 99+ vol-%. If the upgraded hydrogen is
to be used as a primary source of make-up hydrogen to a high pressure hydrotreater or hydrocracker, the
impact of high purity hydrogen on the design and economics of the hydroprocessor can be significant,
because additional impurities in the make-up hydrogen must be purged from the system or the operating
pressure increased in order to dissolve them in the liquid hydrocarbons. Purging results in increased
hydrogen losses and increased operating pressure increases the hydroprocessor investment costs and
make-up compression utility requirements. The PSA process is most often used to upgrade the bulk of the
make-up hydrogen for new hydroprocessor installations.
20
If the upgraded hydrogen is only an incremental portion of the make-up hydrogen to a hydroprocessor,
lower product purity is usually acceptable because the relative amount of inerts entering with the
incremental hydrogen is small. Membrane and PSA systems are commonly used in these applications.
If the feedstocks available for upgrading contain only hydrogen and hydrocarbons, then the principle
impurity in the hydrogen product will be methane. The amount of methane which can be tolerated in the
product hydrogen should be carefully determined, since it has an important effect on the recovery
obtainable with membrane and cryogenic systems. Allowing 3-10 vol-% methane in the hydrogen product
typically results in the most economical design of membrane and cryogenic systems, if the downstream
hydrogen-consuming process is not overly sensitive.
If the feed to the upgrading process contains substantial quantities of CO and CO2, then PSA units are
most often selected. The major stream in this category is the effluent from a steam reformer, where the
cryogenic and membrane processes are not suitable. It is possible to remove CO by using a methane wash
in a cryogenic system, and CO and CO2 can be removed using a methanator. However, both of these
options add considerable cost and operating complexity.
If nitrogen is to be removed, then the PSA process is also favored, because nitrogen can be removed to any
desired level. Both the membrane and partial condensation cryogenic processes will remove a portion of the
feed nitrogen, but the extent of nitrogen removal is typically less than 50% and is not easily controlled.
Nitrogen is much less soluble in hydrocarbon liquids than methane, and builds up rapidly in
hydroprocessor recycle loops; its removal can have a significant impact on the hydroprocessor.
Selection Guidelines for Specific Applications:
Catalytic Reformer Off-Gas
The largest source of easily recovered hydrogen in a refinery is the off-gas from catalytic reforming. This
off-gas typically contains from 70-90+ vol-% hydrogen with the balance being C1 to C6+ hydrocarbons.
The stream also contains small amounts of aromatics and ppmv levels of HCl. It is usually available at
pressures from 250-400 psig and near ambient temperature.
If large quantities of reformer off-gas are to be upgraded for use as a primary source of make-up hydrogen
for a hydrocracker or hydrotreater, the PSA process is normally used. The pressure is optimum for the PSA
process, and the typical flow rates (10-80 MMSCFD) allow good economies of scale. The high hydrogen
content makes the adsorbent requirements low, and the hydrocarbons in the tail gas sent to fuel are
relatively small with respect to the feed gas. The high purity hydrogen produced is of benefit. The aromatic
and HCl content of the feed is not of concern and no special pretreatment is required. The PSA tail gas is
21
normally provided at 2-5 psig and compressed to the fuel header pressure in order to increase hydrogen
recovery to approximately 82-90%, depending on the PSA system configuration.
In some cases, there is a requirement for relatively small quantities of hydrogen at 98+ vol-% purity for
uses such as catalyst regeneration. Membrane systems using feed compression may be most economical for
these applications requiring less than about 5 MMSCFD of hydrogen product, due to low capital costs. If
low recovery is acceptable because of feed gas being available in excess, then PSA systems should also
be considered.
For large flows, cryogenic upgrading has sometimes been used. However, the feed hydrogen purity is often
too high, and external refrigeration is required. If the reformer is of the semi-regenerative type, differences
between start-of-run and end-of-run conditions can have a significant effect on the heat exchanger area
required, with the high feed hydrogen case controlling. Aromatic removal in the pretreatment section is
also an important design consideration. Unless recovered hydrocarbons are of high value, the cryogenic
process is not normally used to process reformer off-gas alone.
Hydroprocessor Purge Gases
The high pressure and low pressure purge gases from high pressure hydrocrackers and hydrotreaters are
good candidates for hydrogen upgrading. The recovered hydrogen is returned to the hydroprocessor with the
make-up hydrogen. High pressure product hydrogen is of value. Many hydroprocessors have both high and
low pressure purge streams. The high pressure purge streams are available at 800-2500 psig and contain 75-
90 vol-% hydrogen, with the balance being hydrocarbons. Low pressure purge streams are available at
much lower pressures, typically 100-250 psig, and have hydrogen contents ranging from 50-75 vol-%. The
total amount of hydrogen contained in the low pressure purge stream is usually much larger than that in the
high pressure purge stream when both are present.
As mentioned previously, the membrane process is the most economical process for high pressure purge
gas upgrading. The membrane system is normally designed to produce hydrogen at 300-600 psig, 92-98
vol-% purity, and 85-95% hydrogen recovery. The product delivery pressure is chosen to allow the product
to enter one of the stages of the make-up hydrogen compressors.
Low pressure purge gases are usually upgraded by the PSA process. The PSA process is better suited than
the cryogenic process because the flow rates are relatively small and the stream composition can be highly
variable. The combination of lower pressure and lower hydrogen content makes the membrane system less
economical than the PSA system.
22
Upgrading low pressure purge gases at pressures below 180-200 psig normally requires feed compression
upstream of the PSA system, and may not be economically viable. Operation at high tail gas pressure will
usually give the highest rate of return on investment.
If both high pressure and low pressure purge gases are available for upgrading, consideration must be given
to whether to upgrade them together. This will depend on the pressure levels and relative flow rates. It is
usually better to combine the streams by letting down the high pressure stream rather than compressing the
low pressure stream.
TDA Purge Gas
The purge gas from the toluene hydrodealkylation (TDA) process contains about 55 vol-% hydrogen, with
the remainder being mostly methane. This gas also contains approximately 0.5 vol-% of valuable
aromatics. Feed gas pressure is 400-500 psig. This stream can be upgraded by the cryogenic or PSA
process, with the cryogenic process normally being preferred.
The cryogenic process is well-suited for this application because the feed pressure is optimum and
the major impurity to be rejected is methane. The removal of aromatics from the feed, which is
accomplished in a toluene wash column, is not a penalty because of the value of the recovered aromatics.
The cryogenic unit is normally designed to produce a hydrogen purity of 90 vol-%, at a hydrogen
recovery of approximately 90%. Impure make-up hydrogen can be combined with the purge stream before
cryogenic processing.
For smaller streams, a PSA unit may be used. The PSA unit would have a lower capital cost in these
instances, which would be offset by a lesser hydrogen recovery and the consequential increase in make-up
hydrogen requirements. The PSA would normally operate at a high tail gas pressure to avoid tail gas
compression, and would produce a 99+ vol-% purity product at a recovery of about 65-70%. The impact of
lower recovery is reduced somewhat by the increased product purity; the ratio of hydrogen recovered to
impurities rejected is the appropriate basis for comparison, and the PSA unit rejects a much larger fraction
of the impurities entering the feed. A separate aromatics recovery step can be used if cost-effective, but is
not required by the process.
Membrane systems are not normally economical because of the loss of hydrogen pressure and the low feed
hydrogen content.
FCC Off-Gas and Other Refinery Purge Steams
Hydrogen can be recovered from FCC off-gas and other low pressure refinery purge streams of low
hydrogen content. These streams typically contain 15-50 vol-% hydrogen and are available at 100-250 psig.
23
Depending on flow rate, feed composition and variability, feed pressure, and required hydrogen product
purity, either the cryogenic or membrane process can be used. In almost all cases, the stream is not
upgraded for its hydrogen content alone; the tail gas is also of value.
If there are valuable hydrocarbons, particularly olefins, that can be recovered in addition to hydrogen, or if a
hydrogen product purity in excess of 90 vol-% is required, the cryogenic process is normally used. The
cryogenic process can recover a mixed C2 stream containing >99 vol-% C2+ components, and produce
hydrogen at 95 vol-% purity. Typical feed pressures are 250-400 psig, and feed compression may be
required. Feed quality variations and contaminant levels are important considerations in determining
whether the cryogenic process is appropriate.
The membrane process can efficiently recover hydrogen from these streams at a hydrogen purity 80-90
vol-%. The tail gas can be sent to downstream hydrogen recovery units. The low purity hydrogen product
can be used effectively in some applications, such as low pressure hydrotreaters, and the tail gas can be
sometimes sent to downstream hydrocarbon recovery units. If the tail gas is to be used as fuel, extraction
of the hydrogen will upgrade the heating value of the stream. When the membrane process is used, the feed
is usually compressed to 400+ psig, and the hydrogen product it produces at 100-250 psig. Both the feed
and hydrogen product may require further compression. Hydrogen recovery is often not critical and ranges
from 50-85%.
Impurities in the hydrogen product from either process can include nitrogen, CO and H2S. The amounts of
these impurities in the product depend on numerous factors and must be determined on a case-by-case basis.
Steam Reforming
Hydrogen plants employing the steam reforming of hydrocarbons are necessary to support many
hydroprocessing projects because there is an insufficient amount of hydrogen available from other sources.
The effluent from stream reformers is most often processed in a PSA unit. The tail gas is sent to the
reformer furnace as fuel gas, and is used directly at low pressure. The PSA-based hydrogen plant process is
more thermally efficient and economical in most cases compared to the traditional process which uses the
separate steps of low temperature shift, CO2 scrubbing and methanation instead of the PSA unit. The
membrane and cryogenic processes are not economical for this application due to the large amounts of CO,
CO2, and water in the feed.
It should be noted, however, that the tail gas streams from either a membrane system or a cryogenic system
should be considered as candidates for the hydrocarbon feed to the reformer. When this is done, the
previously unrecovered hydrogen in the tail gas is returned in the steam reformer effluent, reducing net
hydrogen losses.
24
Ethylene Off-Gas
While not a refinery process, the manufacture of ethylene produces large amounts of hydrogen, and this
hydrogen can be easily upgraded for refinery use if the ethylene plant is in close proximity to the refinery.
The ethylene process uses a series of cryogenic units to separate the products from the ethylene furnace, and
a high purity hydrogen stream is produced. Typically, only a small fraction of the available hydrogen is
used in the ethylene plant (for acetylene hydrogenation) and the balance is sent to fuel unless it can
be exported.
The hydrogen-rich ethylene off-gas from the ethylene plant’s cryogenic separation train normally contains
80-90 vol-% hydrogen, with CO, CH4, ethylene and nitrogen as impurities. In some cases, the cryogenic
system will produce a hydrogen purity as high as 95 vol-% with the same impurities through use of
external refrigeration. The hydrogen stream is available at pressures from 250-400 psig and ambient
temperature.
Regardless of the hydrogen purity, the ethylene off-gas must be processed to remove CO to ppmv levels
for general refinery use. For off-gas with 80-90 vol-% hydrogen, the PSA process is most often used for
upgrading. The pressure is optimum, and the PSA system will produce a very high purity product, e.g.,
99.95 vol-%. Tail gas compression, from 2-5 psig to fuel system pressure, is used in large systems when
high recovery is desired.
For off-gas at 95 vol-% hydrogen purity, methanation of the CO is possible. In this case, the hydrogen
product contains 5 vol-% hydrocarbons as well as the water produced by methanation, which can effect the
hydrogen-consuming processes.
Occasionally, methanated hydrogen is available from an ethylene plant at 80-90 vol-% hydrogen purity. In
these cases, membrane upgrading can be considered. The choice between the membrane and PSA processes
will primarily depend upon the cost of compressing the membrane hydrogen product compared to the cost
of compressing the PSA tail gas, assuming high hydrogen recovery is desired in both cases. The product
purity from the membrane system will be lower (95-97 vol-%) than for the PSA system.
25
Combinations of Upgrading Processes
Potential combinations of the three hydrogen separation processes under consideration have been receiving
increased attention in recent years, particularly combinations involving the more recently developed
membrane process. Integrations of the processes are designed to take advantage of the different process
characteristics, e.g.:
The ability of the PSA process to produce a high purity hydrogen product and to completely remove
low boiling components.
The ability of the membrane process to achieve high hydrogen recovery and to provide tail gas at
feed pressure.
The ability of the cryogenic process to efficiently separate the feed stream into multiple streams at high
recovery.
This being said, there are still relatively few commercial applications involving combined processes. One
reason for this is that the combined processes typically have significantly higher capital costs than any of
the individual processes. The value of the improved separation performance does not often justify these
higher costs at current product values. High capital costs are sometimes unavoidable, because many
applications require high hydrogen recovery from each process, and the capital costs of the membrane and
PSA processes increase significantly with recovery.
One of the more common integrations is the combined PSA/cryogenic process. The cryogenic process is
used to make a bulk separation, usually with by-product production, and the PSA process is used to further
upgrade the product hydrogen from the cryogenic unit, either to increase hydrogen purity or to remove
specific impurities. The tail gas may be recycled back to the cryogenic unit. In this integration, the
cryogenic unit can be made simple and less expensive (by avoiding for example, a methane wash column)
and the PSA unit can be made smaller and achieve higher hydrogen recovery because of the reduced amount
of impurities to be adsorbed. This approach can be used for upgrading ethylene off-gas or low hydrogen
content streams such as FCC off-gas. The generalized flow scheme is illustrated in Figure 11.
A membrane unit can replace the cryogenic unit upstream of the PSA unit in some applications. The
membrane unit is used to reject the bulk of the impurities at high hydrogen recovery, and the PSA unit
upgrades the relatively low purity hydrogen produced by the membrane system. Hydrocarbons in the
nonpermeate
from the membrane system can be recovered. The combined system achieves both high recovery
and high hydrogen product purity, and low pressure tail gas is minimized. This process combination can
be used when there are two hydrogen streams available, one at high pressure and one at low pressure. In
26
this case, the low pressure stream is combined with the membrane hydrogen product upstream of the PSA
unit. An example of this application is hydrogen recovery from both high pressure and low pressure
hydrocracker purge gases.
Other refinery applications of combined processes exist, but apply only to special situations.
Figure 11
Flow Schematic
Integrated Cryogenic and PSA Systems
(Optional Recycle)
Product H2
(99+ vol-%)
Feed
PSA
Unit
Cryogenic
Unit
By-product
Tail Gas
Tail Gas
H2 Rich Stream
UOP 3111-8

Conclusions
Hydrogen upgrading in refinery applications can be achieved by the PSA, membrane, or cryogenic
separation processes. Each of these processes has different characteristics which are of advantage in different
situations. Selection of the appropriate hydrogen separation process can depend on several factors in
addition to design-point economics. Consideration of other project requirements, such as turndown,
reliability, flexibility in processing variable feedstocks, pretreatment requirements, etc., are often important
to the selection, and may help in deciding between processes with similar economics.
General selection guidelines can be helpful in process selection, or at least in eliminating an inappropriate
process. In order to use such guidelines, feed characteristics, contaminant levels, required product purity,
allowable product impurities, pressure levels, and flow rates must be known. These parameters can be used
in conjunction with experience-based, application-specific guidelines to select the optimum process.
27
Combinations of these three separation processes can be used in certain applications, to take advantage of
the complementary properties of the different processes. However, these combinations typically have higher
capital costs than single-process alternatives, and are usually justified only when by-product recovery is
also practiced.
This paper was presented at the 1989 NPRA Annual Meeting held March 19-21, 1989, at the San Francisco Hilton, in San Francisco, California.

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