Hydrogen management

R
efners are facing the challenge of meeting
increasingly higher quality product specif-
cations to make clean fuels product, while
at the same time purchasing lower-quality
H
2
-defcient crudes. As a result, H
2
requirements
have been steadily increasing and refneries are
fnding that proper H
2
management is increas-
ingly important to their long-term viability.
This article will describe the process KBC has
successfully used to eliminate H
2
availability
constraints and prioritise H
2
use in order to
improve proftability.
Increasing renery complexity and H
2
requirements
Refneries have various levels of complexities
and operating objectives. The simplest refnery
type is the hydroskimming refnery. Figure 1
show a typical hydroskimming refnery confgu-
ration. Hydroskimming refneries typically do
not need a H
2
plant, as the H
2
demand can be
adequately met by the naphtha reformer.
Margins are often low at hydroskimming refner-
ies unless there is a large marketing advantage,
usually based on location.
Rick Manner KBC Advanced Technologies
It is typically advantageous to maximise the
production of higher-value transportation fuels
instead of lower-value fuel oil products. As a
result, most proftable refneries are either
moderately complex or highly complex facilities
that have cracking and conversion units. H
2

requirements can vary greatly from one confgu-
ration to the next.
Figure 2 shows a typical confguration for a
moderately complex refnery, which employs an
FCC and a visbreaking unit to increase product
value. The addition of a gas oil hydrotreater for
the FCC feed increases the refnery H
2
demand
beyond what the reformer alone can provide. A
small H
2
plant is therefore also needed.
Figure 3 shows a complex carbon rejection
refnery. A coker is added to convert fuel oil to
more valuable products. Light coker gas oil is
hydrotreated in the diesel hydrotreater and
heavy coker gas oil is hydrotreated in the gas oil
hydrotreater. Now, a medium-sized H
2
plant is
required.
Figure 4 shows a complex hydrocracking refn-
ery confguration. Substituting a hydrocracker
for the FCC unit increases H
2
requirements to
www.digitalrening.com/article/1000333 April 2012 1
Figure 1 Hydroskimming renery conguration
2 April 2012 www.digitalrening.com/article/1000333
Figure 2 Moderately complex renery
Figure 3 Complex carbon rejection renery
2 April 2012 www.digitalrening.com/article/1000333
the point where a large H
2
plant is required.
Finally, Figure 5 shows that the addition of
residua hydrocracking to reduce the size of the
coking unit and the amount of coke produced
requires a very large H
2
plant.
The most complex refneries generally have the
highest incremental value for H
2
. These refner-
ies can beneft the most from a H
2
management
study when H
2
availability becomes a refnery
limit.
H
2
management study methodology
Like most successful refnery studies, H
2
manage-
ment is a concept that starts with the unit review
and ends with implementation of the results in
the feld. The goal is to improve the use of H
2
at
the refnery and improve the proftability of the
refnery.
During the identifcation phase, the H
2
system
is reviewed to identify areas for opportunity by
improving the utilisation of H
2
at the refnery. In
the evaluation phase, the identifed opportunities
are then further studied using individual or
combined tools to determine the value to the
refnery and the implementation cost. The imple-
mentation phase is the fnal piece of the study.
In this phase, the identifed solutions are put
www.digitalrening.com/article/1000333 April 2012 3
into place at the process units in order to achieve
improved refnery proftability. All three phases
of the project are necessary to have a successful
project.
H
2
management study goals
The goal of a H
2
management study is to develop
a thorough understanding of the refnery H
2

system. The process begins by building a
complete H
2
system fow diagram and develop-
ing a reconciled balance of the entire refnery H
2

system. Orifce fow meters are notoriously inac-
curate in measuring H
2
fow, primarily because
of the signifcant variations of MW that can
occur in H
2
rich streams. In addition to meter
corrections, a basic understanding of the typical
range of chemical H
2
consumption and solubil-
ity/purge losses for each H
2
consumer is often
essential to closing the H
2
balance properly.
Once a balance is developed, it is important to
determine the value of incremental H
2
at each
consumer and the cost of producing H
2
at each
H
2
source. A complex refnery can have many
distinct H
2
subsystems segregated by geography,
H
2
purity and/or pressure. The incremental cost
and value of H
2
at each system is likely different,
and some H
2
subsystems may be highly
Figure 4 Complex hydrocracking renery conguration
vulnerable to upsets that could be mitigated if
connections between isolated systems are
established.
The primary goal of a H
2
management study is
to identify the constraints imposed by the overall
system and various H
2
subsystems, and fnd
ways to remove these constraints to improve
overall refnery proftability. Typical solutions
can be as simple as rerouting streams to maxim-
ise high-margin units at the expense of others or
more complex and capital intensive, such as
building H
2
recovery units, debottlenecking
steam-methane reformers or installing additional
compression to provide additional fexibility and
increase profts.
4 April 2012 www.digitalrening.com/article/1000333
H
2
management study tools
Refnery H
2
systems can be extremely complex.
As a result, it may be very diffcult to evaluate all
of the possible H
2
management opportunities
without the aid of specialised tools. KBC has
developed two software products that are used in
our H
2
management studies. The combination of
KBCs HydrogenPinch and Petro-SIM software
is extremely effective in evaluating the value of
rerouting streams and/or removing constraints
in order to improve overall refnery proftability.
HydrogenPinch is KBCs proprietary software
designed primarily to identify H
2
system oppor-
tunities such as the optimal routing of H
2

streams at a refnery. This software evaluates the
Figure 5 Addition of residua hydrocracking
Figure 6 Study methodology diagram
4 April 2012 www.digitalrening.com/article/1000333
H
2
pressure, purity and fow of each supplier and
consumer in the refnery using a pinch method
that is analogous to the Energy Pinch concept,
which revolutionised energy conservation a few
decades ago. For this analysis, the H
2
outlet of
each consumer is a potential supplier for a differ-
ent process. The software also conducts a
sensitivity analysis to determine the economic
cost or beneft of changing each of these param-
eters for each supplier and consumer. With this
information, the benefts and costs of rerouting
H
2
streams and relieving real or perceived
constraints are clearly illustrated.
Several different tools (such as the refnery LP,
individual unit models or test run data) can be
used to provide HydrogenPinch with the infor-
mation it requires to conduct its sensitivity
studies. Petro-SIM is KBCs full refnery simula-
tion software that can be confgured to rigorously
model any combination of refnery process units.
It is the most effective tool for determining the
actual value of H
2
pressure, purity or rate at any
given point in the refnery for numerous scenar-
ios. Combining Petro-SIM with HydrogenPinch
provides an extremely robust and insightful
picture of the value of H
2
opportunities within a
refnery.
Cost and value of H
2
depends on marginal
disposition
The value of H
2
at a refnery depends primarily
on the cost or the limiting factor of making the
next increment of H
2
and the use the refnery
would have for the next increment of H
2

produced. Table 1 illustrates the wide range of
values a refnery might have for incremental H
2
.
At the low end, the value could be the cost of
replacing incremental H
2
at a modern highly eff-
cient H
2
plant that is not constraining the
refnery. In this case, the value of recovering 5
MMSCFD of H
2
from fuel and backing out
production at the H
2
plant is about 0.6 MM$/yr.
The value of H
2
progressively increases as the
cost of incremental H
2
increases and the alter-
nate disposition is lower. The cost of the same 5
MMSCFD of H
2
is around 4 MM$/yr if an upset
is routinely requiring H
2
to be fared and the H
2

is replaced by purchasing pipeline H
2
at a cost
that refects a fair return of capital costs to the
H
2
vendor.
The value of H
2
is much higher if replacement
H
2
is not available and the throughput of a high
margin unit like a hydrocracker is limited by H
2
availability. Usually the refnery is aware when a
high-margin unit is constrained on a day-to-day
basis by H
2
availability and will actively seek out
a H
2
management study.
However, some more subtle marginal mecha-
nisms could result in an extremely high value.
Crude selection is often the single most impor-
tant decision that affects refnery proftability.
There are often distressed crudes available that
offer a very high margin to refneries that can
process them. Refneries usually choose these
crudes based on a refnery-wide LP that models
all of the constraints in the refnery. In some
instances, the LP will choose not to purchase a
particular low-cost crude because of hydrotreat-
ing constraints that may or may not be real H
2

availability constraints. Under these circum-
stances, removing a H
2
availability constraint
could be extremely proftable. This type of
constraint often requires a complete refnery
proft improvement program (PIP) to identify,
though such constraints can also be identifed by
well-trained refnery staff working with their
planning group.
H
2
routing and recovery options are
often desirable
A thorough H
2
management study usually results
in recommendations to reroute H
2
-rich streams
from lower- to higher-value dispositions. An
www.digitalrening.com/article/1000333 April 2012 5
Marginal mechanism Value of 5 MMSCF/D of H
2
High-efciency H
2
plant
Excess H
2
to fuel 0.6 MM$/yr
Low-efciency H
2
plant
Excess H
2
to fuel 1 MM$/yr
High-efciency H
2
plant
Excess H
2
to are 2 MM$/yr
Purchased H
2
Excess H
2
to are 4 MM$/yr
Reduce hydrotreating 9 MM$/yr
Reduce hydrocracking 23 MM$/yr
Crude selection 35 MM$/yr
Note: Values based on a low heating fuel value of $4/MMBtu and
an average crude upgrade value of approximately $5/BBL.
Wide range of values a renery might have for
incremental H
2
Table 1
example of this could be as simple as preferen-
tially sending lower-purity H
2
streams to process
units like kerosene hydrotreaters that do not
require high purity to more complex opportuni-
ties to connect distinct separated H
2
systems
based on purity, pressure or geography.
It is important to continue evaluating rerout-
ing options even after a more proftable option is
found. An option is not necessarily the most
proftable option just because it is an improve-
ment over the base case.
Recovering H
2
from fuel gas is often a very
attractive recommendation from H
2
management
studies. The most attractive technologies that
refneries typically use for this purpose are:
Pressure Swing Adsorption
Membrane H
2
recovery
Feeding H
2
-rich streams to SMR H
2
plants to
recover H
2
.
Pressure Swing Adsorption
Pressure Swing adsorption (PSA) H
2
purifcation
units produce a 99.9%+ purity H
2
product typi-
cally from process streams containing 60-80%
H
2
that would otherwise go into the refnery fuel
gas system. The process uses proprietary adsorb-
ents that capture essentially all non-H
2

compounds at system pressure (typically 250-
300 psig) and desorbs the adsorbed material to
fuel gas at very low pressures (typically 5 psig).
A PSA usually consists of 4-12 beds that alter-
nate between adsorption, depressuring and
purging to fuel. The pressuring and depressuring
sequences are optimised to minimise the amount
of H
2
sent to fuel. Typical H
2
recoveries vary
between 80-90%.
PSA is a proven H
2
recovery option
that is the clear choice when 99.9%+
H
2
purity is required. The major
drawback to PSA H
2
recovery units
is the cost of compressing the fuel
gas by-product. It is the clear
preferred choice in situations where
there is a large fuel gas user that can
accommodate low-pressure fuel gas
like a Steam Methane Reforming
(SMR) H
2
plant furnace.
UOP and Linde are the two
primary suppliers of PSA technology.
Both licensors provide excellent
units that work well, although they
do not always achieve design H
2

recovery. ExxonMobil and QuestAir have a
lower-cost version of the process called Rapid
Cycle PSA (RCPSA) that uses a rotating cylinder
instead of multiple beds and produces a lower-
purity product at lower recoveries. There is a
niche application of this technology that allows
refners to improve recycle H
2
purity at diesel
hydrotreating units that may make it a good
choice for some refneries.
Membrane H
2
recovery
Membrane H
2
recovery units operate based on
the difference in permeability between H
2
and
the contaminants present in the H
2
recovery
unit feed. The H
2
permeates through a
membrane and is recovered at a pressure that
is typically one-third of the inlet pressure. The
non-permeate gas contains about 10-15% of the
H
2
, and most of the non-H
2
, and is available at
high enough pressure for fuel gas. The compo-
sition of permeate and non-permeate along the
membrane was calculated based on typical rela-
tive permeabilities of H
2
and non-H
2

components. Based on these calculations, a
curve describing H
2
recovery as a function of
permeates purity for three different feed puri-
ties. Based on the location of the design point
near the bend in each curve, an operating curve
was developed to allow for estimation of H
2

recovery and H
2
purity at various feed qualities.
Figure 7 illustrates this relationship. Air
Products (PRISM), Air Liquide (Medal) and
UOP (PolySep) are major vendors of membrane
H
2
recovery technology. A typical performance
curve for a membrane H
2
recovery unit is shown
in Figure 7.
6 April 2012 www.digitalrening.com/article/1000333
Figure 7 Typical performance curve of a membrane H
2
recovery unit
Membrane H
2
recovery units
produce a lower-pressure H
2

product and a high-pressure fuel
gas product. Membrane units are
a good choice for improving the
purity of high-pressure purge gas
off of a hydrotreater or hydroc-
racker and recycling the lower
pressure H
2
to the make-up
compressor. If make-up compres-
sor capacity is not available, it is
more diffcult to justify a
membrane H
2
recovery unit
instead of a PSA.
Membrane H
2
recovery is a
proven technology that has been
in continuous use in many refn-
eries for over 25 years. However,
membrane units cannot tolerate any liquids in
contact with the membranes and many refneries
have experienced this problem. In addition,
membrane units require some attention to start-
up or shutdown modules as conditions change as
run length progresses. They are not diffcult to
operate, but the learning curve is much more
diffcult than with a PSA
Route H
2
-rich feed to an SMR H
2
plant
H
2
plants are excellent H
2
recovery units. H
2
in
H
2
plant feeds typically appears as product at
very high recoveries and causes little or no
increase in fred duty. Refners that have hydrau-
lic capacity should consider using their H
2
plants
as H
2
recovery units. Debottlenecking H
2
plants
is another option available that may be relatively
low cost for many H
2
plants.
Cryogenic H
2
recovery
Cryogenic H
2
recovery is a proven technology
that requires low temperatures to separate H
2

from light hydrocarbons in a cold box. A simpli-
fed diagram of a cryogenic H
2
recovery unit is
shown in Figure 8.
H
2
recoveries are typically 95% and H
2
product
purities are 97% or higher at a typical cryogenic
H
2
recovery unit. However, cryogenic H
2
recov-
ery units are very expensive and do not scale
down easily. As a result, they are usually only
economical if there is an incentive to recover the
light hydrocarbons in the feed as discreet
streams and the plant is very large (>100
MMSCFD).
Recontacting to improve H
2
purity
Recontacting H
2
-rich streams with lean oils that
can absorb light hydrocarbon may be an inex-
pensive way to improve H
2
purity at some units.
Recontacting is frequently used by UOP in some
of their Platformer designs to recover LPG and
improve H
2
purity. It is less common in
hydrotreaters, although it can be just as effective.
Recycling liquid from a low-pressure fash drum
or a product stripper/fractionator back to the
high-pressure separator to sponge out heavier
hydrocarbons can be an effective way to improve
recycle gas purity. However, it is usually only
economical if the hydrotreater was originally
designed for a much higher feed rate or the fash
drums are signifcantly oversized.
Summary and conclusions
As refneries have got more complex, the need
for H2 has increased, and understanding the
details of the refnery H
2
system has become
increasingly important. A H
2
management study
can help identify opportunities, evaluate and
implement an action plan that will lead to
increased refnery proftability and fexibility.
A proper H
2
management study will give the
refner a complete understanding of the H
2

system and identify valuable opportunities to
improve system performance. Options for
improvement include identifying the cost and
value of H
2
at each producer or consumer and
rerouting H
2
-rich streams, exploring H
2
recovery
schemes, H
2
plant debottlenecking options and
additional operational changes that can be easily
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Figure 8 Cryogenic H
2
recovery unit
implemented to help maximise refnery
proftability.
Petro-SIM is a trademark of KBC Advanced Technologies plc, and
it is registered in various territories.
Rapid Cycle PSA (RCPSA) is a trademark of Exxon Mobil Corporation
and QuestAir and it is registered in various territories.
PRISM is a trademark f Air Products and it is registered in various
territories.
Medal is a trademark of Air Liquide and it is registered in various
territories.
PolySep is a trademark of UOP and it is registered in various
territories.
8 April 2012 www.digitalrening.com/article/1000333

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