M

ost refiners have now moved

toward a higher standard of
s u l p h u r - r e c o v e ry efficiency to
comply with clean fuels regulations that
impose a reduction of sulphur in refined
products. While refiners have chosen
various avenues and process solutions to
address these sulphur cap requirements,
reliance on the refinery s previously
installed sulphur complex has presented
one of the most effective and cost-
efficient solutions. Comprised of a Claus
s u l p h u r - r e c o v e ry unit (SRU) and a tail
gas-treating unit (TGTU), the sulphur
complex processes both lean and rich
hydrogen sulphide (H
2
S) bearing acid gas
streams and ammonia-bearing sour
water stripper off-gas streams to recover
elemental sulphur.
H o w e v e r, the existing sulphur
complex in many refineries may not
provide enough process capacity to meet
the current regulatory requirements.
Current trends indicate that as crudes
become increasingly heavier and contain
higher concentrations of sulphur, many
refineries will need at least two or more
Claus units also referred to as trains
to meet current environmental
regulations. This has increased the
throughput of many SRUs, which may
lead to the SRU reaching its hydraulic
limitation (maximum air) and m o r e
frequent shutdowns for maintenance.
This can force the refinery to shut down
its upstream operations unless there is
another way to remove sulphur from the
acid gas and off-gas streams.
To prevent unscheduled shutdowns of
this nature, many refineries have a
parallel Claus unit. If one of the trains
needs to be taken off-stream for
maintenance, the other can handle at
least some of the additional throughput.
H o w e v e r, in instances where the
remaining SRU is unable to provide
adequate sulphur-recovery capacity, the
r e f i n e ry may be forced to reduce its
upstream operations substantially.
To ensure that a plants Claus unit
complex can meet the demands for
increased throughput, even in instances
where one of the trains is not in serv i c e ,
a refiner can do one of two things: either
install another SRU or retrofit a unit to
provide oxygen enhancement to the
Claus process. Since investment in any
kind of sulphur-reduction technology is
r e g u l a t o ry driven rather than revenue
and profit driven, solutions that get the
job done effectively for the least amount
of money are generally preferred.
Oxygen enhancement has become one
of the most viable, cost-effective
alternatives to installing a new SRU.
Claus combustion process
The classic Claus process has been the
most common method for processing
H
2
S-rich streams and recovering sulphur
from both amine acid gas and sour water
stripper gas. The Claus process can be
broken down into two steps. In the first
step, which is called the oxidation
process, about one-third of the H
2
S
contained in the feed is oxidised with
oxygen from ambient air to create
sulphur dioxide. The oxidation takes
place in the burner/thermal reactor of
the SRU. In the second step, which is the
actual Claus reaction, the remaining H
2
S
is reacted with the sulphur dioxide to
form elemental sulphur. This step takes
place in the thermal and catalytic reactor
of the SRU. The reactions are listed
b e l o w :
H
2
S + 1.5 O
2
S O
2
+ H
2
0
2 H
2
S + SO
2
3 / n S
n
+
2
H
2
0
To obtain the oxygen needed for the
combustion process, ambient air is
supplied to the SRU burner via an air
b l o w e r. Ambient air usually contains
about 21 per cent oxygen; the balance is
primarily nitrogen and some water
v a p o u r, both of which are inert in the
combustion process. Since these inert
components comprise nearly four times
as much volume as the oxygen, the unit
reaches its hydraulic limitation quickly
once these components are introduced,
which limits the sulphur-recovery
capacity of the SRU.
S u l p h u r - r e c o v e ry capacity becomes
further constrained by other contam-
inants in the acid gas feeds, such as
ammonia, hydrocarbons, cyanides and
carbon-sulphur compounds. Since sour
water stripper gas feeds contain more
ammonia gas than ever before, it is now
n e c e s s a ry for refiners to increase the
amount of ambient air supplied to the
SRU. This ensures that not only the
n e c e s s a ry amount of H
2
S is burned to
keep the plant compliant with
environmental regulations, but also that
the ammonia gas contained in the feed
is properly destroyed. However, as more
air is fed into the Claus unit, the amount
of inerts (nitrogen and water) added to
the system increases even more rapidly,
leading to the hydraulic limitation of the
unit and, eventually, to a need to
increase the size of the unit or invest in
another SRU.
The best way a refiner can avoid this
situation is to use an oxygen-enriched
air supply, which not only replaces the
nitrogen in the ambient air, but also
provides enough oxygen to destroy
t h e contaminants in the feed while
maintaining adequate oxidisation
levels. In fact, by substituting pure
oxygen for most or all of the ambient
air, space is made available to increase
the throughput of the acid gas feeds
t o the SRU, which, in turn, gives
t h e system greater sulphur-recovery
capacity.
Oxygen levels in the SRU
As previously stated, in an air-based
combustion system oxygen typically
comprises about 21 per cent of the
ambient air, with nitrogen comprising
the remaining 79 per cent when the air
is dry (water vapour and other small
inerts can displace some of the oxygen
and nitrogen in humid conditions). By
not contributing to the combustion
process, nitrogen does nothing more
than take up additional space, dilute the
Claus reactants and reduce the overall
s u l p h u r - r e c o v e ryprocess. Thus, in order
to increase the capacity in the SRU to
Enhancing SRUs with
oxygen-enriched air
As clean fuels regulations become more stringent, refiners looking for new ways
to boost the capacities of their existing sulphur-recovery units are turning to
oxygen-enhancement technologies
Mukesh Mehta CB&I TPA
Aaron Stryk CB&I
PLANT MAI NTENANCE
PTQ Q2 2005
w w w. ep t q . c o m
1 0 5
process more acid gas, it is first necessary
to reduce the nitrogen.
There are various levels of oxygen
enhancement that can be applied to
increase the capacity of the SRU. Most
technologies, however, are grouped into
three categories. The first level of oxygen
enrichment encapsulates those tech-
nologies that increase the oxygen level
from 2128 per cent (low-level oxygen
combustion). The second level includes
the technologies that raise the oxygen
level up to 40 per cent (medium-level
oxygen combustion), while the third
level of oxygen combustion encom-
passes those technologies that increase
the oxygen concentration to levels in
excess of 40 per cent in some cases,
even 100 per cent. It is important to note
that for every level increase in the
oxygen concentration, certain plant
modifications must be made, for both
retrofitted SRUs and newly installed
units.
Low-level oxygen combustion, the
simplest and most cost-effective means
of increasing the oxygen concentration
of the combustion air, is often referred to
simply as oxygen enrichment. Low-level
oxygen enrichment involves the
injection of pure oxygen into the
combustion air piping system of the
SRU, upstream of the burner. This
method will typically raise oxygen levels
up to 28 per cent and increase SRU
capacity by 25 per cent. With a rise in
the oxygen concentration levels, a
substantial portion of nitrogen is
eliminated from the Claus reaction.
While virtually every sulphur-
recovery unit at a minimum cost can, in
concept and in practice, achieve low-
level oxygen enrichment, the system
itself has several limitations. For
instance, the oxygen level is generally
limited to 28 per cent, because anything
higher would require special piping
system materials and cleaning
procedures.
Generally, the existing SRU
equipment (including the metallurgy
and refractory) can be used without
modification, as the combustion temp-
erature should not exceed 2600F (Figure
1). However, additional safeguards for
the oxygen system must be taken into
account, and the control system
required should be designed to minimise
the consumption of pure oxygen to
protect the equipment in place.
For newly installed Claus SRUs that
are designed for the future installation of
oxygen enhancement, safeguards will
include a refractory system in the front
of the thermal zone, as well as a waste
heat boiler tubesheet-protection system,
lines/equipment that are designed to
withstand the high temperature, and an
adequate quench system in the TGTU.
For retrofit applications, it is likely that
this equipment, after inspection, will
require upgrades to handle the increase
in oxygen concentration.
Medium-level oxygen combustion
can be considered when the desired
capacity increase exceeds that made
available by simple enrichment. Tech-
nologies are available that inject oxygen
directly into the thermal reactor rather
than into the piping system upstream of
the burner (Figure 2). Oxygen-injection
PTQ Q2 2005
106
PLANT MAI NTENANCE
AAG 1852 MSCFD
SWSAG 291 MSCFD
Combustion air
2295 MSCFD
Oxygen
506 MSCFD
9 PSIG
60 LTPD
Figure 1 Modified Claus SRU with oxygen injection
AAG 1481 MSCFD
SWSAG 291 MSCFD
Combustion air
2932 MSCFD
Oxygen
220 MSCFD
48 LTPD SRU
Figure 2 Modified Claus SRU with low-level oxygen enrichment
cbi 16/2/05 8:22 PM Page 2
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PLANT MAI NTENANCE
systems, which are regarded as medium-
level oxygen-enrichment tools, were
developed to maximise the amount of
acid gas processed in the SRU by
replacing the diluent nitrogen in the air
with reactants (oxygen and acid gas) to
o v e rcome the hydraulic limitations of
the existing unit.
Oxygen-injection systems typically
are licensed technologies that not only
eliminate the metallurgical limitations
of low-level oxygen enrichment, but also
produce SRU capacity increases of up to
70 per cent for refinery acid gas feeds.
This capacity increase further removes
nitrogen from the Claus reaction.
Since the oxygen concentration is
increased from 2840 per cent, combus-
tion temperatures are likely to reach at
least 2800F. Careful consideration must
therefore be given to the design of the
r e f r a c t o rysystem and the protection of
the waste heat boiler tubesheet. In
addition, the technology must include a
p r o p r i e t a ry burner that features an
oxygen-injection port separate from the
combustion air inlet. The waste heat
boiler and the sulphur condensers need
to be evaluated to ensure they have
adequate heat-transfer capabilities. If the
SRU is followed with a TGTU, the
quench and amine systems need to be
evaluated for the increase in capacity.
To ensure that the thermal reactor of
the SRU is using the proper amount of
pure oxygen and not exceeding
temperatures of 28002900F, which can
cause refractory damage, it is important
that refiners install an automated
control system. This system should act
to minimise oxygen consumption and
maximise combustion air consumption,
as well as to ensure a smooth transition
from air regime to oxygen-enhanced
regime and back to air. The thermal
reactor combustion chamber temper-
ature controller will limit oxygen feed to
the SRU if the temperature gets higher
than 2800F to prevent damage to the
r e f r a c t o ry system.
Once the necessary adjustments and
modifications are made to compensate
for the introduction of a medium-level
injection system to the SRU, including a
new burner configuration, adequate
r e f r a c t o ry system, proper heat-transfer
equipment, and acid gas and other
piping that can handle the pressure
drops and added capacity, a medium-
level system can increase capacity up to
5070 per cent and can be retrofitted to
most Claus designs.
When is high-level oxygen
combustion feasible? If low-level oxygen
enrichment can increase capacity by 25
per cent and medium-level injection
systems can increase capacity by up to
70 per cent, what are the implications
for refiners that want to increase their
capacity to more than 100 per cent? To
achieve such capacity levels, it is neces-
s a ry to increase the oxygen concentra-
tion to levels in excess of 40 per cent
and, in many instances, approaching
100 per cent. When the oxygen concen-
tration reaches these levels, the ambient
air is almost completely eliminated from
the combustion process.
It is important to note that any
oxygen injected into a thermal reactor in
the absence of ambient air will quickly
cause combustion temperatures to
exceed the limits of the refractory
system. To prevent this, several
p r o p r i e t a ry technologies are available
that can handle 100 per cent oxygen.
The use of a 100 per cent pure oxygen
system may require additional equip-
ment, including a specialised burner to
handle the pure oxygen, as well as the
normal requirements for the oxygen-
injection (mid-level oxygen) system.
While this extra equipment will increase
SRU plant costs, it will also boost the
SRU capacity by 100 per cent or more.
Impact of oxygen processes
on SRU
Whether refiners replace part or all of
the ambient air with pure oxygen, the
concept of using oxygen-enriched air to
expand existing Claus units or of
building peaking capacity into new units
has become widely accepted. However,
despite the enormous benefits an
oxygen-enhanced system provides,
especially as crudes get sour and
environmental regulations become more
stringent, the addition of oxygen to
combustion air requires careful
consideration of numerous design and
operational features to ensure desired
safety and reliable operations. When
determining whether to retrofit a unit or
install an SRU designed for the future
installation of oxygen enhancement, it
is important to review the following:
Oxygen control system
Elevated combustion temperatures
Heat-transfer equipment
Increased pressure drops
T G T U s
Safety considerations.
The control system for oxygen
injection is designed to accomplish the
following main objectives: provide safe
and efficient operation, maximise unit
throughput and minimise oxygen
c o n s u m p t i o n .
To do so, it is imperative that
additional safeguards are implemented
along with the oxygen-injection system.
Such measures include an interlock,
which is used to shut off oxygen in the
event that temperatures exceed their
normal levels in the thermal reactor or
when the entire SRU needs to be shut
down. When processing oxygen, the
shutdown system needs to be fully
implemented and functional to ensure
that the SRU will be operated in a safe
and reliable manner.
The control system for oxygen
injection is designed in such a way that
the oxygen is only supplied when the
SRU reaches its hydraulic limitations
from using the maximum air provided
by the air blower. Once the oxygen is
introduced in the burner, a portion of
ambient air is taken out, thus creating a
hydraulic capacity to feed more acid gas
to the SRU. As soon as this portion of
ambient air is taken out of the process,
the temperature in the reactor will
increase. The climbing temperature
needs to be carefully monitored, so that
when it reaches certain high levels the
oxygen flow can be promptly reduced to
prevent any refractory damage.
As more inert nitrogen is replaced
by pure oxygen, the combustion
temperature will steadily increase. For
this reason (with elevated combustion
temperatures), it is necessary to
r e v i e w all materials of construction
beforehand including the refractory
fire brick, insulating brick and castable
r e f r a c t o ry to ensure that all materials
have the acceptable chemical composi-
tion and physical properties required for
higher operating temperatures. The
waste heat boiler tubesheet is partic-
ularly susceptible to high temperatures,
which can lead to rapid deterioration of
the tubesheets. To prevent this, refiners
can install a tubesheet-protection system
(a patented licensed technology) that
improves the protection of the tubesheet
against the high process temperatures of
oxygen enhancement. This system can
be used on new units, as well as retrofit
a p p l i c a t i o n s .
As temperatures rise in the
combustion chamber with the use of
oxygen, the load on the downstream
heat-transfer equipment is substantially
increased. Also, when pure oxygen is
added to the SRU, the mass flow
decreases more rapidly with each
condensation cycle, resulting in lower
pressure drops in the latter stages of the
unit, as well as slightly higher mass flows
in the waste heat boiler and first sulphur
c o n d e n s e r. This combination of higher
temperatures and higher mass flows
should lead to an evaluation of the waste
heat boiler to ensure it can handle the
extra flow and higher temperatures, as
well as an evaluation of the sulphur
c o n d e n s e r s heat-transfer capabilities.
A c c o r d i n g l y, these items and their safety
valves must be inspected before installing
an oxygen-enhanced unit to determine
whether they need to be upgraded.
PTQ Q2 2005
1 0 8
PLANT MAI NTENANCE
It also is important to note that the
increased temperature in the combus-
tion chamber will subsequently affect
downstream temperatures. For instance,
the temperature rise in the catalytic
reactor beds will be higher for the
oxygen-enhanced unit because the
concentration of the reactants (hydro-
gen sulphide and sulphur dioxide) has
been increased, while the inert nitrogen
(which absorbs the increased temper-
ature) has been decreased. Also, each
condenser load will be greater because of
the higher temperature and increased
sulphur condensation. In general,
s u l p h u r - r e c o v e ry efficiency can be
expected to improve in the oxygen-
enhanced unit.
Due to the increased flow rate of the
feed gases to the SRU, all of the acid gas
feed lines and the knockout drums need
to be evaluated. Increases in pressure
drops in all feed lines and front-end
equipment including the control
valves and flow meter can create the
hydraulic limitation for processing more
acid gas in the SRU. This needs to be
reviewed before retrofitting an SRU for
oxygen enhancement. Also, with the
increased sulphur production, it may be
n e c e s s a ry to check the performance of
the sulphur seals, sulphur piping and
pumping capacities.
Since the mass flow decreases more
rapidly with each condensation step in
an oxygen-enhanced SRU, TGTUs
usually receive less mass flow when
oxygen enhancement is added. How-
e v e r, because there is a higher perc e n t a g e
of hydrogen sulphide and sulphur
dioxide and less nitrogen, the
temperature rise across the TGTU is
higher than the unit is typically
designed to handle. In addition, because
the quench water equipment has to
handle a greater load of condensing
w a t e r, this must also be reviewed for the
increased workload. To compensate for a
large increase in the upstream feed
c a p a c i t y, the tail gas amine system
c i rculation capacity may need to be
increased as well.
For safety considerations, the unique
properties of pure oxygen should be
given full consideration when installing
pure oxygen piping in the unit. In high
oxygen content atmospheres, materials
normally not combustible in atmo-
spheric air can burn rapidly. To curtail
the risk of fire or injury, it is crucial for
all components introduced into the
system to be clean for oxygen serv i c e .
Grease, oil, particulates and iron scale
present a serious hazard due to
combustibility and impingement, which
could result in a pipe fire or other injury.
Particular care must be taken during the
maintenance activities to ensure that
only proper materials and parts are used.
Care must also be taken to ensure that all
new systems, parts and components are
appropriately cleaned.
These features are the most prominent
ones that need to be reviewed with
respect to oxygen-enrichment applica-
tions in existing plants. It cannot be
overemphasised that these adaptations
for increasing oxygen and supply
m u s t be carefully planned, designed,
controlled and implemented by experts
with practical experience.
Case study
Oxygen-enhancement technologies
have been successfully implemented in
various sulphur complexes throughout
the world. To maximise efficiency, some
of these systems are configured to
automatically increase or decrease the
level of pure oxygen being injected
directly into the burner, depending on
the capacity level of the SRU.
One such system was recently
introduced to a US refinery. This refinery
has three SRUs, each one designed to
process sulphur in the amine acid gas and
sour water stripper gas feed using ambient
a i r. Each unit also is designed and
equipped with mid-level-type oxygen-
injection systems, in which pure oxygen
is directly injected into the burner. Wi t h
an oxygen level of 36 per cent, each unit
can process up to 5060 per cent more
acid gas load (capacity) in the amine acid
gas and sour water stripper gas feed.
When the refinery throughput is near
normal levels, the SRU relies on ambient
air to process the sulphur in the feed.
H o w e v e r, once these units reach their
maximum capacities through the use of
ambient air, the patented oxygen-
control system used in the sulphur
complex automatically introduces pure
oxygen into the burner to process the
excess acid gas feed. As soon as the
r e f i n e rythroughput is reduced back to a
level that no longer requires the
enhanced capacity, the control system
automatically switches back to the
ambient air regime to minimise the
operational costs of the SRU.
This patented advanced control
system not only helps the refinery
reduce costs, but also allows it to remain
compliant with current regulations. In
the event that one SRU becomes
inoperable, the feed going to that SRU is
automatically redirected to the other
two trains. Once these units reach their
hydraulic limitations, pure oxygen is
automatically injected into the SRU to
satisfy the oxygen requirements for the
increased feed. Since all of this is
achieved with the advanced oxygen-
control system, operator intervention is
not required, ensuring the refinery
remains compliant with environmental
regulations at all times.
Meeting future needs
As refiners continue to meet clean fuels
regulations for diesel and install more
SRU trains for redundancy purposes,
SRUs designed for the future installation
of oxygen injection may provide a sound
capital investment. Whether this
capability is installed in a new unit or a
retrofit, oxygen has become a cost-
effective and efficient solution for the
inevitable capacity increase required in
SRU throughput. The challenge for the
future lies with ensuring the control
systems work well with the oxygen-
enhanced systems and implementing
the necessary safety features to ensure
refiners experience a smooth transition.
Table 1 provides an example of how
SRU capacity is increased using both
low-level and medium-level oxygen
enhancement (as compared with regular
ambient air). For illustrative purposes,
typical (rather than maximum) oxygen
levels have been used within each of the
scenarios to show the capacity increases.
In this example, an oxygen level of 21
per cent is used for combustion air, 26
per cent for the low-level air-enrichment
mode of operation, and 35 per cent for
the injection system mode.
Mukesh Mehta is manager of process
engineering for CB&I TPA and has 17
years experience designing sulphur-
r e c o v e rysystems. Email: mmehta@cbi.com
A a ron Stry k is manager of corporate
communications for CB&I and serves as
chief editor of the companys internal
publications. Email: astry k @ c b i . c o m
PTQ Q2 2005
1 0 9
Combustion air Air enrichment Injection system
21% oxygen 26% oxygen 35% oxygen
AAG, MSCFD 1184 1481 1822
SWS AG, MSCFD 291 291 291
Combustion air, MSCFD 3384 2932 2295
Oxygen, MSCFD 0 220 506
Total, MSCFD 4859 4924 4944
Capacity, LTPD 40 48 60
SRU capacity increases using both low-level and medium-level
oxygen enhancement (as compared with regular ambient air)
Table 1
PLANT MAI NTENANCE