You are on page 1of 9

Eliminating the Claus furnace

F
uel sources are becoming increasingly sour
and society is increasing pressure on envi-
ronmental regulatory agencies to improve
emissions standards in a desire for a cleaner
environment. As a result, producers and proces-
sors in the gas processing, refning,
petrochemical and other industries have a grow-
ing focus on sulphur removal technologies that
not only will improve the quality of their product
streams but will also enable them to comply with
the more stringent environmental regulations
being imposed by governmental agencies. Since
the price of sulphur is not suffciently high for
sulphur recovery processes to be proftable, the
value of a sulphur recovery unit (SRU) is defned
by the lost opportunity cost associated with
downtime of the associated hydrocarbon
processing unit as well as by its cost of opera-
tion. Then, for the producers and processors, it
is important to understand the various sulphur
removal and recovery technologies available so
that the most reliable, lowest cost processes can
be selected and used in their facilities.
Over the past decade, researchers at Phillips
66 developed a catalytic combustor that can be
used to replace the burner and thermal reactor
in Modifed Claus units and improve the opera-
tions of the SRU.
1-9
This new approach to the
Claus sulphur recovery process was presented at
the Laurance Reid Gas Conditioning Conference
in 2009.
10
Since that time, GTC Technology has
acquired the exclusive licensing rights to the
catalytic combustion technology that replaces
the conventional Claus burner and thermal reac-
tor and markets it under the name
GT-CataFlame. GTC markets the complete
process of GT-CataFlame integrated with the
downstream Claus converters under the name
GT-Spoc (Sulphur Partial Oxidation Catalysis).
Matt Thundyil, Sameer Pallavkar, Ramiro Vazquez and David Seeger GTC Technology US, LLC
The ultimate design of GT-Spoc is a single verti-
cal vessel that contains all the components of
GT-CataFlame, followed by the Claus converters
and sulphur condensers.
Background: conventional Claus
The Claus process was patented by Carl
Friedrich Claus in 1883, and introduced in 1936.
The Modifed Claus process is the most success-
ful commercial method for sulphur recovery. In
this framework, the reaction of H
2
S with oxygen
is separated into two stages: (1) a highly exother-
mic thermal stage where approximately 50% of
the H
2
S is converted to elemental sulphur and,
of the remaining H
2
S, a third of it is converted to
SO
2;
and (2) a moderately exothermic catalytic
stage where the remaining H
2
S in the gas stream
reacts with the rest of the SO
2
to produce more
elemental sulphur. The reactions are reversible,
and conversions are highly dependent on
temperature, sulphur content and moisture
content. To achieve sulphur conversions greater
than 60-70%, the thermal stage is followed by
sulphur condensation and separation which is
followed by reheating upstream of a catalytic
stage operated at temperatures higher than the
sulphur dew point. Additional catalytic stages
may be added to increase the effciency of
sulphur removal.
The fame stability of the combustion section
is a critical parameter in Claus operations. At a
H
2
S content of above 55%, the acid gas can be
sent directly to the furnace. Between 3055%
H
2
S, the acid gas or combustion air (or both)
may need to be preheated. At concentrations
below 30% H
2
S, the Claus unit operates in a
split fow mode with preheat and, as the H
2
S
content drops below 10%, fuel gas may need to
be added.
www.digitalrening.com/article/1000922 PTQ Q2 2014 1
A novel approach to the conversion of hydrogen sulphide to elemental sulphur
is expected to extend the economic range for Claus plants
A two-stage Claus unit can deliver 9095%
sulphur recovery effciency, with a three-stage
confguration delivering 9598% recovery. The
tail gas is generally sent to an incinerator if
9697% sulphur recovery effciency is accept-
able. If sulphur recovery in the 9999.5% range
is required, tail gas operations based on a
continuation of the Claus reaction under
sub-dew point is generally undertaken either
on a solid bed, or in the liquid phase. If
sulphur recovery effciencies of 99.9% are
required, the sulphur in the tail gas is generally
converted to H
2
S by hydrogenation and hydroly-
sis. Then the H
2
S is captured and recycled to the
Claus unit.
Modifed Claus units are challenging to oper-
ate reliably, and are particularly prone to
problems during start-up and shutdown. For
example, the furnace is usually started up and
shut down using a fuel gas stream as the fuel,
rather than the acid gas. When the feed shifts
from acid gas to predominantly fuel gas, with an
associated shift in oxidant ratio (air ratio),
higher temperatures and soot formation often
may result, among other undesirable conse-
quences. The soot has a tendency to foul the
Claus catalyst downstream of the furnace.
The operating cost associated with sulphur
removal for a Claus unit with tail gas clean-up is
in the $100/t range when considering utilities
and maintenance costs. The sulphur that is
recovered is generally bright yellow and
preferred in the marketplace.
2 PTQ Q2 2014 www.digitalrening.com/article/1000922
GT-Spoc: process description
GT-Spoc uses a patented, durable
catalyst in a short-contact-time
reactor, GT-CataFlame, to achieve
near-equilibrium H
2
S conversion
and sulphur selectivity in one
tenth of the volume used by a
conventional Claus burner and
reaction furnace.
10,11
The catalyst
also contains components that
eliminate classic Claus catalyst
deactivation mechanisms of
sulphur poisoning and coke depo-
sition of the catalyst in the frst
Claus converter during normal
sulphur recovery operation and
start-up/shutdown using fuel gas.
A simplifed process fow
diagram for GT-CataFlame inte-
grated with the waste heat boiler (WHB), frst
Claus converter and sulphur condensers is shown
in Figure 1. This diagram shows an expected
application where the catalytic combustor is
installed in place of a poorly performing Claus
furnace.
In GT-CataFlame the air and the acid gas are
preheated to approximately 220C (428F) before
they are mixed. The gases are blended in a
specially designed chamber to thoroughly mix the
two gases upstream of the catalyst reactor bed.
The gas contacts the front face of the reactor at a
specifc actual velocity, passes through the cata-
lyst bed in under one second, and immediately
contacts the WHB. In the reactor, approximately
70% of the H
2
S is converted to sulphur and H
2
or
H
2
O, 10% is converted to H
2
O and SO
2
, and most
of the hydrocarbons are converted to H
2
, CO and
H
2
O, and any ammonia is converted to N
2
and
H
2
. The gas exiting the WHB may be sent to a
sulphur condenser where elemental sulphur is
removed; after the condenser, the gas may be
re-heated to pass into the frst Claus converter.
Alternately, the gas exiting the WHB may pass
directly into the frst Claus converter and the
previously mentioned sulphur condenser and
re-heater may be eliminated; passing directly
from the WHB into the frst sulphur condenser
the process effectively jumps the Gamson and
Elkins curve and 90% sulphur recovery occurs
after the frst Claus converter.
12
The process that
includes sending the gas directly from the WHB
into the frst Claus converter is part of the patents
Reheat
Catalyst
bed
Condenser
Sulphur pit
Condenser
GT-CataFlame
WHB
Acid gas
Air
Boiler
feed water
HP steam
LP steam
Figure 1 Simplied process ow diagram of GT-CataFlame integrated with
the rst Claus converter and sulphur condensers
2 PTQ Q2 2014 www.digitalrening.com/article/1000922
that are included in GT-Spoc.
The gas path after the frst Claus
converter is the same as that of a
conventional Claus SRU.
A conventional Claus furnace
and a GT-CataFlame reactor
designed for the same acid gas
application are shown for
comparison in Figure 2; the
conditions used to design both
units are summarised in Table
1. In the fgure, the furnace and
GT-CataFlame are drawn to the
same scale which shows the
relatively larger size require-
ment for the furnace. This size
difference saves signifcantly on
footprint and the amount of
refractory material required.
The GT-CataFlame refractory
volume is 1/40
th
that of the
refractory volume required for the furnace. This
large reduction in refractory is due in part
because the refractory lining the mixing section
is only for protection and good engineering
practice.
The ultimate design intended for GT-Spoc is a
vertical arrangement; that is, GT-CataFlame is
integrated with the WHB and the downstream
Claus unit equipment, all combined in a single
vertical tower. A simplifed diagram of the verti-
cal GT-Spoc with two Claus converter stages is
shown in Figure 3. The acid gas and air are frst
pre-heated as they were in the horizontal
arrangement described above.
The preheated gases are then
combined at the top of the unit
in the mixing chamber. The
well-mixed gas then travels
downwards to the catalyst
where the H
2
S is converted to
sulphur. Next, the gas passes to
the frst Claus converter without
frst passing through a sulphur
condenser. In the vertical
GT-Spoc arrangement, the
sulphur condenser located
between the WHB and the frst
Claus converter is removed. The
WHB operating temperature is
adjusted so that the gas out of
the frst Claus converter remains
www.digitalrening.com/article/1000922 PTQ Q2 2014 3
above the sulphur dew point temperature. The
gas exits the WHB and passes directly to the frst
Claus converter bed. After the Claus converter,
the gas is cooled in the frst sulphur condenser
and molten sulphur forms as it does in the
conventional Claus SRU. The molten sulphur
collects on a chimney-type separation tray where
the liquid sulphur exits the side of the unit and
the gas passes down through the chimney. After
this molten sulphur separation tray, the remain-
der of the process is the same as a conventional
SRU except that it is arranged in a vertical
confguration.
Acid gas
Air
GT-CataFlame reactor
Equivalent conventional Claus furnace
Waste heat recovery
Waste heat recovery
Figure 2 A conventional Claus furnace and a GT-CataFlame designed for the
same application showing the relative size difference
Stream Acid gas from amine unit Sour water stripper gas Combustion air
Mass ow, kg/h 4050 730 10 900
Flow rate, Nm
3
/h 2671 675 8500

Composition, kg-moles/h
C
1
0.48 0 0
C
2
0.72 0 0
C
3
1.19 0 0
C
4
0.60 0 0
CO
2
1.19 0 0
H
2
O 2.86 6.00 5.4
H
2
S 112.21 12.00 0
Hexene 0 0.04 0
Phenol 0 0.02 0
N
2
0 0 295.6
O
2
0 0 78.5
NH
3
0 12.00 0
Conditions for comparison of GT-CataFlame and a Claus furnace
Table 1
The process that includes removing the frst
sulphur condenser (the one located after the
WHB and upstream of the frst Claus converter)
is patented by Phillips 66 and licensed by GTC.
This step has the advantage of reducing the
number of pieces of equipment, the overall SRU
footprint, and reducing the cost of the SRU; this
confguration may be applied to a conventional
Claus SRU with or without a GT-CataFlame as
well as in the vertical GT-Spoc
SRU.
GT-Spoc: operating data
Phillips 66 conducted a large
number of tests on a catalytic
combustor that could be used to
replace the conventional Claus
furnace with the goal of provid-
ing improved operation of Claus
SRUs. After extensive develop-
ment, the inventors arrived at a
robust catalyst formulation and
a combustor design that deliv-
ered results which could be
used to model and design
commercial facilities. The
summary results presented in
Table 2 are from tests using the
catalytic combustor compared
to measurements taken at the
SRUs of four refneries. The
results showed signifcant
improvement in hydrogen and
sulphur yields over what was
typically observed in refnery
Claus furnaces. Higher sulphur
and hydrogen yields were
believed to result from direct
oxidation and subsequent split-
ting of H
2
S at high reaction
temperatures.
11
The results were
gathered with no hydrocarbons
in the inlet gas, therefore the
hydrogen must come from NH
3

and H
2
S.
Operating results
The researchers from Phillips
66 undertook a project to
demonstrate the catalytic
combustion section of GT-Spoc,
GT-CataFlame. A pilot unit
installed at a refnery location in the US oper-
ated intermittently for more than a year. Testing
was performed to identify the operating parame-
ters and catalyst formulation that resulted in:
The highest H
2
S conversion to sulphur
Producing the necessary amount of SO
2
for the
downstream Claus converters
The least amount of unwanted byproduct
formation, primarily COS and CS
2
4 PTQ Q2 2014 www.digitalrening.com/article/1000922
HP steam
Boiler feed water
Boiler feed water
Boiler feed water
LP steam
Liquid sulphur
LP steam
Condensate
LP steam
Liquid sulphur
Tail gas
Preheated acid gas
Preheated air
GT-CataFlame catalyst
Claus catalyst
Claus catalyst
Figure 3 Ultimate vertical design of GT-Spoc with two Claus converters in series
Unit GT-Spoc Renery A Renery B Renery C Renery D
NH
3
present? Yes Yes Yes Yes No
% S yield 74.0 63.4 48.1 54.9 68.2
% H
2
yield 7.0 6.3 3.5 5.4 4.2
Laboratory results for GT-Spoc catalyst compared with renery Claus
reaction furnace sulphur and H
2
yields
Table 2
The destruction of ammonia
Formation of H
2
and CO,
rather than any unwanted
hydrocarbon byproducts.
The results shown in Figure 4
indicate the performance of a
particular catalyst formulation
that was tested for an extended
period in the unit. During this
testing period, air-to-H
2
S ratios
and gas velocities were being
evaluated so, throughout the
duration of the testing, these
parameters were varied to
observe the effects and to arrive
at optimum operating condi-
tions. However, even though
conditions were changed, H
2
S
conversion and selectivity
towards forming elemental
sulphur remained high throughout the period. At
certain points, the data refect operating condi-
tions that achieve better conversion and sulphur
yield so those operating conditions will be used
for commercial unit design and operation.
Throughout the test period, the range of gas
composition was approximately 80-82 mol% H
2
S,
11-12 mol% CO
2
, 5-6 mol% water, and 1 mol%
hydrocarbon content; the remaining 1-2 mol% is
nitrogen and the typical analytical measurement
error.
The results indicate that over 80% of the H
2
S
was converted with approximately 69-70% yield
of elemental sulphur; the remainder was unre-
acted H
2
S and SO
2
, and less than 1% formation
of COS and CS
2
combined. In addition there was
an average 7% yield of H
2
. This performance was
better than that of a conventional Claus furnace
where 5070% of the inlet H
2
S is converted and
the elemental sulphur yield is 4065% of the
inlet sulphur.
Advantages
Based upon the results of the testing that have
been presented here and previously,
10
several
process and economic advantages have been
identifed from having a short contact time cata-
lytic combustor versus a fame reaction furnace.
Process advantages
Reactants are pre-mixed prior to passing
through the GT-CataFlame reactor. The reaction
is uniform through the cross section of the reac-
tor eliminating the problems of post-combustion
mixing for contaminant destruction
Close-coupling of the catalyst zone and waste
heat boiler (WHB) improves overall sulphur
yield and reduces air requirement due to rapid
reaction quenching
No fames, fre-eyes, nor burner management
systems: a small retractable burner or access to
a hydrogen containing fuel is all that is needed
to trigger the catalyst at start-up
Fuel gas oxidation for warm-up takes place at
25% air stoichiometry, eliminating oxygen break-
through to downstream Claus converter beds
during start-up and shutdown
Low molecular weight hydrocarbons are
converted to reduction tail gas unit-friendly H
2

and CO by catalytic partial oxidation. Soot
formation is virtually eliminated. Air/fuel ratios
for fuel gas oxidation closely resemble acid gas/
air ratios, making switching nearly seamless
COS and CS
2
formation are signifcantly
reduced
The sulphur product contains only 25-33% of
the dissolved H
2
S/H
2
S
x
of normal Claus sulphur.
Economic advantages
Signifcant reduction in refractory lining due to
smaller size of GT-CataFlame
Small reactor volume and reduction in byprod-
ucts allows for design changes reducing overall
unit footprint
www.digitalrening.com/article/1000922 PTQ Q2 2014 5 4 PTQ Q2 2014 www.digitalrening.com/article/1000922
60
100
90
80
70
50
40
30
20
10
H
2

c
o
n
c
e
n
t
r
a
t
i
o
n
H
2
S

c
o
n
v
e
r
s
i
o
n
S
u
l
p
h
u
r

y
e
i
l
d
,

%
0
0 100 200 300 400 500 600 700 800 900
Elapsed time, hrs
Sulphur yield
H
2
S conversion
Outlet H
2
Figure 4 Results of H
2
S conversion, sulphur yield and hydrogen concentration
in the outlet gas for 900 hours of testing at various operating conditions in a
GT-CataFlame unit
Design changes eliminate interconnecting
piping and sulphur rundown piping and
equipment
Because GT-CataFlame is smaller than a typi-
cal furnace, there is less refractory and catalyst
mass to heat up or cool down; this in turn
reduces the time required for shutdown or
start-up
The Claus plant can be constructed in a verti-
cal orientation where the unit is self-draining
The frst sulphur condenser and re-heater that
is located downstream of the WHB may also be
eliminated, so that the gas stream exiting the
WHB fows directly to the frst Claus reactor
stage.
COS and CS
2
reduction and implications for
Claus converter bed design
The best way to minimise the effects of hydrocar-
bon contamination of acid gases in any SRU is to
prevent hydrocarbon absorption in the acid gas
removal system (slug and drop catching drums,
aerosol droplet removal, and lean amine/sour gas
differential temperature control) and mitigate
hydrocarbon accumulation (rich fash drums with
skimming and gas removal, carbon fltration, and
regenerator refux purge).
Despite these efforts, hydrocarbon may get into
the acid gas, leading to the undesired byproducts
COS and CS
2
. Nominally, the byproducts result
from reacting after the fame mixing zone where
hot, oxygen-free fame byproducts can mix with
unburned hydrocarbons, for instance CH
4
and S
2
,
in the acid gases as in a typical 1/3-2/3 split-fow
furnace for leaner H
2
S content gases.
14
Since the
gases fowing to the GT-CataFlame reactor are
pre-mixed and pre-heated, the temperature is
hotter than that of a furnace (approximately
2200-2300F, 1200-1260C), and since the time
from reactor to WHB is short, plant data show a
signifcant reduction in the amount of byproduct
COS and CS
2
when compared to a typical Claus
unit.
A study of 24 gas plants with a broad range of
inlet H
2
S concentrations in the gas passing to
the Claus furnace showed that the COS and CS
2

concentration in the gas exiting the WHB was in
the range 0.06-1.7 mol% for COS and 0.011.1
mol% for CS
2.
13
At the optimised operating
conditions for the GT-Spoc pilot unit, 0.120.18
mol% COS and 0.360.48 mol% CS
2
were meas-
ured in the gas leaving the catalytic combustor.
Also, since the formation of COS and CS
2
is
signifcantly decreased, and the frst Claus
converter conditions will be hotter than a conven-
tional Claus SRU design, the Claus converter
following the reactor can be much smaller, help-
ing to reduce the Claus catalyst bed size and
allowing for a more compact footprint. In
GT-Spoc, the frst Claus converter may be hotter
than in a conventional Claus design if the gas out
of the WHB fows directly to the Claus converter
without being cooled in a sulphur condenser.
Acid gas concentration
requirement
Stable operation of the GT-CataFlame catalyst
was demonstrated at acid gas concentrations as
low as 25% H
2
S using only pre-heated air and
pre-heated acid gas. In addition, a wide range of
laboratory tests were conducted on lean H
2
S
streams containing CO
2
or nitrogen diluents and
typical light hydrocarbon components. Sulphur
yields varied with H
2
S concentration, but the
yields were still close to equilibrium computa-
tions, unlike lean acid gas Claus units that
produce little to no sulphur from the thermal
stage.
The GT-CataFlame demonstration unit
confrmed the results obtained in the laboratory.
Turndown
Laboratory testing showed that operations were
stable down to 25% turndown when operating
only with acid gases. However, the laboratory
apparatus was capable of running with any
mixture between pure natural gas and pure H
2
S.
Demonstration plant data were run at as low
as 12% turndown with minimal effect on perfor-
mance. Because of the ability to operate with
nearly any ratio of fuel gas to acid gas, even
lower turndown rates can be achieved.
Air demand and related
operational improvements
While the overall recovery of sulphur will fuctu-
ate signifcantly with air-to-acid gas ratios in
both the Claus and GT-Spoc processes, the
GT-CataFlame catalysts selectivity for sulphur
does not vary signifcantly over a wide range of
air-to-H
2
S ratios.
The combination of pre-mixing before reaction
and close coupling of the reactor to the WHB
aids both hydrogen formation reactions (partial
6 PTQ Q2 2014 www.digitalrening.com/article/1000922
6 PTQ Q2 2014 www.digitalrening.com/article/1000922
oxidation and dissociation) and inhibits the
main hydrogen consumption reaction (recombi-
nation of H
2
and S). As fow rate increases in the
unit, improved heat transfer due to higher
Reynolds number and thermal conductivity of
the gas (due to higher hydrogen content) appear
to aid in inhibiting recombination. This trans-
lates to more capacity with less overall pressure
drop.
Start-up and shutdown
operational improvements
Most of the time, starting up a Claus plant is
spent heating up the large amount of refractory in
the reaction furnace chamber and catalyst in the
catalyst beds. The GT-CataFlame reaction section
is very compact and in close proximity to the
waste heat boiler entrance, so there is a minimum
amount of refractory to be dried and heated to
operating temperature.
The small amount of catalyst and support
materials in the reaction section is easily heated
up by a small preheater such as a Stackmatch,
eliminating one of the biggest problems in start-
ing up or recovering from a shutdown relighting
the main burner. Laboratory testing has shown
that hydrogen rich gases (~40% H
2
) and
air mixtures can be catalytically ignited by the
catalyst, potentially bypassing the need for any
type of fred preheater.
Minimising the formation of contaminants
such as COS and CS
2
and operating the frst
catalyst bed directly after the WHB makes it
possible to reduce the amount of Claus catalyst
needed, speeding up both the shutdown process
(sulphur removal or heat soak) and the start-up
process (warm-up). Elimination of the sulphur
condenser following the WHB and subsequent
reheater eliminates cool-down or warm-up of
equipment and interconnecting piping, again
speeding up the shutdown or start-up process.
When heating up or cooling down a Claus
plant, fuel gas fring at near stoichiometric ratios
is used, especially when Claus catalyst is sulphur
laden. Air-to-fuel gas ratios for most natural gas
streams range from 9.5-10:1, while air to acid
gas ratios are typically in the 1-2.5:1 range,
depending on acid gas concentration. This
makes for diffcult switching from one feed gas
to another. At stoichiometric ratios, the adiaba-
tic fame temperature (~3500F, 1925C) for
most fuel gases is well above the temperature
limits of reaction furnace refractory (~2800F,
1535C) and ferrules, requiring the incorporation
of steam or nitrogen diluent to hold fame
temperatures to a safe operating envelope.
Also, near-stoichiometric fames have a
tendency to form soot which can rapidly plug
catalyst beds downstream of the fame.
GT-CataFlame catalyst can convert fuel gas via
partial oxidation (down to as low as 25% of full
stoichiometric) air, close to the ratios used for
acid gas operations. The catalyst has compo-
nents that resist the formation of coke on the
catalyst surface which translates into less
production of soot.
Firing slightly over stoichiometric can cause
unwanted catalyst exotherms, damaging both
catalyst and vessels. Since the catalyst does not
have to operate near stoichiometric air-to-fuel
ratios, damaging exotherms on Claus catalysts
are eliminated.
In general, the more frequent the shutdown
and start-up of a Claus unit, the more problems
can be expected. During the small demonstra-
tion plants long term catalyst testing, the unit
was shut down and started up over 30 times.
Through all of the start-ups and shutdowns, the
GT-CataFlame catalyst retained its original
activity.
Reduction of H
2
S and sulphanes in
produced sulphur
Experimental data from laboratory tests demon-
strate that the sulphur produced in the GT-Spoc
vertical arrangement contains less dissolved H
2
S
and H
2
S
x
because all the sulphur from both stages
will only be exposed to the H
2
S partial pressure
that would normally be found at the second
condenser of a conventional Claus unit, which is
signifcantly lower than at the frst condenser
following the conventional thermal stage. The
results in Table 3 show the difference in H
2
S and
H
2
S
x
content as the sulphur from the sulphur
condenser immediately following GT-CataFlame
contains fve to six times more dissolved H
2
S and
H
2
S
x
as sulphur from the condenser that follows
both GT-CataFlame and the frst stage Claus
converter.
Capital cost comparison
An independent engineering frm performed a
cost study that compared the capital cost of a
two-stage GT-Spoc unit to a conventional
www.digitalrening.com/article/1000922 PTQ Q2 2014 7
two-stage Claus unit with a furnace. The
GT-Spoc SRU was designed in the single, verti-
cal tower arrangement shown in Figure 3.
The amine unit, the tail gas unit (TGU) and
the sulphur pit were assumed to be similar
for both units and were not included in the
capital cost estimate. Therefore any cost advan-
tage of the effects of reduced duty on the
TGU and less H
2
S and H
2
S
x
dissolved in the
sulphur are not included in the comparison. The
cost study was prepared using the standard engi-
neering cost factors based on US Gulf Coast
prices.
Design basis
The composition of the acid gas fowing to the
GT-CataFlame or to the Claus furnace is shown in
Table 4. For purposes of presentation in the table,
the acid gas and sour water stripper (SWS) off-gas
are added together and reported as the composi-
tion of one stream, as they would be in the case of
the feed gas to the GT-Spoc SRU. However, in the
case of a conventional Claus stream, the SWS
off-gas is added to the burner and the acid gas is
operated in split fow.
The fow rate of the combined acid gas and
SWS off-gas is 42.9 Nm
3
/h (3.8 MMscfd) and
the sulphur production rate is approximately
100 t/d.
Cost comparison results
The results of this cost estimate
indicated that the capital cost of
a GT-Spoc unit is approximately
20% less than that of a conven-
tional Claus unit. A few major
differences between the two
processes are the reasons for
the savings and they are:
The GT-CataFlame reactor is
approximately 20% of the volume of an equiva-
lent Claus furnace
GT-CataFlame requires much less refractory
(as little as 1/40
th
the amount required for a
conventional Claus furnace)
The sulphur condenser located after the WHB
and before the frst Claus converter in a conven-
tional Claus SRU is eliminated in the vertical
GT-Spoc SRU design
The frst reheater that follows the frst sulphur
condenser in a conventional Claus SRU is also
eliminated as it is unnecessary in GT-Spoc
Interconnecting piping is reduced in GT-Spoc
as the stages are close coupled in a vertical
arrangement as compared the conventional
Claus SRU.
Summary
Conventional Modifed Claus technology with a
free-fame thermal section is well known to have
a number of operating challenges associated
with the reactions that occur in the fame. An
alternative, proven approach is presented
here, where the free-fame thermal section is
replaced with a catalytic combustor that
utilises a durable catalyst that enables sulphur
partial oxidation catalysis. This change at the
front end of a conventional Claus process results
in signifcant process and economic advantages,
including improved sulphur
yield, reductions in COS and
CS
2
formation, reduced impact
of hydrocarbons on air demand,
improved start-up and shut-
down operations, and
reductions in the Claus
converter catalyst bed sections.
Overall, GT-CataFlame allows
upgrades of aging Claus burners
and enables a 2030% reduc-
tion in capital costs associated
with Claus plants, while reduc-
8 PTQ Q2 2014 www.digitalrening.com/article/1000922
Conditions:
Air/H
2
S 2.4
H
2
S ow 750 cm
3
/min After GT-CataFlame After GT-CataFlame and one Claus stage
% Sulphur yield 72.3 85.8
H
2
S in sulphur, ppmw (FTIR) 308.4 60.3
H
2
S
x
in sulphur, ppmw (FTIR) 340.1 54.2
Reduction of H
2
S and H
2
S
x
in sulphur passing through Claus catalyst
Table 3
Component Mole % Component Mole %
CO
2
0.20 nC
4
0.00
H
2
S 67.80 nC
5
0.02
C
1
0.11 nC
6
0.00
C
2
0.09 H
2
O 19.80
C
3
0.02 NH
3
11.94
iC
4
0.00 H
2
0.05
Acid gas composition used for a capital cost comparison of GT-Spoc and a
conventional Claus SRU
Table 4
ing the tail gas unit load due to its higher
conversion effciencies.
GT-SPOC and GT-CataFlame are marks of GTC Technology US, LLC.
References
1 US 6,403,051 Recovery of Sulfur from
H
2
S and Concurrent
Production of H
2
Using Short Contact Time Reactors.
2 US 6,579,510 SPOX Enhanced Process for Production of
Synthesis Gas.
3 US 6,800,269 Short Contact Time Catalytic Sulfur Recovery
System for Removing H
2
S from a Waste Gas Stream.
4 US 6,946,111 Short Contact Time Partial Oxidation Process
for Recovering Sulfur from an H
2
S Containing Gas stream.
5 US 7,122,170 Catalysts for GT-SPOC Enhanced Synthesis
Gas Production.
6 US 7,138,101 Two Stage Catalytic Process for Recovering
Sulfur from an H
2
S Containing Gas Stream.
7 US 7,226,572 Compact Sulfur Recovery Plant and Process.
8 US 7,326,397 Catalytic Partial Oxidation Process for
Recovering Sulfur from an H
2
S Containing Stream.
9 US 7,357,908 Apparatus and Catalytic Partial Oxidation
Process for Recovering Sulfur from an H
2
S Containing Gas Stream.
10 Keller A, Is there direct oxidation of H
2
S to sulfur?, Laurance
Reid Gas Conditioning Conference, Feb 2009.
11 Partial Oxidation of H
2
S to sulfur, a Claus Alternative, British
Sulphur Conference, Oct 2003.
12 Paskall H G, Sames J A, Sulphur Recovery, 13th Edition, 2010,
1-14.
13 Paskall H G, Sames J A, Sulphur Recovery, 13th Edition, 2010,
2-80.
14 Borsboom H, Clark P, Goar B G, New insights into the Claus
thermal Stage, chemistry and temperatures, Laurance Reid Gas
Conditioning Conference, Feb 2009.
Matt Thundyil is Manager of Sulfur Business for GTC Technology
US, LLC, in Houston, Texas. He has over 15 years experience in
the petrochemical and energy industry and is the inventor on a
number of patented separations technologies. He holds a degree
in chemical engineering from the Indian Institute of Technology
(IIT), Madras, India, and a PhD from The University of Texas,
Austin, in advanced separations technology for natural gas
processing.
Sameer Pallavkar is a Sulfur Process Engineer with the Sulfur
Business Group at GTC Technology US, LLCs Houston ofce.
During his PhD program at Lamar, he worked as a research
assistant in the Department of Chemical Engineering, and was
assigned to the Microwave Reaction Engineering Laboratory as a
research candidate. He holds a degree in chemical engineering
from the University of Mumbai, Bombay, and a Masters from
Lamar.
Ramiro Vazquez is a Licensing Manager, Sulfur Business Unit, at
GTC Technology US, LLCs Houston ofce, where he is responsible
for technology licensing and sales. He holds a degree in chemical
engineering from the University of Nuevo Leon, Monterrey,
Mexico, and a Masters in chemical engineering from the
University of Houston.
David Seeger, Senior Scientist for GTC Technology US, LLCs
Sulfur Group in Houston, holds a BA degree in chemistry from
St. Thomas University (St. Paul, MN) and MA and PhD degrees in
chemistry from the University of Michigan (Ann Arbor, MI). He is
the inventor of a selenium removal process for FGD and has led
research efforts to develop and improve processes for HAP, FGD
and sulphur removal. He is one of the founders of CrystaTech.
www.digitalrening.com/article/1000922 PTQ Q2 2014 9 8 PTQ Q2 2014 www.digitalrening.com/article/1000922

LINKS
More articles from: GTC Technology
More articles from the following categories:
Emissions Control
Sulphur Removal, Recovery & Handling