36 Sulphur 320 |

January- February 2009

CLAUS TAIL GAS TREATING
SuperClaus/DynaWave process
Jacobs Comprimo and MECS have com-
bined their respective experience in sul-
phur recover y and wet gas scrubbing to
provide a simpler and less expensive Claus
tail gas treating process.
The Jacobs Comprimo SuperClaus

pro -
cess, the incinerator and the MECS
DynaWave

reverse jet scrubber used in

series provide ultra low SO
2
emissions
(stack emissions below 50 ppm SO
2
) and
an overall sulphur recover y efficiency of
over 99.9% (see Fig. 1).
SuperClaus
The SuperClaus process was developed to
catalytically recover elemental sulphur from
H
2
S containing gases originating from refin-
ery and natural gas treating plants such as
alkanolamine units or physical solvent
plants. The SuperClaus process has been
in use in industr y since 1988 and today
more than 150 units are under license and
over 140 in operation.
The SuperClaus process consists of a
thermal stage followed by three or four cat-
alytic reaction stages with sulphur removed
between stages by condensers. In the ther-
mal stage, the acid gas is burned with a
substoichiometric amount of controlled
combustion air so that the tail gas leaving
the last Claus reactor typically contains 0.5
to 0.9 vol-% of H
2
S. The first two or three
reactors are filled with standard Claus cat-
alyst while the last reactor is filled with a
special, proprietary catalyst developed for
selective partial oxidation of H
2
S directly to
sulphur. The reaction occurring over the
SuperClaus catalyst is:
H
2
S +
1
/
2
O2 S + H
2
O
The above reaction is a non-equilibrium
reaction, and therefore is not limited by an
approach to equilibrium. The SuperClaus
catalyst is very selective in the formation
of sulphur, resulting in limited SO
2
forma-
tion. A certain amount of air is injected into
the process gas entering the SuperClaus
stage and about 98% of the H
2
S present in
the gas is converted. Since the final cat-
alytic stage is not equilibrium limited, an
overall SRE of 98.8-99.2% can be achieved
when preceded by two Claus catalytic
stages (basis: at least 60-70 mol-% H
2
S in
the acid gas feed). When a third Claus cat-
alytic stage is added, an overall SRE of
99.2 to 99.4% can be achieved.
Two main principles are applied in oper-
ating the SuperClaus process:
G operating the Claus plant with excess
H
2
S to suppress the SO
2
content in the
Claus tail gas;
G selective oxidation of the remaining H
2
S
by the SuperClaus catalyst selectively
converts the H
2
S in the presence of
water vapour and excess oxygen to ele-
mental sulphur only.
DynaWave process
The DynaWave scrubbing process was devel-
oped to remove SO
2
from flue gases and
vent gas streams in general. The DynaWave
wet gas scrubber is a unique open bore,
reverse jet scrubber that utilises froth zone
technology to perform desulphurisation in a
wet gas environment. Since its introduction
Ideas for better cleanup
Higher sulphur recovery efficiency, lower capital and operating costs, greater flexibility and
lower CO
2
emissions are some of the many factors influencing the latest new process concepts
and enhanced process designs for Claus tail gas treating. Lisa Connock reports on how these
objectives are being achieved using the latest technology and catalysts.
acid gas
feed
acid gas
feed
tail gas tail gas
fuel
gas
fuel
gas
air air
air air
steam steam
steam steam
condenser condenser
Claus sulphur recovery unit Claus sulphur recovery unit Superclaus stage Superclaus stage Incinerator stage Incinerator stage Dynawave scrubber stage Dynawave scrubber stage
circulation pump circulation pump
vent to atmosphere vent to atmosphere
contact
zone
contact
zone
incinerator incinerator
combustion
chamber
combustion
chamber
SS SS SS SS
SS
Fig 1: Claus SuperClaus

-Dyna Wave

in the 1970s, over 300 DynaWaves have

been installed worldwide on various flue gas
and process vent streams, both for removal
of SO
2
and other components.
For SRU applications, DynaWave is
installed after the incinerator and before
the stack. In the DynaWave, scrubbing liq-
uid is injected through a non-restrictive jet
nozzle counter current to the inlet inciner-
ator flue gas. Liquid containing caustic
reagent (NaOH) collides with the down-com-
ing gas to create the froth zone, a region of
extreme turbulence with a high rate of
mass transfer. Quench, SO
2
removal and
particulate removal occur in the froth zone.
The clean, saturated gas and charged liq-
uid continue through a separation vessel.
The saturated gas continues through
the vessel to mist removal devices. The liq-
uid descends into the vessel sump for recy-
cle back to the reverse jet nozzle. In-situ
oxidation of the scrubbing effluent to a
benign Na
2
SO
4
solution is achieved by air
spargers in the bottom of the separation
vessel. This represents a cost saving com-
pared to other scrubbers which require
separate oxidation tanks. Sulphites are oxi-
dised to sulphates which can be sent to
waste water treatment without increasing
chemical oxidation demand (COD) load.
To date, four DynaWave scrubbers have
been installed and are in operation on SRU
tail gas streams for SO
2
removal, three for
Sinclair Refining Co. and one for Marathon
Refining Co. All of these DynaWave scrub-
bers are installed on the tail gas from con-
ventional SRUs with two or three catalytic
stages, and which are achieving a sulphur
recovery efficiency of about 95-96% in the
upstream SRUs. In each case, a waste
heat boiler is used to reduce the gas tem-
perature and to produce 450-550 psig
steam, and thus recover waste heat from
the hot gas stream. However, the cooling
or quench step is not required, since the
hot incinerator effluent can be handled
directly by the DynaWave scrubber. If waste
heat recover y is not desired or feasible,
the waste heat boiler can be eliminated,
thus saving the capital and operating cost
of this step.
If a Claus SRU achieves an overall SRE
of 95% and a DynaWave scrubber is used
to remove the last 5% of the SO
2
, the caus-
tic consumption and operating cost is rela-
tively high. However, if a SuperClaus stage
is employed upstream, and a SRE of
99.0% is realised, this leaves only 1.0% of
the SO
2
to be removed by the DynaWave
stage, and its operating cost is reduced by
about 80%. In most applications, the oper-
ating cost of the SC/DW TGCU process is
expected to be very competitive with that
of an amine-based type TGCU.
The estimated capital cost of the
SC/DW TGCU process is projected to be
only 60-65% or less of the capital cost of
an amine-based type TGCU process.
The SC/DW TGCU process has been
selected over a conventional TGCU process
for three new 150 long t/d SRUs, each with
two Claus stages, followed by a Super-
Claus stage, followed by a DynaWave
scrubber (using caustic) for the final tail
gas cleanup at the Sinclair refiner y in
Tulsa, Oklahoma. Licensor packages are
complete and the project is scheduled for
construction in the near future.
Extremely low stack emission limits are
being imposed on new sulphur recover y
plants in some US locations. In California,
stack SO
2
limits less than 50 ppm, even
as low as 10 ppm, are possible, The
SuperClaus/DynaWave process can be
operated to SO
2
emission levels as low as
10 ppm without equipment changes by
simply increasing the liquid to gas ratio in
the unit, with only a slight increase in caus-
tic consumption.
The typical TGCU process train requires
24 different pieces of equipment compared
to 16 pieces of equipment for the compara-
ble SuperClaus/DynaWave process. The
smaller equipment count indicates less
complexity, lower capital cost, lower main-
tenance cost and smaller footprint. Flexibil-
ity is also important for tail gas clean up.
With the SC/DW process the SuperClaus
can be temporarily bypassed and the
DynaWave scrubber can handle the full
Claus tail gas SO
2
load and still maintain the
required SO
2
stack limit allowing refiners to
meet regulations at all operating conditions.
RCTI (Rameshni Catalytic Tail Gas
Incineration)
RCTI (patent pending) is one of the latest
technologies developed by WorleyParsons
as an alternative to the conventional Wor-
leyParsons BSR-Amine tail gas unit. It is a
tail gas incineration process that has the
advantage of operating at lower tempera-
tures, which can provide savings in
reduced fuel gas costs.
The conventional thermal oxidiser/incin-
eration scheme operates at high tempera-
tures requiring high quantities of fuel and
thus generating high CO
2
emissions.
WorleyParsons offers the catalytic Selectox
TM
oxidiser as an alternative to reduce fuel con-
sumption and reduce CO
2
emissions.
Selectox catalyst was developed by
WorleyParsons and UOP many years ago
for sulphur/TGU applications. It is a
rugged, proven catalyst, also suitable for
promoting the Claus reaction in combina-
tion with in situ oxidation of dilute H
2
S.
The concept of the catalytic Selectox
TM
oxidiser is to heat the Claus tail gas to
meet the required inlet temperature to the
reactor. The tail gas feed is heated by indi-
rect heat exchange with HP steam. The
temperature required for oxidation is
much lower than that of a conventional
incinerator. The heated gas enters the
reactor and all sulphur compounds are
converted to SO
2
.
The stream leaving the reactor is
processed in the caustic scrubber where
the majority of SO
2
is absorbed by the caus-
tic. The overhead of the caustic scrubber is
routed to the conventional incinerator
where less fuel will be used to operate the
system, and therefore less CO
2
emissions.
The RCTI process consists of low-tem-
perature catalytic reduction of Claus tail
gas and subsequent low-temperature oxi-
dation of H
2
S using a selective direct oxi-
dation catalyst such as Selectox
TM
. The tail
gas feed is heated indirectly by HP steam
or hot oil. Eliminating the reducing gas gen-
erator will eliminate natural gas consump-
tion and reduce CO
2
emissions. If
neces sary, resultant SO
2
is captured by
non-regenerable caustic, or a regenerable
solvent such as Cansolv.
RCTI uses two proven catalysts the
new low temperature TGU hydrogenation
catalyst and the long established Selectox
TM
catalyst. Compared to other oxidation cata-
lysts, the active components of the Selec-
tox catalyst, bismuth and vanadium, are
particularly effective for the gas phase oxi-
dation of H
2
S to SO
2
in the presence of
water vapour below about 600F/315C. At
the proper operating conditions, oxidation of
H
2
, CO and NH
3
is minimised while simulta-
neously suppressing the formation of SO
3
.
The RCTI process consists of three sec-
tions. In the first section, tail gas feed from
the sulphur recovery unit(s), is heated to
the appropriate temperature before enter-
ing the downstream reactors. The heating
system may be any appropriate heating
system such as indirect heating systems,
fired reheaters, or any commonly-used type
of reheater, such as a steam reheater or a
moisture separator reheater (MSR).
Sulphur 320 |
January- February 2009 37
CLAUS TAIL GAS TREATING
The second and the third sections com-
prise two different catalysts, which can
either be installed in one vessel with two
separate catalyst beds, or in two separate
vessels. Preferably, the catalysts are con-
tained in a single vessel to reduce the cap-
ital cost of the overall unit.
The second section of the system is a
hydrogenation reactor. The heated gas
flows to a catalytic reactor using hydro-
genation catalyst of the type commonly
employed in the Claus tail gas hydrogena-
tion unit (cobalt-molybdenum hydrogena-
tion catalyst) preferably low temperature
hydrogenation catalyst such as those
employed in units that treat tail gas from
Claus sulphur recovery units.
The catalyst promotes the Claus reac-
tion and shifts CO and H
2
O to CO
2
and H
2
,
consumes residual H
2
to further reduce
SO
2
to H
2
S and hydrolyses COS and CS
2
to
H
2
S and CO
2
.
Hydrogen is required in the hydrogena-
tion reactor. The hydrogen is supplied as an
external source to the reactor, or if the heat-
ing system is a commonly-used BSR reduc-
ing gas generator, then hydrogen will be
produced or if the sulphur plant operates
as off ratio the adequate amount of hydro-
gen exists in the gas entering the reactor.
The third section is the direct oxidation
catalyst reactor. Gas from the first reactor
enters the second reactor where external
air from a low-head blower promotes the
oxidation of H
2
S to SO
2
. A key feature of
the process is the utilisation of reaction
heat from the first bed to achieve the initi-
ation temperatures necessary for subse-
quent oxidation.
Different configurations of the RCTI
process are available, for example, the out-
let stream from the second reactor can be
vented to the stack, based on the allow-
able emission regulations. Alternatively,
the outlet of the second reactor is routed
to a unit for SO
2
recovery (Fig. 2).
Table 1 shows a heat duty comparison
for conventional versus RCTI tail gas
treatment.
Ammonia destruction
in a Claus TGTU
Crude oil from several areas in the world,
including Brazil and Venezuela, contains
high levels of nitrogen, which results in a
very high level of ammonia in the sulphur
recovery unit feed. Traditionally, high levels
of ammonia have been combusted in the
Claus reaction furnace, where the amount
of NH
3
, which can be processed, is gener-
ally considered to be limited to 30-35% of
the total Claus feed on a wet basis. Any
additional NH
3
not processed in Claus
units is typically converted to ammonium
thiosulphate fertilizer, or purified in order
to be suitable for marketing or incineration.
WorleyParsons offers a new approach
to handling gaseous NH
3
streams the
RAC (Rameshni Ammonia Combustion)
process for ammonia destruction in a
Claus tail gas treating unit.
Ammonia destruction in a Claus tail gas
treating unit has several advantages:
G the sulphur recovery and tail gas unit
together have the capabilities of ammo-
nia destruction beyond 30 to 35% for
any new or existing Claus unit;
G a proven and established process that
does not require any pilot testing;
G flexibility of mode of operation with air
only, oxygen-enriched air, or oxygen only;
G plant flexibility for turndown, ability to
handle different feeds, and changes in
production rate;
G high reliability and easy maintenance;
G reduces plot space with fewer modifi-
cations, less impact on downstream
equipment for revamp applications;
G no concerns about plugging of down-
stream equipment;
G no oxygen enrichment required for high
ammonia content;
G reduces capital and operating costs
compared to alternatives.
This new approach may find applications in
many situations. For example, purification
38 Sulphur 320 |
January- February 2009
CLAUS TAIL GAS TREATING
Conventional RCTI
T1 T2 MMBtu T1 T2 MMBtu
Heat input (F/C) (F/C) hr (F/C) (F/C) hr
TGU reheat 280 / 138 600 / 316 4.2 280 /138 450 / 232 2.2
Incinerator 100 / 38 1,100 / 593 8.3 n/a n/a 0
Total 12.5 2.2
Table 1: Heat duty comparison for conventional versus RCTI tail gas treatment

Claus tail gas
AC
FC
FC
LP steam
or nitrogen
low temperature
hydrogenation
catalyst
selective
oxidation
catalyst
O
2
heater
External H
2
(optional)
tail gas
air blower
to SO
2
recovery unit
Fig 2: WorleyParsons catalytic tail gas incineration (RCTI)
facilities may have been installed to pro-
duce saleable NH
3
where such markets no
longer exist, or elimination of expensive
purification steps may be desirable. Also,
with bulk H
2
S removal from the NH
3
gas via
established processes, it provides an eco-
nomical means of increasing Claus sulphur
recover y capacity or processing greater
quantities of NH
3
than otherwise practical.
Two variations have been presented
depending on whether the associated TGU
is reductive or oxidative.
A process description of RAC in a reduc-
tive Claus tail gas unit has been reported
in Sulphur 314 and 316. A process
description of RAC in an oxidative tail gas
unit is given below.
RAC in an oxidative TGTU
In an oxidative TGTU scheme, a fuel is typ-
ically burned, with excess air, so that sub-
sequent combination of the flue and Claus
tail gas streams will result in a net tem-
perature sufficient for thermal oxidation of
all combustible sulphur compounds. In
some cases the resultant SO
2
can be dis-
charged to atmosphere, but environmental
regulations will more typically require that
the SO
2
be recovered by an absorption
medium. In the latter case the hot tail gas
stream will typically be cooled in, for exam-
ple, a waste heat boiler prior to gas/liquid
contact in the absorber.
In this case (Fig. 3) the NH
3
gas is
combusted sub-stoichiometrically in zone
1, thus supplanting most of the fuel oth-
er wise required, usually a hydrocarbon
gas. The ratio of air to NH
3
gas is auto-
matically adjusted to oxidise most of the
NH
3
, while maintaining sufficiently reduc-
ing conditions to avoid, or at least
minimise, NOx formation.
A supplemental fuel, typically a hydro-
carbon gas, is combusted with excess air
in parallel zone 2 at a rate necessar y to
achieve the desired temperature elevation
of the Claus tail gas stream. When no sup-
plemental heat is required, a minimum fire
is preferably maintained to facilitate a
prompt increase in the firing rate in the
event of NH
3
gas curtailment.
Combustion gases from zones 1 and 2
are combined in zone 3, where residual H
2
and potential CO, H
2
S and other miscella-
neous combustibles are thermally oxidised
by excess O
2
from zone 2.
Zone 3 effluent gases are combined with
the Claus tail gas stream in zone 4 to
achieve the net average temperature neces-
sary for the desired oxidation of com-
bustibles, which will typically include H
2
S, Sx,
COS, CS
2
and CO. The temperature required
for thermal oxidation will typically be in the
range of 425-815C, depending on prevail-
ing environmental regulations, residence
time and the nature and concentration of key
combustibles. If necessary, additional com-
bustion air may be injected to supplement
residual O
2
in the zone 3 effluent.
A typical target would be 1-3% residual
O
2
on a molar wet basis in the combined
tail gas stream.
Improved HCR

process
Siirtec Nigis HCR technology has been
improved in order to reduce the fuel gas
consumption in the sulphur recovery block,
thus reducing CO
2
emissions while achiev-
ing more than 99.9 % sulphur recovery effi-
ciency. The cut in CO
2
emissions has been
achieved without the need for additional
investment by utilising the latest catalysts
and by plant optimisation to reduce oper-
ating costs (Fig. 4).
HCR is a tail gas treatment based on
the catalytic reduction with a reducing gas
(CO + H
2
or a mixture of both), of the oxi-
dised sulphur compounds present in the
Claus off-gas species. The resultant H
2
S is
removed from the off gas by absorption
using an aqueous solution of MDEA.
Traditionally, the catalyst used for the
reduction reactions required a feed at a
temperature of 280C, thus a heater was
required to raise the temperature of the tail
gas from the final sulphur knockout drum
of the Claus unit from 130C up to 280C.
In general, in-line burners were used to
supply heat to the system while also gen-
erating the reducing gas needed for the
reducing reactions.
The operating condition of the Claus,
unique to HCR, eliminates the generation of
the reducing gas with the in-line burner, thus
the energy consumption of the HCR, and in
turn the equivalent carbon dioxide emission,
is intrinsically less than other tail gas treat-
ing units based on the catalytic process.
At the outlet of the reducing reactor, the
sulphur in the process gas is present
mainly as hydrogen sulphide. This species
is eventually removed and returned to the
SRU by means of a regenerative absorption
using MDEA.
Typically, the low pressure steam con-
sumption of the regeneration section is in the
range of 100-110 kg of steam per m
3
of sol-
vent when 50 wt-% MDEA is used and the tar-
geted sulphur recovery efficiency is 99.9+%:
herein lies a potential energy saving.
In order to enhance the environmental
impact of HCR the technology has been
improved by using a new generation cata-
lyst and by improving the MDEA regenera-
tion section.
Implementation of new catalyst
The catalyst most widely used for the
reducing step has for a long time been an
aluminum oxide catalyst containing about
2 wt-% cobalt and 6 wt-% molybdenum. The
activity of this catalyst is of industrial inter-
40 Sulphur 320 |
January- February 2009
CLAUS TAIL GAS TREATING
zone 4
air
NH
3
gas
to waste heat boiler
Claus tail gas
refinery fuel gas
air
air
zone 1
zone 3
zone 2
Fig 3: WorleyParsons ammonia destruction in an oxidative CTG unit
est at a temperature greater than 270 C.
In addition to the reduction reactions,
the above catalyst also promotes the shift
reaction: the conversion of H
2
O and CO to
CO
2
and hydrogen, and the hydrolysis of
COS and CS
2
to less harmful species.
Recently a new catalyst has been intro-
duced to the market that contains signifi-
cant more cobalt (1-5 wt-%) and much more
Mo (10-20 wt-%). At 230-240C this cata-
lyst shows catalytic activity towards both
the reduction and the hydrolysis reactions
equivalent to that of the old style cata-
lyst at 280C. Siirtec Nigi has modified its
way of designing the HCR technology and
adapted the design of the Claus section in
order to accommodate this new catalyst
into the sulphur recovery unit.
The implementation of the new genera-
tion of catalyst has been tested in an
industrial plant for two years and has now
become a standard for HCR.
The operation of the plant at a lower
temperature brings a number of advan-
tages including:
G lower duty of the heat that brings about
a reduction of the fuel consumption
when an in-line burner is used;
G simpler integration of the tail gas clean
up unit with the other sections of the
SRU making possible, for example, the
supply of heat directly from the heat
recovery section of the Claus unit.
From the environmental standpoint this
means that for a 135 t/d Claus unit arranged
with an in-line burner in the tail gas unit, the
reduction of 40C leads to a saving of about
320 kW, equivalent to a reduction of about
550 t/a of carbon dioxide emissions. Greater
emissions reduction can be achieved by
replacing the in-line burner with an indirect
heater integrated with the Claus unit. This
arrangement re sults in the reduction of CO
2
emissions by about 1,860 t/a (equiv.
44,640 Euros/year in the CO
2
market).
Regeneration of MDEA.
As mentioned earlier, the regeneration of
the solvent is an energy consuming
process and improvements in this area can
help reduce environmental impact.
Since the first commercial application of
the HCR in 1988, more than ten units are in
operation, therefore a consistent set of data
has been collected from the field that have
allowed Siirtec Nigi to improve the correla-
tions between steam consumption and
residual acid gas in the lean amine solution.
The residual acid components in the
lean amine is the key parameter upon
which the per formance of the tail gas
scrubbing depends, thus the accurate iden-
tification of the asymptote in the curve lean
amine content versus steam rate provides
a valuable tool for the prediction of the
marginal benefit each kilogram of steam
brings to the stripping section.
On the other hand, the steam rate is
related to the stripper arrangement and
operating conditions, more specifically to
the tower feed temperature and the stripper
overhead system adopted: a refluxed recti-
fying section reduces steam requirement.
The feed temperature is typically raised
against cooling the lean amine in a feed-
bottom heat exchanger: the higher the effi-
ciency of this heat transfer, the higher the
temperature at the stripper inlet and thus,
the lower the steam demand.
Combining the implementation of a high
efficiency feed-bottom heat exchanger and
the adoption of a refluxed rectifying section
under the conditions suggested by the
updated correlations has led to a significant
reduction of the steam consumption in the
stripper reboiler. For the 135 t/day SRU,
this means a further reduction of about
1,250 t/year of carbon dioxide emissions.
Overall, the improvement achieved in
both the reaction section and the solvent
regeneration end, results in a global CO
2
cut
of 3,110 t/year equivalent to more than
80,000 Euros per year in the CO
2
market. I
References
1. Goar, B.G. (Goar Sulfur Ser vices & Assis-
tance) and Meyer S. F. (MECS, Inc.): Claus
tail gas cleanup can be better, easier and
less expensive to meet Federal EPA regula-
tions, GPA, 2008.
2. Rameshni M. (WorleyParsons): RCTI A new
standard for Claus tail gas per formance,
presented at Sulphur 2008, Rome, Italy (Nov
2008).
3. Rameshni M. (WorleyParsons): Ammonia
destruction in a Claus tail gas treating unit,
Sulphur 2007, Montreal (Oct 2007).
4. Micucci L. (Siirtec Nigi): Improved HCR
TM

High Claus Ratio TGT paper submitted to

N+S (Dec 2008)
Sulphur 320 |
January- February 2009 41
CLAUS TAIL GAS TREATING
HPC HPS
CWS
CWR
start up blower
quench
tower
reduction
reactor
heater
water blow down
water pumps
coolers
tail gas
process gas to
amine unit
LS
BFW
cooler
Fig 4: Siirtec Nigis HCR

technology