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CLAUS TAIL GAS TREATING

Low cost and reliable


sulphur recovery*
By combining a selective oxidation process with a wet gas scrubber technology, Jacobs and
MECS have developed a cost effective alternative to amine-based Claus tail gas treating.
Sulphur recovery and SO2 emission reduction requirements can be met at significantly lower
capital and operating costs. This article compares the capital and operating costs of a typical
140 t/d SRU with an amine-based TGTU versus a SUPERCLAUS® /DynaWave®.

election of an appropriate and cost

S effective tail gas treatment process


to follow existing Claus plants is a
challenge facing refiners and natural gas
Fig 1: SUPERCLAUS® process

reheater Claus reactor


selective
oxidation reactor incinerator
plant owners around the world. New emis-
sion regulations, interest in increasing sul- steam
phur recovery and processing of higher stack
sulphur crudes are the main drivers.
waste heat H2S
The most common approach is to boiler steam
install an amine-based Tail Gas Treatment QC
Unit (TGTU) however lower installed cost
combustion
and higher reliability can be achieved by chamber
combining two well established processes,
Jacobs SUPERCLAUS® selective oxidation condenser
S S S S
process and MECS’ DynaWave® wet gas
scrubber technology. Owners can lower ABC control
capital and operating costs significantly system
with this solution. +

SUPERCLAUS® FC

The SUPERCLAUS® process was developed

H2S + 1/2 O2 →
to catalytically recover elemental sulphur air
from H2S containing Claus tail gases to 2H2S + SO2 3S + 2H2O
feed gas S + H2O
improve the overall sulphur recovery level
of the sulphur recovery facility. The process
was commercially demonstrated in 1988,
and today more than 160 units are under enters the SUPERCLAUS® reactor for selec- Unlike the conventional Claus process,
license and over 140 are in operation. tive oxidation of the H2S to elemental sul- the SUPERCLAUS® process controls to a set
The SUPERCLAUS® process achieves phur. The formed sulphur is then condensed H2S concentration entering the SUPER-
high sulphur recovery levels by suppressing and recovered by the SUPERCLAUS® con- CLAUS® stage. This is achieved by imple-
SO2 formation in the Claus stages, and denser. Tail gas from the SUPERCLAUS® mentation of Jacobs proprietary control
selectively oxidising H2S in the presence of stage is typically routed to an incinerator for system called the Advanced Burner Control
oxygen over a proprietary catalyst (see Fig. thermal oxidation of the residual sulphur (ABC system), which controls the thermal
1). Claus tail gas from the last Claus con- components and venting of the flue gas to stage combustion air through combined
denser is reheated, mixed with air and then atmosphere via the incinerator stack. feedforward and feedback logic. The

*Authors: Dennis Koscielnuk and Frank Scheel of Jacobs Comprimo® Sulphur Solutions, Steven F. Meyer and Andrea Trapet of MECS, Inc. DynaWave®
and B. Gene Goar of Goar Sulphur Services & Assistance.

Sulphur 326 | January -February 2010 1


CLAUS TAIL GAS TREATING

required quantity of combustion air is cal- with high L/G ratios. In general, higher liq- SO2 (v) + NaOH (l) → NaHSO3
SO2 (v) + 2NaOH (l) → Na2SO3 + H2O
culated by measuring the amine acid gas uid-to-gas ratios will result in higher SO2
and the sour water acid gas (SWS) flows. removal efficiencies.
The total air demand is then compared with The DynaWave® achieves high L/G and
the feedback signal from the air demand infinite turndown using reverse jet technol- In most cases, the sodium sulphite/
analyser (located upstream of the SUPER- ogy. Tail gas from the SRU incinerator, or sodium bisulphite salts formed in the
CLAUS® reactor) to adjust air supply to the waste heat boiler, enters the scrubber inlet above reactions must be further oxidised
thermal stage. The ABC system ensures duct and collides with the circulating scrub- to sodium sulphate in order to reduce the
that the required H2S content is achieved at ber liquor (see Fig. 2). The liquor is injected COD of the scrubber effluent to acceptable
the inlet of the SUPERCLAUS® stage for opti- countercurrent to the gas flow through a levels. The reactions are as follows:
NaHSO3(soluble salt) + 0.5O2 + NaOH →
mum sulphur recovery efficiency of the unit. large bore, open throat nozzle known as
SUPERCLAUS® catalyst is not sensitive the reverse jet nozzle. The contact zone
Na2SO4 (soluble salt) + H2O
Na2SO3 (soluble salt) + 0.5O2 → Na2SO4
to excess O2, nor the presence of SO2 or where the gas and liquor collide is referred
H2O because the selective oxidation reac- to as the froth zone.
tion is not equilibrium based like the Claus The froth zone is an area of high mass (soluble salt)
reaction: transfer and turbulence where quench and
Claus reaction acid gas absorption take place simultane- After the gas exits the inlet duct, it flows
2H2S + SO2 ↔ 3S + 2H2O
ously. The amount of recirculation liquid through the top portion of the vessel and
required to develop the froth zone is cal- exits to atmosphere through an integral
SUPERCLAUS® reaction culated based on the maximum process stack. Before exiting the vessel, the clean,
H2S + 1/2 O2 → S + H2O
conditions. The liquid flow is constant, saturated gas flows through a set of
which means that when the inlet gas flow chevrons which maximise liquid droplet
SUPERCLAUS® is compatible with conven- decreases, the L/G increases and acid gas removal from the gas stream.
tional SRU designs that properly destroy removal efficiency increases. The scrubbing liquor falls to the bottom
ammonia present in the SWS feed gases Compared to packed towers, where of the scrubber vessel which is used as a
with no added risk to ammonia salt deposi- high liquid flow rates can cause flooding, reservoir for continuous feed to the recir-
tion. Close to 50% of the SUPERCLAUS® the DynaWave® can operate at liquid circu- culation pumps. The vessel also provides
installations in the world are effectively oper- lation rates which are 5 to 7 times normal the oxidation zone for in-situ oxidation of
ating in ammonia processing Claus units. packed tower flow rates. This allows the sulphite salts to sulphate salts.
SUPERCLAUS® is a non-cyclic process DynaWave® to handle extremely high levels The DynaWave® wet gas scrubber has
that has repeatedly shown simplicity of of SO2, present at SSM when a portion of been installed in over 300 applications
operation, high online reliability, and sul- the SRU must be bypassed. worldwide. The DynaWave® has been designed
phur recovery guarantees up to 99.3%. To react with SO2, owners prefer to use for 11 SRU tail gas treatment projects in the
sodium based reagents such as caustic United States, and installed in seven. The
DynaWave® reverse jet scrubber (NaOH). The reaction between SO2 and caus- DynaWave® is leading all other SO2 absorption
tic is a strong acid-base reaction and is prac- technologies in total SRU installations.
DynaWave® is a unique wet gas scrubber tically instantaneous. Once the SO2 is in
technology which offers a number of advan- solution, the reaction proceeds as follows: SUPERCLAUS®/DynaWave® process
tages in the SRU application. The most
important challenges in the SRU scrubber Fig 2: DynaWave® reverse jet scrubber By combining the SUPERCLAUS® and
application are turndown, the need for a high DynaWave® technologies, the overall system
liquid to gas (L/G) ratio, and the requirement dirty gas in can achieve greater than 99.9% sulphur
for oxidation. An SRU tail gas scrubber must removal at compelling capital and operating
be able to handle a varying range of inlet costs. Approximately 99.0% of the H2S is
flow conditions and inlet SO2 concentrations captured and recovered as elemental sul-
which occur during the critical stages of phur by the SUPERCLAUS® and the remain-
startup, shutdown and malfunction (SSM). ing sulphur is scrubbed and converted to
Oxidation of the liquid effluent may be Na2SO4 by the DynaWave®. Figure 3 is a
required in order to reduce chemical oxygen clean gas out schematic of the combined technologies:
demand (COD) to levels acceptable to waste-
water treatment facilities. Technology comparison
Wet gas scrubbers circulate a liquid
reagent which absorbs SO2. The liquid-to- When comparing SUPERCLAUS®/DynaWave®
gas (L/G) ratio is a key process parameter with an amine-based TGTU, one must fully
for a scrubber, and must be high enough in assess the advantages or disadvantages
the SRU application to fully quench the hot of each factor, e.g. capital costs, operating
process gas and absorb the SO2 without pump costs, number of equipment items, plot
make-up
suppressing the pH in the absorber reac- foot-print, liquid discharges, chemical
tion/contact zone. Momentary pH depres- effluent requirements, achievable sulphur recovery
sion in the contact zone can be avoided rate and operability/reliability.

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CLAUS TAIL GAS TREATING

Fig 3: Combined SUPERCLAUS® / DynaWave® process


Claus reactor selective oxidation reactor
reheater incinerator

steam

waste heat H2S


boiler steam outlet
QC
combustion
chamber

condenser
S S S S
make-up

ABC control caustic


system
+

FC

air blowdown

feed gas SUPERCLAUS® DynaWave®

SO2 emissions all auxiliary equipment such as waste heat SUPERCLAUS®/DynaWave® process will
boilers, incinerators, stacks, amine/ hold for a wide range of sulphur loads.
The basis of the comparison assumes an caustic storage tanks, drain tanks, pumps,
EPA stack SO2 outlet limit of 50 ppm. Both scrubbers, etc. Costs for catalyst, Operational/equipment complexity
technology offerings can achieve greater chemicals, royalties, etc. were also Simplicity of operation and equipment
than 99.9% removal of the sulphur and dis- included for a more comprehensive complexity are key considerations when
charge less than 50 ppm SO2 at their comparison. No costs were included for choosing a process to install. Compared to
respective outlets. sulphur storage or handling facilities. an amine-based TGTU, the SUPERCLAUS®/
To achieve this low SO2 outlet value, Table 1 provides a comparison of the DynaWave® process has 35% less
the amine-based TGTU normally requires an relative capital costs. In each case a grass equipment and fewer complex equipment
amine additive to allow for very lean roots installation is assumed and a ther- items because complex towers with
solvent stripping. Also required are additional mal stage followed by a two-stage Claus pumparound systems are not required.
trays in the towers, as well as increased unit is included. Normalising the SRU plus The SUPERCLAUS®/DynaWave® process
solvent circulation and reboiler duties. amine-based TGTU system cost to a rela- essentially requires a reheater, reactor,
The SUPERCLAUS®/DynaWave® option tive value of 185, the combined SUPER- sulphur condenser and caustic scrubber.
achieves low SO2 emission levels simply CLAUS®/DynaWave® process cost is only This translates into less maintenance costs,
through the combination of the two tech- 140. This indicates an overall 24% capital less operational attention and manhours
nologies. The SUPERCLAUS® process uses cost savings when choosing the SUPER- and the probability of a higher on-stream
proprietary selective oxidation catalyst to CLAUS®/DynaWave® process. factor if equipment redundancy is equivalent.
reduce tail gas SO2 levels to 1,600 ppm. When a two-stage Claus unit already
The DynaWave® scrubber takes the incin- exists and a TGTU is to be added, the eval- Plot footprint
erated tail gas and reduces its SO2 content uation shows that the SUPERCLAUS®/ A factor that is sometimes overlooked
from 1,600 ppm to 50 ppm or less. DynaWave® process provides approxi- when comparing technologies is the plot
mately 53% savings on the capital cost of footprint required of the installation.
Comparative capital costs an amine-based TGTU. Most of the savings The SUPERCLAUS® /DynaWave® process
A capital cost analysis was per formed are realised through a simpler flow requires approximately 40% less plot
based on a 140 t/d sulphur recovery scheme, less complex equipment (fewer space than the amine-based TGTU. The
facility processing acid gas containing 77 towers and pumparounds) and approxi- equipment count is 24 for an amine-based
mol-% H2S and 8 mol-% NH3. For both the mately 35% less equipment count. TGTU compared to 16 for SUPERCLAUS®/
amine-based TGTU and SUPERCLAUS®/ Savings will depend on the size of the DynaWave®. The SRU section with two reac-
DynaWave® process, costs were calculated SRU system, however, it is reasonable to tors common to both process schemes
on a “turnkey” installed basis and include assume that the cost advantage of the has 23 pieces of equipment.

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CLAUS TAIL GAS TREATING

Comparative operating costs


Table 1: Technology capital cost comparison (140 t/d SRU)
Comparative operating costs, i.e. utilities,
can be broken down into several cate- Item Unit description Relative Approximate Comparison
gories; power, steam, fuel gas, water, and cost savings (%) basis
chemicals. For a 140 t/d SRU, Table 2 pro-
1 2-Stage Claus SRU 100
vides a utility cost comparison between an
2 2-Stage Claus SRU + amine-based TGTU 185
amine-based TGTU and a SUPERCLAUS®/
3 2-Stage Claus SRU + 140 24% Item 3 vs 2
DynaWave®.
SUPERCLAUS® /DynaWave®
As Table 2 illustrates, there is approxi-
4 Amine-based TGTU alone 85
mately 20% operating cost savings with the
5 SUPERCLAUS® / DynaWave® alone 40 53% Item 5 vs 4
SUPERCLAUS®/DynaWave® Process.
The SUPERCLAUS®/DynaWave® process
typically does not require cooling water Unique SRU solutions ing startup, shutdown and malfunction
because the only cooling needed is to (SSM). Emission levels during SSM are
condense the steam from the final sulphur Sometimes an owner does not require a potentially unpredictable. In the case of
condenser. The amine-based TGTU requires complete TGTU. This might be the case SRUs with TGTUs, normal emissions can be
2,050 gpm of cooling water for a 140 t/d SRU. when the Claus SRU is small or another between 200-1000 ppm SO2. During SSM,
With regards to overall fresh water TGTU technology is already installed. Both emissions can reach 4,000 to 10,000 ppm
make-up, the SUPERCLAUS®/DynaWave® SUPERCLAUS® and DynaWave® offer solu- SO2 or even higher, and gas flow rates can
process will consume 18.5 gpm. This is tions even in this situation. fluctuate as well. The technology that follows
the amount of water required to quench the the SRU must be able to handle this wide
gas from the incinerator waste heat boiler Reducing Claus unit operating costs range of process variables. As explained pre-
plus any effluent discharged from the For example, some owners have installed viously, one of the major advantages of the
scrubber system. The amine-based TGTU caustic scrubbers, such as the DynaWave®, DynaWave® scrubber is its capability to han-
does not require direct fresh water make- directly after their Claus units. This has dle very wide turndown operations.
up, but Table 2 takes into consideration allowed them to meet air permit require-
water evaporated in the cooling tower. ments without installing complete amine- New requirements for very low SO2
The SUPERCLAUS®/DynaWave® process based TGTUs. emissions
requires caustic to react with the 1,600 When caustic is expensive, the operating Typical emission requirements for SRUs in
ppm SO2 from the incinerator waste heat costs of an inefficient Claus unit followed by the United States range between 50 to 250
boiler. The amount of caustic required by a caustic scrubber can be high. The SUPER- ppm. The Air Quality Management District
the SUPERCLAUS®/DynaWave® process is CLAUS® process offers a solution with the in Los Angeles, California is investigating
in the order of 3.5 long t/d, dry basis for a simple retrofit addition of SUPERCLAUS® cat- the feasibility of limiting SO2 emissions to
140 t/d sulphur processing facility. The alyst into the third Claus reactor and possi- below 10 ppm. The DynaWave® is a robust
reaction products result in a 10 gpm liquid bly a new sulphur condenser for the and reliable wet gas scrubbing process
effluent stream that contains 10% sodium additional heat load generated by SUPER- which can meet these future emission
sulphate which is typically sent to the CLAUS®. If the 3rd Claus stage does not requirements at a reasonably low operating
waste water treatment plant. exist, then the addition of a new SUPER- cost. In addition, since many owners will be
The amine-based TGTU process effluent CLAUS® stage would be required. required to retrofit a wet gas scrubber into
is a 17 gpm waste water stream, contain- an existing facility, the small footprint of the
ing 20-50 ppm H2S, which requires further SRU process unit redundancy DynaWave® provides the possibility to
treatment before being sent to the waste In the future, process units may no longer install this technology where real estate is
water treatment plant. be able to exempt emissions excesses dur- at a premium. ■

Table 2: Utility comparison (140 t/d SRU)


Amine-based TGTU SUPERCLAUS® /DynaWave®
Utility type $/Unit cost Consumption $/Day cost Consumption $/Day cost
Electric power $.08/kWh 499 kW 958 485 kW 931
60 psig steam consumed $4/1000 lb 10,200 lb/hr 979 none 0
60 psig steam produced $4/1000 lb none 0 7,500 lb/hr (produced) -720 (credit)
Fuel gas (incinerator) $3.50/1000 SCF 14,800 SCFH 1,243 16,600 SCFH 1,394
Fuel gas (heater or RGG) $3.50/1000 SCF 3,500 SCFH 294 1,340 SCFH 113
Cooling water $0.10/1000 gal 2050 gpm 295 none 0
Fresh water $1.30/1000 gal 22 gpm 42 18.5 gpm 35
Amine make-up $1.40/ lb 55 lb/day 77 none 0
Caustic make-up $0.175/lb ($350/ton) none 0 7,721 lb/day 1,351
Total $3,888/day $3,104/day

4 Sulphur 326 | January -February 2010

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