Screening of Alternative Processes

Natural gas is considered sour if it contains significant amounts of H 2S, generally 4 parts
per million (ppm) or greater. Sour gas is caused due to development of shale oil & gas
plays, efforts to increase field life, and the use of Enhanced Oil Recovery (EOR) methods
like water injection often result in reservoir souring. High H2S concentrations in produced
gas creates safety hazards for operations, increases corrosion and sulphide -stress-
cracking risks, and results in an export gas of lower value. To minimize these factors,
various H2S removal methods can be utilized. In this work, four main alternatives for
Sulphur production were reviewed. They are different in terms of operating conditions,
reactants, used catalysts. In some methods, number of reaction is not one only, thereby more
by-products are formed. Every method has some advantages as well as disadvantages.

1. Solid Scavengers

Solid scavengers are very effective in stripping H2S from gas streams down to trace
levels. They require significant CAPEX (capital expenditure) and are often labour
intensive during media change out. However, they require little OPEX (operating
expenditure), are predictable in their removal rates, generally do not require additional
chemicals, and generally do not impact downstream processes or overboard water.

These systems comprise of a fixed bed filled with absorbent material of metal oxides such
as zinc, copper, iron, or magnesium. These beds take up significant space and require two
trains to maintain operation during servicing. The media is non-regenerative and requires
significant time and labour to charge with fresh media. Confined space entry and
potentially pyrophoric waste create unwanted operations hazards. These systems are very
efficient in removing almost all the H2S from a gas stream, are highly reliable, and very
predictable in their removal rates and change cycles. Figure 1 shows a typical metal oxide
medal bed design.
 Figure 1: Diagram of Metal Oxide Bed.

The design of the solid scavenger system is dependent on the mass flowrate of the H 2S over
the media, so large gas flow rates with low H2S concentrations will tend to have large vessels,
with long reactor bed lives. The opposite is true for high H2S concentration gas streams. Also
the gas should be water saturated to achieve maximum efficiency. A key benefit of this system
is that there is virtually no operator involvement. The gas flows over the media and reacts. A
downturn in flowrate and/or H2S concentration doesn’t require any involvement, as the media
will simply react with whatever H2S is in the gas stream.

In a single vessel configuration, when the catalyst is spent, and H2 S “breakthrough” occurs,
the vessel must be taken out of service and the media replaced, possibly causing an interruption
in production and/or an undesirable H2S in the product gas stream… In contrast, a dual vessel,
lead-lag system allows the “lag” vessel to become the “lead” vessel, allowing continued plant
operation while the spent media in the former “lead” vessel is taken out of service and the
media changed-out. A diagram of the “lead-lag” configuration is shown in Figure 2. The benefit
of this system is more efficient use of the media, as the media in the “lead” vessel can be reacted
to virtual completion because of the “back-up” afforded by the “lag” vessel.
 Figure 2: Diagram of Dual Vessel Lead-Lag Solid Scavenger System.

2. Liquid Scavenger

The most common liquid scavenger is an amine-aldehyde condensate manufactured from

monoethanolamine and formaldehyde. The resulting “scavenger” product is a
hexahydrotriazine, and is commonly called “triazine” in the industry. The “triazine” is typically
offered in a water-based solution. In most applications, the reaction products are also water
soluble, with very low toxicity characteristics and biodegradable, making this a relatively
simple system to handle.

Liquid scavengers generally take up less space and weight than solid scavengers, but are
significantly less efficient. OPEX (operating expenditure) is increased compared to solid
scavengers, but liquid scavengers offer more options for retrofitting an existing facility.
Liquid scavengers can also be employed in two different processing schemes. After separation
of liquid hydrocarbons and water from the gas, the liquid scavenger can be either injected
directly into the gas stream or the system can be operated in a batch mode by passing the gas
through a vessel filled with the scavenger. Numerous tests have shown that the direct injection
method is much more efficient and has a lower capital cost. A typical direct inject flow scheme
is shown in Figure 3. The scavenger is injected into the pipeline through a nozzle and either a
static mixer or a long length of pipe mixed the gas/liquid mixture. The mixture is then separated
in a coalescing filter.
 Figure 3: Diagram of Liquid Scavenger Direct Injection Scheme.

Direct injection of liquid scavengers does have problems. First, the degree of gas/liquid contact
is dependent on the type of contacting device, the gas velocity and the residence time.
Consequently, the degree of mixing and hence efficiency is sensitive to changing gas flow. In
addition, positive separation of the gas and liquid must be achieved since the triazine can
interfere with the operation of a glycol dehydration unit by causing severe foaming.

As the most common triazine products are water-based, with water soluble and biodegradable
reaction products, the system has the potential for a relatively simple disposal option. In many
onshore and offshore operations, the amount of water requiring treatment is very large relative
to the amount of liquid scavenger consumed. Thus, the incremental cost of treating this
incremental, low-toxicity, biodegradable waste stream can be very small.

4. Liquid Redox

The iron-based liquid redox process has been continuously improved since it was first
introduced in the early 1980’s, with significant improvements in the areas of operation, capital
cost, and operating cost. Currently, the liquid redox of choice is the LO-CAT® process licensed
by Gas Technology Products. The liquid redox process employs aqueous-based solutions
containing metal ions, usually iron, which are capable of transferring electrons in reduction-
oxidation (redox) reactions. In the LO-CAT process, a non-toxic, chelated iron catalyst is
employed to accelerate the reaction between H2S and oxygen to form elemental sulphur.
All reactions take place in the liquid phase, and 99.9+ % removal efficiency of the H2S is
routine. When treating natural gas streams, liquid redox systems may treat the gas stream
directly or may treat the acid gas stream produced from an amine unit. The direct treatment
scheme is generally economical for low volume systems while the liquid redox (auto
circulation LO-CAT) scheme is more economical at higher flowrates or higher pressures. In
the past, much has been made about pressure limitations in direct treating high-pressure gas
with liquid redox. However, direct treat installations have demonstrated the ability of the direct
treat configuration to treat gas streams up to 900 p.s.i. pressure.

The liquid redox process operates at ambient temperature; consequently, the sulphur is
produced as a solid that is most often removed in the form of a filter cake that is 65% sulphur,
35% water. This sulphur product can be upgraded to a 99.9% pure molten sulphur product;
however, there is a significant unmet demand for the LO-CAT sulphur cake for the sulphur in
cake form makes a superior fertilizer product, acting as a soil amendment and plant nutrient.

Most liquid redox installations are in onshore processing facilities, though there have been
several successful offshore applications, including both new platform and retrofit installations.
However, the footprint and weight can be issues for applying this technology offshore. These
issues are being addressed through the development of modified mass transfer devices in the
oxidizer system, which promise to reduce capital cost and dramatically shrink the overall size
of the system.

The capital cost of the auto circulation LO-CAT is largely dependent on the amount of sulphur
being processed. The combination of operating and equipment costs, generally makes the liquid
redox systems economical up to 20 to 25 tons per day of sulphur, although much larger systems
have been installed, such as when the H2S concentration is too low for successful Claus
operation.
5. Claus Recovery System + Tail Gas Unit

Figure 3: Diagram of Typical Claus Sulphur Recovery unit (Triple Catalytic Converter).
CW= Cooling Water. HP= High Pressure. LP= Low Pressure. MP= Medium-Pressure.
BFW= Boiler Feed Water.

Claus systems are well established in oil and gas processing facilities, however, the process
has limitations at low capacities. In Claus recovery system, the overall reaction is carried out
in two stages, thermal and catalytic. In the first stage (thermal section), enough air is added to
oxidize only one-third of the incoming H2S to SO2. This reaction is highly exothermic and is
not limited by equilibrium. Reaction (1) occurs entirely in the combustion furnace.

H2S + 3/2 O2 → SO2 + H2O (1)

In the reaction furnace, the unburned H2S in the acid gas reacts with the produced SO2 to yield
elemental sulphur vapor. This reaction is referred to as the Claus reaction and is shown by
Reaction (2). This reaction is endothermic and is limited by equilibrium. Usually, 60–70% of
the total conversion of H2S to elemental sulphur is achieved in the thermal stage (Gamson and
Elkins, 1953; Opekar and Goar, 1966).
 2 H2S + SO2 ↔ 3/n Sn + 2 H2O (2)
Overall: 3H2S + 3/2 O2 ↔ 3/n Sn + 3 H2O (3)

In the thermal section, The hot combustion products from the reaction furnace flow through
the tubes of waste heat boiler (WHB) and are partially cooled to 315–426 °C (600–800 °F) by
generating high-pressure or medium-pressure steam. As the gases from the reaction furnace
are cooled in the WHB, the S2 sulphur vapor species shift through a number of exothermic
reactions to other sulphur species, primarily S6 and S8 (Goar and Fenderson, 1996).

The cooled gases from the WHB are further cooled to 171–191 °C typically (to 340–375 °F)
in the first sulphur condenser by generating low-pressure or medium-pressure steam, where
most of the sulphur vapor formed in the reaction furnace is condensed. The condensed
sulphur is separated from the gas and drained from the condenser through a hydraulic seal
and rundown line to the sulphur collection pit.

An interesting property of liquid sulphur is its increase in viscosity with temperature. This is
due to polymerization of sulphur at around 157°C (314 °F). Therefore, the temperature of
condensed sulphur should be closely monitored to prevent polymerization and clogging of
pipes used in the process. Care must also be taken in order not to pass condensed sulphur
through the catalyst, which would become fouled and inefficient. Liquid sulphur adsorbs to
the pores and deactivates the catalytic surface. Therefore, reheat stages using the previously
generated steam are needed in order to keep the sulphur in gas phase.

In a well-run unit up to 90% of the sulphur can be formed by non-catalytic means in the
combustion furnace. While the scavenger and liquid redox systems operate at ambient
temperatures, the Claus reactions require high temperatures with the combustion furnace
operating at approximately ranging from 980 to 1540°C (1800 to 2800°F) with pressures rarely
higher than 70 kilopascals (kPa).

The catalytic section has three processing steps. The first is the reheater step, which raises the
temperature of the gas from the sulphur condenser to avoid condensation of sulphur vapor, as
sulphur continues to form by the Claus reaction. Typically, the first reheater is required to
increase the temperature to about 315°C (600 °F), which is necessary to promote the
destruction of COS and CS2 by converting it to H2S in the first catalytic stage in which these
side products were produced in the thermal reactor. The hydrolysis of carbonyl sulphide (COS)
and carbon disulphide (CS2) reaction is as shown below:

COS + H2O → CO2 + H2S (4)

CS2 + 2H2O → CO + 2H2S (5)

In the second step, the hydrogen sulphide and sulphur dioxide are reacted over an activated
alumina catalyst in a series of catalytic reactors which usually consists of 1 to 3. The catalytic
reactors operate at lower temperatures, ranging from 200 to 315°C (400 to 600°F). Other
catalysts may be used to promote COS and CS2 destruction such as . Alumina itself is same as
Titanium dioxide (TiO2) to have COS and CS2 destruction function, and its sulphate resistance
is better than alumina. The catalyst with TiO2 as the carrier has a great activity, and high
mechanical strength at low temperature. Although the specific surface area of TiO2 is low, the
price is high.

The first catalyst used historically in a commercial low-temperature converter was made of
active carbon stabilized with about 6.6% silica (Krill, 1973). The carbon catalyst had a very
high surface area of more than 1000 m2/g and a large pore volume. Currently, the catalyst used
for the Claus process is the active alumina catalyst. This material offers several advantages
over carbon (Cameron, 1974) such as a lower regeneration temperature is needed, lower plant
capital cost results from the use of a carbon steel vessel, which is satisfactory at the lower
regeneration temperature. Also, the greater mechanical strength of alumina reduces the
consequences of attrition and alumina exhibits better catalytic stability.

The Claus reactions in the catalytic section are slightly different from the thermal section
reaction. The following reversible reaction occurs over activated alumina in a catalytic reactor:

2H2S + SO2 ↔ 3/n Sn + 2H2O (6)

n = 6,8

In the following, physical properties of each reactants in the catalytic section are shown.
 Component Molecular State Molar Mass Boiling Melting
Formula (g/mol) Point (°C ) Point (°C )
Hydrogen H2S Colourless 34.1 -60 -82
sulphide chalcogen
hydride gas

Sulphur SO2 Colourless 64.066 -10 -72

dioxide gas

Table 1 : Physical description of components for hydrogen sulphide and sulphur dioxide
reaction in the catalytic converter (reactor) of Claus process.

Reactions (2) and (6) use the same reactants to produce different forms of sulphur and under
different thermal conditions. Reaction (2) produces S or S2 in the high temperature zone of the
reaction furnace and is endothermic by nature. Reaction (6) produces S6 and S8 at a much
lower temperature in the catalytic beds and is exothermic.

In the third step, the sulphur condenser is used to remove liquid sulphur, the product of reaction.
This shifts the equilibrium so that further reaction may take place in the next catalytic converter
(reactor). The final sulphur condenser is typically at 132°C (270 °F) to minimize sulphur vapor
losses in the vent gas (Goar and Fenderson, 1996). The effluent (tail) gas, which still contains
appreciable amounts of sulphur compounds and a small amount of sulphur as vapor and
entrained liquid, is routed either to a tail gas treating unit (TGTU) for further sulphur recovery
and minimizing impacts on the environment or to a thermal oxidizer to incinerate all the sulphur
compounds in the tail gas to sulphur dioxide before dispersing the effluent to the atmosphere.

The sulphur recovery depends on such things as feed composition, age of the catalyst, and
number of reactor stages. Typical sulphur recovery efficiencies for standard Claus units are
90–96% for a two-stage catalytic conversion and 95–98% for a three-stage catalytic
conversion. Although there are thousands of Claus units in operation today, the process does
have some drawbacks and limitations. The process produces extremely harmful and toxic gases
such as COS and CS2 where it may cause serious health problems if released into the
environment or if not completely destroyed in the reaction. They are normally regarded as a
significant poison which can cause the deactivation of the catalyst. Even only a trace amount
of COS and CS2 can result in the deactivation of catalysts and can lead to corrosion of reaction
equipments. Also, since it is a combustion process, Claus units can only process acid gas
streams. Combustible components other than H2S make it impossible to control the SO2/H2S
ratio, which is critical to good Claus operation. In addition, acid gas streams containing less
than 15–20% H2S are very difficult to process requiring more elaborate Claus processing
schemes. Moreover, this process requires multiple reactors in order to convert H2S to liquid
sulphur which highly affects the capital expenditure of the process as well it requires high
temperature and pressure to operate in which would increase the operating expenditure . Lastly,
because of equilibrium limitations and other sulphur losses, overall sulphur recovery efficiency
in a standard Claus unit is typically limited to 98% (Lagas et al., 1989).
Process Selection

Natural gas processing in the future will encounter significantly more raw sour gas, for
instance, gas containing 15 to 20 mol % H2S or greater. Deciding whether to make the
significant investment to build a sour gas treating and sulphur recovery plant involves many
considerations. An operator selecting the optimum gas treating, sulphur recovery, and tail gas
clean-up processes must choose each carefully because each upstream step can affect design
and operation of subsequent downstream steps. Major factors that affect the selection of an
overall gas-processing scheme are the following:

 Plant design capacity and expected throughput

 Concentration of sour components in the raw gas
 Gas contactor treating pressure
 Ratio of H2S /CO2
 Permissible CO2 content in the sales gas
 Presence of trace sulphur compounds (COS, CS2, mercaptans, etc.)
 Tonnage of sulphur to be recovered
 Overall sulphur recovery efficiency (%) to be achieved to meet local environmental
regulations.

Reviewed here are current as treating and sulphur recovery processes in use today.
THIPOAQ Process

Advantages

Reliability

 Less equipment compared with conventional desulfurization processes.

 No plugging or fouling problems because of the biological sulphur’s hydrophilic
nature.
 Use of thiobacillus bacteria, which are naturally occurring, robust, self-sustaining, and
self-regulating.
 Reliable operation of more than 150 low-pressure systems worldwide.
 Replacement of amine treating, Claus recovery and tail gas treatment or alternatively
liquid redox processes.
 Minimal chemical consumption.
 Gas treatment as well as sulphur recovery.
 99.99% H2S removal for gas streams.
 100% conversion of sulphide in the bioreactor with 95-98% selectivity to S°.
 No deactivation of the biological catalyst.

Simplicity of operation

 Easy-to-control operating parameters.

 Minimal supervision requirements.
 Massive buffering capacity that minimizes the impact of upsets.
 Wide turndown in gas flow and H2S inlet concentration.

Low operating costs

  Much lower chemical makeup compared with alternative aqueous technologies.
 Less equipment to maintain and operate compared with conventional amine or Claus
technology. The process operates at ambient temperature and does not require
equipment such as burners and reboilers. The regeneration and sulphur recovery
section always operates at ambient pressure and temperature.
 The expensive chemicals required for liquid redox processes are not necessary; only
sodium hydroxide and nutrients are required.

Simplicity of design

 Operation at low inlet pressures.

 Integration of gas purification and sulphur recovery in one process.
 Elimination of the need to filter carbon or particulates.
 Process regeneration that does not require heat.

Intrinsic safety

 H2S not concentrated at any time during the process.

 H2S physically bound to the gas scrubbing solution.
 There is no free H2S available anywhere downstream the scrubber inlet, therefore the
unit is very safe and easy to manage.

Environmental consciousness

 Air vent gas with less than 1-ppm H2S.

 Sulphur slurry and cake that can be used as fertilizer.

Disadvantages

Solid Scavengers