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Small Capacity Sulfur Recovery Units

Gary J. Nagl
Merichem

Introduction

In the good old days, natural gas production was a lot easier. Gas was
relatively plentiful, easy to find, and sweet. Today, it is generally accepted
that natural gas production is becoming more sour. Gas sweetening
technologies tend to be expensive, which can be especially troublesome for
the small natural gas producer. This paper examines the natural gas
sweetening technologies at the small capacity end of the spectrum, and
the issues involved in selecting one method versus another.

Small capacity for the purpose of this paper is defined as less than 20
tonnes per day of sulfur production. Above 20 tons per day of sulfur, amine
gas sweetening units in conjunction with catalytic Claus type reactors are
generally the process scheme of choice, with some notable exceptions. The
most notable exception is the processing of very dilute acid gas streams.
CO2:H2S ratios above 5:1 can become troublesome for the Claus reactor.

The processes of choice for small capacity applications tend to be solid and
liquid scavengers, which have non-regenerable reaction systems, aqueous
iron-redox based systems, which are regenerable catalytic systems, and
certain gas phase catalytic processes, which are at various stages of
development. Selection of the best technology for a given situation need to
examine factors well beyond the capital and operating cost of the process
itself, and evaluate factors such as operational simplicity, operator attention,
footprint and weight, and waste generation and disposal costs.
Solid Scavengers

Solid scavengers are generally iron-based materials. The original solid-


scavenger was iron-sponge, which consists of hydrated ferric-oxide
impregnated on wood chips. The ferric oxide reaction can be characterized
by the following equation:

2 Fe2O<sub">3 + 6 H<sub">2S 2 FeS + 2 H2O (1)

This process works very well until the media becomes spent and needs to be
changed. Unless kept wet, the iron sulfide will react exothermically with
oxygen in the air and cause the wood media to catch fire. Due to safety
concerns, iron-sponge has fallen from favor in the gas processing industry.
The solid scavengers employed in the industry today, such as Sulfa-Treat
and SULFUR RITE use an iron oxide, which reacts with H2S to form
innocuous iron pyrite as the reaction product. Unlike iron sulfide, iron pyrite
is not pyrophoric.

The design of the solid scavenger system is dependent on the mass flowrate
of the H2S 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
doesnt require any involvement, as the media will simply react with
whatever H2S is in the gas stream.

One design decision facing the operator deals with the reactor configuration
and associated operating costs. The decision was whether to use a single
reactor vessel, or a dual vessel, lead-lag configuration.
In a single vessel configuration, when the catalyst is spent, and H2S
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 1. 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.

In a properly operating solid scavenger system, approximately 5 pounds of


spent media is required per pound of H2S removed. This equates to a media
cost of about $3.50 per pound of H2S removed. As the spent media is stable
iron-pyrite, the waste generated is non-hazardous and typically disposed of
in a landfill. This is generally not a problem in the Western Hemisphere, but
is a big problem in Europe and parts of the Far East where disposal in landfills
is severely restricted.

Media change-out can typically be done in a day. This can be a messy


operation with high pressure water hoses required to cut the spent material
out of the vessel, but the infrastructure for media changeout is well-
developed in the Western Hemisphere with a number of service companies
capable of performing this operation.

Solid scavenger systems are very common onshore. However, logistics and
media changeout have prevented broad use of this system on offshore
platforms. The cost of shipping fresh and spent media to and from the
platform, and the space requirement for vessel changeout are issues. Vessel
size for sweetening dilute gas streams is also an issue.

One potential application for the solid scavenger on offshore platforms is


potentially the sweetening of the gas required to power the platform. In this
case, only a limited amount of gas needs to be processed, limiting the vessel
size and media consumption and the simplicity of the solid scavenger system
become a major advantage. For this application, Gas Technology Products
has designed SULFUR RITE systems where the entire vessel is replaced on
the platform. The vessel with the spent media is shipped to shore where
fresh media is installed, and the vessel is readied for delivery back to the
platform.

Liquid Scavengers

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 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(1) 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 2. 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.

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. In
the North Sea, spent liquid scavenger is dumped directly into the sea.

Assuming efficient mixing and efficient reaction, the cost of the liquid
scavenger can range from a low of $5/pound of H2S to $15/pound. This
relatively high chemical cost can often be offset by the low capital cost and
often small incremental disposal costs.

The combination of low capital, particularly in the direct injection scheme,


simple logistics, and simple wastewater treatment has made this scheme a
favorite for gas treatment offshore where there is a very small amount of H2S
that needs to be treated. The same feature can be just as attractive onshore
as well.

An indicative capital cost comparison of solid and liquid scavengers is shown


in Figure 3 as a function of gas flowrate.
Liquid Redox

The iron-based liquid redox process has been continuously improved since it
was first introduced in the early 1980s, with significant improvements tin
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 sulfur.

H2S + O2 So + H2O (2)

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 amine/liquid redox (autocirculation 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


sulfur is produced as a solid that is most often removed in the form of a filter
cake that is 65% sulfur, 35% water. This sulfur product can be upgraded to a
99.9% pure molten sulfur product; however, there is a significant unmet
demand for the LO-CAT sulfur cake in North America for the sulfur in cake
form makes a superior fertilizer product, acting as a soil amendment and
plant nutrient. Registrations of the product as a fungicide is underway and
tests show very promising results. Commercial activities are also in process
to expand this fertilizer business to parts of Europe.

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.

Compared to scavenger systems, liquid redox systems are relatively


expensive to install but very inexpensive to operate. Total operating costs
(utility + chemicals) usually range between $0.13/pound of sulfur and
$0.16/pound of sulfur. A diagram of the autocirculation LO-CAT is shown in
Figure 4.
The capital cost of the autocirculation LO-CAT is largely dependent on the
amount of sulfur being processed. Approximate capital costs for
autocirculation LO-CATs are illustrated in Figure 5. The combination of
operating and equipment costs, generally makes the liquid redox systems
economical up to 20 to 25 tons per day of sulfur, although much larger
systems have been installed, such as when the H2S concentration is too low
for successful Claus operation.

Claus Systems

Claus systems are well established in oil and gas processing facilities;
however, the process has limitations at low capacities. The Claus process
converts H2S to elemental sulfur by the following reactions:

H2S + 3/2 O2 SO2 + H2O (3)


2 H2S + SO2 3 So + 2 H2O (4)
Overall: H2S + O2 So + H2O (5)

The Claus system consists of a combustion furnace followed by two or three


catalytic reactors with intermediate cooling and reheating. Reaction 3 occurs
entirely in the combustion furnace while reaction 4 occurs in the combustion
furnace and the subsequent reactors. In a well run unit up to 90% of the
sulfur 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 1830F and the catalytic
reactors operating at approximately 725F. Unfortunately, the chemical
equilibrium of reaction 4 towards the formation of elemental sulfur is favored
at low temperatures; consequently, the overall conversion to sulfur is limited
to 9597% depending on the number of catalytic reactors. To achieve higher
removal efficiencies a tail gas cleanup unit is required.

Although there are thousands of Claus units in operation today, the process
does have some drawbacks and limitations. 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 1520% H2S are very difficult to process requiring more elaborate Claus
processing schemes. Ammonia also presents plugging and corrosion
problems, which require special design and operating techniques to
overcome.

Summary

Each application for sulfur removal will have a unique set of circumstances.
However, the first screening criteria in the selection of the most cost
effective sulfur removal technology is likely to be sulfur removal capacity. In
cases where the application can economically be served by more than one
technology, other factors to be considered are: the end users sensitivities to
capital vs. operating costs, operator involvement, sulfur movements and
disposal of waste streams. As a rule of thumb, systems with less than 200
kg/day of sulfur should employ scavengers, while systems with greater than
20 tons per day should employ amine/Claus/tailgas systems. Anything in
between should seriously consider liquid redox.

These findings are summarized in the following selection table

SULFUR REMOVAL SELECTION TABLE


Liquid Solid Liquid Amine + Claus + Tailgas
Scavenger Scavenger Redox
Gases treated
Acid gas Yes Yes Yes Yes
Natural gas Yes Yes Yes No
Turndown Not Not Sensitive
Sensitive
sensitive sensitive
Products streams Biodegradable Non- Sulfur cake for Pure
liquid hazardous fertilizer sulfur
solid
Costs
Operating $10/lb. of S $3.50/lb. of S $.15/lb. of S Very small
Equipment Low Moderately Moderately High
Low High
General 100 lb. of sulfur 300 lb. of Less than 20 tons Greater than 15 tons per day of
application per day sulfur per day per day of sulfur sulfur and greater than 15% H2S
guidelines