A MORE EFFICIENT AND EFFECTIVE IRON BASED H2S SCAVENGER

Laurance Reid Gas Conditioning Conference

February 25-28, 2019 – Norman, Oklahoma USA

Mike Callaway
H2SZERO, LLC
14724 Lone Star Road
Sapulpa, Oklahoma USA 74066
+1 918-384-9600
mcallaway@h2szero.com

Chad Dainty
H2SZERO, LLC
14724 Lone Star Road
Sapulpa, Oklahoma USA 74066
+1 918-978-7509
cdainty@h2szero.com

ABSTRACT
The use of iron oxide based H2S scavengers have been used in various forms for approximately
140 years. Iron oxide coated on wood chips (IRON SPONGE) may be the oldest method most of
us can remember. Iron oxide coated on clay, developed in the 1990’s, was a huge improvement.
However, it has drawbacks with run times and difficult clean outs.
H2SZERO is a granular iron oxide based H2S scavenger that has proven to be a superior process.
It is based on 100% active forms of iron oxides/hydroxides. This process has predictable
performance and does not agglomerate which allows for much easier clean outs. It can be used to
scavenge H2S from dry or water saturated gas. The spent product is non-pyrophoric, non-
hazardous, passes the TCLP test and can be placed in most landfills. H2SZERO technology has
been proven to remove not only H2S but other sulfur compounds such as mercaptans from gases
and hydrocarbon liquids.
This paper will give specific examples of laboratory data on relative reaction rates of competitive
products. The case studies of actual field applications will demonstrate the improved economics
and ease of use when removing various sulfur compounds from gases and hydrocarbon liquids.
A MORE EFFICIENT AND EFFECTIVE IRON BASED H2S SCAVENGER

Mike Callaway, H2SZERO LLC, Sapulpa, OK, USA

Chad Dainty, H2SZERO LLC, Sapulpa, OK USA

Introduction

During the 2017 Laurance Reid Gas Conditioning Conference, there were several papers that did
an excellent job at addressing the removal of low levels of H2S from sour gas. During the
Fundamentals part of the conference, two sections of the presentation, titled “Solid Scavengers”
by Dennis Leppin1 and “Liquid Scavengers” by Bud Warren2, offered tremendous insight into
scavenging technology. Later in the conference, Marcus W. Schulz’s3 paper, titled “The New
World of H2S Scavenging Applications,” continued to pull the curtain back on available techniques
and applications involving the removal of H2S from sour gas.

The purpose of this paper is to provide some additional information on the topic of “Solid
Scavengers,” with the intent of targeting applications that produce 2,000 lbs. or less of sulfide
contaminants per day. The additional information herein will hopefully offer some new insights,
methodologies, and evaluative criterion for addressing treatment methods for the removal of
sulfide contaminants from sour gas streams, as well as sour liquid hydrocarbon streams.

History

Both solid and liquid scavengers are utilized to remove sulfides from streams with 2,000 lbs. or
less of sulfide contaminants per day. For the purposes of this paper, an analysis of the pros and
cons of each methodology will not be discussed. Nevertheless, some overview of the two is
provided.

Liquid Scavengers

Liquid scavengers most commonly use a product called triazine, which is a commodity chemical
made from monoethanolamine (MEA) or methylamine (MA) reacted with formaldehyde.
Different vendors offer a range of proprietary formulations. These chemicals can be utilized in
various configurations, but some of the most common are direct injection, “bubble towers,” and
multiple contact towers with packing and re-circulation.

Direct injection of liquid scavenger occurs when the scavenger is atomized directly into the flow
lines. This is accomplished with a metering system and a storage container of liquid scavenger.

A bubble tower is basically a cylindrical vertical vessel that is filled with liquid triazine. The gas
is introduced from the bottom and “bubbles” up through the triazine. As the gas “bubbles” through
the triazine, the chemical reaction occurs removing the H2S, and the “sweet” gas exits the top of
the vessel.
In basic terms, the multiple towers/packing/re-circulation method is a stand-alone unit that houses
storage tanks of liquid scavenger. The liquid scavenger is metered and pumped into the gas stream
based on constant monitoring of the H2S concentration present in the gas stream. The liquid
scavenger reacts with the H2S and chemically removes it from the gas stream.

Solid Scavengers

Deployed technology in the “solid scavenger” marketplace has remained relatively static over the
past century. While there have been, and currently are, several other commercial technologies
available, there have been two main technologies which have historically dominated the solid
scavenger market:

IRON SPONGE – by Connelly-GPM Inc.4

SulfaTreat – by Schlumberger5

Both technologies are based on the reaction of iron oxide with H2S to sweeten gas streams, as is
shown in the following equation:
Fe2O3 + 3H2S = Fe2S3 + 3H2O (Equation 1)

Technology providers for both the IRON SPONGE and SulfaTreat either require or prefer that the
gas stream be at or near water saturation entering the treatment system.

Additionally, with both the IRON SPONGE and SulfaTreat, the iron oxide is present on an inert
support substrate base.

IRON SPONGE has been utilized in the oil and gas industry for well over 100 years. At the time
of its introduction, IRON SPONGE represented a considerable evolution as a product and process
for the removal of H2S from sour gas. For IRON SPONGE, the support substrate is traditionally
wood chips.

SulfaTreat was first introduced in 1990 and deployed the iron oxide on a support substrate of
calcined clay. At the time, this new deployment methodology represented a very large step
forward over other technologies. SulfaTreat provided users with an improved experience in the
form of longer comparative run times. These improved run times resulted from an increased
capacity, which was due in large part to the fact that each granule of SulfaTreat contained more
iron oxide, comparatively, than IRON SPONGE. These longer run times equated to less clean
outs, ultimately giving the customer a reduced cost per treated mcf of gas.
 Surface Reactive Iron Oxides

With reactive iron oxides present as simply surface coatings, reaction speeds and capacity are
somewhat limited. Having only surface reactive iron oxides available for process improvement
proved a challenge for developing the next step forward in solid scavenger-based products,
systems, and economics.

Fixed bed pressure vessels, sometimes called contact towers, had to be sized to achieve certain gas
flow velocities through the solid scavenger that would allow for the scavenger reaction to take
place. This resulted in system designs with large diameter vessels to achieve targeted velocities.

Pressure vessel height was also a factor. Where vessel diameter is correlated to velocity, vessel
height is directly correlated to length of run time. Large vessel heights were required to maximize
the length of time between scavenger replacement.

Gas capacity was also a consideration. In the event that a significant amount of gas needed to be
treated, the velocity and bed height requirements of surface reactive iron oxides additionally
necessitated a system design with large banks of vessels, configured either in parallel, utilizing
flow control, or series.

Despite these system design elements, both the IRON SPONGE and SulfaTreat technologies
provided tremendous economic benefits to sour gas producers in the form of increasingly lower
treated cost with every step forward in product development.

Still, being constrained to only surface reactive iron oxide proved challenging in developing the
next significant step forward in product capability.

New Era – 100% Reactive Media

For nearly a decade, H2SZERO has been deployed both domestically and internationally, offering
not only a leap forward in product development, but also system design and economics.

Although still based on iron oxides, this new technology converged three new landmark
methodologies and strategies for how the media construction is approached.

By eliminating the inert support substrate, now 100% usage of the solid scavenger material is
possible. This means 100% of the media is available for reaction, allowing for the maximum
return on investment.
Secondly, this new technology introduced manipulation of the iron oxide particles involved in
constructing the media. Having the ability to construct iron oxide particles in the nanometer range
makes it now possible to manipulate:

- Surface area
- Hardness
- Water resistance
- Porosity, and
- Bulk density
…of the finished product.

Finally, the H2SZERO technology incorporates several forms of reactive iron oxides, such as ferric
hydroxide [Fe(OH)3] and iron oxyhydroxide [FeO(OH)], along with non-crystalline (amorphous)
structures. X-ray analysis confirms that H2SZERO is approximately 60% amorphous non-
crystalline iron forms, with approximately 40% being traditionally crystalline iron forms. The
precise role that the 60% amorphous non-crystalline structures have on the overall performance of
H2SZERO requires further study.

This potent combination of 100% active material, particle manipulation, and incorporated unique
forms of iron oxides, makes possible a leap forward in product development, offering a new era
of system design and economic impacts.

In order to help quantify and illustrate this leap forward, standardized tests were performed to
better understand the performance of H2SZERO and its competitors. The testing utilized the
following:

Standardized vessel
Standardized volume of media
Standardized pressure
Standardized gas flow rate
Standardized inlet gas mixture – 2,000 ppm H2S, 1% CO2, balance N2

The outlet H2S concentration was then measured over time for H2S breakthrough. The outlet H2S
concentration is indicative of the speed at which the media is able to remove H2S from the stream.
This test is intended to mimic real life applications; 4 ppm H2S is the generally accepted pipeline
sales specification for H2S, and the test is considered to be over once the outlet H2S concentration
exceeds that level.
Two commercially available competitive scavengers were tested in this manner against the
H2SZERO technology, with the following results:
Table 1 - Comparative Performance Test

Product Time @ 0 ppm Test End Notes

Competitor A N/A 1300 ppm @ 0 min. Was never able to be at 0 ppm
outlet H2S
Competitor B 3 min. 250 ppm @ 5 min. Breakthrough curve was instant
H2SZERO 60 min. 10 ppm @ 190 min.

The results are reflected in the following chart.

The left-hand axis shows the results for Competitors A and B. The right-hand axis shows the results
for H2SZERO.

Figure 1 - Comparative Performance Chart

The results clearly indicate that the reaction speed of H2SZERO is significantly higher than other
competing solid scavengers as it can sustain the desired treatment at a given gas velocity. The
competing products can remove only 30-80% of the incoming H2S, indicating slower reaction
kinetics and lower treating capacity.

Gas flow velocities through the solid scavenger bed are correlated to vessel diameter. The ability
to utilize 100% reactive iron oxides in combination with unique iron oxide forms enables the
scavenger reaction to happen at a much faster rate. A media with faster reaction rates enables
treating at higher gas velocities through the media bed, facilitating smaller diameter vessels. For
the same gas flow rate, the ability to treat the same amount of gas by deploying a smaller diameter
vessel is an economic advantage for producers.

Vessel height is directly correlated to length of run time. The ability to utilize 100% reactive iron
oxides in combination with unique iron oxide forms now enables increased scavenger capacity,
translating to run times that can be in excess of 3-5X those of other available technologies. For
the same gas flow rate, the ability to produce 3-5X amount of gas in the same height vessel, or a
comparable amount of gas in a shorter vessel, is an economic advantage for the producers.

System design to maximize gas treating capacity is still a consideration. Since the H2SZERO
reaction rate is higher than other commercial offerings, large “parallel design” or “series designed”
systems can now either facilitate:

- Much higher produced volumes, or

- Same volumes with much smaller equipment.

Scavengers that have a slow reaction speed circumvent this product hurdle with system design.
Multiple vessels must be utilized in a system design to slow gas velocity through the media beds.
This is accomplished by either employing very large diameter vessels or multiple vessels,
sometimes both. While this situation provided some economic benefits over previous
methodologies, it can still be capital intensive and operationally cumbersome.

Conversely, a product with an extremely fast reaction rate positively impacts both system design
and economics. Systems can now be designed with smaller diameter vessels, often without the
need for multiple vessels. Increased capacity also means longer run times, resulting in longer
intervals between vessel clean outs. All of these system design factors culminate in beneficial
economic impacts from reduced capital and operating expenses.

Competing iron oxide scavenger providers either require or prefer that the inlet gas stream be at or
near water saturation entering the treatment system, on the premise that water saturation improves
reaction efficiency. This can require additional capital and operational expenses in cases where
the stream being treated is not water saturated. H2SZERO is able to break from this because of its
faster reaction rates. Testing has demonstrated that H2SZERO can perform in saturated or dry gas
and deliver similar performance results. This is a significant benefit in applications where the
stream being treated is not water saturated, as downstream dehydration can be avoided, and water
consumption can be minimized.
 Additional Sulfur Species

Further testing has revealed that H2SZERO can also scavenge other sulfur species, including, but
not limited to, mercaptans. To support these findings, a lab test was conducted in the following
manner:

A fixed amount of H2SZERO media was loaded in a pressure vessel and contacted with an inlet
gas stream consisting of:
Table 2 - Mercaptan Test Inlet Stream

Mercaptan Concentration
Methyl 10.73 ppm
Ethyl 10.28 ppm
iso-Propyl 10.83 ppm
n-Propyl 10.41 ppm
iso-Butyl 10.95 ppm
n-Butyl 10.93 ppm

…with the balance of the inlet gas being methane. This inlet gas stream was at a constant flow
rate of 24.42 scfd.

Similar to the previously described test, the goal was to see how effectively H2SZERO would
remove these specific mercaptans from the gas stream, as measured by the outlet gas
concentrations of each of these mercaptans. It would have revealed if H2SZERO targeted a
specific mercaptan over another, and how effectively H2SZERO was able to scavenge those
mercaptans at these parameters.
The testing lab indicated that most iron oxide-based scavengers do not work well for removing
mercaptans and were quite surprised by the ability of this new technology. From the test results,
one can see that H2SZERO lasted 24 hours scavenging 100% of all the mercaptans. The test was
stopped at 24 hours because of the expense of the inlet gas, leaving some question as to the
continued ability of H2SZERO to effectively remove these contaminants under these conditions.

Figure 2 - Extended Mercaptan Study

One of the advantages of iron oxide-based scavengers has been, and continues to be, the fact that
both the new, as well as the spent, scavenger is non-hazardous. Once the scavenger is spent and
has been removed from the pressure vessel, it can be disposed of, in most cases, at a municipal
landfill. This assumes that the scavenger has only been exposed to sulfides during its time in
service. H2SZERO also maintains this advantage, being non-hazardous before and after,
permitting disposal of spent H2SZERO in a municipal landfill.

The only time that any iron oxide-based scavenger becomes hazardous is if it is exposed to some
kind of hazardous material during service that is not chemically transformed to an inert compound.
For instance, if mercury was present in the gas stream that is being scavenged, then of course the
scavenger would adopt some of the mercury, thus making the scavenger hazardous.

One of the chief concerns among customers has to do with cleaning out the vessel when the
media is spent. Because H2SZERO delivers a performance advantage in extended run times, the
customers naturally want to know if the increased service time correlates to a more difficult
clean out.
This concern has been deeply ingrained in iron-oxide users over a long period of time because
traditionally iron-oxide scavengers have the tendency to agglomerate, or “brick up,” inside the
vessel. This naturally lends itself to very difficult clean outs involving days and many man hours.

In the case of H2SZERO, the same physical characteristics that enable improved performance are
what also make possible the ease of clean out. Higher water resistance and hardness, as well as
the lack of an inert substrate, mean that H2SZERO is easily fluidized, facilitating quick and easy
cleanouts, no matter the length of service.

A vast majority of applications can be cleaned out and refilled in one day, with a semi-experienced
crew. Ease of clean out means faster vessel turnaround, meaning less money spent on crews and
less production down time.

Case Studies

The following case studies are presented to illustrate the performance improvement offered by the
latest solid scavenger development, which enables a shift in system design and economic impact.

Case Study #1

H2SZERO can be used as a direct drop-in replacement for competitive solid scavengers. That was
the circumstance in this case study for natural gas treatment, offering a head to head comparison
with the same gas flow and composition in the same vessels.

This case study highlights the longer run times afforded by deploying H2SZERO in place of other
competitive materials. In this particular case, the H2SZERO ran approximately 5.6x longer that
the competitive material. This is significant in that just by utilizing H2SZERO technology in their
existing vessels, the customer saved roughly 4 cleanout and refill cycles compared to what they
were previously doing.

Anytime a cleanout and refill cycle is saved, the customer saves not only on time being down (not
producing), manpower, and resources, but also in disposal costs for the spent media. By simply
switching to H2SZERO, this customer had a 4x decrease on disposal.
Table 3 - Case Study #1

Flow rate 1,050,000 scfd

Pressure 57 psi
Temperature 77 F
Inlet H2S Concentration 400 ppm

Previous run time (to 4 ppm outlet) 43 days

H2SZERO runtime (to 4 ppm outlet) 242 days

Net run time improvement 5.6x

Case Study #2

In similar fashion to Case Study #1, this second case study is also a head to head comparison
utilizing the same gas flows and compositions, and the same vessel in a natural gas treating
application. For customers that already have solid H2S scavenging systems in place, the effort to
take advantage of the numerous economic advantages is minimal.

This case study also demonstrates the extended run times the H2SZERO technology is able to
deliver to the customer. In this application, with the inlet H2S concentration being 1,200 ppm, the
competitive material was only able to achieve pipeline sales spec (4 ppm or lower) for 21 days.
By simply switching over and filling their existing vessel with H2SZERO, the customer was able
to achieve pipeline sales spec for 125 days, almost a 6x improvement.

This means that with H2SZERO, this customer only had 3 vessel turnarounds a year, compared to
17 vessel turnarounds a year.
Table 4 - Case Study #2

Flow rate 100,000 scfd

Pressure 80 psi
Temperature 90 F
Inlet H2S concentration 1,200 ppm

Previous run time (to 4 ppm outlet) 21 days

H2SZERO run time (to 4 ppm outlet) 125 days

Net run time improvement 5.9x

Case Study #3

For this 3rd case study, the scope of the comparison is much broader. This customer had been
treating their natural gas stream with liquid triazine being deployed though the multiple
towers/packing/re-circulation method. The first comparison here is solid vs. liquid treating. While
beyond the scope of this paper, there are significant advantages to a solid system over a liquid
system, not only from a chemistry perspective, but also from a hardware and intangibles
perspective.

Once the H2SZERO system was deployed, the customer was able to realize the economic benefit
offered by the technology. Just from a pure treated cost vantage, the annualized savings were
about 55%, or around $204,000. This savings more than covered the cost to switch from liquid
treating to solid treating. When all of the other systemic / qualitative benefits of solid scavenger
treating were added to these quantitative savings, the end result was not only increased
profitability, but also system-wide increased level of asset efficiency.
 Table 5 - Case Study #3

Flow rate 2,000,000 scfd

Pressure 1,300 psi
Temperature 82 F
Inlet H2S concentration 455 ppm

Previous cost/mcf $0.51 USD

H2SZERO cost/mcf $0.23 USD

Net savings/mcf 55%

Case Study #4

Case study #4 demonstrates H2SZERO’s ability to operate and remove H2S from an amine unit
acid gas stream.

This solid scavenger system with H2SZERO has been removing the H2S down to 0 ppm for well
over a year now.
Table 6 - Case Study #4

Flow Rate 90,000 scfd

Pressure 15 psi
Temperature 120 F
Inlet H2S concentration 1,800 ppm

H2SZERO cost/mcf $0.88 USD

New Applications – Liquid Hydrocarbon Streams

Traditionally, iron oxide-based scavengers have not been used in treating liquid hydrocarbon
streams, in large part due to the insufficient reaction speed. Low reaction speed, combined with
the multiple sulfur species usually present in hydrocarbon streams, meant that what little activity
was available was quickly used by all of the sulfur species, resulting in minimal effectiveness in
such applications.

The higher reactivity of H2SZERO means that more diverse treating applications have found a
good fit with the technology. The increased speed, and the lower media cost compared to more
exotic scavengers, like mixed metal oxides, have made way for H2SZERO to make impacts
treating liquid hydrocarbon streams.
The combination of 100% reactive media incorporated with the unique forms of iron oxides makes
possible scavenging various other sulfur compounds, including but not limited to mercaptans, from
liquids such as propane and NGLs, establishing a shift in system design and economic impact for
liquid hydrocarbon streams and NGLs.

Case Study #5
H2SZERO was deployed in a propane treating (copper strip test) application, where 250,000
barrels of propane were stored in an underground storage cavern. 8,000 # of H2SZERO treated
the entire storage volume, delivering a 0 ppm outlet specification.

Conclusions

H2SZERO offers new breakthroughs in product development, providing the opportunity to

orchestrate significant leaps forward in process improvement. The technology affords the ability
to treat more gas and more liquid at higher efficiencies and with less infrastructure than competing
scavengers. The culmination of a product influencing system design and therefore economic
opportunities all fuse together in delivering, in most instances, the lowest treated cost per mcf (or
barrels) currently available today.
 REFERENCES

1. Leppin, Dennis (2017). “Solid Scavengers.” 67th Annual Laurance Reed Gas Conditioning
Conference, February 2017
2. Warren, Bud (2017). “Liquid Scavengers.” 67th Annual Laurance Reed Gas Conditioning Conference,
February 2017.
3. Schultz, Marcus W. (2017). “The New World of H2S Scavenging Applications.” 67th Annual Laurance
Reed Gas Conditioning Conference, February 2017.
4. IRON SPONGE - http://www.connellygpm.com/ironsponge.html
5. SuflaTreat - https://www.slb.com/services/production/production-technologies-chemicals-
treatments/CURE-technologies/hydrogen-sufide-mercury-adsorbents/hydrogen-sulfide-
removal-from-gas.aspx