PRODUCTION TECHNOLOGY

Cost-effective scavengers for H2S mitigation

reduce problematic solids in production equipment
NON-triazine-based scavengers decrease
the occurrence of amorphous polymeric
dithiazine solids, providing a best value-
driven chemical solution to mitigate H2S
issues in the field.
ŝŝDR. JONATHAN WYLDE and DR. GRAHAME TAYLOR,
Clariant Oil and Mining Services
The removal of hydrogen sulfide (H2S) from produced gas,
oil and water has been a challenge to producers for many years.
H2S is a highly toxic, corrosive and undesired component,
produced alongside both liquid and gaseous hydrocarbons. It
originates from either biological or geological processes, which
occur in the reservoir formation over long periods of time. H2S
is relatively widespread and must be removed prior to export of
hydrocarbon gas and fluids. Produced gas can, quite common-
ly, have many thousands of parts per million (ppm) H2S, and
in some areas can reach tens of percent (in some Canadian gas
wells there is more H2S than methane). Chemical removal of
H2S, which is the major focus of this article, is typically con-
strained to gas concentrations of 5,000 to 10,000 ppm of H2S.
Beyond these concentrations, other methods are used, such as
amine recycling units or steam stripping units.
to this aspect of the scavenger and can determine the choice of
chemistry employed.
One chemistry that keeps emerging in chemical scaveng-
ing applications is hexahydro-1,3,5-tris(hydroxyethyl)-s-tri-
azine (also referred to as MEA triazine or simply triazine).
MEA triazine has been the most widely used H2S scavenger
for several decades, and for good reason. It is cost-effective,
efficient, and reacts rapidly with H2S; the kinetics of the re-
action are ideal for numerous application methods, including
gas contact towers, multi-phase fluids and direct gas injection.
While often successful in deployment, it does have several
well documented drawbacks, Table 1.
MEA triazine solid by-products. Perhaps the most prob-
lematic operational drawback from using MEA triazine is the
formation of solid by-products. The reaction pathway of MEA
triazine with H2S is widely known and is diagramed in Fig. 1.
The subsequent formation of insoluble and polymeric by-prod-
ucts is more complex, Fig. 2.
The reaction of MEA triazine with H2S proceeds via a se-
quential substitution of the nitrogen atoms in the triazine mol-
ecule with the sulfur atoms. The first reaction step (Fig. 1) is
kinetically fast; the thiadiazine from MEA triazine reacts rapid-
ly and cannot be observed or isolated. The second step results
Fig. 1. Reaction pathway of MEA triazine with H2S.

HOH2CH2C CH2CH2OH CH2CH2OH

SCAVENGER TECHNOLOGIES N N S N S S
The removal of H2S using process chemicals involves the
reaction of H2S with scavengers. There are two classes of H2S N N N
scavengers: oxidative and non-oxidative. Oxidative scavengers
react with H2S and change the valence state of the sulfur atom CH2CH2OH H2S CH2CH2OH H2S CH2CH2OH
from negative two to zero or greater. These scavengers can
produce elemental sulfur or, in some cases sulfate, as by-prod-
ucts. This may seem highly desirable, however the chemicals MEA-triazine Thiadiazine Dithiazine
required, and the reaction by-products, are often problematic.
Typical oxidizers used include alkaline sodium nitrite and chlo- Fig. 2. Reaction pathway for formation of amorphous polymeric
dithiazine.1
rine dioxide, which require special handling and are very corro- S S
sive to carbon steel. N
(II) Dithiazine ring fracture
As a result, this type of scavenger has seen a substantial de- H2N H2S HS H3N OH S S S S
S
N
S S

HN
S
S
N

cline in usage in recent years. Non-oxidative scavengers do not

S
N N OH
HO HO SH OH (X)

change the valence state of the sulfur, but they can chemically (VIII) Thiol formation (IX)
S S
Bisulphide attack
Ethanolamine elimination

convert the H2S molecule into either an inorganic sulfide, or OH

NH2 S S S S S S
N
N

NH2
S S S S S S
+
more commonly, an organic sulfide; the latter forming new N
S
S

S S
SH
N
S
S S
S HN
S
OH
N
S
S S
SH
+ HO

carbon-sulfur bonds. Organic sulfides are favored, since this (XIII)

N
OH
(XI)
Dithiazine ring incorporation
is an irreversible process under normal conditions encoun- OH
(XII)

N
tered in upstream operations. The chemical constitution and S
N
S S S
S
S S
S
S
HN
S S

condition of the spent scavenger is of utmost importance and S

(XIV)
will be discussed in detail later. Significant attention is given OH

World Oil® / MAY 2020 37

PRODUCTION TECHNOLOGY

in the dithiazine, which itself theoretically gives no challenges, based scavenger (NTBS). More recently, significant effort has
however it further and easily reacts and polymerizes to yield been invested to develop a NTBS that can equal triazine in
problematic solids. terms of efficacy and kinetics. To successfully achieve the goal
Most often the reaction of dithiazine proceeds via a polym- of a NTBS that competes with MEA triazine, any new product
erization process to form amorphous polymeric dithiazine (ap- must have a solid depositional control system built into the
DTZ), a highly insoluble and enormously problematic deposi- chemistry or formulation that prevents unwanted reaction solid
tion process for the oil and gas industry often known as fouling, deposition while remaining cost- effective, kinetically favorable
Fig. 2. A detailed explanation for this complex mechanism of and, ideally, a lower pH.
polymerization was published by Taylor in 2012.1 In today’s market, there are five categories of product
The apDTZ solids manifest as intractable solids in oil and that can be considered as an NTBS—summarized in Table
gas processes, and can cause major plant upset, especially when 2, along with their major advantages and disadvantages. It
MEA triazine is applied in gas contact tower applications (both is commonly perceived by industry thought leaders and
static and dynamic types). A typical system is pictured in Fig. 3. subject matter experts that none of these candidate NTBS
In a tower system, gas bubbles up from the bottom of the tower chemistries fulfill all desired goals for a triazine replace-
and through a column of scavenging liquid. As the gas bubble ment. This is especially the case for contact tower applica-
passes through the liquid scavenger, the H2S diffuses across the tions, where the degree to which any chemical is spent is
gas liquid interface and chemically reacts with the scavenger. higher, and the by-products concentrate to a higher degree
Dynamic towers are, therefore, very efficient and can use a high than any other application type. For these applications, a
degree of the chemical’s theoretical capacity. Unfortunately, this product that can withstand high degrees of spend and re-
leads to heavily spent triazine fluids, which often produce huge main solid-free is highly desirable.
amounts of the amorphous polymeric dithiazine by-product.
This requires physical cleaning and dismantling of the equip-
ment; a costly and time-consuming process. A severe example Fig. 3. Dynamic gas contact tower.
of this condition is depicted in Fig. 4.

Non-triazine based scavenger systems. The apDTZ sol-

ids problem is sometimes so severe that the industry has called
for an alternate scavenger, a “non-triazine” product that has
all the desirable attributes of triazine, but without this serious
shortcoming. The industry has long searched for a non-triazine-

Table 1. Drawbacks from using MEA triazine.

Drawback Comment
High pH High pH of unreacted and reacted scavenger
can increase mineral scale formation
(CaCO3), if in contact with produced water.
Refinery impact Monoethanolamine (MEA) is released during
reaction of MEA triazine with H2S, which
can cause overhead corrosion in refinery
processes.
Solid by-products After sufficient reaction with H2S, the
resultant by-product polymerizes to form
very insoluble, persistent solids.
Fig. 4. Heavily fouled gas contactor from dynamic gas contact
Table 2. Comparison of non-triazine based scavengers. tower.
Chemical class Example Structure Advantages Disadvantages
Metal carboxylates Zinc neodecanoic acid O
R
R Oil-soluble, very rapid Surface-active, oil and
O Zn Zn O
O O kinetics water separation
R O O O R challenges, relative high
O Zn O Zn O
R
cost
O
O
R = C7H15 R
Dialdehydes Glyoxal Acid resistant Slow kinetics, corrosive

Oxazolidines 3,3’ methylenebis-[5-methyl Rapid kinetics, Hydrolyzes to triazine

oxazolidine], MBO O 100% active product in aqueous systems
(only partial nontriazine
N option)
N
O

Hydantoins (1,3-Bis(hydroxymethyl)-5,5- OH None Very slow kinetics

dimethylimidazoline-2,4-dione,
DMDMH N O

N
O OH

Other aldehyde Typically, proprietary technology N/A N/A N/A

releasers

38 MAY 2020 / WorldOil.com
 PRODUCTION TECHNOLOGY

Aldehyde releasers, and more specially formaldehyde
releasers, are not new chemistries and have given way to tri-
azine-based solutions over the years. More recently, these old
chemistry types have had a resurgence in the oil industry. They
represent a way of using formaldehyde (much used years ago
and discontinued, due to the extreme chemical hazards associ-
ated with its use) in a latent or chemical bound form. The form-
aldehyde is liberated, only upon demand by the chemical sys-
tem in a Le Chatelier’s type model. Therefore, the amount of
free formaldehyde in the product is extremely low, and formal-
dehyde is released when, and where, it is needed by design. The
kinetics of this liberation can be tuned and tailored to suit an
application by careful choice of a synergist within the formula-
tion. In this way, the release of formaldehyde occurs only upon
contact with H2S and then at a rate suited to the application.
For example, this is most noticeably important in gas contact
towers, where the flight time of the bubble through the medi-
um is extremely low, despite the internal design of the contact
tower itself. This is likely on the order of 2-3 sec at most, and
for many “uncatalyzed” formaldehyde releaser products would
not be enough contact time to perform an efficient scavenge.
Solid deposition can still become a challenge—any scav-
enger reaction will result in by-products and the likelihood
of these by-products becoming insoluble in a given medium,
upon a high enough concentration, is always very high. Alde-
hyde releasers are no exception. The solids that form from the
reaction of formaldehyde and H2S are different to that of MEA
triazine and H2S, in that they are somewhat more predictable
and ordered in terms of their structure. This means that it is
possible to control them to a degree and allow for solids to be
dispersed, allowing for a greater scavenger spend and therefore
cost performance.
VALUE PROPOSITION
There are several proprietary technologies available from
the industry leaders in the non-triazine landscape. This clear-
ly remains an area where active research and development are
occurring, driven by the unmet need in the marketplace for a
non-triazine-based scavenger that can provide better cost per-
formance ratio to that of MEA triazine. Until that time, the in-
dustry will continue to use MEA Rtriazine-based products for
the majority of H2S scavenging applications.
REFERENCE
1. Taylor et al., Ind. Eng. Chem. Res. 2012, Vol. 51, pp 11,613−11,617.
DR. JONATHAN WYLDE is the head of global application development
and innovation at Clariant Oil and Mining Services. Since joining Clariant
in 2002, Dr. Wylde has successfully contributed to advancement across
multiple Clariant services channels, including technical, operational,
sales and business development. Dr. Wylde also serves as an Honorary
Associate Professor at Heriot Watt University in Edinburgh, Scotland.
DR. GRAHAME TAYLOR is the global innovation manager for hydrogen
sulfide scavengers for Clariant Oil and Mining Services. Prior to joining
Clariant in 2016, he was the H2S scavenger scientist at BJ Chemical
Services. Dr. Taylor has worked in other areas of oilfield chemicals
including emulsion breakers, surfactants, acid corrosion inhibitors,
fracturing fluids, conventional oilfield corrosion inhibitors and scale
inhibitors.

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