SPE 164134

The Formation and Chemical Nature of Amorphous Dithiazine Produced

From Use Of Hexahydrotriazine Based Hydrogen Sulfide Scavengers and
The Use of an Alternative Scavenger to Minimize Solid Formation in Sour
Gas Applications
Grahame N. Taylor (Baker Hughes), Philippe Prince (Baker Hughes), Ron Matherly (Baker Hughes), Ramakrishna
Ponnapati (Baker Hughes), Rose Tompkins(Baker Hughes), Vaithilingam Panchalingam (Baker Hughes), Vladimir
Jovancicevic (Baker Hughes) and Sunder Ramachandran (Baker Hughes)

Copyright 2013, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium on Oilfield Chemistry held in The Woodlands, Texas, USA, 8–10 April 2013.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
The most commonly used hydrogen sulfide (H2S) scavengers, hexahydrotriazines, are cost effective, efficient solutions to sour
gas treatment. As the product consumes H2S and the by-product concentration increases, very often solid deposits occur, the
most problematic of which is “amorphous dithiazine”. It is produced from a solution of, for example, tris-(2-hyroxyethyl)-
hexahydro-s-triazine. Recent findings have confirmed that this material is not a different physical form of the monomeric
dithiazine but rather a polymeric structure which results from opening of the dithiazine ring. Evidence is presented here for the
first step in this polymerization reaction. Thereafter, a ring opening of the dithiazine occurs to yield a polymeric, highly
insoluble material. It has been observed that the critical chemical species in the initiation of this chain reaction is the bisulfide
anion that is produced from the reaction of H2S with ethanolamine liberated in the sulfur insertion reaction undergone by tris-
(2-hyroxyethyl)-hexahydro-s-triazine. This process has been artificially induced by the reaction of monomeric or crystalline 5-
hydroxyethyl dithiazine and ethanolammonium hydrosulfide. It is hoped that a better understanding of the chemical process
giving rise to this intractable solid will enable more efficient, environmentally favorable disposal of the waste fluids and, at
best, total avoidance of this undesirable condition.
A novel approach to address this issue of troublesome solids, the use of an alternative scavenger type, is presented in
this paper. The disposal of the waste fluids was a key issue in our consideration since the disposal of spent triazine based
scavenger fluids is becoming ever more challenging and costly. Scaling tendencies at high pH is another issue for any new
scavenger and plays a key role in the method of waste fluid disposal. Recent field trial data are also presented to demonstrate
the efficacy of the new scavenger.

Introduction
Hexahydrotriazine based hydrogen sulfide scavengers have been used extensively for the past 20 years. Throughout their use
much information has been gathered regarding the chemistry and shortcomings of this very ubiquitous product. Although
some misconceptions were originally communicated the generally accepted reaction pathway when the most commonly used
hexahydrotriazine, namely 1,3,5-Tris(hydroxyethyl)-hexahydro-s-triazine (I), reacts with hydrogen sulfide is shown in Figure
1.
2 SPE 164134

R R R
N N S N S S S S

N N N S
H 2S H2S
R R R

R R

NH 2 NH 2

(I) R = CH 2 CH 2 OH (II) R = CH 2CH 2OH (III) R = CH 2 CH 2 OH (V)

(V) R = CH 3 (VI) R = CH 3 (VII) R = CH 3

Figure 1 - 1,3,5-Tris(hydroxyethyl)-hexahydro-s-triazine reaction mechanism.

Reaction with a third molecule of hydrogen sulfide, while theoretically possible, is known not to occur and the reaction
terminates at the 5-hydroxyethyldithiazine (III) stage. Early reports that trithiane (IV) was the ultimate byproduct of this
reaction have been replaced with a generally held and well proven view that the dithiazine is the ultimate product. The story is
far from over at this point. (III) is most often initially formed at elevated temperatures and once its solubility in the aqueous
medium is exceeded it separates from the aqueous scavenger fluid as a lower, highly dense organic layer. (I) has enjoyed
unmatched success partly due to the fact that it’s dithiazine still retains a hydroxyl group and has a relatively high solubility in
water, as compared, for example with 5-methyldithiazine (VII), produced from 1,3,5-Trimethylhexahydrotriazine (V).
Ultimately, however, using scavenger fluid concentrations often found in the oilfield industry, the solubility will be exceeded
and (III) comes out of solution.

Figure 2 – Spent 1,3,5-Tris(hydroxyethyl)-hexahydro-s-triazine field samples.

The initially formed lower organic layer, which can be induced to crystallize, if its cooled upon initial formation has
been conclusively analyzed and shown to be the expected dithiazine (Figure 3). The crystalline solid is a very pure form of
monomeric dithiazine and is very readily identified by its molecular ion at 165 together with the expected population of 167
ion, whereby 34S is clearly indicative that there are two sulfur atoms present.
SPE 164134 3

S S

OH

Figure 3 – Gas Chromatogram Mass Spectrum of Monomeric Dithiazine (III).

A further reaction of the monomeric dithiazine can and often does occur. In this case the ultimate product is the troublesome,
intractable, highly insoluble solid material. It has been called many things, scavenger solids, scavenger scale, solids and even
amorphous dithiazine. The latter designation is somewhat misleading since it implies that the solid is simply another form of
the dithiazine molecule. Our work has shown conclusively that this is not the case. The solid is in fact a polymeric material
which originates from further reaction of the dithiazine molecule in the presence of excessive amounts of hydrogen sulfide.
4 SPE 164134

This scavenger solid does have certain properties similar to trithiane and it is easy to see why it was originally thought to be
so. The detailed analysis that we have carried out on this material clearly shows that this is not the case.
In our studies of the formation of amorphous dithiazine we have been able to routinely simulate this transformation in
laboratory experiments. Spending a solution of (I), for example, to completion with pure hydrogen sulfide (as judged by the
uptake of 4 equivalents of hydrogen sulfide) yields the expected two phase fluid. Upon standing at room temperature overnight
the entire fluid turns solid. This heavy suspension can be readily filtered and the pure white solid is filtered, washed and dried
in a vacuum oven ready for analysis. In our studies we compared this laboratory synthesised amorphous dithiazine with the
equivalent material collected at field locations. These have been designated as a-DTZ-l and a-DTZ-f for laboratory and field
amorphous dithiazine respectively. The analysis of an extremely insoluble material such as this presents problems but it was
decided to concentrate upon a) Elemental analysis, b) X-Ray Diffraction and c) Solid State IR. A limited success was achieved
using 1H NMR and sufficient material was dissolved in hot d6DMSO to, at least, give a somewhat useful NMR spectra.
Wherever possible the amorphous dithiazine was compared with the crystalline or monomeric material in order to demonstrate
they are very significantly different in molecular structure.
SPE 164134 5

Experimental Data

Elemental Analysis

Theoretical c-DTZ Difference Difference

Element a-DTZ-l a-DTZ-f
(II) from c-DTZ from c-DTZ

Carbon 5.0 9.8 4.8 7.2 2.2

Hydrogen 11.0 21.5 10.5 15.1 4.1

Nitrogen 1.0 1.0 0.0 1.0 0.0

Sulphur 2.0 7.8 5.8 4.6 2.6

Oxygen * 1.0 1.0 0.0 1.2 0.2

Figure 4 – Empirical Formulae calculated from Elemental Analysis for c-DTZ, a-DTZ-l and a-DTZ-f

* Oxygen was actively determined not calculated by difference.

The amorphous dithiazine samples have increased carbon, hydrogen and sulfur compared with crystalline dithiazine c-
DTZ. The is explained later when a mechanism for the formation is postulated.

X-Ray Diffraction

[a-DTZ-L.MDI] Scan Data

[a-DTZ-F.MDI] Scan Data

4000

3500

a-DTZ-f
3000
Intensity(Counts)

2500
a-DTZ-l
2000

1500

1000

500

0
10 20 30 40 50 60 70
Theta(deg)

Figure 5 – X-Ray Diffraction for a-DTZ-l and a-DTZ-f.

6 SPE 164134

[c-DTZ.MDI] Scan Data

7500

Intensity(Counts)

5000

2500

0
10 20 30 40 50 60 70
Theta(deg)

Figure 6 - X-Ray Diffraction for c-DTZ-l.

The X ray diffraction pattern for both samples of amorphous dithiazine are very similar as shown in Fugure 5 and
very substanatially different from the crystalline dithiazine (Figure 6).

Solid State IR

Figure 7– IR Spectrum of a-DTZ-l.

SPE 164134 7

Figure 8- IR Spectrum of a-DTZ-f.

Figure 9 - IR Spectrum of c-DTZ.

An in depth analysis of these IR spectra is not offered here other than to indicate once again how similar are a-DTZ-l
and a-DTZ-f and how different both are from c-DTZ.
8 SPE 164134

Proton NMR

Figure 10– Proton NMR of a-DTZ-f, a-DTZ-l and c-DTZ in d6-DMSO.

Figure 11– Expanded Proton NMR of a-DTZ-f, a-DTZ-l in d6-DMSO.

The proton NMR of c-DTZ is very clearly assigned as shown. a-DTZ-l and a-DTZ-f are much more complex than c-
DTZ and have many protons in magnetically different environments fromc-DTZ. Once again an exhaustive analysis is not
SPE 164134 9

presented other than to highlight the differences.

As part of the research program we endeavoured to discover if there was anything about the molecular structure of
1,3,5-Tris(2-hydroxyethyl)-hexahydro-s-triazine that gave it such a strong propensity to form amorphous dithiazine. To that
end a structure-activity relationship was carried out with the study of 1,3,5-Tris(3-hydroxypropyl)-hexahydro-s-triazine (VIII),
1,3,5-Tris(2-hydroxypropyl)-hexahydro-s-triazine (IX), 1,3,5-Tris(1-ethyl-2-hydroxyethyl)-hexahydro-s-triazine (X), 1,3,5-
Tris(2-methoxyethyl)-hexahydro-s-triazine (XI) and 1,3,5-Tris(3-methoxypropyl)-hexahydro-s-triazine (XII).
OH

OH

N
N
OH OH

OH N N OH
N N

(VIII) (IX)

OH
OCH 3

N
N
OH OH
OCH 3 OCH 3
OCH 3
N N
N N

N
(X) (XI)

H 3CO N N OCH 3

(XII)
Figure 12 – Substituted Hexahydrotriazines.

Each hexahydrotriazine was synthesized from the appropriate amine and fully spent with pure hydrogen sulfide
according to standard laboratory conditions. It was discovered that those hexahydrotriazines with a terminal hydroxyl
functionality had a very strong tendency to form the amorphous solids. Hexahydrotriazines with a terminal substituent methyl
or methoxyl group produced either no amorphous solid at all or very substantially reduced quantities of this material. It was
felt that this was a very significant discovery in unraveling the mystery of this solid and how it is formed.
It was initially postulated that in order to account for the additional carbon and sulfur present in the amorphous dithiazine, over
and above that in the monomeric dithiazine, an interaction occurred that involved thioformaldehyde, a highly reactive, initially
formed product from the reaction of formaldehyde with hydrogen sulfide. The typical structures proposed are as shown in
Figure 13 with an ultimate structure such as (XV) which involves the opening of the dithiazine ring.
10 SPE 164134

OH O S H
S S

H 2 C=S
N N

S S S S
OH

(III) (XIII)
N

S S

S S
S S O S
S S HN
O S
S S HN

N
OH
N S S
O S * S S
S S
n
(XV) (XIV)

Figure 13 – Inial proposed mechanism for amorphous dithiazine formation.

Later experimentation showed that the tendency to form amorphous dithiazine was greatly influenced by the presence
of carbon dioxide. This was important since very often carbon dioxide is present with hydrogen sulfide in produced gas and
will compete with part of the capacity of a hexahydrotriazine scavenger (the salting of the liberated ethanolamine produced
upon each sulfur insertion reaction). It was found that the more carbon dioxide was present the lower was the tendency to
produce amorphous solids. Triazine spent with 90% carbon dioxide and 10% hydrogen sulfide remained completely free of
amorphous dithiazine for several weeks and could only be forced to produce some amorphous solids by elevating the
temperature. This observation gave rise to the theory that the bisulfide anion, present in high concentration only when no
carbon dioxide is present is in some way involved in the formation of amorphous dithiazine.
Further a model experiment was undertaken whereby aqueous ethanolaminium bisulfide and (II) dissolved in 10%
methanol in water were prepared separately and co mixed in the same proportions as they would occur in a typical fully spent
oilfield atrazine based scavenger fluid. The solution while initially clear formed a complete white solid mass of amorphous
dithiazine within 48 hours. Thus for the first time to our knowledge, a pure isolated sample of (III) has been directly converted
into amorphous dithiazine in a laboratory simulated experiment.
Since it has previously been demonstrated that terminal hydroxyl group was essential to rapid and facile amorphous
dithiazine it is now postulated that the initial step in this process is the reaction of bisulfide anion with the terminal hydroxyl
group to yield a mercaptoethyl functionality. This is the polymerization initiating species which goes on to cause ring opening
and further reaction of dithiazine to yield a polymeric structure as shown in Figure 14. The polymerisation is most likely
arrested when the species come out of solution.
SPE 164134 11

S S

N
(II)
H2N CO 2 O 3CH H 3N
OH
H2N H 2S HS H 3N
HO HO
HO HO
XVII)
(XVI)

S S S S S S H
S S
N N
S
N
S HN
SH OH
OH

(XVIII) (XIX)
S S (a)

N
S S S S
NH 2 S S
H
HO N S S S S S S NH 2
S SH S S S S S +
S OH HO
N S HN N SH
S S S S
(XXII
N
(b)
OH
(XXI) (XX)

OH
H
S S S S S S S Bisulfide attack (a) and Dithiazine
S S
ring incorporation (b) processes
N S S HN continue to form complex oligomeric
S and polymeric structures.

(XXIII) OH

Figure 14 - Current proposed mechanism for amorphous dithiazine formation.

It appears that the formation of this amorphous solid is a legacy and inherent property of the molecule itself. The
terminal hydroxyl group, while conferring high water solubility upon the by-product does come with a price. Under conditions
where the concentration of the dithiazine never reaches saturation point and remains in aqueous solution, the solid formation is
normally far less bothersome. It is only when the dithiazine is in its pure state as a separate lower layer, that the polymerization
reaction really takes off and become the overriding process in the two phase fluid. Avoiding conditions where the formation of
amorphous dithiazine is in imminent danger is the best solution to this problem. We have found that aqueous scavenger fluids
below 60% spent typically will remain homogenous but above that value phase separation occurs and the pathway to
polymeric dithiazine is initiated

Field Operations and Product Development

A recent case history for an H2S static gas tower treated with triazine based scavengers clearly illustrates the
magnitude of the problem. The business was awarded away from a competitor and when the time came to charge the gas tower
with scavenger fluid, only approx. 60% of the expected volume could be charged. The ensuing investigation revealed that one
third of the tower was filled with a solid cake of amorphous dithiazine due to repeated partial charge and drainage of the tower
(Figure 15). The lower dithiazine layer was never removed and built up over time. It then solidified in a manner previously
described and could only be removed by physical means through the man hole.
12 SPE 164134

Figure 15 – Heavy deposit of amorphous dithiazine removed from gas tower.

A research program was initiated to search for a scavenger which did not have such a propensity for high solids
deposition and involved screening many novel and existing scavengers. A laboratory gas tower scavenger evaluation method
has been previously developed.1 In order to proceed with the current project the method was modified in such a way that it
could a) use a full field strength scavenger solution (as opposed to a millimolar concentration previously) and b) include high
level of carbon dioxide in the sparging gas stream. In order to spend the full field strength fluid in a conveniently useful time
an sparging gas composition of 10% H2S and 90% CO2 was employed. The gas breakthrough for this mixture was measured
using the equipment depicted in Figure 16.
SPE 164134 13

H2S/CO2 Gas Mixture

Flow Controller
Mini-Gas Tower

Auxilliary Sampling Vessel

In Line H2S Detector

Figure 16 – Mini-tower gas scavenger testing system.

It has been designated as the “Mini-Tower” since it basically represents a miniature version of the tower described
previously.1 In place of the sulfur specific gas chromatograph for analysis, the effluent gas was analysed using an in line H2S
detector linked to a data capture software was employed. The breakthrough data was then exported to a CSV file and plotted in
an Excel spreadsheet. Some typical breakthrough data is shown in Figure 17. Breakthrough or Tbt is described as the time point
at which the effluent gas contains a concentration of greater than 100 ppm H2S. Once breakthrough occurs the H2S
concentration typically climbs very rapidly and exceeds the capability of the detector is less than a minute. It is recognized that
the conditions in this miniature gas tower experiment may represent a more extreme condition than that which will be
encountered in a field tower, however, this test methodology was found to be very useful in screening the potential candidates
for consideration as a replacement for triazine based scavengers.
The scavenger ultimately selected is shown in Figure 17 and is compared to a typical triazine based fluid. In this test
the formulated products were compared on an equal mass basis, most closely simulating how they would be used on a
commercial basis. The molar proportions and stoichiometry are not the same but it was recognized that the cost performance
comparison is the most important for commercial scavengers. As can be seen by a purely direct comparison of H2S scavenger
capacity ESCV-1 is inferior to triazine. Taking into account molecular weight and stoichiometry ESCV-1 should be about 60%
as effective as triazine. However as stated before, this is not the only consideration and disposal of the spent triazine based
fluids is becoming increasingly troublesome and expensive. It was discovered that ESCV-1 could under certain extreme
conditions also produce a solid byproduct, conditions that were unlikely to be encountered in the field application, however
14 SPE 164134

this solid material was not in any way like amorphous dithiazine, not polymeric and could, if necessary, be readily removed
with the appropriate innocuous wash solvent.

Figure 17 – Comparative H2S Breakthrough Data

The H2S scavenger capacity (sometimes called efficiency) was recorded for ESCV-1 and is defined as the gallons of
scavenger required to consume 1 ppm of H2S from 1 million cubic feet of produced gas. The lower the number the more
efficient or higher capacity is possessed by the scavenger. ESCV-1 has a theoretical efficiency of 0.14 and that for (I) is 0.08.
In a recent field trial ESCV-1 was indeed seen to be less efficient than triazine. When the product was applied in a
field Ultrafab tower field trial, it was found to be sufficiently effective such that it could, with increased volume throughput,
replace a triazine based fluid. The very significant advantage shown by ESCV-1 in the field was that rather than storing the
spent, highly malodorous, triazine in a separate tank for disposal, the spent ESCV-1 was introduced quite harmlessly into the
production water stream and disposed of in that manner. Thus the need to remove and separately dispose of spent triazine was
removed. Further the chemistry of ESCV-1 does not introduce the danger of a scaling event typical of the high pH triazine
based fluids. This was a very significant consideration in the development of the product and the need for co-injection of a
scale inhibitor was also eliminated, another cost saving for this product. ESCV-1 was formulated without the need for a
methanol cosolvent, another evvironmental benefit for this product. Other considerations addressed were typical of the oilfield
application, such as foaming tendancy, corrosivity and low temperature stability. ESCV-1 has more tolerance to lower
temperatures, with a pour point of 14°F compared to 50°F. Viewed overall the use of ESCV-1 represented a total cost saving
of $90,000 per annum for the two test gas production wells compared with the use of a typical triazine based product. The
product continues successfully in it field application and more data is being gathered to further support its value to the
customer.

Reference

1. SPE 140401. SPE International Symposium on Oilfield Chemistry, The Woodlands, Texas, USA, 11–13 April 2011.
“The Laboratory Evaluation and Optimization of Hydrogen Sulphide Scavengers Using Sulphur Specific Flame
Photometric Gas Chromatography.” - Grahame N. Taylor and Ron Matherly, (Baker Hughes, Tomball, Texas 77375).