Triazine Literatur

UNIVERSITY OF CALGARY
Formaldehyde-MEA Triazine Based Hydrogen Sulfide Scavenger

Behavior Study and Applications in the Oil and Gas Industry
by
Steven Yuhai Du
A THESIS
SUBMITTED TO THE FACULTY OF GRADUATE STUDIES
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF MASTER OF ENGINEERING
GRADUATE PROGRAM IN CHEMICAL AND PETROLEUM ENGINEERING
CALGARY, ALBERTA
AUGUST, 2020
© Steven Yuhai Du 2020

Abstract
Hydrogen sulfide (H2S) is an environmentally hazardous, corrosive and toxic gas in oil and gas
productions. It must be removed to meet the pre-determined specification. There are many chemicals
being used in the gas sweetening process. Formaldehyde-MEA Triazine is one of the common H2S
scavengers in use.
The objective of this research was to review different chemistries and field applications applicable as
H2S scavengers in oil and gas, understand the Formaldehyde-MEA Triazine’s properties and behaviors
in the sweetening process, and determine technical achievements on custom-made finished blends for
successful field applications.
The Formaldehyde-MEA Triazine is synthesized by the reaction of formaldehyde and

monoethanolamine (MEA). Triazine, water, free formaldehyde or free MEA are fundamental
components. Each ingredient has its unique function in process scavenging H2S. There are three steps
for triazine’s chemical reaction absorbing H2S. Free formaldehyde can boost the capacity and
breakthrough efficiency. However, it makes triazine degradation for shorter shelf life as well. A
sufficient water amount, minimum 40% more than triazine, is a must to avoid pre-mature breakthrough
in bubble tower uses.
Triazine based H2S scavengers are custom made blends for field use. Besides the Formaldehyde-MEA
Triazine, other factors such as the solvent package, other additives, plant synthesis, low temperature
operation, spent solids treatment, sour liquid sweetening and capacity monitoring are all important
considerations for successful H2S sweetening applications in the western Canadian oil and gas industry.
ii
Acknowledgments
First and foremost I am sincerely thankful to my supervisor, Dr. Zhangxing (John) Chen, who has
supported me throughout my thesis with his patience and support.
I would also like to thank the defense committee members, Dr. Hua Song and Dr. Kazi Sumon from
the Chemical & Petroleum Engineering Department, for taking time out of their busy schedule to serve
as my thesis committee members.
Lastly, I express my respects and dedications to all of those who have supported me during the
completion of this thesis.
Steven Du
iii
Dedication
I would like to dedicate this work to my wife and my daughter, Sabrina Wang and Jessica Du, for their
love and caring support which they have given to me.
iv
Table of Contents
Abstract…………………………………………………………………………………………….....ii
Acknowledgements……………………………………..…………………………………...……….iii
Dedication…………………………………………………………………………………………....iv
Table of Contents……………………………………………………………………….....................v
List of Tables……………………………………………………………….……............................vii
List of Figures and Illustrations……………………………………………………………………....x
List of Symbols, Abbreviations and Nomenclature……………………………………………...…..ix
Chapter One: Introduction………………………………………………………………....................1

1.1 Overview……………………………………………………………………………………….…1
1.2 Objectives of this Research…………………………………………………………………….…2
Chapter Two: Background and Literature Review…………………………………...…………….…4

2.1 Hydrogen Sulfide Properties…………………………………………...……………………….…4
2.2 Sweetening Methods……………………………………………………………….......................7
2.2.1 Amine Plant………………………………………………………………………………...7
2.2.2 Non-regenerable H2S Scavenger…………………………………………………………...8
2.3 Scavenger Types……………………………………………………………………………….….8
2.3.1 Formaldehyde……………………………………………………………….......................8
2.3.2 Glyoxal………………………………………………………………………………….….9
2.3.3 Morphysorb………………………………………………………………………………..11
2.3.4 LO-CAT Process…………………………………………………………………………..13
2.3.5 Other Types………………………………………………………………………………..16
Chapter Three: Field Applications…………………………………………….……………………..18

3.1 Application Techniques…………………………………………………………………………..18
3.2 Tower Application…………………………………………………………................................19
3.3 Batch Treatment……………………………………………………….………………………….23
v
Chapter Four: Technical Approach on Formaldehyde-MEA Triazine……………………………...24
4.1 Formaldehyde-MEA Triazine………………………………………………….….....................25
4.2 Formaldehyde-MEA Triazine Behavior Study……………………………….…………………28
4.2.1 Free Formaldehyde Enhances Capacity……………………………….………………….29
4.2.2 Aging Study…………………………………………………………….………………...30
4.2.3 Breakthrough Efficiency in a Bubble Tower………………………….………………….31
4.2.4 Water Content and Pre-mature Breakthrough………………………….………………...33
4.3 Field Applications………………………………………………………….……………………34
4.3.1 Solvent Packages and Additives in Formulation…………………….…………………..34
4.3.2 Plant Triazine Synthesis………………………………………..…….…………………..38
4.3.3 Paraformaldehyde Option…………………………………………….…….....................40
4.3.4 Poor Chemical Contact Sweetening………………………………….…………………...41
4.3.5 Trithiane Solids Treatment………………..…………………………….….....................44
4.3.6 Sour Water/Oil Sweetening by Triazine………………………………….……………...46
4.3.7 Relationship of Capacity vs Density of H2S Scavenger……………….………………....47
Chapter Five: Conclusions and Discussions……………….………………….………....................49

5.1 Existing Knowledge……...……………………………………………….……………………..49
5.2 New Contributions………………………………………………………………………………49
5.3 Further Discussion……………………………………………………….……………………....51
5.3.1 Aging Questions…………………………………………………………….....................51
5.3.2 MMA-Triazine…………………………………………………………………………....51
5.3.3 TEA Uses………………………………………………………………………………....53
References…………………………………………………………………………………………...54
vi
List of Tables
Table 1.1: Worker Exposure Limits for H2S……………………………….……………………...…2

Table 2.1: H2S Solubility in Pure Water……………………………………………………………...5
Table 4.1: B Company H2S Scavenger Product List 1996 – 2010……….………………………....24
Table 4.2: Triazine and Spent Triazine Anti-biotic Performance Test………………......................26
Table 4.3: C Company products………………….………………………………………………….29
Table 4.4: Aging Triazine…………………………………………………………………………...30
Table 4.5: Breakthrough Efficiency vs Free formaldehyde…...........................................................32
Table 4.6: Glycols Solids-dispersant Performance…………………………………....................…35
Table 4.7: Scale Inhibitors Solids-dispersant Performance………………………………………....36
Table 4.8: Triazine based H2S Scavengers in western Canadian Oil & Gas…………………….....37
Table 4.9: RM-HR Component List………………………………………………………………...38
Table 4.10: B Company T vs New-T H2S Scavenger…………………………………………….…39
Table 4.11: Formaldehyde Solutions……………………………………………………………......39
Table 4.12: Vapor Phase Scavenging Performance Test Results…………………………………...43
Table 4.13: Trithiane Dissolved in MEA…………………………………………………………...45
Table 4.14: 37% Triazine in Sour Water and Sour Oil Treatment……………………....................47
vii
List of Figures and Illustrations
Figure 1.1: Average Sulfur Content of US Refinery Crude Oil Inputs………………………………2

Figure 2.1: Hazard Identification of H2S………………….………………………………………….5
Figure 2.2: H2S Solubility VS Pressure (T=25°C)…………….……………………………………..6
Figure 2.3: H2S Solubility VS Temperature (P=1atm)………………….…………….......................6
Figure 2.4: Simplified Two-Stage Claus Process Plant………………………………………………8
Figure 2.5: Glyoxal Properties (BASF)……………………………………………………………..10
Figure 2.6: NFM and NAM Molecule Structures…………………………………………………...12
Figure 2.7: Morphysorb Duke Energy Kwoen Gas Plant in BC Canada…………………………...13
Figure 2.8: LO-CAT Process Diagrams…………………………………………………………..…15
Figure 2.9: Typical Simple Caustic Scrubber Unit……………………………………………..…...16
Figure 3.1: Batch and Continuous Towers for H2S Removal………….……………………..……..21
Figure 3.2: Bubble Towers in Alberta Field………………………………………………..……….22
Figure 4.1: Monothiazine/ Dithiazine in Spent H2S Scavenger………….………………..………...28
Figure 4.2: Monothiazine/ Dithiazine vs Trithiane in Spent Scavenger Solution………..…………29
Figure 4.3: Before and After Aging……………………………………………………...…………..31
Figure 4.4: B Company H2S Lab Bubble Tower……………………………………........................32
Figure 4.5: Breakthrough Efficiency vs Free formaldehyde………………………….......................32
Figure 4.6: Water Content Factor in Triazine Bubble Tower Breakthrough …….............................33
Figure 4.7: Vapor Phase Scavenging Performance Test……………………………….....................42
Figure 4.8: H2S Detector Tubes………………………………………………………......................43
Figure 4.9: Trithiane in MEA and Toluene settling 10min. vs 2-day…………………………..…...45
Figure 4.10: Trithiane in MEA @ 75°C Settling 10hr…………………………………...................46
Figure 4.11: Remaining Capacity vs Scavenger Density…………………………………..………..48
Figure 5.1: MMA-triazine Overview……………………………………………………..………....52
Figure 5.2: MMA-triazine vs MEA-triazine in scavenging H2S……………………….…………...53
viii
List of Symbols, Abbreviations and Nomenclature
Hydrogen sulfide, H2S, CAS#7782-06-4

Methyl Diethanolamine, MDEA, CAS#105-59-9
Formaldehyde, CAS#50-0-0
1,3,5-Trithiane, trithiane, CAS#291-21-4
Glyoxal, ethanedial, oxalaldehyde, CAS#107-22-2
N-formyl-morpholine, NFM, CAS#4394-85-8
N-acetyl-morpholine, NAM, CAS#1696-20-4
DMDMH hydantoin, CAS#6440-58-0
Monoethanolamine, MEA, CAS#141-43-5
Hydroxymethylaminothanol, CAS#34375-28-5
1,3,5-Triazinetriethanol, MEA-triazine, CAS#4719-04-4
Water, H2O, CAS#7732-18-5
Monoethylene glycol, MEG, CAS#107-21-1
Triethylene glycol, TEG, CAS#112-27-6
Bis[hexamethylenetriaminepenta(methylenephosphonic)] acid, CAS#34690-00-1
Paraformaldehyde, (CH2O)n (n=6-100), CAS#3052589-4
Diethylamie, DEA, CAS#109-89-7
Triethylamine, TEA, CAS#121-44-8
Monomethylamine, MMA, CAS#74-89-5
1,3,5-Trimethylhexahydro-1,3,5-triazine, MMA-triazine, CAS#108-74-7
Sodium Hydroxide, caustic soda, NaOH, CAS#1310-73-2
ix
Chapter One: Introduction
1.1 Overview
Hydrogen sulfide (H2S) is a naturally occurring gas often produced along with other fluids and/or
gases. It may also be a result of a bacterial activity (SRB: Sulfate Reducing Bacterial). Gas containing
H2S is often described as sour, while gas with no H2S is described as sweet. At present, approximately
30% of the natural gas produced in Alberta is sour, which accounts for nearly 85% of Canada’s sour
gas [21]. A general industry rule-of-thumb is that gas is often considered sour if it contains more than
4ppm of H2S (Clean Air Act, 1989).
H2S is flammable and colorless. H2S has a very distinctive odor that is often described as similar to
rotten eggs. It can be detected by smell at very low levels (about 1ppm). H2S is very toxic. It can be
fatal to healthy young adults at a concentration of 250 to 500ppm (death is immediate at a
concentration of 1,000ppm). Allowable long- and short-term exposure is dependent on concentration
but should be minimized. Children, the elderly, and people who are ill may be susceptible at much
lower concentrations than 250ppm. In addition to being toxic, H2S can cause severe corrosion
problems (H2S is known as an acid gas). See Table 1.1 below for the Canada Worker Exposure Limits.
New Market demands globally are expanding hydrocarbon processing and the distribution
infrastructure. At the same time, the average sulfur content of crude oils being processed in the world’s
petroleum refineries continues to increase; see Figure 1.1.
1
Table 1.1: Worker Exposure Limits for H2S [1]
CEILING
8-HOUR TIME 15-MINUTE TIME
LEGISLATION (NEVER EXCEED WITHOUT
WEIGHTED AVERAGE WEIGHTED AVERAGE
RESPIRATORY PROTECTION)
Alberta 10 ppm n/a 15 ppm
British Columbia n/a n/a 10 ppm
Manitoba 1 ppm 5 ppm n/a
New Brunswick 1 ppm 5 ppm n/a
Newfoundland 1 ppm 5 ppm n/a
Northwest Territories 10 ppm 15 ppm 20 ppm
Nova Scotia 1 ppm 5 ppm n/a
Ontario 10 ppm 15 ppm n/a
Prince Edward island 1 ppm 5 ppm n/a
Quebec 10 ppm n/a 15 ppm
Saskatchewan 10 ppm 15 ppm n/a
Yukon 10 ppm 15 ppm n/a
Federal 1 ppm 5 ppm n/a
Figure 1.1: Average Sulfur Content of US Refinery Crude Oil Inputs [14]
1.2 Objectives of this Research

Removal of H2S is often necessary to meet sales specifications, environmental specifications, and
mechanical requirements (i.e., for gas to be transported down lines not rated for sour gas). H2S may
also be removed to prevent down-stream operational problems such as the formation of iron sulfides
2
when sour liquids are mixed with high iron content sweet liquids. For these reasons, H2S is often
removed from produced gas through a process called sweetening to a concentration of less than 4ppm
(Clean Air Act, 1989). There are numerous methods of sweetening. The most economical method
depends largely on the amount of gas being processed and the amount of H2S present.
The purpose of this thesis is to review and understand all sweetening chemistries and processes
applied in the western Canadian oil and gas industry with a focus on the non-regenerable
Formaldehyde-MEA Triazine based H2S scavengers. The main objectives of this thesis are listed below:
• Analyze the Formaldehyde-MEA triazine chemistry and its synthesis,

• Examine the Formaldehyde-MEA triazine behaviour in the sweetening process, including the
influence factors of free formaldehyde, water content, product aging and breakthrough
efficiency in bubble tower applications,
• Oil and gas field application study, including solvent package selection in finished blends, plant
synthesis for cost reduction, additives for poor chemical contact applications,
paraformaldehyde option, spent solids removal, sour liquid treatments, relation of capacity and
density.
3
Chapter Two: Background and Literature Review
2.1 Hydrogen Sulfide Properties
Hydrogen sulfide is a colorless, highly flammable, and extremely toxic gas with a characteristic odor
of rotten eggs. The odor threshold for humans is as low as 1ppm. It is slightly soluble in water (0.4%
w/w at 20°C) and the pH value of a H2S-saturated aqueous solution is 4.5. One-thousand ppm H2S in
air can be fatal for people exposed in five minutes. The symptoms include headache, nausea,
nervousness, cough, eye irritation and insomnia [17]. High doses can cause death. Figure 2.1 below
shows the detailed hazards identification from SDS of H2S provided by Airgas [2]. H2S in solution is
corrosive and, therefore, damages the equipment which it contacts and it is poisonous to many
industrial catalysts as well.
4
Figure 2.1: Hazard Identification of H2S [2]
To summarize below the presence of H2S in hydrocarbon streams presents many environmental and
safety concerns [14].
• Toxic: H2S is highly flammable and toxic when inhaled, and strongly irritates the eyes and
other mucous membranes.
• Corrosive: sulfur-containing salts can deposit in and plug or corrode transmission pipes, valves,
and regulators.
• Pollution: the combustion products with H2S will contain unacceptable amounts of pollutants,
such as SO2 – a component of “acid rain”.
H2S is water soluble. Its solubility increases with an increase in pressure, and decreases with an
increase in temperature. The maximum solubility is about 0.4% at conditions 1atm and 20°C. The H2S
removal in water is another requirement in the oil and gas industry. See Table 2.1, Figure 2.2 and 2.3
below for its solubility information details [18].
Table 2.1: H2S Solubility in Pure Water [18]

Table: Calculated H2S Solubility (ppm) in Pure Water
T, Deg. C
P, psi 30 60 90 120 150 180 210 240
15 2975 1503 405 0 0 0 0 0
73 15062 8884 5780 3288 224 0 0 0
145 29352 17830 12400 8731 4967 0 0 0
290 55019 34660 25245 19533 14559 8656 734 0
435 62611 49912 37465 30155 24235 17622 8956 0
580 64474 63342 48929 40508 33939 26833 17612 5192
725 66229 68935 59503 50507 43602 36247 26676 13651
5
870 67857 70958 69027 60058 53159 45808 36125 22722
1160 74637 82212 77425 71682 65181 56032 42663
1450 77772 86948 91729 88951 84514 77027 64926
1740 80301 91001 101708 104404 103357 98770 89345
2031 82168 94350 108389 117565 121275 120880 115699
2321 83324 96948 113696 128357 137884 142967 143715
2611 83752 98753 117915 137176 152946 164669 173070
2901 83433 99736 120992 144435 166396 185654 203415
H2S Solubility VS Pressure (T=25C)
18000
16000
14000
H2S Solubility, ppm
12000
10000
8000
6000
4000
2000
0
0 10 20 30 40 50 60 70
Pressure, psi
Figure 2.2: H2S Solubility VS Pressure (T=25°C) [18]
H2S Solubility VS Temperature (P=1atm)
8000
7000
6000
H2S Solubility, ppm
5000
4000
3000
2000
1000
0
0 10 20 30 40 50 60 70 80 90 100
Temperature, Deg.C
Figure 2.3: H2S Solubility VS Temperature (P=1atm) [18]
6
2.2 Sweetening Methods
2.2.1 Amine Plants

Amine plants, also known as amine gas treating and gas sweetening, refers to a group of processes that
use aqueous solutions of various alkylamines (commonly referred to simply as amines) to
remove hydrogen sulfide (H2S) and carbon dioxide (CO2) from gases. It is a common unit process used
in refineries, and is also used in petrochemical plants, natural gas processing plants and other industries
[26].
Amine plants are most commonly used for large volumes of gas or systems with high concentrations of
H2S. Amine is used to remove H2S from the natural gas and is then re-generated and re-used. H2S is
most often subsequently converted to elemental sulfur in a Claus process [20]. Amine plants require
considerable capitals to install and are complex to operate, and, therefore, are only typically used in
relatively large operations. Amines are considered process chemicals.
The Claus process was first patented in 1883 by the chemist Carl Friedrich Claus. Its principal
objective is recovery of sulfur from gaseous hydrogen sulfide or, more commonly, from acid gas
streams containing hydrogen sulfide in high concentrations. Typical streams of this type are the acid
gases stripped from regenerable liquids such as the alkanolamine solutions. The reaction proceeds in
two steps shown below and in Figure 2.4 [20]:
2H2S + 3O2 → 2SO2 + 2H2O

4H2S + 2SO2 → 3S2 + 4H2O
7
Figure 2.4: Simplified Two-Stage Claus Process Plant [20]
The commonly used amines in amine plants are the alkanolamines Diethanolamine,
Monoethanolamine and Methyldiethanolamine. Methyl Diethanolamine, CAS#105-59-9, also known
as N-methyl Diethanolamine and more commonly MDEA, is the most common amine used in industry
[22]. It is a tertiary amine. As introduced in many patents, tertiary amines have better selectivity
towards H2S versus CO2 in comparison to primary (such as monoethanolamine MEA) and secondary
amines (such as diethanolamine DEA).
The other advantages for MDEA in amine plants are [3]:

• Low vapour pressure which allows for high amine compositions without appreciable losses
through an absorber and regenerator.
• Resistant to thermal and chemical degradation and largely immiscible with hydrocarbons.
• Relatively low heat of reaction with H2S and CO2 which allows for lower reboiler duties and
thus lower operating costs.
2.2.2 Non-regenerable H2S Scavengers

For a system with low levels of H2S (<1,000ppm), or small volumes of gas, liquid phase non-
regenerable H2S scavengers are commonly used. In marginally sour systems the most economical and
efficient method of sweetening the gas is through the use of an H2S scavenger. These products are easy
to use in remote locations and require a low capital investment compared to other means of H2S
8
scavenging. H2S scavengers require only a minimal capital investment as opposed to amine sweetening
units. They are ideal for use in marginally sour systems that cannot justify more elaborate sweetening
systems but still require sweetened gas. H2S scavengers are formulated to quickly and selectively
remove H2S from gas streams. See Section 2.3 for details.
2.3 Scavenger Types
2.3.1 Formaldehyde
Historically, the most common types of H2S scavengers have been based on formaldehyde (CAS#50-0-
0). Formaldehyde water solution has the advantage that it is both cheap and very reactive. It is by all
accounts, a very good H2S scavenger. However, it does have significant drawbacks. Formaldehyde is
very toxic and its reaction with H2S forms a solid reaction product (trithiane CAS#291-21-4). These
solids are highly insoluble and often must be manually removed from sweetening systems. Also, the
solids have to be disposed of appropriately which adds significant costs to sweetening programs.
3CH2O + 3H2S = (CH2S)3 + 2H2O
The formula (CH2S)3 above is 1,3,5-Trithiane (CAS#291-21-4) which is a colorless solid and slightly
soluble in water.
2.3.2 Glyoxal
Glyoxal was discovered in 1856 and has become an important component in successful chemical
applications. It has advantages including but not limited to: versatile crosslinker, biodegradability,
9
appropriate for food packaging and substitution potential [4]. Its chemical and physical properties are
in Figure 2.5.
Figure 2.5: Glyoxal Properties (BASF) [4]
Glyoxal can work as an H2S scavenger marketed by BASF. It is an efficient solution for sulphur
scavenging applications, for example, as a scavenger for sulphur compounds like H2S in gas
sweetening. It shows many benefits against the current market standard triazine [5].
• Glyoxal can be four times more efficient on a weight by weight basis at typical sulphide levels
in comparison to a typical triazine.
• Glyoxal is effective and can be applied in neutral, acidic, and alkaline conditions (pH
environment), where triazine is effective and stable only under alkaline conditions.
10
• Glyoxal can be efficiently used at acidic pH where it can be anticipated that an alkaline triazine
can cause carbonate scale formation.
• Glyoxal displays a continuous scavenging activity over longer time periods in comparison to
triazine.
• No precipitation products from a sulphide glyoxal reaction were observed during testing under
experimental conditions, whereas triazine products have documented cases of precipitation
being formed.
• Glyoxal has very good temperature stability; there is no decomposition until temperatures
exceed 150°C (onset of exothermal reaction).
• Glyoxal when diluted in water (pH below neutral) does not produce an increased quantity of
formaldehyde as a by product, where MEA triazine does.
• Glyoxal is readily biodegradable. Effluent discharge into sewage treatment plants has shown
that concentrations of up to 1000mg/L are unlikely to disturb the efficacy of activated sludge.
In acute studies, glyoxal is not hazardous to algae, daphnia or fish. A low octanol/ water
coefficient also indicates a low potential to bio-accumulate.
• Glyoxal does not need to be treated before it is discharged into waterways, whereas triazine
does, because it is harmful to fish and daphnia.
2.3.3 Morphysorb [6]
The Morphysorb technologyis a new acid gas removal process based on the use of a physical solvent
consisting of morpholine derivatives, i.e. N-formyl-morpholine (NFM) and N-acetyl-morpholine
(NAM); see Figure 2.6. It is a result of thorough laboratory research and a series of field tests by the
Gas Technology Institute (GTI) and Uhde's R&D Centre. The Morphysorb field test unit is located in
Shell's Exploration & Production facilities in Fandango, Texas, USA. The first commercial application
of the Morphysorb process is the Kwoen Gas Plant in Canada (Figure 2.7).
11
Figure 2.6: NFM and NAM Molecule Structures [7]
The key advantage of the Morphysorb technology is the high acid gas capacity together with the low
solubility of C1 to C3 hydrocarbons, resulting in a higher product yield and a lower recycle flash
stream. Moreover, the Morphysorb solvent is capable of removing mercaptans from the feed gas at the
same time.
The Morphysorb technology is not only the process of choice for feed gases containing mainly
methane and lower contents of C4+ hydrocarbons, it is also well suited for the removal of benzene,
toluene and ethylbenzene (BTEX components). Due to the high selectivity of the solvent, the
Morphysorb process is capable of generating an acid gas stream that is suitable for Claus-plants even
in unfavorable applications with high CO2 and low H2S contents in the feed gas. The process feature of
possible partial or total regeneration of the solvent under higher pressure offers additional benefits in
cases where the acid gas is disposed into high-pressure reinjection wells.
12
Figure 2.7: Morphysorb Duke Energy Kwoen Gas Plant in BC Canada
2.3.4 LO-CAT Process [8]
The LO-CAT technology was developed to provide an isothermal, low operating cost method for
carrying out the modified Claus reaction. The technology has been adopted by a number of industries,
including oil and gas, coal, power, and food & beverage.
The first commercial installation of LO-CAT technology took place in 1980. Starting with oil and gas
production (upstream and midstream), and oil refining (downstream), the basic process has been
continually improved and modified over time to allow for expanded use into other markets and
industrial segments. From petrochemicals to metals (coke oven gas and direct reduced iron off-gas),
water and waste water treatment (municipal and industrial) to carbon dioxide products (food and
beverage), this simple, robust technology has found success in multiple applications. More recently,
unconventional resources and alternative energy sources such as shale gas, stranded offshore gas,
biogas, and gasification syngas have been added to the portfolio of applications that successfully
utilize LO-CAT technology for sulphur recovery.
13
LO-CAT technology contains a proprietary liquid redox catalyst that converts H2S to solid elemental
sulphur by carrying out the direct oxidation of H2S as follows:
Direct Oxidation Reaction H2S + 1/2 O2 → H2O + S°
As embodied in LO-CAT technology, the direct oxidation reaction is divided into five sequential steps:
1 – Absorption of H2S: H2S (Gas) + H2O (Liquid) → H2S (Aq) + H2O (Aq)
2 – Ionisation of H2S: H2S (Aq) → H+ + HS–
3 – Sulphide Oxidation: HS– + 2Fe+++ → S° + 2Fe++ + H+
4 – Absorption of Oxygen: 1/2 O2 (Gas) + H2O (Liquid) → 1/2 O2 (Aq) + H2O (Aq)
5 – Iron Oxidation: 1/2 O2 (Aq) + H2O + 2Fe++ → 2 OH– + 2Fe+++
The LO-CAT II process provides cost effective H2S removal for all types of gas streams in many
different industries (Figure 2.8). The LO-CAT and LO-CAT II processes have achieved H2S removal
efficiencies of 99.9+% in many different applications and industries. These applications include natural
gas production, oil refining, biogas, landfill gas, coke oven gas, geothermal steam power production,
CO2 production for beverage use, lube oil production, and many others. These applications range in
size from a few SCFM to several hundred MM SCFD and from a few pounds of sulfur produced each
day to greater than 20 long tons of sulfur produced each day. The sour gas entering these LO-CAT
systems contains anywhere from 100 ppmv H2S to 100% H2S. The sour gas pressure ranges from a few
inches water column up to 300 psig [9].
14
Figure 2.8: LO-CAT Process Diagrams [9]
15
2.3.5 Other Types
Other scavenger types include inorganic compounds and organic based chemistry.
For the inorganic portfolio there are Zn-based scavengers (by formation of zinc sulphides), Fe-based
scavengers (by formation of iron sulphides) and Cu-based scavengers (by formation of copper
sulphides).
Scrubbing of H2S using sodium hydroxide (NaOH) solution is also a well-established technology; see
Figure 2.9. Since this process uses a solvent that cannot be easily regenerated, caustic scrubbers are
most often applied in situations where small volumes of H2S must be removed [13].
Figure 2.9: Typical Simple Caustic Scrubber Unit [13]
16
Organic based chemicals include DMDMH hydantoin (CAS#6440-58-0). Its pH is 6.5-7.5, lower than
triazine’s 9-10 which is helpful in scaling control applications. The commercialized products include
Nipaguard DMDMH from C Company and Sourban PW from L Company. However, its capacity and
reaction activity are much lower than triazine. In C Company it was mixed with triazine for field use.
17
Chapter Three: Field Applications
H2S scavengers may be applied by either continuous injection into a sour gas stream or via batch
applications – most commonly through the use of bubble towers. In most cases, it is best to treat the
gas after separation to avoid having to treat the liquids as well.
3.1 Continuous Injection

H2S scavengers can be injected continuously into a sour gas stream to sweeten the gas. The sweetening
process takes place in the line itself so minimal additional equipment is required. This method of
sweetening, although less efficient than tower applications, is very attractive to some producers as no
other equipment aside from the chemical pump and a storage tank is required. It is possible to initiate
the program with minimal capital investment. The scavenger must be applied at a location sufficiently
upstream of the location by which the gas must be sweet (i.e., where it enters a flow-line licensed for
only sweet production). This application is useful to treat gas that feeds into a plant that is not set-up
for sour production. Scavengers can be injected either into a flow-line or into a well.
In continuous injection flow-line applications, the H2S scavenger is injected into a flow-line
immediately after a wellhead separator to avoid having to treat the produced liquids. Injection is
typically prior to dehydration. The spent material is then removed in a free water knock out or
separator some distance from the injection point. Spent scavenger dissolves into produced water and is
disposed of when the water is re-injected in disposal wells.
As with other applications, it is imperative in continuous injection applications that good contact
between the liquid scavenger and the sour gas is achieved. There are certain techniques used to try and
optimize the contact between the liquid scavenger and the H2S in continuous injection applications.
These can greatly improve the efficiency of the product and allow it to treat significantly more gas in
some instances. Contact can often be improved by using application aids such as atomizers, nozzles or
in-line static mixers. Atomizers, or spray nozzles, create a fine mist of chemical with a large surface
area and thus produce more efficient contact with H2S in the gas. Nozzles producing a wide angle,
hollow cone sprays are best suited for pipeline applications. Static mixer elements can be installed into
18
flow-lines to create fluid mixing with minimum pressure drop. The internals are a series of baffles that
cause changes in a flow direction.
A line heater can also be used to warm the gas and improve treatment rates in these types of
applications. Warming the gas to 20°C - 40°C will help to speed up the reaction which is important in
situations where limited contact was available.
Continuous injection directly into a flow-line is often the choice sweetening technique when it is not
necessary to remove all of the H2S from a particular gas stream. To save on sweetening costs producers
will often choose to sweeten just to the level required. This is particularly applicable when a
marginally sour gas is blended with sweet gas in order to meet gas line specifications.
Another option is injection of a H2S scavenger down the annulus of a well. This type of application is
also suitable for a H2S scavenger that will not accumulate down-hole as almost any scavenger will
eventually form solids if severely over-spent. These kinds of H2S scavengers are usually combined
with foaming agents to ensure that spent scavenger is removed from the well in a timely manner.
In this type of application the entire depth of a well is used for the sweetening process thus increasing
the contact time of the scavenger with the sour gas. There is usually an excess of residence time and
sufficient turbulence to provide adequate contact. The spent material mixes with produced fluids and is
disposed of with the produced water removed from on-site separators.
A factor influencing the performance of H2S scavengers in down-hole applications is the presence of
water or hydrocarbons that may also be produced. Most H2S scavengers, such as triazine based ones,
are water-soluble products which can react with H2S in produced fluids in the presence of oil as well as
with H2S in the gas.
3.2 Tower Applications

Typical tower applications fall into two categories: bubble towers and packed towers. In both systems,
sour gas is passed through a tower filled with scavenger which removes the H2S (Figure 3.1). After a
period of time (ranging from days to several months), the outlet H2S concentration begins to rise as the
19
scavenger is spent. The used scavenger must then be replaced with fresh scavenger to prevent H2S
concentrations from exceeding the maximum specification. The spent scavenger is then disposed. De-
foamers may be used to prevent carryover of scavenger and to increase efficiency of the tower.
Bubble Towers
Bubble towers are the simpler of the two systems. Bubble towers are essentially a contact vessel filled
with scavenger through which the sour gas bubbles through (Figure 3.2). They are often re-cycled
separators. They are sized to provide sufficient contact time so that the volume of scavenger in a tower
lasts an acceptable amount of time (i.e., three weeks). Typically, a tower is sized such that the chosen
volume of scavenger fills the tower approximately half full to help prevent carry-over. A sparger at the
inlet of the tower allows for an even distribution of the gas in the tower and is recommended to
improve contact and efficiency of the scavenger. In some instances, scavenger is injected into the gas
stream upstream of the tower to provide for a longer contact time and to improve performance
although in most cases, this is not required.
For new applications, discussions with the producer need to be held to determine what an acceptable
lifetime for the scavenger would be. This will typically be in the range of 3-4 weeks. A tower is then
designed by calculating the volume of scavenger required to treat 3-4 weeks worthy of gas, then
doubling the volume for the size of the tower. The size of the tower may also depend on the application.
Truck mounted scrubbers and vent gas scrubbers are often simplified miniature bubble towers.
20
Figure 3.1: Batch and Continuous Towers for H2S Removal [25]
21
Figure 3.2: Bubble Towers in Alberta Field
Packed Towers
Packed contact towers are less common sweetening systems used to reduce the concentration of H2S in
gas streams. Packed contact towers have been designed to optimize the use of H2S scavengers.
Typically, a sweetening unit will contain structured packing in the top section, a scrubber, storage
tanks and plunger pumps. Sour gas enters the bottom of the contactor and passes through the packing
that is continuously coated with an H2S scavenger. Scavenger is continuously injected into the tower to
ensure that the packing remains fully coated. A mixture of re-circulated (partially spent) scavenger
from the bottom of the tower or scrubber and fresh scavenger is continuously added to the top of the
tower. The ratio of re-circulated and fresh scavenger is optimized to suit particular conditions. The
portion of the scavenger that is not re-circulated is continuously drained to a spent tank.
The purpose of re-circulating the scavenger is two-fold. During the initial pass through the contactor,
some of the scavenger will not be spent. Therefore, with recirculation, the scavenger is used more
efficiently. Also, this re-circulating system allows for a smaller volume of fresh scavenger to be used
when compared to a one-pass system (such as a bubble tower).
22
The gas leaving the top of the contactor may flow into a fuel gas scrubber (essentially a secondary mini
bubble tower). This scrubber contains the same H2S scavenger and is in place to ensure that the gas is
sweetened to specifications. Also, when there are fluctuations in the production or H2S content of the
gas, the H2S scavenger in the scrubber sweetens any spikes of H2S that are not caught by the contact
tower.
In packed contact tower systems, it is imperative that the H2S scavenger used does not form solids
when reacted with H2S. Solids can cause erosion of the packing in the pumps and plugging in the
contact tower. Replacement of pump packing and cleaning of the contact tower is expensive and labor
intensive.
3.3 Batch Treatments

Batch treatments using H2S scavengers are typically limited to small applications. The most common
of these is to treat sour fluids in trucks used to transfer fluids around a field. A small amount of
scavenger is added to the truck prior to filling with the sour fluid. By the time the truck arrives at the
next stop, the fluids have been sweetened and are more easily handled. Sour fluids in tanks can be also
treated in the same way. Proper heating, agitation and circulation are needed.
Another similar application is used to clean/sweeten tanks prior to inspection or work being done on
them. In this case, the gas inside the vessel is treated with the scavenger so that it is safe for people to
enter. For this type of application less hazardous and odorous products are recommended for the safety
concerns of people entering the vessel afterwards.
23
Chapter Four: Technical Approach on Formaldehyde-MEA Triazine
Formaldehyde-MEA Triazine is the most common non-regenerable H2S scavenger used in the western
Canadian oil and gas industry. Below is a local production chemical supplier’s H2S scavenger product
list from 1996 to 2010 (Table 4.1). From here we can see that almost all products were MEA-triazine
based.
Table 4.1: B Company H2S Scavenger Product List 1996 - 2010

Formulated Year Product Type Free Formaldehyde Special Additives Active Concentration
BT143-01 1996 No No 12-24%
BT143-02 1996 No No 30-60%
BT143-03 1996 MEA-triazine No No 12-24%
BT143-04 1997 based No No 16-33%
BT143-05 1999 No No 16-33%
BT143-06 1999 No No 30-60%
BT143-07 1999 No No 23-38%
BT143-08 1999 No Scale inhibitor 1.8% 28-47%
BT143-12 1996 No No 23-38%
BT143-13 1998 Butylamine-AEP No Scale inhibitor 1.8% 23-38%
BT143-14 1998 triazine based No No 12-20%
BT143-15 1998 No No 18-30%
Scale inhibitor 1.6%
BT143-19 2000 No 17-28%
Surfactant 6.8%
BT143-20 2000 No No 12-32%
BT143-21 2000 No No 13-37%
BT143-22 2001 No No 12-32%
MEA-triazine
BT143-23 2001 No No 8-22%
based
BT143-24 2001 No No 12-32%
Scale inhibitor 1%
BT143-25 2002 No 14-29%
Surfactant 2.5%
BT143-26 2002 Yes No 19%
BT143-27 2002 MEA-triazine Yes No 24%
BT143-28 2002 based Yes No 22%
BT143-29 2003 Yes No 14%
BT143-30 2009 Yes Scale inhibitor 2% 19%
BT143-31 2009 Yes Scale inhibitor 2% 24%
BT143-32 2009 MEA-triazine Yes Scale inhibitor 2% 22%
BT143-33 2009 based Yes Scale inhibitor 2% 14%
BT143-34 2010 No No 50%
BT143-35 2007 No Scale inhibitor 1% 37%
24
Scale inhibitor 1%
BT143-40 2006 No 27%
Surfactant 0.5%
4.1 Formaldehyde-MEA Triazine

Triazine is a synthesized product of a primary amine(s) (R-NH2) and C1-C4 aldehyde(s) [15]. In the oil
and gas industry the most common triazine for H2S scavenging is the Formaldehyde-
Monoethanolamine (MEA) Triazine (1,3,5-triazinetriethanol CAS#4719-04-4) since it has the best
performance-price ratio in commercial applications. The chemical equation is below. The mid-product
is hydroxymethylaminoethanol.
+3H2O
The equation is also shown below:
3MEA + 3 Formaldehyde = MEA-triazine + 3H2O
(MW=61x3=183)(MW=30x3=90) (MW=219) (MW=18x3=54)
Those components’ CAS numbers and molecule weights are below.

• Formaldehyde, CH2O, CAS#50-00-0, MW=30
• Monothanolamine (MEA), C2H7NO, CAS#141-43-5, MW=61
• Hydroxymethylaminothanol, CAS#34375-28-5, MW=273
• Triazine (1,3,5-Triazinetriethanol), C9H21N3O3, CAS#4719-04-4, MW=219
• Water, H2O, CAS#7732-18-5, MW=18
The MEA-triazine based H2S scavenger has the following benefits in oil and gas applications:
• Good for applications of small volume gas flowing with low H2S content.
• Simple treatment process with low investment.
25
• Water-soluble products, chemical reaction with H2S, and single-use (which is different from
regenerated amine systems in gas plants).
• As introduced the spent scavenger has anti-corrosive and anti-biotic functions. However, the
anti-biotic property might not be correct. See my test in Table 4.2 below.
• The spent scavenger can be disposed in Class 1B disposal well or any non-hazardous waste
disposal site.
Table 4.2: Triazine and Spent Triazine Anti-biotic Performance Test

Chemical
SRB White Bottle Chemical Name Temperature Time The First Non-bacteria Bottle Bacteria in Original
Injection
1-1 Blank 0 Room 22C 2 weeks 3 1X10^3/ml
1-2 T-352 500ppm Room 22C 2 weeks 1 Less than 1X10/ml
1-4 35% triazine 500ppm Room 22C 2 weeks 6 1X10^6/ml
1-5 Spent triazine 500ppm Room 22C 2 weeks 5 1X10^5/ml
Chemical
APB Red Bottle Chemical Name Temperature Time The First Non-bacteria Bottle Bacteria in Original
Injection
2-1 Blank 0 Room 22C 6 weeks 1 Less than 1X10/ml
2-4 35% triazine 500ppm Room 22C 6 weeks 1 Less than 1X10/ml
2-5 Spent triazine 500ppm Room 22C 6 weeks 1 Less than 1X10/ml
MEA-Triazine can react with H2S for in three steps by mole ratios.
First step:
Triazine reacts with the 1st mole of H2S, forms monothiazine and releases 1st mole of MEA:
MEA-triazine + H2S  Monothiazine + MEA
Second step:
Monothiazine reacts with the 2nd mole of H2S, forms dithiazine and releases 2nd mole of MEA:
Monothiazine + H2S  Dithiazine + MEA
Third step:
Dithiazine reacts with the 3rd mole of H2S, forms trithiane and releases 3rd mole of MEA:
Dithiazine + H2S  Trithiane + MEA
26
These steps are summarized again below:
Step 1: mole ratio 1/1 reacts with H2S and releases MEA for monothiazine – liquid.
Step 2: extra ratio 1/1 reacts with H2S and releases MEA for dithiazine – liquid.
Step 3: extra ratio 1/1 reacts with H2S and releases MEA for trithiane – solid.
HO HO
N N S
S N S S S S
OH
Monothiazine Dithiazine Trithiane
If there is free formaldehyde present, the released MEA continues to react with formaldehyde to form
triazine. Generated triazine keeps absorbing H2S until all free formaldehyde is consumed up.
There is a side reaction that formaldehyde (if there is free formaldehyde present) can react with H2S to
produce trithiane directly.
From above the H2S scavenging capacity calculation is concluded below:
Phenomenon one
Without free formaldehyde: maximum capacity 100% conversion for solids trithiane:
MEA-triazine ~ 3H2S
(MW=219) (MW=34x3=102)
Phenomenon two
Without free formaldehyde: field capacity 100% conversion for liquid dithiazine:
MEA-triazine ~ 2H2S
(MW=219) (MW=34x2=68)
Phenomenon three
With free formaldehyde: maximum capacity 100% conversion for solids trithiane. Here the portion of
formaldehyde is the one before triazine is formed (before reaction with MEA):
27
3Formaldehyde ~ 3H2S
(MW=30x3=90) (MW=34x3=102)
Phenomenon four
With free formaldehyde: field capacity 100% conversion for liquid dithiazine. Here the portion of
formaldehyde is the one before triazine formed (before reaction with MEA).
3Formaldehyde ~ 2H2S
(MW=30x3=90) (MW=34x2=68)
4.2 Formaldehyde-MEA Triazine Behavior study

In field applications, the formation of trithiane (C3H6S3 CAS#291-21-4) should be avoided because
these solids are highly insoluble and often must be manually removed from sweetening systems which
adds significant costs to the process. Thus, 100% conversion to dithiazine (colorless liquid) is the
target or maximum capacity for field applications. Dithiazine, and monothiazine, are colorless liquids
slightly soluble in water. Below are photos showing them in spent solution with lab bubble tower
testing (Figure 4.1 and 4.2).
Figure 4.1: Monothiazine/ Dithiazine in Spent H2S Scavenger
28
Figure 4.2: Monothiazine/ Dithiazine vs Trithiane in Spent Scavenger Solution
4.2.1 Free Formaldehyde Enhances Capacity

As mentioned in Section 4.1 we can conclude,
• Triazine reacts with H2S and releases MEA.
• If there is free formaldehyde (moles of formaldehyde > moles of MEA) present in blend, it will
react with the released MEA forming an additional molecule of triazine. The newly formed
triazine will then react with H2S.
Thus, free formaldehyde will enhance the triazine’s capacity for reaction with H2S. Table 4.3 is a
product list in C Company. Products C/G/H/I are all 40% active triazines with free formaldehyde 0,
5%, 10% and 15%. Their capacities are significantly different 8.1/6.2/5.0/4.2 ppm scavenger per 1ppm
H2S. More free formaldehyde yields a higher capacity.
Table 4.3 C Company products

Product Name MEA-Triazine Free Formaldehyde Capacity
10.7ppm scavenger per 1ppm H2S
Product A 30.00% 0
(100% dithiazine conversion)
Product B 35.25% 0
Product C 39.75% 0
Product D 45% 0
Product E 50.25% 0
29
Product F 30% 5%
Product G 40% 5%
Product H 40% 10%
Product I 40% 15%
4.2.2 Aging Study

It was observed that triazine based H2S scavengers containing free formaldehyde can experience
degradation – the product’s appearance becomes darker and darker with capacity decreasing with time.
Two samples were examined (Table 4.4).

• Sample 1: lab-made triazine with free formaldehyde
• Sample 2: lab-made triazine with free MEA (non-free formaldehyde)
The appearances were observed and the capacities were measured before and after storage at 60C for
14 days (aging conditions in fields, Figure 4.3).
Table 4.4: Aging Triazine

Sample 1 Sample 2
Free Formaldehyde in Blend 9.40% Zero
Free MEA in Blend none 3.62%
Compositions
MEA-triazine in Blend 22.55% 49.52%
Free MEA in Spent 4.27% 31.21%
Capacity
Maximum Capacity 14.10 15.38
G H2S/ 100ml Scavenger
Appearance Colorless clear Colorless clear
Fresh Samples Broken Efficiency in Lab 64.00% 53.64%
Broken Capacity in Lab 9.00 8.55
Storage Aging Conditions 60°C for 14-day
Appearance Dark red Slightly yellow
Aged Samples
Broken Capacity in Lab 0.00 8.55
30
VS
Figure 4.3: Before and After Aging
We observed that Sample 1 (with 9.4% free formaldehyde) became darker and darker with time.
Finally it became dark red and lost all capacity. Compared to that, Sample 2 (with free MEA) had no
changes on both appearance and capacity. It was the same phenomenon as reported in the field.
Aging was only reported to occur with free formaldehyde present. It was an assumption that triazine’s
degradation reaction can happen between triazine and free formaldehyde. It could be a future work in
Section 5.3.1. The degradation reaction is accelerated at high temperatures. Based on that finding, the
shelf life for the H2S scavenger containing free formaldehyde was revised to three months in summer
and six months in winter for a local vendor.
4.2.3 Breakthrough Efficiency in a Bubble Tower

Bubble towers are a common method for the gas sweetening process at a wellhead or battery. Bubble
towers are essentially a contact vessel filled with scavenger where the sour gas bubbles through it to
provide proper contact time and temperature (heat is optional in some fields). A sparger or dispenser is
usually installed at the inlet of the gas into the tower to distribute the gas more evenly through the
scavenger to improve contact and efficiency.
However, even when a sparger is used, the chemical contact between H2S and scavenger is still
considered “poor” in almost all bubble towers. The retention time or contact time is usually seconds or
sometimes even less. The poor contact time makes it such that the scavenger’s conversion capacity
cannot reach the theoretical point before the H2S stream breaks through.
In B Company lab the scavenger’s capacity was measured by utilizing a laboratory scale bubble tower
with a gas flow rate at 0.4L/min. with a gas content of 6000ppm H22S, 5% CO2, the balance with N2,
31
and monitoring by GC for H2S breakthrough (Figure 4.4). Several triazine formulations were made
with excess MEA (displaying as negative free formaldehyde) and excess formaldehyde. Their
breakthrough capacities were measured to calculate the breakthrough efficiency.
Figure 4.4: B Company H2S Lab Bubble Tower
The calculation of Breakthrough Efficiency is:

Breakthrough Efficiency=Breakthrough Capacity/Theoretical Capacity (100% dithiazine)
Table 4.5 Breakthrough Efficiency vs Free formaldehyde

Free formaldehyde (wt/wt) -3.62%* -1.18%** 9.40% 12.36%
Breakthrough Efficiency 53.64% 56.73% 64% 86.98%
* Free MEA=3.62% (wt/wt)
** Free MEA=1.18% (wt/wt)
Breakthrough Efficiency vs Free formaldehyde

0.9
0.8
Efficiency
0.7
0.6
0.5
0.4
-0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14
Free formaldehyde (wt/wt)
Figure 4.5: Breakthrough Efficiency vs Free formaldehyde
32
It confirmed our assumption and observations from the field that formaldehyde not only enhanced the
capacity but also increased breakthrough efficiency in bubble tower applications (Table 4.5 and Figure
4.5).
4.2.4 Water Content and Pre-mature Breakthrough

It was also observed in field bubble tower applications that pre-mature breakthrough happened
sometimes for dry gas sweetening. Pre-mature breakthrough means that the breakthrough point was
much earlier than expected based on theoretical capacity. Many tests were performed in the lab (with
testing method in Section 4.2.3) and the results are shown below (Figure 4.6):
• Sufficient water quantity is a must to avoid pre-mature breakthrough. Furthermore we
confirmed that a water/triazine ratio equal to 1.4 (or saying water should be 40% more than
triazine) is the minimum water content for expected capacity in a bubble tower.
• Notably, other solvents, such as methanol or glycol, cannot be used to replace water without
observing pre-mature breakthrough.
Water Content Factor in Triazine Bubble Tower Breakthough

60
50
40
H2S Breanthrough, ppm
30
20
10
0
Water/Triazine>1.4 Water/Triazine<1.4
Figure 4.6: Water Content Factor in Triazine Bubble Tower Breakthrough
33
This finding told us that proper quantity of water is needed in triazine blends for dry gas bubble tower
applications. The function of water is to provide a continuous phase for chemical molecules’ contact
for reactions, as well as in most other water-phase chemical reactions.
4.3 Field Applications
4.3.1 Solvent Packages and Additives in Formulation

MEA-triazine based H2S scavengers are usually blended with different solvent packages and additives
for specific applications.
• Formaldehyde: as studied in Section 4.2.1 the free formaldehyde can not only enhance the
capacity, but also boost the breakthrough efficiency in bubble tower applications. Also, it is
helpful for poor chemical contact or low temperature condition applications.
• Methanol: the most common and the economic solvent for winterization purposes. The
winterization specification in C Company is that fluids must be pumpable at -40°C.
• Glycol: mostly monoethylene glycol or MEG (CAS#107-21-1), absorbs water in a wet gas
stream. It is also a key component to make scavengers less volatile/ heavier in a bubble tower
with gas flow. Additionally, it is helpful for solids control, due to over spending of a scavenger,
to avoid any plug-in deposits. A vendor’s patent claimed triethylene glycol for reducing
amorphous trithiane solids [16].
• Phosphate based scale inhibitor: it works as a stabilizer in a mixture and it is also a good solid
dispersant in over-spent solution. Usually it is less than 3% in formulation. In some high
scaling tendency applications, e.g., sour water flow pipelines, a scale inhibitor can be up to
10%. Bis[hexamethylenetriaminepenta (methylenephosphonic)] acid (CAS#34690-00-1) is one
of the commonly used scale inhibitors.
• Silicone based defoamer: to kill bubbles. It is usually added at 0.2% or even less.
Table 4.6 below is a test sheet showing that ethylene glycol displayed solids dispersing properties
compared with diethylene glycol, triethylene glycol and tetraethylene glycol with the testing method
detailed in Section 4.2.3.
34
Table 4.6: Glycols Solids-dispersant Performance
Mother Solution
Formaldehyde 37%
51.00% 40.80 G
methanol 14%
Monoethanolamine 19.00% 15.20 G
Antifoam B Emulsion 0.05% 40 ul
Sample 3 Sample 4 Sample 5 Sample 6

Mother Solution 700ul 700ul 700ul 700ul
Water 20G 20G 20G 20G
Ethylene Glycol 700ul
Diethylene Glycol 700ul
Triethylene Glycol 700ul
Tetraethylene Glycol 700ul
H2S 0.4L/min 60 min 60 min 60 min 60 min

GC Foaming No No No No
GC Scale No No No No
Residue Cloudy Cloudy Cloudy Cloudy
Cloudy with white Lighter cloudy with white Lighter cloudy with white
Residue (1 day) Clear with white sediment
sediment sediment sediment
Residue (7 days) Few sediment More sediment More sediment Most sediment
Table 4.7 below shows H2S scavenger performance data with the addition of a scale inhibitor to
provide for solids dispersion. The two candidates shown are both phosphates based and they seemed to
work quite well.
Table 4.7: Scale Inhibitors Solids-dispersant Performance

Mother Solution
Formaldehyde 37%
51.00% 40.80 G
Methanol 14%
Monoethanolamine 19.00% 15.20 G
Ethylene Glycol 29.95% 23.96 G
Antifoam B Emulsion 0.05% 40 ul
Blank Sample 1 Sample 2

Mother Solution 1000ul 1000ul 1000ul
Water 20G 20G 20G
Bellasol S-30 20ul
Arquest 6360 20ul
H2S 0.4L/min 60 min 60 min 60 min

GC Foaming No No No
GC Scale No No No
Residue Cloudy Lighter cloudy Lighter cloudy
35
Residue (1 day) Cloudy Lighter cloudy Lighter cloudy
Residue (7 days) Clear with white sediment Clear with less sediment Clear with less sediment
H2S 0.4L/min 30 min 30 min 30 min

GC Foaming No No No
GC Scale No No No
Residue Lightly cloudy Clear Clear
Residue (1 day) Lightly cloudy Lighter cloudy Lighter cloudy
Residue (7 days) Lightly cloudy Lighter cloudy Lighter cloudy
From the discussion above we conclude that the MEA-triazine based H2S scavenger formulation can
contain the components listed below:
• Triazine
• Free formaldehyde or free MEA
• Methanol and/or glycol
• Phosphate based scale inhibitor
• Defoamer
Table 4.8 shows a detailed breakdown of the components in some commercialized H2S scavengers in
the western Canadian oil and gas industry – the scavenger blends are consistent with our research
conclusions.
Table 4.8: Triazine based H2S Scavengers in western Canadian Oil & Gas
Ethylene Triethylene
Component MEA-Triazine Formaldehyde MEA Methanol Phosphate
Glycol Glycol
CAS# 4719-04-4 50-00-0 141-43-5 67-56-1 107-21-1 112-27-6
Product A-1 30-60% 5-10% 10-30%
Product A-2 30-60% 1-5% 10-30% 1-5%
Product A-3 30-60% 1-5% 5-10%
Product A-4 30-60% 1-5% 5-10%
Product A-5 30-60% 1-5% 5-10%
Vendor A
Product A-6 30-60% 1-5% 5-10%
Product A-7 30-60% 1-5% 10-30%
Product A-8 30-60% 1-5% 5-10%
Product A-9 30-60% 1-5% 5-10%
Product A-10 10-30% 10-30%
Product B-1 80-100%
Product B-2 60-100% 10-30%
Product B-3 n/a 0.1-10% 10-30%
Vendor B
Product B-4 30-60% 10-30%
Product B-5 30-60% 1-5% 5-10% 5-10%
Product B-6 60-100% 10-20%
36
Product B-7 n/a 10-20%
Product B-8 60-100% 10-30% 1-5%
Product B-10 n/a 5%
Product B-11 n/a
Product B-12 60-100% 5-10% 3-7% 1-5%
Product B-13 NA 7% 4-5%
Product B-14 30-60% 1-5% 1-5%
Product B-15 n/a
Product B-16 n/a
Product B-17 30-60% 5-10%
Product B-18 30-60% 5-10%
Product B-19 n/a 9%
Product B-20 10-30% 5-10%
Product B-21 40-70% 10-30% 1-5%
Product B-22 30-60% 1-5% 10-30% 1-5%
Product B-23 30-60% 1-5% 5-10%
Product B-24 30-60% 1-5% 5-10%
Product B-25 n/a 12%
Product B-27 60%
Product B-29 n/a 5-15% 5-15%
Product B-30 n/a
Product B-31 60-100% 15-40%
Product B-32 30-60% 1-5% 10-30%
Product B-34 n/a 40-70% 10-30% 1-5% 1-5%
Product B-35 n/a 21% 1-5%
Product B-36 60-100% 10-30% 1-5%
Product B-37 40-70% 10-30% 1-5%
Product B-38 30-60% 1-5% 5-10%
Product B-39 30-60% 1-5% 10-30%
Product B-40 30-60% 1-5% 5-10%
Product B-43 n/a
Product B-44 n/a
Product B-45 n/a
Product B-49 n/a 5%
Product B-50 80-90% 11%
Product B-51 n/a 8%
Product B-53 <10% 33% <14%
Product B-54 60-100% 7-13% 7-13%
Product B-55 60-100% 10-30% 1-5% 1-5%
Product B-56 40-70% 10-30% 1-5%
Product B-57 40-70% 10-30% 1-5%
Product C-1 40-60% 10-30%
Product C-2 30-60% 1-5% 10-30%
Vendor C
Product C-3 40-60% 10-30% 10-30%
Product C-4 30-60% 7-13% 10-30%
37
Product C-5 30-35% 15-40%
Product D-1 n/a <20% 5-10%
Vendor D
Product D-2 n/a 50-60%
4.3.2 Plant Triazine Synthesis

In Section 4.1 we decoded the components in the MEA-triazine – before and after reactions. In Section
4.3.1 we discussed the solvent package and additive selections. Lab-made H2S scavengers performed
well. Plant synthesis became possible instead of purchasing commercialized commodity for a material
cost reduction purpose to make the production chemical more competitive in market.
For instance, B Company once purchased RM-HR from a vendor at $2.48/kg in 2009. The technical
group performed NMR spectroscopy analysis and calculated the recipe before reactions (Table 4.9).
Table 4.9: RM-HR Component List

RM-HR NMR spectroscopy Analysis Before Reaction
Free Formaldehyde 20.80% 28.554%
Monoethanolamine 0.00% 15.766%
Hydroxymethylaminoethanol 12.80% 0.000%
Triazinetriethanol 8.60% 0.000%
Ethylene Glycol 28.80% 28.800%
Water 29.00% 26.880%
Sum 100.00% 100.000%
B Company T-product was a diluted product from RM-HR with additional MEA and methanol. Based
on the recipe analyzed, a new T-Product was developed with exactly the same components in blend.
The plant synthesis process was designed below.
Formaldehyde selection [23]:

Formaldehyde/water solutions of up to 50% activity are commercially available. However, high
activity or lower methanol content solutions mean that higher storage temperatures are required.
Formaldehyde 50% is stable at a minimum of 60°C. Formaldehyde 37%/methanol 14%, also known as
formalin, is stable from 12.8°C to 37.8°C, and is applicable in Canadian warehouse operations.
Formaldehyde 37%/methanol 25%, has a storage temperature from -17.8°C to 29.4°C, is another
38
option for cold temperature uses. As we discussed in Section 4.2.4, methanol is good for winterization.
However, a proper water amount is also necessary for dry gas treatment. Custom made formulations
are needed for each field application. See Table 4.11 for detailed formaldehyde solution options.
Heat exchanger:
A heat exchanger was the only additional equipment needed for triazine production providing for
temperature control.
Synthesis Process:
Solvents, additives and MEA were pumped into a reaction vessel first. Formaldehyde solution was
slowly added in to keep the temperature no higher than 50°C.
Table 4.10 and 4.11 below are the comparison for T and New-T H2S scavengers. The material cost was
down from $2.30/kg to $1.13/kg, providing 51% reduction (in year 2009). H2S scavengers are usually
treated as commodities so it is a cost-driven market. By plant synthesis we increased sales in this
category from 208MT in 2008 to 500MT in 2009 or saying 140% more sales.
Table 4.10: B Company T vs New-T H2S Scavenger

B Company-T Product New T-Product (before reaction)
Monoethanolamine 4.50% Monoethanolamine 4.500%
Methanol 4.50% Methanol 4.500%
Free Formaldehyde 25.984%
Monoethanolamine 14.347%
Hydroxymethylaminoethanol 0.000%
RM-HR 91.00%
Triazinetriethanol 0.000%
Ethylene Glycol 26.208%
Water 24.461%
Sum 100.00% 100.000%
RM Cost $2.300/kg $1.126/kg
Table 4.11: Formaldehyde Solutions

No Formaldehyde Methanol Other Specific Gravity Flash Point, F Storage Temp. F Storage Life
1 25% 1.074-1.078 >210 68-100 30 days Max.
2 25% 7% 1.057-1.060 158 50-100 30 days Max.
3 28% 7% 1.066-1.069 158 50-100 30 days Max.
4 30% 1.089-1.093 >210 77-140 30 days Max.
39
5 35% Low NA 1.104-1.108 >210 86-145 30 days Max.
6 35% 7% 1.087-1.090 158 68-100 30 days Max.
7 36% 5% 1.094-1.106 161 86-140 30 days Max.
8 37% 1.110-1.114 >210 95-140 30 days Max.
9 37% Stabilized 1.110-1.114 >210 77-140 30 days Max.
10 37% 11% 1.083-1.088 147 60-100 30 days Max.
11 37% 11% Low NA 1.083-1.088 147 60-100 30 days Max.
12 37% 12% 1.080-1.083 144 59-100 30 days Max.
13 37% 13% 1.078-1.083 142 59-100 30 days Max.
14 37% 14% 1.075-1.083 140 55-100 30 days Max.
15 37% 15% 1.075-1.083 140 55-100 30 days Max.
16 37% 20% 1.062 min 130 40-100 30 days Max.
17 37% 25% 1.047-1.055 120 0-85 30 days Max.
18 37% 6% 1.098-1.101 160 70-100 30 days Max.
19 37% 7% 1.093-1.096 160 68-100 30 days Max.
20 37% 9% 1.088-1.096 149 68-100 30 days Max.
21 40% 1.118-1.123 185 113-140 30 days Max.
22 40% 5% 1.107-1.111 171 95-113 30 days Max.
23 44% 1.130-1.135 176 130-155 30 days Max.
24 44% Stabilized 1.130-1.135 176 95-140 30 days Max.
25 44% Uninhibited Low Acid 1.130-1.135 176 130-155 30 days Max.
Uninhibited Low
26 44% Sodium
1.130-1.135 176 130-155 30 days Max.
27 46.5% 1.136-1.143 171 140-150 30 days Max.
28 46.5% 12% 1.109-1.115 143 95-104 30 days Max.
29 49% 6% 1.127-1.136 158 122-140 30 days Max.
30 50% 1.148-1.153 171 145-155 30 days Max.
31 50% Stabilized 1.148-1.153 171 122-155 30 days Max.
32 51.5% Stabilized 1.152-1.157 167 130-150 30 days Max.
33 52% 1.154-1.159 160 150-155 30 days Max.
34 52% 2% 1.152-1.154 160 145-155 30 days Max.
35 53% 1.156-1.161 160 150-155 30 days Max.
36 56% Low Acid 1.161-1.168 151 145-155 30 days Max.
37 51% 1.152-1.154 170 145-155 30 days Max.
4.3.3 Para-formaldehyde Option

The highest activity formaldehyde water solution is 50%. MEA is 100% active. By calculations the
highest activity triazine synthesized from these materials is 60% (assuming that no water evaporation
process is applied).
Is there a higher active formaldehyde in market? Paraformaldehyde is an option. Paraformaldehyde

(CH2O)n (n=6-100, CAS#3052589-4) is a white solid polymerized product of formaldehyde of 6-100
units. It is 93-96% active which can be used for up to 80% triazine production with MEA.
40
Lab synthesis was applied and confirmed that paraformaldehyde had the same chemical properties as
formaldehyde/water solution in triazine production because it can be depolymerized to formaldehyde
monomer by heating – the heating was provided by the exothermic reaction between formaldehyde and
MEA. Lab observations showed that it had gentle heat generation in MEA liquid (different from
formaldehyde’s instant reaction). No heat exchanger was needed if paraformaldehyde replaced
formaldehyde solution. This finding can be applied for a further reduction in operation costs.
4.3.4 Poor Chemical Contact Sweetening

For a particular filed application, a commercially available product, C600X worked well in the T
Company F field but B Company’s product did not perform. FTIR confirmed that C600X was a
triazine based product.
It was a line application without good chemical spray. Also the operation temperature was low at only
5°C. In this case the key factor was gas sweetening performance in the vapor phase with poor chemical
contact at low temperature.
B Company used methanol as solvent package plus added 10% free formaldehyde. The field
performance improved (an injection rate from 80L/day to 60L/day). However, it was still much worse
than the competitor’s – their C600X was applied at only 20L/day.
We argued that there was small amount low flash point secondary amine or tertiary amine which
played the key role.
Testing Methods [12]:

The protocol was for testing H2S scavenging ability in the vapor phase (Figure 4.7).
41
Figure 4.7: Vapor Phase Scavenging Performance Test
Sour water was generated in the laboratory. As measured, the vapor phase contained H2S at 820ppm
and CO2 at 700ppm. Temperature was 20°C.
Testing protocol:
1. Inject 10ml sour water into a 1000ml funnel from a top left entry. The liquid drops down to the
bottom directly through a small glass pipe inside the funnel.
2. Shake for 20 seconds and settle for 20 minutes.
3. Drain out sour water from the bottom of the funnel.
4. Extract 100ml gas from the top right exit through a H2S Detector Tube and measure the H2S
content. This is for the blank (control) only.
5. Inject 1ml chemical into the funnel from the top left entry. The liquid drops down to the bottom
directly through the small glass pipe inside the funnel.
6. Settle for 10 minutes.
7. Extract 100ml gas from the top right exit through the H2S Detector Tube and measure the H2S
content.
8. Rinse pipes and vessels with water.
42
Testing Results:
The testing results below (Table 4.12) showed that low flash point diethylamine (DEA) worked
perfectly as we expected. The H2S content in the gas phase was reduced to zero from 55ppm (blank)
and 20ppm with the addition of DEA.
Table 4.12: Vapor Phase Scavenging Performance Test Results

MEA Diethylamine Triethylamine
Flash Point 85C -28°C -8°C
Amine Odor Normal Very strong Strong
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5

T4555T2 C600SX T4555T2
Chemical Blank Diethylamine
with 5% DEA about 1% DEA no DEA
H2S in Vapor Phase 55 ppm < 5 ppm 0 0 20 ppm
Figure 4.8 below is a photo for H2S Detector Tubes used for this test. From bottom to top: Blank, DEA,
T4555T2 with 5% DEA, C600SX and T4555T2 (no DEA).
Figure 4.8: H2S Detector Tubes
43
Conclusions:
1. Diethylamine reacted with H2S in the vapor phase, Sample 2 vs Sample 1. The reason why
Sample 2 did not absorb all H2S was due to the non-selective nature of DEA, as it would react
with CO2 as well. As measured, the sour water contained very high concentration of CO2 as
well.
2. Our T4555T2 blended DEA had much better H2S scavenging performance in the vapor phase,
Sample 3 vs Sample 5. DEA enhanced the H2S Scavengers’ performance in the vapor phase.
3. C600SX worked better than T4555T2 (no DEA version) in the vapor phase, Sample 4 vs
Sample 5. The reason was that it contained low flash point secondary or tertiary amine.
The result of these findings was that a new triazine blend was developed which contained 9.4% free
formaldehyde, 5% Diethylamine and 25% methanol. It worked successfully in the field at only a
15L/day injection rate.
Experience Learnt:
1. Free formaldehyde enhances the activity of H2S Scavengers. In addition, it increases the
capacity of triazine scavengers.
2. Diethylamine, the low flash point secondary amine, enhanced scavenging performance in a
vapor phase. It can be an effective additive in similar applications. Secondary and tertiary
amines will not react with formaldehydes.
4.3.5 Trithiane Solids Treatment

When triazine is overspent or free formaldehyde reacts with H2S the solids trithiane will be formed and
the precipitation can plug or deposit in a valve, tank or pipe. Trithiane is not readily soluble in water. It
is a field requirement that these solids are removed when required.
We tested many solvents and found that MEA was the best solvent to dissolve trithiane (Table 4.13).
Heating and long retention times were helpful. The colorless MEA became green when trithiane was
44
dissolved. Some researchers suggest that trithiane is soluble in benzene [19], but our laboratory testing
did not support this.
Table 4.13 Trithiane Dissolved in MEA

Trithiane : MEA 1:20 @ 41°C
1 Hour 1 Day 2 Days
Field Trithiane Dispersed into small solids > 60% dissolved, liquid became green > 90% dissolved, liquid became green
Lab-made Trithiane 100% dissolved, liquid became green
More confirmation tests were performed below (Figure 4.9 and 4.10).
Figure 4.9: Trithiane in MEA and Toluene settling 10min. vs 2-day
45
Figure 4.10: Trithiane in MEA @ 75°C Settling 10hr
The conclusions are:

• MEA can be applied in field applications for removal trithiane. The maximum solubility is ~
9.6g trithiane per 100g MEA at 75°C.
• The process is time-dependent, where multiple days were required. A high temperature can
accelerate the dissolution speed of trithiane in MEA and increase the capacity.
• Color changing to green is an indicator of trithiane dissolution.
4.3.6 Sour Water/Oil Sweetening by Triazine

We described bubble tower and pipe applications in Sections 4.2.1/4.2.3/4.2.4/4.3.4. Can triazine
scavenger chemistries work for sour water or sour oil (most time sour water with oil present)?
46
For H2S scavenging with a 37% active triazine, 1:7.8 is the ratio for 100% trithiane conversion
(maximal capacity) and 1:11.7 is the ratio for 100% dithiazine conversion (field capacity). This test
was designed for triazine’s performance in a liquid phase (water and oil) by monitoring the H2S in the
liquid and gas phase. As shown in Table 4.14 below at ~ 1:7 ratio (the theoretical ratio) all H2S was
removed.
Table 4.14: 37% Triazine in Sour Water and Sour Oil Treatment
Tested Realist 1-hour 2-day
Tested H2S H2S/37% Triazine
No. Water H2S H2S Measured H2S Measured H2S Measured
(in Vapor) Ratio
(in Water) (in Water) (in Vapor) (in Water)
1-1 10g 150 ppm > 8000 ppm 1:4 150 ppm > 60 ppm 50 ppm
1-2 10g 150 ppm > 8000 ppm 1:7 125 ppm > 60 ppm 6 ppm
1-3 10g 150 ppm > 8000 ppm 1 : 10 125 ppm 22 ppm 0
1-4 10g 150 ppm > 8000 ppm 1 : 15 100 ppm 14 ppm 0
Calculated H2S Tested H2S H2S/37% Triazine H2S Measured
No. Oil
(in Oil) (in Vapor) Ratio (in Vapor)
2-1 10g 190 ppm 4800 ppm 1:7 0
2-2 10g 190 ppm 4800 ppm 1 : 10 0
2-3 10g 190 ppm 4800 ppm 1 : 15 0
The conclusions are:

• MEA-triazine works in sour water or sour oil to remove H2S.
• The conversion rate is exactly the theoretical point. A proper injection rate is needed to avoid
the solids trithiane generation if solids are a concern.
• Hours or even days retention time is recommended. Heat or circulation can help.
4.3.7 Relationship of Capacity vs Density of H2S Scavenger

In a gas sweetening process, the H2S scavenger will continue reacting with H2S until spent. When the
scavenger becomes spent (H2S breakthrough) it will be disposed of and re-filled with new batch of
chemical. Field operation asked for a way to monitor the scavenger’s remaining capacity in a bubble
tower.
As more H2S is absorbed, the density of the scavenger liquid becomes heavier, and its remaining
capacity drops. This indicates that the remaining capacity can be monitored by measuring the
scavenger’s density. Figure 4.11 was an example in field Sword Energy Countess.
47
Lab-GC Broken Capacity vs SG of T4555T
10
9
8
G H2S/100ml Scavenger
7
6
5
4
3
2
1
0
1.08 1.09 1.1 1.11 1.12 1.13 1.14 1.15
Specific Gravity
Figure 4.11: Remaining Capacity vs Scavenger Density
Conclusions:
• Density is an indicator for scavenger’s remaining capacity. Higher density, lower remaining
capacity (because more H2S was absorbed).
• A specific calibration curve should be set up for each field application. They changed by
scavenger types, gas properties, and other parameters.
48
Chapter Five: Conclusions and Discussions
At the end of each chapter detailed conclusions on each covered topic were presented. The following
provides a summary of key findings of this thesis.
5.1 Existing Knowledge

• Formaldehyde-MEA triazine is a product of a reaction between formaldehyde and MEA. Either
free formaldehyde or free MEA will be present. If an application requires a “non-free
formaldehyde” scavenger, 1-5% more MEA over chemical equilibrium is a must.
• Formaldehyde reacts with MEA to form a triazine. The intermediate form is
Hydroxymethylaminothanol. As measured by Karl-Fisher, the intermediate form is roughly 75%
and final products are about 25% in the liquid mixture.
• Triazine reacts with H2S (a 1:3 mole ratio) in three steps to form liquid monothiazine, liquid
dithiazine and trithiane solids, releasing equivalent moles of MEA. The maximum capacity
calculation is based on 100% trithiane conversion. Field reasonable capacity calculations are based
on 100% dithiazine conversion.
• Triazine based H2S scavengers are widely used in industry. Solvent package and additive selection
are needed for specific field applications. Formaldehyde is discussed above. Methanol is used for
winterization. Phosphate-based chemistries are for solids dispersant. Glycol is for low volatile
purposes and scale dispersing. Silicone compounds are used for decreasing foaming tendency.
Most commercialized H2S scavengers are made of those components by different percentages.
5.2 New Contributions

• Free formaldehyde enhances the capacity of triazine. More free formaldehyde, higher capacity. For
40% triazine, 15% more free formaldehyde can double the capacity.
• Free formaldehyde in a scavenger blend can lead to degradation of the triazine: the product
becomes darker and darker until finally dark red; capacity keeps decreasing with time until finally
zero.
o Limited shelf life for H2S scavengers containing free formaldehyde. The capacity can decrease
to zero in four months storage at 50°C.
49
o No free formaldehyde H2S scavengers (which usually means excess MEA) have a long shelf
life maintaining the original capacity and with no noticeable change to the appearance up to
years.
• Free formaldehyde increases the triazine’s breakthrough efficiency in bubble tower applications.
MEA has the opposite function. Triazine with 15% free formaldehyde has the breakthrough
efficiency 87%. In comparison, a 3% free MEA blend has a breakthrough efficiency of only 54%.
• A minimum water/triazine ratio of 140/100 is needed to avoid triazine’s pre-mature breakthrough
in bubble tower applications. For dry gas treatment, the proper amount of water is a must in H2S
scavenger formulations.
• Triazine can be synthesized in from MEA and formaldehyde to replace commodity triazine for
material cost control. Formaldehyde 37%/methanol 14% and formaldehyde 37%/methanol 25% are
preferred raw materials. A heat exchanger is required due to the exothermic reaction that occurs.
The process is to slowly add formaldehyde into MEA with temperature control at no more than
50°C. The maximum triazine activity is 51% when synthesized this way.
• Paraformaldehyde can be used in triazine synthesis to replace the liquid formaldehyde/water
solution. Heat generation is minimal. Up to 80% active triazine can be produced.
• Low flash point secondary amine DEA (flash point -28°C) or tertiary amine TEA (flash point -8°C)
can be an effective additive in H2S scavenger for poor chemical contact applications, typically in
the vapor phase. Secondary amines work for both H2S and CO2. Tertiary amines have good
selectivity for H2S against CO2.
• Over-spent trithiane solids can be dissolved in MEA for field treatments. Multiple days settling
time is recommended. 9.6% is the maximum solubility. Green color is an indicator of dissolution.
• Triazine based H2S scavenger works not only for sour gas but also for sour water and oil. The
performance capacity is exactly the same as theoretical calculations. Hours or even days retention
time is recommended.
• The density of spent H2S scavengers can be an indicator for remaining capacity monitoring. Higher
density, lower remaining capacity.
50
5.3 Further Discussion
Further discussions are those which were not fully investigated in this thesis. Additional research is
required in the future work.
5.3.1 Aging Questions

In Section 4.2.2 we discussed the free formaldehyde triazine’s aging issue: appearance becomes darker
with capacity lower. However, why does it happen? What are the reaction mechanisms behind? The
cause could be a reaction between free formaldehyde and triazine. Hexion, the world biggest triazine
manufacturer mentioned it but no evidence or detailed information was found.
5.3.2 MMA-triazine
MEA-triazine is being widely used in upstream oil and gas applications. Another triazine chemistry,
MMA-triazine is also popular in the refinery industry (Figure 5.1). MMA is monomethylamine
(CAS#74-89-5), the smallest molecule weight primary amine. Reacting with formaldehyde, the formed
monomethylamine triazine (CAS#108-74-7) has almost the same molecule structure as MEA-triazine
but much smaller molecule weight [24]. It is believed that spent MMA-triazine could mostly partition
in the water phase (rather than spent MEA-triazine that is dissolved in the oil phase). This property
makes MMA-triazine more popular in a downstream process to decrease any residuals in the oil phase
prior to refinery treatment.
51
Figure 5.1: MMA-triazine Overview [10]
Worldwide, the most prevalent reactive chemistries in use today in the Petroleum and Refining
Industry fall into the chemical family known as triazine chemistry. The general formula and reaction
schemes for monomethylamine and monoethanolamine triazine chemistries with H2S are shown in
Figure 5.2 below. Both MMA and MEA triazines react with two moles of H2S to form the MMA
dithiazine (I) or MEA dithiazine (II) derivatives splitting off the corresponding amine as the by-
product.
Theoretically, a third mole of H2S could potentially react with the remaining amine group in the
dithiazine derivatives (I and II) to form the trithiane, but it is kinetically slow [11].
52
Figure 5.2: MMA-triazine vs MEA-triazine in scavenging H2S [11]
5.3.3 TEA Uses

As discussed in Section 4.3.4 the low flash point DEA (diethylamine) was successfully applied in a
poor chemical contact sweetening process. As a tertiary amine, low flash point TEA (triethylamine)
should have a similar function with better selection on H2S against CO2 for field poor chemical contact
uses. Appropriate performance tests are needed when possible.
53
References
1. HYDROGEN SULPHIDE TRAINING, ENFORM, Version 7.4

2. Safety Data Sheet of Hydrogen Sulfide, Airgas USA
3. Methyl Diethanolamine, WIKIPEDIA, 2020
4. Glyoxal the Sustainable Solution for your Business, BASF, 2008 Edition
5. BASF Intermediates – Glycol from BASF as an H2S Scavenger, BASF, 2006
6. Morphysorb – Uhde’s Physical Solvent for Acid Gas Removal, Uhde
7. Dennis Leppin, “New Technology for Trace Contaminant, Acid Gas Removal and Sulfur
Recovery from Coal Gasification Syngas”, Presented at GTC 2005
8. William Rouleau and John Watson, “LO-CAT: a flexible hydrogen sulphide removal process”,
Merichem Company, 2015
9. LO-CAT Process for Cost Effective Desulfurization of All Types of Gas Streams,
MERICHEM COMPANY
10. MMA Triazine, an effective H2S scavenger for sour aqueous and hydrocarbon streams,
TAMINCO
11. John M. Garcia, “Chemistry and Impacts of Commonly Used Amine-based H2S Scavengers on
Crude Unit Towers and Overheads”, Nalco Company, Paper No. 07574, NACE CORROSION
2007
12. Standard Test Method for Measurement of Hydrogen Sulfide in the Vapor Phase Above
Residual Fuel Oils, ASTM D 5705-95
13. D. MAMROSH, C.BEITLER, and K.FISHER, Consider improved scrubbing designs for acid
gases, Trimeric Corp., Buda, Texas; and S.STEM, Montana Refining Co., Great Falls, Montana
14. Hydrogen Sulfide Management, Mitigation options in petroleum refining, storage and
transportation, BAKER HUGHES
15. Russell Poinds, Richmond; Doyle Cherry, Kemah, both of Tex., HYDROGEN SULFIDE
SCAVENGING PROCESS, Crescent Holdings Limited, Kemah, Tex., United States Patent
Number: 5,462,721
16. OWENS, THOMAS ROBERT, Formulation for Hydrogen Sulphide Scavenging from
Hydrocarbon Streams and use thereof, Canadian Patent Application 2603022, CANWELL
ENVIRO-INDUSTRIES LTD.,
54
17. Hydrogen Sulfide, WIKIPEDIA, 2020
18. Zhenhao Duan, Rui Sun, Rong Liu, and Chen Zhu, Accurate Thermodynamic Model for the
Calculation of H2S Solubility in Pure Water and Brines, Energy & Fuels 2007, 21, 2056-2065
19. 1,3,5-Trithiane, WIKIPEDIA, 2020
20. Arthur L. Kohl, Richard B. Nielsen, Gas Purification (Fifth Edition), 1997
21. Natural gas overview, Production, Alberta.ca, 2020
22. Oilfield Production Chemicals and Microbiology, HTS Consultants, 2011
23. Storage of Formaldehyde Solutions, HEXION Specialty Chemicals, 2010
24. Kishan Bhatia, Allan R. Thomas, Daniel S. Sullivan, Method of Treating Sour Gas and Liquid
Hydrocarbon Streams, European Patent Application #94305225.8, Jul. 1994
25. Production Field Manual, Brenntag Canada, 2008
26. Amine Gas Treating, WIKIPEDIA, 2020
55

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UNIVERSITY OF CALGARY

Formaldehyde-MEA Triazine Based Hydrogen Sulfide Scavenger

GRADUATE PROGRAM IN CHEMICAL AND PETROLEUM ENGINEERING

© Steven Yuhai Du 2020

The Formaldehyde-MEA Triazine is synthesized by the reaction of formaldehyde and

Chapter One: Introduction………………………………………………………………....................1

Chapter Two: Background and Literature Review…………………………………...…………….…4

Chapter Three: Field Applications…………………………………………….……………………..18

Chapter Five: Conclusions and Discussions……………….………………….………....................49

Table 1.1: Worker Exposure Limits for H2S……………………………….……………………...…2

Figure 1.1: Average Sulfur Content of US Refinery Crude Oil Inputs………………………………2

Hydrogen sulfide, H2S, CAS#7782-06-4

1.2 Objectives of this Research

• Analyze the Formaldehyde-MEA triazine chemistry and its synthesis,

2.1 Hydrogen Sulfide Properties

Table 2.1: H2S Solubility in Pure Water [18]

H2S Solubility VS Pressure (T=25C)

Figure 2.2: H2S Solubility VS Pressure (T=25°C) [18]

H2S Solubility VS Temperature (P=1atm)

Figure 2.3: H2S Solubility VS Temperature (P=1atm) [18]

2.2.1 Amine Plants

2H2S + 3O2 → 2SO2 + 2H2O

The other advantages for MDEA in amine plants are [3]:

2.2.2 Non-regenerable H2S Scavengers

2.3 Scavenger Types

3CH2O + 3H2S = (CH2S)3 + 2H2O

Figure 2.5: Glyoxal Properties (BASF) [4]

2.3.3 Morphysorb [6]

2.3.4 LO-CAT Process [8]

Direct Oxidation Reaction H2S + 1/2 O2 → H2O + S°

Figure 2.9: Typical Simple Caustic Scrubber Unit [13]

3.1 Continuous Injection

3.2 Tower Applications

3.3 Batch Treatments

Table 4.1: B Company H2S Scavenger Product List 1996 - 2010

4.1 Formaldehyde-MEA Triazine

Those components’ CAS numbers and molecule weights are below.

Table 4.2: Triazine and Spent Triazine Anti-biotic Performance Test

From above the H2S scavenging capacity calculation is concluded below:

4.2 Formaldehyde-MEA Triazine Behavior study

Figure 4.1: Monothiazine/ Dithiazine in Spent H2S Scavenger

4.2.1 Free Formaldehyde Enhances Capacity

Table 4.3 C Company products

4.2.2 Aging Study

Two samples were examined (Table 4.4).

Table 4.4: Aging Triazine

4.2.3 Breakthrough Efficiency in a Bubble Tower

Figure 4.4: B Company H2S Lab Bubble Tower

The calculation of Breakthrough Efficiency is:

Table 4.5 Breakthrough Efficiency vs Free formaldehyde

Breakthrough Efficiency vs Free formaldehyde

Figure 4.5: Breakthrough Efficiency vs Free formaldehyde

4.2.4 Water Content and Pre-mature Breakthrough

Water Content Factor in Triazine Bubble Tower Breakthough

Figure 4.6: Water Content Factor in Triazine Bubble Tower Breakthrough

4.3 Field Applications

4.3.1 Solvent Packages and Additives in Formulation

Sample 3 Sample 4 Sample 5 Sample 6

H2S 0.4L/min 60 min 60 min 60 min 60 min

Table 4.7: Scale Inhibitors Solids-dispersant Performance

Blank Sample 1 Sample 2

H2S 0.4L/min 60 min 60 min 60 min

H2S 0.4L/min 30 min 30 min 30 min