ALBERTA SULPHUR RESEARCH LTD.

Basic Triazine Chemistry and Gas Scavenging Evaluation

General Types of H2S Scavengers

Metals
 Iron Sponge (Fe2O3), Sulfatreat (Fe2O3, Fe3O4)  Zinc and copper sulfates, sulfites, oxides

Caustics
 NaOH and KOH solutions

Oxidizers
 HOOH/H2O oxidizes H2S to Sulfur and then SO4

Amine/Aldehyde
 Formaldehyde (late 1970s)  Triazines

Concerns with Scavenger Formulations Fresh Chemical

      

Cost H2S capacity Foaming tendencies physical carryover Stability thermal, pH, chemical Scaling tendencies Viscosity at different temperatures (freezing point) Toxicity and Odour

Spent Chemical
 Disposal and transportation concerns  Solubility of reaction products solid formation?

Triazine Synthesis
O 3 H 2N O OH H 3 H H H C N OH

+
OH

3 H2O

H 2N

HO N C N H OH OH N N

OH

HO N and N N

OH

H 3

O HO

Detection and Analysis of Triazines

ASRL
 1H and 13C NMR are used to directly detect and analyze triazine mixtures.  Capacity tests are used to determine the H2S scavenger capacity.

Attempts to analyze triazines (MEA/HCHO) using gas chromatographic techniques have been reported to be unsuccessful due to them being thermally labile.

Triazine Chemistry Reaction with H2S

HO N N N OH 1) H+ 2) HS- or S2S N N OH 1) H+ 2) HS- or S2S S N OH

+
OH OH H 2N OH OH

+
H2 N OH S S N 1) H+ 2) HS- or S2slow S S S

H 2N

OH

mp 39 C

Spent Material
O O S
Dithiazines

O S

S
2S

S S S S

+ C O ( eat)

1,2,4-Trithiolane

1,2,4,6-Tetrathiopane

Scavenger Capacity Experimental Set-up Gas Stream Applications

Feed Gas sampling point

Rotameter Pressure Gauge

Outlet Gas sampling point

Project: H2S/CO2 Scavenger Testing Test Duration: 6-7h per day

3-way Valve

Bubble Tower Liquid sampling point Scavenger 50mL

Water Saturation of Gas Mixture

Stirrer By-pass line CH4 H 2S

Trap 1

Trap 2

Trap composition: 160mL of 1:1 Acetone to Formaldehyde

Gas composition: H2S CO2 CH4

CO2

Mass Flow Controller PWR

To Exhaust

To Exhaust

KOH trap

KOH trap

Dry trap

KOH trap

KOH trap

Dry trap

Scavenger Capacity Data Collection and Analysis GC Chromatography  Measures inlet and outlet gas composition  Outlet [H2S] > 0.1% constitutes breakthrough point used as a bench mark to compare different formulations Total Sulfur Analysis  Measures total H2S uptake as a function of time by analyzing the total sulfur content at regular time intervals Physical Changes  Color  Foaming  Formation of solids or new layers

400SX / 600SX / 800SX

H2S% Outlet Stream

400SX : 90 min 600SX : 116 min 800SX : 200 min

2

50

100

150

200

250

Time (min)

Thermal Degradation Long Term

Degradatio of Air Sat rated () Cansweet 600SX at ~19rC
H2S Capacity (in minutes) (Capacity = H S% > 0% in outlet gas) 2
200

Degradation of Cansweet 800SX at ~19 r C ( ) and ~0r C ( )

250

H2S Capacity (in min tes) Capacity = H2S% > 0% in outlet gas

200

150

Experiment Stopped
100

150

100

50

50

Experiments Stopped
0 0 50 100 150 200 250 300 350

50

100 150 200 250 300 350 400 450

Ti e of Capacity Tests (Days)

Time of Capacity Tests (Days)

(600SX) H2S capacity % = ((-0.1942 x number of days left +117) / 117) x100% (800SX) H2S capacity % = (e(-0.00333 x number of days left at 20C)) x 100%

Thermal Degradation High Temp

 The primary product produced from the thermal decomposition of 800SX and 600SX is DMAE. This is a reaction product between formaldehyde and MEA since formaldehyde and triazine/amine condensates disappear as DMAE is produced.  Insulating the flask accelerates the reaction of 800SX: the reaction is doubled at 54C and almost three times faster at 75C. This suggests that the reaction is exothermic and insulating the flask raises the solution temperature which causes a higher rate of thermal degradation.  Mixing previously degraded 800SX with fresh 800SX does not accelerate the decomposition of fresh 800SX. Thus, adding fresh 800SX to towers which already contain old 800SX will not have any detrimental effects other than those caused by dilution.  The best results have been obtained with 800SX with added methanol (50% by Volume); this formulation reduces degradation by almost a factor of seven. Even when insulated this formula still effectively inhibits degradation.