SulfaTreat-DO: Direct Oxidation

for Hydrogen Sulfide Removal

Samir Jategaonkar, Brian Kay and Thomas Braga

SulfaTreat, A Business Unit of M-I L.L.C.
17998 Chesterfield Airport Road, Suite 215, Chesterfield,
MO 63005, USA

Girish Srinivas and Steven Gebhard

TDA Research, Inc.
12345 W. 52nd Avenue, Wheat Ridge, CO 80033, USA
 SulfaTreat-DO Partners

• SulfaTreat-DO uses a proprietary,

patented, mixed-metal-oxide catalyst that
was developed by TDA Research, Inc.
(Wheat Ridge, CO)

• Engineering and fabrication of plants is

done in collaboration with Westfield
Engineering (Houston, TX)
 H2S Direct Oxidation Chemistry
• SulfaTreat-DO converts hydrogen sulfide in various gas
streams into elemental sulfur and water by catalytic
oxidation with air.
1
TDA Catalyst
H2 S(g) + 0.5O2(g)     
→ S8 (g) + H2O(g)
8

• SulfaTreat-DO treats the gas directly; no pre-separation of

H2S is required (i.e. no amine unit is needed).
• The selectivity of the process is better than 99% for sulfur
with little (< 50 ppm) or no SO2 formed.
• 90% conversion of H2S into elemental sulfur is obtained
in a single pass .
SulfaTreat-DO Catalyst Development
• The commercial catalyst has been tested and
proven at the:
• Laboratory scale
• Few grams of catalyst and milliliter/min flowrates
• Field bench scale
• Pounds of catalyst and flowrates of several liters/min
• Pilot plant scale
• 1700 lb of catalyst and a flowrate of 300,000 SCFD
• H2S concentrations from a few hundred ppm to 3-4%
can be processed
• Humidity can be from sat. at 100°F to 10% water
• Catalyst temperatures range from 350°F to 570°F
depending on the sulfur dew point.
• O2/H2S ratio typically stoichiometric (i.e. 0.5)
 SulfaTreat-DO Process Flow
Air

Gas preheat
Air-fin cooler

Direct Oxidation

water
Reactor

265F sat steam

Sour Gas In
Liquid Desulfurized gas
knockout

Sulfur
condenser

To Sulfur Storage
Liquids

• SulfaTreat-DO is very simple: 1) knockout drum, 2) gas

preheater, 3) catalytic reactor and 4) sulfur condenser
 Liquid Knockout
• A liquid knockout drum is
located upstream of the
direct oxidation reactor to
minimize exposure of the
catalyst to hydrocarbons.

Liquid • The knockout is equipped

SOUR GAS
knockout with standard level
FROM controls, automatic
WHITING
drainage and a flare
bypass.
Sour liquids
Catalytic Reactor

• Carbon steel
• Refractory lined
• Operated adiabatically
• Adiabatic operation limits
H2S to 3-4% maximum
(because of temperature
rise)
• 1700 - 2000 lb catalyst
charge
• Typically 1/8 in x ¼ in pellets
 H2S Concentration Determines
Catalyst Operating Temperature
3.0
S
• Equilibrium calculation
2.5
between liquid sulfur
and different vapor
phase sulfur species
2.0
for 3% sulfur (100%
conversion of 3% H2S)
1.5 at 1 atm pressure
Sulfur dew point • Dew point is
S2(g)
1.0
temperature where
liquid sulfur
concentration “S” goes
0.5
S8(g)
to zero
S6(g)
S7(g) S5(g) S3(g)
• Dew point in this
0.0
Tem example is about 210°C
100 150 200 250 300 350 400 450 500 C
lf ii
(410°F)
z Direct oxidation is done in the vapor phase
z Minimum catalyst temperature depends on sulfur dew point
z Sulfur dew point depends on H2S concentration and system pressure
 Sulfur Condenser
• Sulfur condenser
operates at constant
Air fin cooler
temperature by boiling
water in the shell
• Sulfur vapor condenses
tubeside
265F sat steam

water

• Controlling steam
pressure controls
condenser temperature
• 33 psia saturated steam
Desulfurized gas gives Tsat = 256°F
• Want to keep sulfur
temperature above 240°F
Sulfur
condenser
(melting point) and below
315°F (high viscosity
region).
 Pilot Plant Test of SulfaTreat-DO
Demonstrated in West Texas (near Plains)
z Whiting Petroleum gas plant

• Associated gas (0.3 MMSCFD from an oil field)

• 0.8% H2S (8000 ppm)
• 20% methane
• 15% ethane
• 10% propane
• Balance CO2 (ca 55%)
• > 2300 ppm BTEX
• ~ 100 ppm mercaptans
Photograph of the Pilot Plant
Close Up of Sulfur Condenser Area
 Pilot Test Data – Feed Gas
9000 300

250
H2S inlet concentration (ppm)

8000

Sour gas flow rate (CFM)

200

7000 150

100
6000
50

5000 0
0 200 400 600 800 1000 1200
Time on stream (hours)
H2S inlet (ppm) Sour gas flow CFM

z Inlet H2S concentration stabilized at about 8000 ppm

z Feed gas flowrate varied between 275 and 150 SCFM
 Pilot Plant Feed and Product
Gas Analysis
Component Mol% (inlet) Mol% (outlet) Component Mol% (inlet) Mol% (outlet)
H2S 0.8000 0.095 cyclohexane 0.17 0.14
N2 1.6 2.9 n-heptane 0.09 0.07
CH4 17.7 17.8 methylcyclohexane 0.05 0.04
CO2 58.6 58.7 toluene 0.02 0.01
Ethane 8.7 8.6 n-octane 0.005 0.003
Propane 6.5 6.3 ethyl benzene 0.003 0.002
isobutane 0.98 0.92 p and m xylene 0.003 0.003
n-butane 2.38 2.32 o-xylene 0.0007 0.0004
isopentane 0.74 0.71 n-nonane 0.0022
n-pentane 0.77 0.75
cyclopentane 0.01 0.01 Mercaptans (ppm) 101.00 20
2-methylpentane 0.15 0.14
3-methylpentane 0.13 0.12 Specific gravity 0.45
(air =1 )
n-hexane 0.27 0.24 Gross BTU/CF dry 731.00
methylcyclopentane 0.14 0.12 Gross BTU/CF wet 718.00
benzene 0.21 0.17

z 88+ % removal of H2S

• 80% removal of mercaptans
• Negligible change in hydrocarbon content (i.e. no
significant hydrocarbon oxidation)
 Pilot Test Data – H2S conversion
100% 10

90%

80%
7.5
70%
H2S conversion

Air flow (cfm)

60%

50% 5

40%

30%
2.5
20%

10%

0% 0
0 200 400 600 800 1000 1200
Time on stream (hours)

H2S conversion AIR FLOW (cfm)

• Average H2S conversion approximately 90%

• Over 1000 hours of operation with no catalyst deactivation
 Pilot Test Data – Catalyst Selectivity
100 6.0

5.0
75
4.0
SO2 outlet (ppm)

Air Flow (CFM)

50 3.0

2.0
25
1.0

0 0.0
0 200 400 600 800 1000 1200
Time on stream (hours)
SO2 outlet (ppm) AIR FLOW (cfm)

• Selectivity to sulfur > 99%

• Never more than 80 ppm of SO2 formed during the 1000 hour test
• SO2 selectivity can be controlled by increasing the temperature or
increasing the air flow rate.
Laboratory Test of Fresh and Used
Pilot Plant Catalyst
95
o
T = 180 C
P = 1 atm No SO2 Detected
8000ppm H2S
90
3200-4400ppm O2
Bal N2

85
Percent Conversion

Used Catalyst Fresh Catalyst

80

75

70

65
0.8 0.9 1.0
O2 Concentration (Percentage of Stoichiometric)

• Laboratory testing of fresh catalyst, and catalyst removed from the pilot
plant after the 1000 hour test, gave identical performance under carefully
controlled conditions
 Pilot Test - Summary
Field Test Case No Sulfur Recovery Case
Average sour gas flow rate (SCFM) 228 228
Average air inlet flow rate (SCFM) 3.5 0
Average H2S inlet (ppm) 7341 7341
Average H2S outlet (ppm) 790 0
Selectivity to elemental sulfur 100% N/A
Average sulfur yield 89% 0
Total sulfur inlet (lbs) 7953 7953
Total sulfur inlet (tons) 3.9 3.9
Total sulfur recovered (lbs) 7097 0
Total sulfur recovered (tons) 3.6 0
Total sulfur flared as SO2 (tons) 0.86 7.95

• Results from 1000+ hour test indicate an average

removal of 89% of the H2S with 99+% selectivity
for elemental sulfur
 Landfill Gas Bench Scale Test

Test conditions for bench-scale landfill gas experiment

Inlet gas flow 200 sccm
Inlet air flow Varied to maintain O2/H2S= 0.5
Reaction temperature (°C) 210 ± 5
GHSV (cm3gas/cm3 catalyst/hour) 750
Pressure (psig) 24.7 psig
H2S concentration (vol%) 1.0 - 2.5

• Small laboratory scale test

• Landfill gas
• Contaminated with 1-1.2% H2S
• Low pressure
 Landfill Gas Test – Apparatus
AIR

INLET
GAS
ELECTRONIC MASS
FLOW CONTROLLERS

REACTOR BYPASS
DO REACTOR IN
FOR SAMPLING
TUBE FURNACE
INLET GAS

SULFUR CONDENSER CONTROL

& COLLECTOR VALVE

SWEET OUTLET
GAS TO
ANALYSIS
(Dräger Tubes)
 Landfill Gas Results
100

80
H2S Conversion (%)

60

40

20

0
0 10 20 30 40 50 60 70 80
Time on Stream (hours)
H2S conversion Selectivity to sulfur

z Initial catalyst stabilization period (ca. 15 hr)

z Average H2S conversion = 92 ± 5%
z Average selectivity to elemental sulfur = 99 ± 1%
 Summary and Conclusions - 1

z SulfaTreat-DO is a simple, cost effective

process for removing up to 3-4% H2S from
natural gas, associated gas and landfill gas
streams.
z SulfaTreat-DO converts 90% of the H2S into
elemental sulfur and water in a single pass
with ≥ 99% selectivity to elemental sulfur
z SulfaTreat-DO produces less than 100 ppm
of SO2 under normal operating conditions.
 Summary and Conclusions - 2

z A pilot plant test was successfully

completed that demonstrates the
reliability of SulfaTreat-DO
z Average flow : 228 Mscfd
z Average H2S: 7300 ppmv
z Average H2S removal: 89%
z Typical SO2 concentration (ca 10 – 15 ppmv)
z 1000+ hours operation with no catalyst
deactivation
 Summary and Conclusions - 3

z A field bench test on landfill gas was successfully

completed that demonstrates that SulfaTreat-DO
can process a wide variety of gas streams
z Average H2S conversion = 90%

z Average selectivity = 99+%

z No catalyst deactivation

z Over 99% of the H2S can be removed when the

tail gas from SulfaTreat-DO unit is treated with

SulfaTreat’s H2S scavenger.
z Adding SulfaTreat’s H2S scavenger greatly

increases the versatility of SulfaTreat-DO.