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
H2 S(g) + 0.5O2(g)
S8 (g) + H2O(g)
8
TDA Catalyst

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 100F to 10% water
Catalyst temperatures range from 350F to 570F
depending on the sulfur dew point.
O2/H2S ratio typically stoichiometric (i.e. 0.5)

SulfaTreat-DO Process Flow

Air

Gas preheat

Sour Gas In

Liquid
knockout

water

Direct Oxidation
Reactor

265F sat steam

Air-fin cooler

Desulfurized gas

Sulfur
condenser

Liquids

To Sulfur Storage

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

preheater, 3) catalytic reactor and 4) sulfur condenser

Liquid Knockout

SOUR GAS
FROM
WHITING

Liquid
knockout

Sour liquids

A liquid knockout drum is

located upstream of the
direct oxidation reactor to
minimize exposure of the
catalyst to hydrocarbons.

The knockout is equipped

with standard level
controls, automatic
drainage and a flare
bypass.

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 in pellets

H2S Concentration Determines

Catalyst Operating Temperature
3.0

Equilibrium calculation

2.5

2.0

1.5

Sulfur dew point

S2(g)

1.0

0.5
S8(g)

0.0
100
lf
z
z
z

150
ii

200

S6(g)
S7(g)

250

300

350

S5(g)

400

450

S3(g)

Tem
500 C

between liquid sulfur

and different vapor
phase sulfur species
for 3% sulfur (100%
conversion of 3% H2S)
at 1 atm pressure
Dew point is
temperature where
liquid sulfur
concentration S goes
to zero
Dew point in this
example is about 210C
(410F)

Direct oxidation is done in the vapor phase

Minimum catalyst temperature depends on sulfur dew point
Sulfur dew point depends on H2S concentration and system pressure

Sulfur Condenser

Air fin cooler

water

265F sat steam

Desulfurized gas

Sulfur
condenser

Sulfur condenser
operates at constant
temperature by boiling
water in the shell
Sulfur vapor condenses
tubeside
Controlling steam
pressure controls
condenser temperature
33 psia saturated steam
gives Tsat = 256F
Want to keep sulfur
temperature above 240F
(melting point) and below
315F (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

300

250
8000
200

150

7000

100
6000
50

5000
0

200

400

600

800

1000

Time on stream (hours)

H2S inlet (ppm)

z
z

Sour gas flow CFM

Inlet H2S concentration stabilized at about 8000 ppm

Feed gas flowrate varied between 275 and 150 SCFM

0
1200

Sour gas flow rate (CFM)

H2S inlet concentration (ppm)

9000

Pilot Plant Feed and Product

Gas Analysis
Mol% (inlet) Mol% (outlet)
H2S
0.8000
0.095
N2
1.6
2.9
CH4
17.7
17.8
CO2
58.6
58.7
Ethane
8.7
8.6
Propane
6.5
6.3
isobutane
0.98
0.92
n-butane
2.38
2.32
isopentane
0.74
0.71
n-pentane
0.77
0.75
cyclopentane
0.01
0.01
2-methylpentane
0.15
0.14
3-methylpentane
0.13
0.12

Component

n-hexane
methylcyclopentane
benzene
z

0.27
0.14
0.21

0.24
0.12
0.17

Component
cyclohexane
n-heptane
methylcyclohexane
toluene
n-octane
ethyl benzene
p and m xylene
o-xylene
n-nonane

Mol% (inlet) Mol% (outlet)

0.17
0.14
0.09
0.07
0.05
0.04
0.02
0.01
0.005
0.003
0.003
0.002
0.003
0.003
0.0007
0.0004
0.0022

Mercaptans (ppm)

101.00

Specific gravity
(air =1 )
Gross BTU/CF dry
Gross BTU/CF wet

0.45
731.00
718.00

88+ % removal of H2S

80% removal of mercaptans
Negligible change in hydrocarbon content (i.e. no
significant hydrocarbon oxidation)

20

Pilot Test Data H2S conversion

10

100%
90%
80%
H2S conversion

60%
5

50%
40%
30%

2.5

20%
10%
0%

0
0

200

400

600

800

1000

Time on stream (hours)

H2S conversion

AIR FLOW (cfm)

Average H2S conversion approximately 90%

Over 1000 hours of operation with no catalyst deactivation

1200

Air flow (cfm)

7.5

70%

Pilot Test Data Catalyst Selectivity

6.0

100

5.0

4.0

3.0

50

2.0

Air Flow (CFM)

SO2 outlet (ppm)

75

25
1.0

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

Percent Conversion

90

T = 180 C
P = 1 atm
8000ppm H2S
3200-4400ppm O2
Bal N2

No SO2 Detected

85
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)
Average air inlet flow rate (SCFM)
Average H2S inlet (ppm)
Average H2S outlet (ppm)
Selectivity to elemental sulfur
Average sulfur yield
Total sulfur inlet (lbs)
Total sulfur inlet (tons)
Total sulfur recovered (lbs)
Total sulfur recovered (tons)
Total sulfur flared as SO2 (tons)

228
3.5
7341
790
100%
89%
7953
3.9
7097
3.6
0.86

228
0
7341
0
N/A
0
7953
3.9
0
0
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

DO REACTOR IN
TUBE FURNACE

SULFUR CONDENSER
& COLLECTOR

REACTOR BYPASS
FOR SAMPLING
INLET GAS

CONTROL
VALVE
SWEET OUTLET
GAS TO
ANALYSIS
(Drger Tubes)

Landfill Gas Results

H2S Conversion (%)

100
80
60
40
20
0
0

10

20

30

40

50

60

Time on Stream (hours)

H2S conversion

z
z
z

Selectivity to sulfur

Initial catalyst stabilization period (ca. 15 hr)

Average H2S conversion = 92 5%
Average selectivity to elemental sulfur = 99 1%

70

80

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.
SulfaTreat-DO converts 90% of the H2S into
elemental sulfur and water in a single pass
with 99% selectivity to elemental sulfur
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
z
z
z
z

Average flow : 228 Mscfd

Average H2S: 7300 ppmv
Average H2S removal: 89%
Typical SO2 concentration (ca 10 15 ppmv)
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
SulfaTreats H2S scavenger.
z Adding SulfaTreats H2S scavenger greatly
increases the versatility of SulfaTreat-DO.